JP6657602B2 - Method for producing cyclic polyolefin film - Google Patents

Description

The present invention relates to the production how the cyclic polyolefin film. More specifically, to reduce the foreign matter failure during film, and by reducing the content and haze of foreign matter finished film relates to the production how to produce high transparency of the cyclic polyolefin film.

  In recent years, if only optical films such as a polarizing plate protective film and a retardation film for a liquid crystal display device or an organic electroluminescence display device as a display device, and a base film such as a base film for a touch panel or a gas barrier base film, are provided. In addition, there is a great demand for a flexible resin film having high transparency, high functionality, and light weight, such as a substrate film for a nanoimprint or a flexible electronic circuit.

  Along with this, the demand for film performance is also increasing, and among them, high transparency is always ranked higher than the required quality. For example, in various displays and the like, higher definition has been advanced, and requirements for light-scattering foreign substances and colored foreign substances in a film that hinder high transparency have become strict.

  In particular, in the case of an optical film, even if the foreign matter is transparent, if it has an action of abnormally refracting transmitted light, it may be an optical defect as a so-called bright spot foreign matter, which may cause a quality problem.

  In order to obtain a highly transparent film, it is required to greatly reduce the content of light scattering foreign matter, colored foreign matter, and the like contained in the film. Causes of contamination of the film by such foreign substances include generation of unnecessary components due to a heterogeneous reaction of the materials used, those caused by additives used, those caused by a manufacturing method, and dust mixed in a manufacturing process. There are many different causes, such as those caused by

  BACKGROUND ART Cyclic polyolefin films have been attracting attention as films having high transparency and excellent stability in moisture absorption and moisture permeability. However, when the melt-casting method, which is a general production method, is used, when the glass transition temperature of the cyclic polyolefin-based resin is 200 ° C. or higher, it is necessary to use a high temperature to adjust the viscosity at the time of melting to a degree that can be cast. It is necessary to heat, and at that time, agglomeration or the like of contained foreign matter is likely to occur due to high-temperature heating, and there is a problem that there are many foreign matter failures during film formation.

  In addition, cellulose acetate films used for optical films such as polarizing plate protective films and retardation films are improved in handling aptitude at the time of film formation by adding inorganic fine particles to adjust the slipperiness. For the same purpose, there is known a cyclic polyolefin film produced by melt-casting a method by adding inorganic fine particles (for example, see Patent Document 1). However, it has been found that in this method, when the particles are heated and melted at the high temperature, the fine particles are biased or agglomerated to form foreign matter, which increases haze which is important as an optical film and impairs transparency.

  On the other hand, a production method for producing a cyclic polyolefin film by a solution casting method without a heating step at a high temperature is disclosed (for example, see Patent Documents 2 and 3). However, recent optical films tend to be wider and thinner, so that the performance required for foreign matter is further increased, and further improvement is required in terms of foreign matter and haze.

JP-A-2004-151573 Japanese Patent No. 4585947 JP 2007-260972 A

The present invention has been made in view of the above-mentioned problems and circumstances, and the problem to be solved is to reduce foreign matter failure during film formation, and to reduce the content and haze of foreign matter in a finished film, thereby achieving high transparency. it is to provide a manufacturing how to produce sexual cyclic polyolefin film.

  The present inventor, in order to solve the above problems, in the process of examining the cause of the above problems, dissolve the cyclic polyolefin resin using an organic solvent, add an additive to prepare a dope, and then filter, Casting on an endless support, drying it and peeling it off from the endless support, stretching, drying, and then winding it as a roll after winding in a method for producing a cyclic polyolefin film, reducing foreign matter failure during film formation, Further, it has been found that a highly transparent cyclic polyolefin film can be obtained by reducing the content of foreign matter and haze in the finished film.

  That is, the above object according to the present invention is solved by the following means.

1. A method for producing a cyclic polyolefin film, at least,
Dissolving a cyclic polyolefin-based resin using an organic solvent, adding an additive to prepare a dope, followed by filtration, and adjusting the content of foreign substances having a major axis of 10 μm or more as a finished film to 5 pieces / 100 cm ² or less,
The content of toluene in the dope is in the range of 0.001 to 0.1% by mass,
Casting the dope on an endless support,
Drying the cast dope and peeling off from the endless support to form a web,
Drying and stretching the peeled web, and winding the stretched web as a roll,
A method for producing a cyclic polyolefin film, comprising:

2. A method for producing a cyclic polyolefin film, at least,
The cyclic polyolefin resin is dissolved using an organic solvent, in preparing the dope by adding additives, further adding toluene as organic solvent, the organic solvent other than toluene content of the toluene in the dope And by adding the above-mentioned additives, the content is adjusted within the range of 0.001 to 0.1% by mass and then filtered, and the content of foreign substances having a major axis of 10 μm or more as a finished film is adjusted to 5 pieces / 100 cm ² or less. Process,
Casting the dope on an endless support ,
Drying the cast dope and peeling off from the endless support to form a web,
Drying and stretching the peeled web; and
Winding the stretched web as a roll,
Method for producing a ring-like polyolefin film you characterized by having a.

3. A method for producing a cyclic polyolefin film, at least,
The cyclic polyolefin resin is dissolved using an organic solvent, in preparing the dope by adding additives, further added cellulose acylate as additive pressurizing agent, the organic content of the cellulose acylate in the dope By adding the above-mentioned additives other than the solvent and the cellulose acylate, the content is adjusted within the range of 0.0001 to 0.1% by mass and then filtered. Adjusting to 100 cm ² or less,
Casting the dope on an endless support,
Drying the cast dope and peeling off from the endless support to form a web,
Drying and stretching the peeled web; and
Winding the stretched web as a roll,
Method for producing a ring-like polyolefin film you characterized by having a.

  4. 2. The method for producing a cyclic polyolefin film according to claim 1, wherein two or more kinds of the cyclic polyolefin-based resin are used.

5. Before Ki添 pressurizing agent, a nitrogen-containing heterocyclic compounds, organic esters, and method for producing a cyclic polyolefin film according to paragraph 1, wherein the at least one selected from the matting agent.

  By the above-described means of the present invention, a manufacturing method for manufacturing a highly transparent cyclic polyolefin film and a cyclic polyolefin film by reducing foreign matter failure during film formation and reducing the foreign matter content and haze of the finished film are reduced. Can be provided.

  Although the mechanism of manifesting or acting the effects of the present invention has not been clarified, it is speculated as follows.

  By employing the solution casting method for the production method of the cyclic polyolefin film, unnecessary components due to the heterogeneous reaction of the cyclic polyolefin resin and additives used can be dissolved in the solvent, and the cyclic polyolefin resin and the additive can be dissolved. By dispersing the agent in a solvent having a low viscosity, foreign substances as solid substances contained therein are easily dispersed, and the foreign substances can be effectively collected by a filtration filter. Therefore, it is possible to cast a dope having relatively little foreign matter, thereby reducing foreign matter failure during film formation and reducing foreign matter and haze of a finished film to produce a highly transparent cyclic polyolefin film. It is presumed that this is possible.

However, it was difficult to adjust the content of foreign substances having a major axis of 10 μm or more to 5 pieces / 100 cm ² or less simply by forming a solution film of a cyclic polyolefin resin.

  Therefore, as a result of repeated studies, it was found that by adding a small amount of toluene as an organic solvent to the dope, the solubility of resin-derived foreign matter was increased, and the effect of reducing foreign matter failure became remarkable. It is presumed that the cyclic olefin-based resin shows high solubility in toluene and dissolves the synthesis failure component generated during the resin synthesis, so that the amount of foreign substances is greatly reduced.

  It has also been found that by adding a small amount of a cellulose acylate-based resin to the dope, the solubility of foreign substances caused by the additives increases, and the effect of reducing the failure of foreign substances becomes remarkable. It is presumed that foreign matter caused by additives that do not dissolve in the cyclic polyolefin-based resin is compatible with the highly polar cellulose acylate-based resin, so that the foreign matter is significantly reduced.

  It has also been found that the use of two or more different cyclic polyolefin-based resins increases the solubility of foreign substances due to additives and makes the effect of reducing the failure of foreign substances remarkable. It is presumed that the foreign matter caused by the additive that does not dissolve in one of the cyclic olefins is compatible with the cyclic olefin having a different polarity, so that the foreign matter is significantly reduced.

Schematic diagram of a production apparatus used in the method for producing a cyclic polyolefin film of the present invention Schematic diagram of a solution casting film forming apparatus for carrying out the method for producing a cyclic polyolefin film of the present invention Sectional view of an example of a filtration device used in the present invention Schematic diagram of the strainer used in this embodiment Sectional view of an example of the separation device used in the present invention Schematic diagram of an example of a drying device used in the present invention Schematic diagram of forming an intervening membrane between a casting membrane and an endless support FIG. 1 is a schematic plan view schematically showing an example of a tenter stretching apparatus used in the method for producing a cyclic polyolefin film of the present invention. Schematic plan view schematically showing another example of the tenter stretching apparatus Schematic diagram of a tenter clip used in the present invention Schematic diagram for explaining the oblique stretching used in the method for producing a cyclic polyolefin film of the present invention. Schematic diagram of a stretching device according to an embodiment of the present invention Side view showing the outline of the winding device Plan view showing the outline of the winding device Explanatory drawing showing the relationship between the welded portion of the band and the region formed on the welded portion of the film (A) is a plan view showing the relationship between the welded portion of the band and the casting film (B) is a plan view of the film Illustration from the drying process to the winding process Explanatory drawing showing a static elimination method using a blower type static eliminator Perspective view showing cyclic polyolefin film and packaging material A perspective view showing an embodiment of a package. Explanatory drawing of operation of this embodiment Perspective view showing the state of attachment of the film tip to the winding core Plan view showing the state of attachment of the film tip to the winding core Sectional view of the state where the film is wound three times around the film tip Sectional view of the second embodiment Sectional view of the third embodiment Sectional view of the film winding state of the same embodiment Sectional view of the fourth embodiment FIG. 7 is a plan view showing a state in which the film tip is attached to a winding core in another embodiment in which the tilt angle of the film tip is changed. Schematic diagram for explaining a method of manufacturing a wound core by a filament winding method Schematic diagram for explaining a method of manufacturing a winding core by a sheet winding method A diagram showing a film roll in which a tape is wound around both ends of a film and wound up. The figure which shows the surface and cross section of the tape which performed embossing or slit processing (A) is a schematic diagram of an example of an embossed region that the cyclic polyolefin film of the present invention may have, (B) is a perspective view perpendicular to the width direction of the film of (A), and (C) is Schematic diagram for explaining an embossed region in the film of (A) (A) is a schematic diagram of an example of an embossed region that the cyclic polyolefin film of the present invention may have, (B) is a perspective view perpendicular to the width direction of the film of (A), and (C) is Schematic diagram for explaining an embossed region in the film of (A) (A) is a schematic diagram of an example of an embossed region that the cyclic polyolefin film of the present invention may have, (B) is a perspective view perpendicular to the width direction of the film of (A), and (C) is Schematic diagram for explaining an embossed region in the film of (A) (A) is a schematic diagram of an example of an embossed region that the cyclic polyolefin film of the present invention may have, (B) is a perspective view perpendicular to the width direction of the film of (A), and (C) is Schematic diagram for explaining an embossed region in the film of (A) Schematic diagram of film production line Top view of winding device Graph showing the relationship between the film stress and the winding length in the circumferential direction of the winding core Explanatory drawing of film stress in the circumferential direction of the core Graph showing the relationship between surface pressure and winding length when wound by straight winding Graph showing the relationship between surface pressure and winding length when wound by oscillating winding Flow chart showing the operation of the winding device Schematic diagram showing an example of a plasma CVD apparatus used for forming an inorganic gas barrier layer The figure which shows the pattern exposure at the time of manufacture of the forgery prevention medium A. Enlarged view of the pattern observed on the anti-counterfeiting medium A via the polarizing plate The figure which shows the photomask used by pattern exposure at the time of manufacture of the forgery prevention medium B The figure which shows the pattern of the slow axis of the forgery prevention medium B.

The method for producing a cyclic polyolefin film of the present invention comprises, at least, dissolving a cyclic polyolefin-based resin using an organic solvent, adding an additive to prepare a dope, followed by filtration, and containing a foreign substance having a major axis of 10 μm or more as a finished film. Adjusting the amount to 5 pieces / 100 cm ² or less,
The content of toluene in the dope is in the range of 0.001 to 0.1% by mass,
Casting the dope on an endless support,
Drying the cast dope and peeling off from the endless support to form a web,
Drying and stretching the peeled web, and winding the stretched web as a roll,
It is characterized by having. This feature is a technical feature common to the inventions according to claims 1 to 5 .

  Toluene is further added as an organic solvent in the dope, and the content of the toluene in the dope is adjusted to a range of 0.001 to 0.1% by mass by adding the organic solvent and the additive other than toluene. As a result, it has been clarified that the solubility of the foreign matter caused by the resin in the dope increases, and the effect of reducing the failure of the foreign matter becomes remarkable. The cyclic olefin-based resin has high solubility in toluene and dissolves poorly-synthesized components generated during resin synthesis, so that the amount of foreign substances is significantly reduced. Therefore, a highly transparent cyclic polyolefin film can be produced by reducing foreign matter and haze of the finished film. Further, by setting the toluene content within the above range, there is also an effect of shortening the dope dissolution time.

  Further, a cellulose acylate is further added as an additive to the dope, and the content of the cellulose acylate in the dope is adjusted to 0.0001 to 0.1 by adding the additive other than the organic solvent and the cellulose acylate. By adjusting the content within the range of mass%, it becomes clear that the solubility of the foreign matter due to the additive of the dope increases and the effect of reducing the failure of the foreign matter becomes remarkable. It is presumed that foreign matter caused by additives that do not dissolve in the cyclic olefin is compatible with the highly polar cellulose acylate-based resin, so that the foreign matter is significantly reduced. Further, by setting the cellulose silate-based resin within the above range, there is also an effect of shortening the dope dissolution time.

  Further, by incorporating the cellulose acylate-based resin, the adhesion to the hard coat base material is increased, and the hardness as the hard coat film can be increased.

  It has been clarified that the use of two or more kinds of the cyclic polyolefin-based resins increases the solubility of foreign substances caused by additives in the dope, and makes the effect of reducing the failure of foreign substances remarkable. Foreign matter caused by an additive that does not dissolve in one of the cyclic olefins is compatible with cyclic olefins having different polarities, so that the foreign matter is significantly reduced. Therefore, a highly transparent cyclic polyolefin film can be produced by reducing foreign matter and haze of the finished film.

  In addition, the additive other than the cellulose acylate is at least one selected from a nitrogen-containing heterocyclic compound, an organic ester, and a matting agent. The cyclic polyolefin film of the above can be produced, which is preferable.

  A cyclic polyolefin film produced by the method for producing a cyclic polyolefin film of the present invention (hereinafter sometimes referred to as the cyclic polyolefin film of the present invention) is a polarizing plate for a liquid crystal display device or an organic electroluminescence display device as a display device. Suitable for optical films such as protective films and retardation films, base films for touch panels and gas barrier base films, and substrate films such as substrate films for nanoimprint and flexible electronic circuits. It is provided in.

  Hereinafter, the present invention, its components, and embodiments and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning including the numerical value described before and after it as a lower limit and an upper limit.

<< Outline of the production method of the cyclic polyolefin film of the present invention >>
The method for producing a cyclic polyolefin film of the present invention comprises, at least, dissolving a cyclic polyolefin-based resin using an organic solvent, adding an additive to prepare a dope, followed by filtration, and containing a foreign substance having a major axis of 10 μm or more as a finished film. Adjusting the amount to 5/100 cm ² or less, casting the dope on an endless support , wherein the content of toluene in the dope is in the range of 0.001 to 0.1% by mass , Drying the cast dope and peeling it from the endless support to form a web, drying and stretching the peeled web, and winding the stretched web as a roll. It is characterized by the following.

  The term “foreign matter” in the present invention refers to a light-scattering foreign matter or a colored foreign matter, particularly in the case of an optical film, even if the foreign matter is transparent, if it has an action of abnormally refracting transmitted light, so-called The bright spot foreign matter includes an optical defect.

  For example, the “foreign matter” includes a poor synthesis component generated during the synthesis of the cyclic polyolefin-based resin, a foreign matter caused by an additive, and the like.

  In addition, the colored foreign substances include aggregates of matting agents (fine particles), in addition to impurities such as additives and dust mixed in the manufacturing process.

  The “foreign matter” observed in the film is various from a relatively hard one such as a colored foreign matter to a relatively soft gel-like foreign matter such as a light scattering foreign matter.

  The gel-like foreign matter refers to a foreign matter detected by the following detection method.

(Method for detecting gel-like foreign matter in dope)
10 mg of the finely ground optical film was placed in an aluminum pan, and heated at 260 ° C. for 60 minutes under a N ₂ flow using TG / DTA6200 (manufactured by SII NanoTechnology Inc.). The heated aluminum pan containing the optical film is put into a 10 ml volumetric flask, and the volume is increased to 10 ml with THF (tetrahydrofuran). After storage at 23 ° C. for 24 hours, the dissolution state of the optical film in the aluminum pan is visually observed and observed as undissolved (gel).

  The presence of a large number of the gel-like foreign substances causes light scattering, lowers the total light transmittance (increases in haze), causes bright spot defects, and the like. It is necessary to reduce as much foreign matter as possible.

The number of gel-like contaminants in the optical film is determined, for example, by cutting 100 cm ² minutes from the winding of the optical film, applying light from a fluorescent lamp to the film, visually confirming the uneven reflection on the surface, and examining the confirmed portion with an optical microscope. Scrutinize the contents by (100x) and separate them from external foreign matter such as dust, and gel those whose major diameter (the length of the longest diameter connecting the ends of the particle projection image) is 10 μm or more. It is counted as the number of foreign substances in a shape.

  Further, in the present application, even in the case of colored foreign substances, those having a major axis of 10 μm or more are counted as foreign substances.

In the case of the highly transparent cyclic polyolefin film of the present invention, the gel-like foreign matter and the colored foreign matter need to be 5 pieces / 100 cm ² or less, and 0 to 3 pieces / 100 cm ^2. Is more preferable, but it is most preferable that none is present.

The present inventors have been intensively studying the production of a cyclic polyolefin film in which a long particle having a diameter of 10 μm or more is 5 pieces / 100 cm ² or less, and use a material such as a cyclic polyolefin-based resin or an additive having a small amount of the foreign substance. In addition, by employing the solution casting method for the production method of the cyclic polyolefin film, unnecessary components due to heterogeneous reaction of the cyclic polyolefin resin and additives used can be dissolved in a solvent, and It has been found that by dispersing a polyolefin-based resin or an additive in a solvent having a low viscosity, foreign substances as solid substances contained therein are easily dispersed, and the foreign substances can be effectively collected by a filtration filter.

  Furthermore, it has been found that the effect of dissolving and removing foreign substances is further enhanced by adding a small amount of toluene or cellulose acylate to the dope.

  It has also been found that the use of two or more resins in combination as the cyclic polyolefin-based resin used is more effective in dissolving and removing foreign substances.

  Therefore, by preparing a dope with a small amount of foreign matter at a stage before casting, foreign matter failure during casting film formation is reduced, and the content and haze of foreign matter (such as bright spot foreign matter) in the finished film are effectively reduced. They have found what they can do and have led to the present invention.

<< Production apparatus and production method for cyclic polyolefin film >>
First, a production apparatus that can be used for producing the cyclic polyolefin film of the present invention will be described.

  The apparatus for producing the cyclic polyolefin film is not particularly limited, and a film forming apparatus by a general solution casting method can be used.

  FIG. 1 is a schematic view of an apparatus used for a method for producing a cyclic polyolefin, which is preferable for the present invention.

  The cyclic polyolefin-based resin is dissolved in an appropriate amount of an organic solvent in a charging tank 41, sent to a filter 44 to remove large aggregates, and sent to a stock tank 42. After that, various additive liquids (for example, a plasticizer, a matting agent, an ultraviolet absorber, etc.) are added from the stock tank 42 to the main dope dissolving pot 1 to prepare a main dope.

  As an additive, a plasticizer, a matting agent, an ultraviolet absorber, and the like are stirred and diluted with a solvent in an additive charging vessel to make an additive liquid, and then appropriately added to the charging vessel 41.

  The main dope is cast from the die 30 onto the endless support 31, separated at a separation position 33 to form a web, conveyed by a number of rollers, and then stretched by a tenter device 34. The stretched web is conveyed while being dried by a number of conveying rollers 36 by a roller drying device 35, and is wound by a winding device 37.

  Although not shown, it is preferable to appropriately provide a slit device for adjusting the film width and an embossing device for imparting irregularities to the film edge to improve the sticking failure of the film during the process.

  Also, JP-A-2000-301555, JP-A-2000-301558, JP-A-7-032391, JP-A-3-193316, JP-A-5-086212, and JP-A-62-037131 JP-A-2-276607, JP-A-55-014201, JP-A-2-111511, and JP-A-2-208650. Applicable to the invention.

The production method of the cyclic polyolefin film of the present invention is at least
Dissolving a cyclic polyolefin-based resin using an organic solvent, adding an additive to prepare a dope, followed by filtration, and adjusting the content of foreign substances having a major axis of 10 μm or more as a finished film to 5 pieces / 100 cm ² or less,
The content of toluene in the dope is in the range of 0.001 to 0.1% by mass,
Casting the dope on an endless support,
Drying the cast dope and peeling off from the endless support to form a web,
Drying and stretching the exfoliated web; and winding the stretched web as a roll.

  Each step will be described in detail. Hereinafter, the “cyclic polyolefin film” may be simply referred to as a “film”.

(1) Dope preparation step (dissolution step)
In an organic solvent mainly composed of a good solvent for the cyclic polyolefin-based resin, the cyclic polyolefin-based resin in a dissolving vessel, depending on the case, a plasticizer or various function developing agents (for example, an antioxidant, a light stabilizer, an ultraviolet absorber, A step of forming a dope by dissolving a retardation adjuster, a release accelerator, an infrared absorber, a matting agent, etc.) with stirring, or a solution obtained by dissolving the plasticizer or various function developing agents in the cyclic polyolefin solution. This is a step of preparing a dope as a main solution by mixing.

  When the cyclic polyolefin film of the present invention is produced by a solution casting method, an organic solvent useful for preparing a dope can be used without limitation as long as it can simultaneously dissolve the cyclic polyolefin-based resin and other compounds. .

  For example, a chlorine-based organic solvent is dichloromethane, and a non-chlorine-based organic solvent is methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolan, 1,4-dioxane, cyclohexanone, ethyl formate, , 2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2 -Methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane and the like. For example, dichloromethane, methyl acetate, ethyl acetate, and acetone can be preferably used as the main solvent, Or particularly preferably ethyl acetate.

  It is preferable that the dope contains a linear or branched aliphatic alcohol having 1 to 4 carbon atoms in the range of 1 to 40% by mass in addition to the organic solvent. When the proportion of the alcohol in the dope is high, the web gels and the peeling from the metal endless support becomes easy, and when the proportion of the alcohol is small, the cyclic polyolefin and other non-chlorine organic solvent system are used. It also has the role of promoting compound dissolution. In the formation of the cyclic polyolefin film of the present invention, in order to enhance the planarity of the obtained cyclic polyolefin film, a method of forming a film using a dope having an alcohol concentration in the range of 0.5 to 15.0% by mass. Can be applied.

  Particularly, a dope composition in which a cyclic polyolefin and other compounds are dissolved in a solvent containing dichloromethane and a linear or branched aliphatic alcohol having 1 to 4 carbon atoms in a total range of 15 to 45% by mass. It is preferred that

  Examples of the linear or branched aliphatic alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol. Of these, methanol and ethanol are preferred because of the stability of the dope, the relatively low boiling point and the good drying property.

In the present invention, contain a small amount of toluene to the organic solvent, the content of toluene in the previous SL-doped, the other organic solvents and additives added in the range of 0.001 to 0.1 mass% you adjustment. The inclusion of toluene increases the solubility of the foreign matter caused by the resin in the dope, and the effect of reducing the failure of the foreign matter becomes remarkable. It is presumed that the cyclic olefin-based resin shows high solubility in toluene and dissolves poorly-synthesized components generated at the time of resin synthesis, so that foreign substances are greatly reduced.

  As the toluene, commercially available purified toluene can be used, and toluene having a purity of 99.0% or more is preferable.

  For dissolving a cyclic polyolefin resin, a plasticizer, or a function developing agent, a method of dissolving at normal pressure, a method of dissolving at a temperature lower than the boiling point of the main solvent, a method of dissolving at a pressure of higher than the boiling point of the main solvent, JP-A-9-95544 Various dissolution methods such as a method performed by a cooling dissolution method described in JP-A-9-95557 or JP-A-9-95538 and a method performed at a high pressure described in JP-A-11-21379 are disclosed. Although it can be used, it is particularly preferable to carry out the method under pressure at a temperature higher than the boiling point of the main solvent.

  It is preferable to use a mixing device shown in FIG. 5 of JP-A-2011-143360 for the cyclic polyolefin-based resin and additives. The mixing device is a liquid supply pipe for supplying a liquid to a mixing tank that mixes a liquid and a solid material, the liquid supply pipe being one or more branch pipes into which the liquid is injected, and a branch pipe connected to the branch pipe. In the projection view from the main pipe axial direction, the liquid movement direction in the branch pipe is different from the main pipe radial direction from the communication position with the branch pipe in the main pipe. Branch pipes are arranged so as to have an inclination angle between them. It is preferable from the viewpoint of reducing foreign matter that the solid matter is introduced from a solid matter introduction pipe having such a branch pipe.

  Specifically, solutions of additives such as a plasticizer, an ultraviolet absorber, a matting agent, and an antioxidant are independently added from the solid matter introduction pipe 5 shown in FIG. Dispersed to form the dope.

  The type of pressure vessel used for dissolving the cyclic polyolefin-based resin is not particularly limited, as long as it can withstand a predetermined pressure and can be heated and stirred under pressure. In addition, instruments such as a pressure gauge and a thermometer are appropriately provided in the pressurized container. Pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or by increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside. For example, a jacket type is preferable because temperature control is easy.

  The heating temperature after the addition of the solvent is higher than the boiling point of the solvent to be used, and in the case of a mixed solvent of two or more, the heating temperature is higher than the boiling point of the lower boiling solvent and the solvent does not boil. Is preferred. If the heating temperature is too high, the required pressure will increase and productivity will suffer. A preferred heating temperature range is from 20 to 120C, more preferably from 30 to 100C, even more preferably from 40 to 80C. The pressure is adjusted at the set temperature so that the solvent does not boil.

  The apparatus for preparing a cyclic polyolefin-based resin dope according to the present invention has a storage tank, a heat exchanger, and a circulation path, and the storage tank and the heat exchanger are connected via the circulation path. Is preferred. The connection via the circulation path means that there is a circulation path between the storage tank and the heat exchanger, and that there is a circulation path between the heat exchanger and the storage tank. The circulation path may be heat-exchangeable, and the circulation path may also serve as a heat exchanger. The dope may return to the storage tank through a heat exchanger from the dope discharge port of the storage tank, or may return to the storage tank through a heat exchanger from a port other than the dope discharge port of the storage tank. Alternatively, two or more dope preparation apparatuses having a circulation path may be connected. In this case, a solvent may be further added in the second storage tank. The circulation path has a function of efficiently shortening the dissolution time, and also has a capability of complete dissolution. In general, in a dissolving vessel provided with a circulator, simply circulating takes too much time to achieve a dissolved state. On the other hand, in a heat exchanger that applies heat to a solution for a short time, a gel is easily generated in the dope, and the time is too short for complete dissolution.

  The storage tank used in the present invention is preferably a pressure-resistant container equipped with a jacket inside or outside the tank and having a stirrer having a shearing force as described below for more uniform dope.

In the process of mixing and dissolving the cyclic polyolefin-based resin and the solvent, it is preferable to stir by applying a shear force of 9.8 to 9.8 × 10 ⁵ N. Stirring within the above-mentioned range of the shearing force allows powder agglomerates to be formed as soon as possible, and even if they are formed, the powder agglomerates can be pulverized and dissolved. If the shearing force is less than 9.8 N, the stirring power is weak and the dispersion efficiency is poor, and the dispersion exceeding 9.8 × 10 ⁵ N becomes too fine, causing clogging in the subsequent filtration step, resulting in a significant decrease in filtration efficiency. Let me do it. The shearing force can be controlled by the rotation speed of the driving motor M.

  After dissolution of the cyclic polyolefin, the polymer is taken out of the vessel with cooling, or withdrawn from the vessel with a pump or the like, cooled with a heat exchanger or the like, and the obtained polymer dope is provided for film formation. May be cooled to room temperature.

  The concentration of the cyclic polyolefin in the dope is preferably in the range of 10 to 40% by mass. The compound is added to the dope during or after dissolution to dissolve and disperse, and then filtered with a filter medium, defoamed, and sent to the next step by a liquid sending pump.

(Water content)
In addition, in the dope preparation step, the water content is 2.0 to 5.0% by mass during startup from the start of production to the steady operation, and the water content is 0.1 to 2.0% by mass during the steady operation. Such adjustment is preferred from the viewpoint of the stability of the dope and the transparency of the film.

  As a method of setting the water content at the start-up within the range of 0.6 to 2.0% by mass with respect to the total amount of the dope, the water content in the dope is determined from the sum of the water content in the resin and the water content in the alcohol. There is a method in which the ratio is calculated, and the shortage is mixed with a solvent and then mixed as a dope.

  Since the line speed is low at the time of the start-up, if the water content is less than 2.0% by mass based on the total amount of the dope, the web tends to peel off from the endless support before peeling. If the film is peeled off, it must be started up again, and the productivity will deteriorate. When the water content is more than 5.0% by mass, the solubility of the cyclic polyolefin-based resin in the solvent is deteriorated, and the endless support is easily stained.

  In addition, at the time of steady operation, if the water content is smaller than 0.6% by mass based on the total amount of the dope, the web is easily peeled off from the endless support similarly to the case at the time of start-up, and productivity is deteriorated. I will. On the other hand, if the water content is more than 2.0% by mass, the endless support will be stained after peeling.

  As means for lowering the water content of the dope within the range of 0.6 to 2.0% by mass from the start-up to the time of steady operation, the predetermined cyclic polyolefin-based resin and other additives are added in-line. To adjust, from the sum of the water content in the resin and the water content in the alcohol, calculate the water content in the dope, and gradually lower the water content by flowing the adjusted low water content dope through the line. And the like.

  In addition, when the fine particles are added to the cyclic polyolefin-based resin dissolving step, the dissolution mixing is preferably performed at a temperature not lower than the boiling point of the main solvent and not higher than the boiling point + 50 ° C. In this way, by setting the temperature for dissolving and mixing the fine particles in the cyclic polyolefin resin dissolving step at a temperature equal to or lower than the boiling point of the main solvent + 50 ° C., the foreign matter generation rate can be reliably suppressed in the dope dissolving and mixing step. it can.

  In addition, it is preferable that the dissolving and mixing of the fine particles in the cyclic polyolefin resin dissolving step is performed for a time period in the range of 30 to 300 minutes. As described above, by defining the time for dissolving and mixing the fine particles in the cyclic polyolefin-based resin dissolving step, the variation coefficient (distribution) of the fine particles in the cyclic polyolefin film is not deteriorated, and also from the viewpoint of production suitability such as foreign matter failure. preferable.

  Further, the fine particles to be added in the step of dissolving the cyclic polyolefin-based resin are added during or after the addition of the cyclic polyolefin-based resin to the dissolving vessel and before the cyclic polyolefin-based resin is completely dissolved in the dissolving vessel. Is preferred. In this way, by defining the timing of adding the fine particles in the cyclic polyolefin-based resin dissolving step, the foreign matter generation rate due to the addition of the fine particles contained in the cyclic polyolefin-based resin solution (dope) can be reduced. It can be reliably suppressed in the process, greatly reducing the load on the filter in the subsequent filtration process, free of foreign matter, and excellent in productivity.

  In the method for producing a cyclic polyolefin film of the present invention, a dispersion of fine particles is prepared in advance, and the fine particle dispersion is added in a step of dissolving the cyclic polyolefin-based resin in a main solvent. It is preferable to dissolve and mix at a temperature.

  As a solvent used for dispersing the fine particles, an organic solvent used for forming a cyclic polyolefin resin film can be used. Alcohols are particularly preferable, and examples thereof include those having 1 to 8 carbon atoms such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol.

  The concentration of the fine particles when the fine particles are mixed with the solvent and dispersed is preferably 5 to 30% by mass, more preferably 8 to 25% by mass, and most preferably 10 to 15% by mass. The higher the concentration of the fine particles in the fine particle dispersion, the lower the turbidity of the liquid with respect to the added amount, which is preferable because haze and aggregates are improved.

  When the fine particles are mixed and dispersed with a solvent and a small amount of resin, the concentration of the fine particles is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, and most preferably 1 to 3% by mass. The resin concentration is preferably 2 to 10% by mass, more preferably 3 to 7% by mass, and most preferably 4 to 6% by mass. This range is preferable because of excellent dispersibility of the fine particles. The above range is preferable because the smaller the content of the fine particles, the lower the viscosity and the ease of handling, and the larger the content of the fine particles, the smaller the added amount and the easier the addition to the main dope.

  An ordinary disperser can be used as a disperser for dispersing the fine particles. Dispersers are broadly divided into media dispersers and medialess dispersers. For dispersing the fine particles, a medialess disperser is preferable because the haze is low.

Examples of the media dispersing machine include a ball mill, a sand mill, and a dyno mill. Examples of the medialess disperser include an ultrasonic type, a centrifugal type, and a high-pressure type. In the present invention, a high-pressure disperser is preferable. The high-pressure dispersing device is a device that creates a special condition such as a high shear or a high pressure state by allowing a composition in which fine particles and a solvent are mixed to pass through a thin tube at a high speed. By treating with a high-pressure dispersion device, for example, it is preferable that the maximum pressure condition inside the device is 9.8 × 10 ² N or more in a thin tube having a tube diameter of 1 to 2000 μm. More preferably, it is at least 1.96 × 10 ³ N. In this case, it is preferable that the maximum arrival speed reaches 100 m / sec or more, and the heat transfer speed reaches 100 kcal / hr or more.

  Examples of the high-pressure dispersing device as described above include an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation or a nanomizer manufactured by Nanomizer, or Ultra Turrax. Homogenizer manufactured by Machinery, product number UHN-01 manufactured by Sanwa Machine Co., Ltd., and the like.

  The content of, for example, silica (Si) in the fine particles contained in the cyclic polyolefin film can be determined by subjecting a completely dried cyclic polyolefin film to pretreatment with a micro digest wet decomposition apparatus (sulfuric acid and nitric acid decomposition) and alkali melting, followed by ICP-AES. (Inductively coupled plasma emission spectrometer).

  In the method for producing a cyclic polyolefin film of the present invention, the same resin as the cyclic polyolefin resin is dissolved and mixed in the fine particle dispersion added in the step of dissolving the cyclic polyolefin resin. It is preferably 0.1 to 0.5 times the solid matter ratio of the cyclic polyolefin resin solution (dope) dissolved in the step.

  Thus, it is preferable that the fine particle dispersion contains a cyclic polyolefin in addition to the fine particles since the viscosity of the dispersion is adjusted and the stagnation stability is excellent.

  Further, in order to perform co-casting, it is preferable to use an apparatus capable of simultaneously preparing a plurality of types of dope as shown in FIG. 2 of JP-A-2009-072963. In FIG. 2, three dope channels 33, 34, and 35 for the intermediate layer, the support surface, and the air surface are sent from the raw material dope 11 by the liquid sending pumps P 3, P 4, and P 5. Then, in the intermediate layer dope flow path 33, after the additive liquid 13 stored in the stock tank 36 is added by the liquid sending pump P 6, the raw material dope 11 and the additive liquid are added by the in-line mixer 39 and the shear mixer 43. 13 are mixed with each other to produce an intermediate layer dope 16. Similarly, in the support surface dope flow path 34, the raw material dope 11 and the additive liquid 14 are mixed by the in-line mixer 40 and the shear mixer 44 to generate the support surface dope 17, and the air surface dope flow path In 35, the raw material dope 11 and the additive liquid 15 are mixed by the in-line mixer 41 and the shear mixer 45 to produce the air-surface dope 18. If necessary, a diluent for adjusting the TAC concentration of the dope may be added to the dope channels 34 and 35 for the support surface and the air surface.

  By the above method, as shown in FIG. 2 of the above publication, for example, three types of dopes 16, 17, and 18 having a cyclic polyolefin concentration of 5 to 40% by mass can be produced. Then, the three types of dopes 16, 17, and 18 are sent to the casting unit through the filter.

(2) Filtration Step In the method for producing a cyclic polyolefin film of the present invention, filtration of the dope is an important step from the viewpoint of reducing foreign matter failure.

  In the present invention, it is preferable to filter the cyclic polyolefin-based resin solution (dope) by filtering the dope at a temperature equal to or higher than the boiling point of the main solvent at 1 atm, so that gel-like foreign matter in the dope can be removed. A preferred temperature range is from 40 to 120 ° C, more preferably from 45 to 70 ° C, even more preferably from 45 to 60 ° C.

  In the filter, the dope is filtered, for example, with a filter medium having a 90% collection particle diameter of 10 to 100 times the average particle diameter of the fine particles.

  There are several methods for the filtration method.For the filtration of the cyclic polyolefin dope, a filter press or a disc filter is suitable.In particular, the filtration by the filter press method is advantageous in that the filtration area can be widened. Suitable from a point of view.

  FIG. 2 shows an example of the flow of filtration. Here, a description will be given of a filtration device in which an ultrafiltration device having a high effect on foreign matter removal is added to the main filtration device.

  The solution (dope) in which the cyclic polyolefin-based resin is dissolved is temporarily stored in a stationary tank (stock tank) 103 from a dissolving tank (not shown). An ultrafiltration device 102 connected to the main filtration device 100 is connected to the main filtration device 100 by a pipe 108. An opening / closing valve 113 is interposed, and a solvent injection pipe 107 from the dilution solvent tank 106 is connected downstream of the opening / closing valve 113. An opening / closing valve 116 near the outlet side of the main filtration device 100 and an opening / closing valve 117 near the entrance side of the main filtration device 100 are interposed in a pipe 108 that connects the ultrafiltration device 102 to the main filtration device 100. I have. The ultrafiltration device 102 is connected to a solvent discharge pipe 118 for discharging the separated solvent. The solvent separated in the ultrafiltration device 102 is sent from the solvent discharge pipe 118 to the solvent reuse return pipe 119 connected to the dilution solvent tank 106, and is reused. An opening / closing valve 115 is interposed in the dope feed pipe 104 on the outlet side of the main filtration device 100 on the downstream side of the branch connection point of the pipe 108.

  When the dope is initially charged into the main filtration device 100, the on-off valve 113 on the way of the dope flow pipe 104 is opened, and the on-off valve 115 on the exit side of the dope flow pipe 104 on the exit side of the main filtration apparatus 100 is closed. The opening / closing valve 114 of the solvent injection pipe 107 is opened for the dope of the cyclic polyolefin resin having a viscosity of, for example, 10 to 50 Pa · s sent from the stationary tank 103 to the inside of the flow pipe 104 by the operation of the pump 105. A solvent is injected from the diluting solvent tank 106, and a dope having a predetermined high viscosity for casting is diluted with the solvent to reduce the viscosity to, for example, a viscosity of 1 to 9 Pa · s. The air in the main filtration device 100 and the air bubbles in the filter medium (not shown) are expelled by being injected into the filtration device 100 and initially filled. When the low-viscosity dope is injected into the main filtration device 100 as described above, the low-viscosity dope easily penetrates into the filter medium, spreads to every corner of the filter medium, and can expel bubbles inside the filter medium.

  Next, the low-viscosity dope discharged from the main filtration device 100 is introduced into the ultrafiltration device 102 via the pipe 108 and the opening / closing valve 116, and the solvent is separated by the ultrafiltration membrane in the ultrafiltration device 102 (not shown). The dope is removed, the dope is concentrated to a predetermined high viscosity, and the predetermined high viscosity dope discharged from the ultrafiltration device 102 is circulated to the main filtration device 100 via the pipe 108 and the opening / closing valve 117.

  In the initial stage of the filling of the main filtration device 100, it is preferable that the opening and closing valve 114 of the solvent injection pipe 107 is opened and the solvent is continuously injected from the dilution solvent tank 106. When the air inside the main filtration device 100 and the air bubbles inside the filter medium (not shown) are completely expelled, the opening and closing valve 114 of the solvent injection pipe 107 is closed, and the low viscosity after filling introduced into the main filtration device 100 is obtained. The dope is circulated through the ultrafiltration device 102 once or several times to gradually concentrate the dope to a predetermined high viscosity. Finally, the predetermined high-viscosity dope discharged from the ultrafiltration device 102 is circulated to the main filtration device 100.

  Thereafter, by opening the on-off valve 115 on the way of the dope flow pipe 104 on the outlet side of the main filtration device 100 and closing the on-off valve 116 of the pipe 108 to the ultrafiltration device 102, the initial filling is completed and bubbles are expelled. Using the main filtration device 100 provided with the filter medium, a dope having a predetermined high viscosity for casting, which is sent from the stationary tank 103 through the flow pipe 104 by the operation of the pump 105, is passed through the main filtration device 100. Is supplied to the casting die 110 from the casting tube 104, and the dope is cast from the casting tube 104 onto the endless support 111 to form a casting film.

  According to such a method, when filling the main filtration device 100 with a dope in the initial stage after newly loading the filter medium into the main filtration device 100, the dead space where the dope is not sufficiently filled in the main filtration device 100 is provided. Can be effectively prevented, and bubbles can be prevented from being generated in the dope from the air trapped in such a dead space.

  According to such a manufacturing apparatus, the generation rate of foreign matter due to a bubble failure generated in the cyclic polyolefin film can be reliably suppressed in the dope filtration step, and the number of foreign matter due to the bubble failure is greatly reduced, and the optical property is reduced. This makes it possible to produce an excellent cyclic polyolefin film, and is also excellent in productivity.

  In the present invention, the filter medium of the main filtration device 100 is preferably filter paper. By using this filter paper, only aggregates such as fine particles that cause foreign matter can be removed, and high-viscosity main dope can be continuously filtered, so there is no foreign matter failure, excellent raw material preservability, and high speed. Film formation becomes possible, and productivity is improved.

  In the above description, the collected particle size of the filter medium of the main filtration device 100 is measured according to JIS Z 8901, and refers to the smallest particle size among particles capable of collecting 90% or more. is there.

  The collection particle diameter of the filter medium of the main filtration device 100 is 0.5 to 5 μm, preferably 1 to 4 μm, and most preferably 2 to 3 μm. If the trapping particle size of the filter material is less than 0.5 μm, fine particles that are not foreign matter are trapped, and the filtration pressure rapidly increases, which is not preferable. Undesirably, the aggregates pass through.

The drainage time of the filter medium of the main filtration device 100 is measured in accordance with JIS P 3801, and is measured at 20 ° C. and 100 ml on a 10 cm ² filtration surface using a Hertzberg filtration rate tester. Means the time for filtering distilled water with a pressure of 0.98 kPa.

  In the present invention, the drainage time of the filter medium of the main filtration device 100 is preferably 10 to 25 sec / 100 ml, more preferably 10 to 20 sec / 100 ml, and most preferably 12 to 17 sec / 100 ml. Here, if the drainage time of the filter medium is shorter than 10 sec / 100 ml, the strength of the filter medium such as filter paper is weak, so that the filter paper is opened by pressure and foreign matter failure increases. If the filtration time of the filter medium is longer than 25 sec / 100 ml, the initial pressure is too high, the filtration resistance is too high, and high-flow filtration cannot be performed continuously, and the filter life is shortened. It is not preferable.

  The collection particle size and drainage time of the filter paper of the main filtration device 100 are determined by selecting the fiber material such as the thickness of the fiber of the filter paper and the material (cotton linter, wood pulp, rayon, polyester fiber, etc.). Can be arbitrarily adjusted depending on the method of producing the filter paper, such as the degree of beating and addition of filler.

  In the present invention, the effect is obtained by using only one filter paper of the main filtration device 100, but it is more preferable to use two to seven filter papers in piles because the filtration efficiency is increased. The same filter paper may be combined, or a filter paper having a small retaining particle diameter may be combined inside. Further, it is preferable to use a guard filter paper for removing large dust on the outside. The guard filter paper is preferably a filter paper such as soft cotton which has a large collecting particle diameter of 20 μm or more, because it can remove large dust without affecting the filtration pressure and can also prevent the main filtration device 100 from leaking. Also, two-stage filtration, in which the main dope that has been filtered once, is filtered again, is preferable because of its large effect of removing aggregates.

In order to obtain a cyclic polyolefin film with less foam failure (foreign matter) in the main filtration device 100, in particular, filtration is performed using a filter paper having a collection particle size of 0.5 to 5 μm and a drainage time of 10 to 25 sec / 100 ml. In this case, it is preferable to form a film by filtering at a filtration pressure of 16 kg / cm ² or less. More preferably, the filtration is performed at a filtration pressure of 12 kg / cm ² or less, even more preferably at a filtration pressure of 10 kg / cm ² or less. The filtration pressure can be controlled by appropriately selecting the filtration flow rate and the filtration area.

  In the present invention, the ultrafiltration membrane of the ultrafiltration device 102 preferably has a porous membrane having a pore diameter of 1 nm to 0.1 μm. For example, a membrane having organic solvent resistance such as an ultrafiltration membrane (UF membrane) or a nanoparticle membrane made of Teflon (registered trademark) (manufactured by Millipore) and polyimide hollow fiber (manufactured by Nitto Denko Corporation) In this case, the matting agent (silica particles) is not separated, and only the solvent can be separated and recovered.

  With such an ultrafiltration membrane, the solvent can be surely separated and removed from the initially-filled low-viscosity dope of the main filtration device 100, and the dope can be gradually concentrated to a predetermined high viscosity. Then, a predetermined high-viscosity dope discharged from the ultrafiltration device 102 is circulated to the main filtration device 100, and thereafter, the main filtration device 100 including a filter medium from which initial filling is completed and bubbles are expelled is used. Thus, the casting film can be reliably formed.

  Filtration filters used in the filtration process can be broadly classified into surface type and depth type according to the media structure. The surface type refers to a type in which the distance of the medium through which the material to be filtered passes is short, and the size of the particles that can be removed is determined by the aperture of the surface. In the present invention, when the surface type filter is used for a long time, the gel-like aggregates come into contact with each other on the surface, grow into larger aggregates, and pass through the filter due to a rise in pressure. There is concern that it will.

  Examples of the surface type include a filter paper pleated cartridge filter TC type manufactured by Advantech Toyo Co., Ltd. and a metal mesh used for a sieve.

  On the other hand, the depth type filter is also called depth filtration or volume filtration, and has a certain thickness of the media. This type of filter has a lower possibility of contact between aggregates in the filter part than the surface type, hardly produces large gel-like aggregates, has a small pressure rise even if used for a long time, It is preferable because the state aggregate can be removed.

  Examples of the depth type include a wind cartridge filter TCW type manufactured by Advantech Toyo Co., Ltd., a depth cartridge filter TCPD type, and a fine pore NF series manufactured by Nippon Seisen Co., Ltd.

  It is preferable that these additive liquids added in-line are filtered through at least two or more types of depth filters having different pore diameters, because it is possible to effectively perform filtration on various aggregates having different sizes. Less preferred.

  These filters may have a particle collection rate of 5 to 10 μm of 20 to 60% when 8 kinds of 0.5 ppm aqueous dispersions of the test powder 1 specified in JIS Z 8901 are filtered. Preferably, the additive liquid is filtered and filtered and then added in-line. The particle collection rate is more preferably 30 to 50%. It is preferable that the particle collection rate is small in that no aggregation is grown, and that the particle collection rate is large in that the aggregation is removed. As the particle collection rate of 20 to 60%, for example, Wind cartridge filters TCW-1N, 3N, 5N, 10N, 25N, 50N, Pleated cartridge filters TCPE-10, 30 manufactured by Advantech Toyo Co., Ltd. Is mentioned. Examples of the particle collection rate of 30 to 50% include wind cartridge filters TCW-3N, 5N, 10N, and 25N manufactured by Advantech Toyo Co., Ltd. Filtering a filter having a particle collection rate of 20 to 60% with a filter having a small particle collection rate, and then filtering the filter with a filter having a high particle collection rate can remove the aggregation without growing the aggregation. Is most preferred. The particle collection rate is defined as follows.

(Particle collection rate)
A 0.5 ppm aqueous dispersion of eight kinds of test powders 1 (material used: Kanto Rohm) specified in JIS Z8901 was filtered at 10 liter / min, and the number of particles in the undiluted solution and the filtrate was counted by an automatic particle counter. The particle collection rate of 5 to 10 μm was determined. At this time, one filter having a size of 250 mm × φ60 was used for filtration. The number of times of filtration was one.
Particle collection rate (%) = (number in stock solution−number in filtrate) / (number in stock solution) × 100
In order to obtain the cyclic polyolefin film of the present invention, in the step of producing the same by the solution casting method, a filter as defined above is used as a filter for filtering an additive liquid to be added in-line to the main dope. Is preferred.

  Also in this filter, a depth type filter is preferable for the above-mentioned reason.

  Filters are classified into membrane type and thread-wound type according to the filter material structure. The membrane type is a type in which there are many holes with a certain size and distribution in the filter medium, and if several filter media with holes of the same size and distribution are stacked, it becomes a membrane type surface type filter, A filter of membrane type and depth type can be made by stacking several filter media, each having a gradually reduced hole size from the filter media toward the core, so as to have a certain thickness (10 to 20 mm).

  Examples of the membrane type include a membrane cartridge filter TCF type and a pleated cartridge filter TCPE type manufactured by Advantech Toyo Co., Ltd.

  The thread-wound type uses endless long fibers such as polypropylene with a certain gap in the filter medium without twisting, and is wound around the core at a certain density, and has a density gradient from the core core. If it is wound in the same direction, it becomes a surface type filter, and if it is made finer in the core direction, for example, by changing the gap of the filter medium or having a density gradient, it becomes a depth type filter. Examples of the thread winding type include a wind cartridge filter TCW type manufactured by Advantech Toyo Co., Ltd. (the core is a hollow core around which a thread or a membrane of a filter medium is wound).

  Since the agglomeration contained in the in-line additive liquid is in the form of a gel of secondary and tertiary agglomeration, it is easy to remove the agglomeration (thing) in the membrane type filter medium, and the thread-wound type has a better ability to catch the agglomeration (thing). preferable.

  Also in this type of filter, a depth type filter is preferable for the above-mentioned reason.

  It is preferable that the filter material of the filter is polypropylene from the viewpoint of solvent resistance. In addition, polypropylene or stainless steel is preferable as the core material of the filter, and stainless steel is more preferable. Stainless steel is preferable because the core does not easily swell with the solvent even after long use, and the aggregates do not come off from the tightening portion. Using these filters, the additive solution is filtered and then added in-line to the main dope. Is preferred. The filtration effect by these filters is improved a certain number of times to improve the effect of removing aggregates. However, if the amount is too large, the effect is reduced for the number of steps, so the number of times of filtration is preferably 3 to 10 times.

  In the method for producing a cyclic polyolefin film of the present invention, it is preferable that the additive is filtered through a metal filter having an absolute filtration accuracy of 30 to 60 µm immediately before mixing the additive solution with the main dope by the inline mixer (in the immediately preceding step). Immediately means that there is a filtration step immediately before in terms of the process, and speaking from the flow, immediately after filtration, continuously without the addition liquid stagnation, for example, a stock tank or a liquid sending pump etc. That is, it is sent to the in-line mixer without passing through and mixed with the main dope. Thereby, it is preferable that the liquid does not stagnate or new aggregates are generated by the liquid sending pump. These filters are disposed immediately before the in-line mixer, and reliably remove relatively large foreign matter by a single filtration from the added liquid during feeding, for example, large aggregates generated from the path due to filter replacement or the like. And a metal filter having the above-mentioned absolute filtration accuracy and having solvent resistance that can be used for a long time is preferable. As the metal, stainless steel is preferable from the viewpoint of durability. Also, unlike the above-mentioned depth type filters, it is preferable that the filters are not replaced very frequently after installation, and therefore, from the viewpoint of clogging, they have a porosity of ε = 60 to 80%. preferable.

  Therefore, it is most preferable to perform filtration with a metal filter having an absolute filtration accuracy of 30 to 60 μm and a porosity of ε = 60 to 80%. Is preferred. Examples of metal filters having an absolute filtration accuracy of 30 to 60 μm and a porosity of ε = 60 to 80% include, for example, NF-10, NF-12, and NF- of Finepore NF series manufactured by Nippon Seisen Co., Ltd. 13 and the like.

  The filter provided immediately before in-line addition is preferably filtered with a metal filter having an absolute filtration accuracy of 30 to 60 μm, more preferably 40 to 50 μm. A smaller absolute filtration accuracy is preferable because of its excellent ability to remove agglomeration, and a larger absolute filtration accuracy is preferable because even when used for a long time, there is little rise in differential pressure, the frequency of filter replacement can be reduced, and productivity is excellent.

(Absolute filtration accuracy)
Absolute filtration accuracy is defined as follows. Glass beads of the test powder 2 and pure water specified in JIS Z 8901 are put into a beaker, and suction filtration is performed while stirring with a stirrer. Here, A represents the filter sample to be measured, B represents the stock solution and C represents the filtrate. The undiluted solution is stirred by a stirrer, and the pressure is maintained at a pressure from atmospheric pressure to -3.99 kPa by a low pressure vacuum pump of P to perform filtration. V represents a valve that can be opened and closed. At this time, the number of glass beads in the undiluted solution and the filtrate is observed with a microscope, and the particle collection rate is determined by the following equation. The particle diameter at a particle collection rate of 95% was defined as the absolute filtration accuracy.

Particle collection rate (%) = (number in stock solution−number in filtrate) / (number in stock solution) × 100
(Porosity)
These filters preferably have a porosity ε of 60 to 80%, more preferably 65 to 75%. A larger porosity is preferable in that pressure loss is reduced, and a smaller porosity is preferable because of excellent pressure resistance. To determine the porosity, first immerse the filter in a solvent with a low surface tension, remove air from the filter, calculate the porosity of the filter from the increased amount of solvent, and divide by the volume of the filter. can do.

(Washing of filtration device)
Next, a method of cleaning a used filtration device will be described.

  As shown in FIG. 3, the filtering device 50 is provided with a filter 70 and a stirring rod 72 rotated by a motor 71, and an air vent pipe 76 is attached to the top of the filter. In addition, although not shown in order to avoid complicating the drawing, a pipe for a cleaning liquid, a pipe for a raw material dope, or a pipe for supplying a filter aid 51 sent from a filter aid tank is provided above the filter device 50. And is provided near the air vent pipe 76. Further, a first outlet 80 for discharging the casting dope 53 and a second outlet 83 for discharging the slurry liquid 52 are provided at a lower portion and a side surface of the filtering device 50. Each of the discharge ports 80 and 83 is a valve, and is connected to a discharge pipe. The filter 70 corresponds to the above-mentioned filter medium, and functions as a support for depositing a filter aid in addition to capturing impurities.

  When a certain period of time has elapsed from the start of filtration, or when the filtration pressure increases and reaches a certain value, the residue on the filter 70 is collected. At the time of recovery, first, the first outlet 80 is closed, and an appropriate amount of the cleaning liquid 65 is supplied into the filtering device 50 through the cleaning liquid pipe. When the inside of the filtration device 50 is immersed in the cleaning liquid 65, the stirring rod 72 is rotated by the motor 71. Accordingly, the residue 54 deposited on the filter 70 is stirred, and becomes a slurry liquid in which the residue 54 is dispersed in the cleaning liquid 65a. The slurry liquid 52 is discharged from the second discharge port 83 to a recovery unit (not shown). By dispersing the residue 54 in the cleaning liquid 65 and collecting the residue in a slurry state, the residue 54 can be efficiently collected without leaving the residue 54 on the filter 70, and the filter 70 can be cleaned without opening and closing the filtration device 50. Therefore, the solvent is not scattered outside and the work site is not contaminated.

  In addition, when the raw material dope 55 is filtered by the filtration device 50 or when the cleaning is performed with the cleaning liquid 65, it is preferable to appropriately release air from the air release pipe 76. The reason for this is, for example, that air enters the filtration device 50 when the filtration device 50 is switched. In addition, the slurry liquid discharge unit includes a discharge pipe having the discharge valve provided in the filtration device 50 as described above, and a stirring means such as a stirring rod 72 for stirring the residue 54. Here, the stirring means is not limited to the stirring rod. For example, a configuration may be used in which a mesh filter is formed in a circular shape, and the mesh filter is rotated by a motor to separate and stir the residue by centrifugal force. .

As described above, as shown in FIG. 5, the recovered slurry liquid 52 is sent to the separation device 56 via the recovery tank. In the separation device 56, as shown in FIG. 4, a metal strainer 90 on a cylindrical shape is used as a filter when separating the residue 54. In order to efficiently separate the waste liquid, the strainer 90 preferably has a mesh number of 50 or more and 490 or less. The number of meshes is a value determined by the diameter of a metal wire constituting the strainer 90 and the like, and refers to the number of meshes per 1 cm ² . The strainer 90 preferably has a relation of D <L, where D is the diameter of the cylinder and L is the length of the cylinder. If such a strainer 90 is used, a sufficient filtration area can be ensured, so that clogging can be suppressed and high filtration efficiency can be maintained. When D ≧ L, clogging is likely to occur because the filtration area is not sufficiently secured. The filtration area of the present invention is an area through which a slurry liquid passes in a filter such as the strainer 90.

  In the strainer 90 suitable for the present invention, in order to efficiently separate the residue from the slurry liquid, the weave of the metal wire is preferably a plain woven weave or a twill woven weave. In addition, a punched metal is used as a reinforcing material for a wire net formed by braiding a metal wire. Here, in order to suppress the generation of filtration resistance due to the reinforcing material, the opening ratio is desirably 30% or more.

  As shown in FIG. 5, the strainer 90 is installed in the tank 91 in a state where the strainer 90 is vertically set inside the separation device 56. The slurry liquid 52 is supplied from above the separation device and flows vertically downward. Here, the solution component passes through the liquid passage hole of the strainer 90, while the residue 54 is captured and deposited on the inner wall surface of the strainer 90. If the flow of the slurry liquid 52 is directed substantially vertically downward, it is possible to efficiently capture the highly sedimentable filter aid contained in the residue 54. The separation device 56 may be configured to supply the slurry liquid 52 so that the residue 54 can be collected on the outer wall surface of the strainer 90.

  The separation device 56 has an air vent pipe 97 attached to the upper part thereof. The air bleeding pipe 97 bleeds air existing in the separation device 56 at an initial stage from the start of the supply of the slurry liquid 52. When the air in the separation device 56 is vented in this manner, the air accumulation of the slurry liquid 52 is suppressed, and a layer having a uniform thickness due to the residue 54 can be formed on the wall surface of the strainer 90. However, if the air bleeding time is lengthened, the filter aid in the slurry liquid 52 tends to settle, and a layer having a uniform thickness cannot be formed. For this reason, it is preferable that the time for air removal be 5 minutes or less. Here, the initial stage refers to a period from the start of supplying the slurry liquid to the lapse of 5 minutes, and the time for air bleeding is included in the initial stage.

  The average thickness of the residue 54 separated and collected in the strainer 90 is preferably 5 to 500 mm. The thickness of the residue 54 can be measured after actually collecting the strainer 90, or can be estimated from the filtration area of the strainer 90, the flow rate of the slurry liquid 52 to be supplied, the supply time, and the like. If the thickness of the residue 54 exceeds 500 mm, it becomes difficult to secure the flow rate of the slurry liquid 52 and the pressure loss increases, so that there is a concern about the pressure resistance of the separation device 56. On the other hand, if the thickness of the residue 54 is less than 5 mm, it is necessary to increase the filtration area, so that the size of the apparatus must be increased.

  Further, a pressure gauge (not shown) for measuring the internal pressure is installed in the separation device 56, and a change in the pressure is measured while the slurry liquid 52 is supplied. Here, the flow rate of the slurry liquid 52 is adjusted to be 10 to 1500 L per the total filtration area of the strainer 90 according to the change in the filtration resistance. Thus, the work can be performed without prolonging the separation time. If the flow rate of the slurry liquid 52 deviates from the above range, it is necessary to prepare a correspondingly large tank, which leads to an increase in equipment cost and makes it difficult to secure an installation space. On the other hand, if the flow rate is less than 10 L, it takes too much work time, which is not suitable.

  The solution recovered in the initial stage after the supply of the slurry liquid 52 into the separation device 56 is taken out from the outlet 98 provided at the lower part of the separation device 56, and then the valve V6 is switched and the pump P4 is used again. It is supplied to the separation device 56 and circulated. Since the efficiency of capturing the residue 54 by the strainer 90 is low in the initial stage from the start of the separation, the recovered solution is in a suspended state. Then, when a certain time has elapsed from the start of the separation and the thickness of the layer due to the residue 54 becomes 5 mm or more, the residue 54 of the suspended solution is efficiently captured. The filtrate obtained after the completion of the separation is sent to the washing liquid tank 65, and is reused as a solvent for washing the filtration device or preparing the dope.

  The used strainer 90 that has captured the residue 54 is removed from the separation device 56 and dried in the drying device 80. In the present embodiment, a drying device 80 as shown in FIG. 6 is used. The drying device 80 is provided with a supply port 80a through which the drying air 83 adjusted to a predetermined temperature range is supplied and an outlet 80b through which the used drying air 83 is discharged. The strainer 90 is left in the drying device 80 with its opening facing up. The drying air 83 is sent into the drying device 80 from the supply port 80a. Here, the temperature of the drying air 83 is adjusted so that the drying temperature is 5 ° C. or more and 140 ° C. or less. Thereby, the solvent component in the residue attached to the strainer 90 can be evaporated and drying can be advanced. On the other hand, if the temperature during drying exceeds 140 ° C., there is a concern that the strainer 90 may be damaged by heat. On the other hand, if the temperature at the time of drying is less than 5 ° C., the drying time is prolonged, and the workability is reduced. The drying means is not particularly limited as long as it can be heated to a predetermined temperature range. For example, a method in which steam is sprayed on the strainer 90 as a target to directly apply heat can also be efficiently dried in a short time.

  The drying air 83 supplied for drying is in a state containing a solvent gas. Therefore, the drying air 83 is once collected by the solvent gas collecting device 81, and the solvent is removed there. Thereafter, the drying air 83 from which the solvent has been removed is heated to a predetermined temperature by the temperature control device 82, and then supplied again as the drying air 83 into the drying device 80. When the strainer 90 is dried in the hermetically-sealed drying device 80, the solvent gas can be recovered without releasing the solvent gas into the atmosphere. Can be reduced.

(3) Casting Step As shown in FIG. 1, the dope is fed to a pressurizing die 30 through a liquid feed pump (for example, a pressurized fixed-quantity gear pump) and transferred endlessly. For example, this is a step of casting a dope from a pressure die slit to a casting position on an endless support such as a stainless steel belt or a rotating metal drum.

  The dope is preferably sent to the die at a rate of 50 to 2000 L / hr in order to suppress the occurrence of a film thickness deviation due to a change in flow rate.

(Casting)
As a method of casting the solution, a method in which the prepared dope is uniformly extruded from a pressure die onto a metal endless support, and a dope once cast on the metal endless support is coated with a blade to form a film. There is a method using a doctor blade for adjustment, a method using a reverse roll coater for adjusting with a roll that rotates in the reverse direction, and the like, but a method using a pressure die is preferable. As the pressure die, there are a coat hanger type, a T-die type and the like, and any of them can be preferably used. Further, besides the methods mentioned here, it can be carried out by various methods for casting a cellulose triacetate resin, which are conventionally known, and each condition is set in consideration of a difference in a boiling point of a solvent to be used. Thus, the same effects as those described in the respective publications can be obtained. As the endless running metal endless support used for producing the cyclic polyolefin film of the present invention, a drum whose surface is mirror-finished by chrome plating or a stainless steel belt whose surface is mirror-finished by surface polishing (band and May be used).

  The metal endless support has a surface energy of a surface of the endless support contacting both ends in the width direction of the casting film of the dope, and a surface energy of the endless support contacting a center portion in the width direction of the casting film of the dope. It is preferable to perform an activation treatment on the surface of the endless support so as to have a surface energy higher than that of the above from the viewpoint of suppressing the fluttering of the ears.

  The activation treatment is preferably performed by atmospheric pressure plasma irradiation or excimer UV irradiation, and after the activation treatment, the surface energy of the surface of the endless support in contact with both widthwise ends of the casting film. Is defined as γse, and the surface energy of the surface of the endless support in contact with the center in the width direction of the casting film is defined as γsc, and the difference Δγ (= γse−γsc) is in the range of 0.1 to 60 mN / m. Is preferred. From the both ends of the casting film in contact with the surface of the endless support having a surface energy higher than the surface energy of the surface of the endless support in contact with the center of the casting film in the width direction of the dope. The width is preferably in the range of 0.05 to 0.25 Wr, where Wr is the width of the casting film.

  The surface energy of the endless support can be measured by measuring contact angles with water, nitromethane, and methylene iodide, and calculating from these values using Young Forks equation. Specifically, it can be measured using a contact angle meter or the like manufactured by Kyowa Interface Science Co., Ltd.

  Further, in the casting film forming area on the endless support, using the endless support having a hydrophobized layer having a water contact angle of 90 ° or more, the casting film is formed on the hydrophobized layer. Preferably, it is formed. The hydrophobic layer is composed of a hydrophobic substance, the endless support is composed of a cooling drum, and the casting film is self-supporting and peeled off by cooling gelation. Preferably, the hydrophobic substance is PTFE or PP.

  In addition, in order to improve the releasability (peelability) of the film from the metal endless support and to produce a cyclic polyolefin film having excellent transparency and flatness, the surface of the metal endless support is coated with iron. (Fe) and / or chromium (Cr) elements, and the composition ratio of component elements on the surface of the metal endless support satisfying the following relationship (i) and / or (ii): It is preferred to use a body.

(I) (Fe ₂ O ₃ + FeO) / Fe = 5 to 50
(Ii) (CrO ₂ + CrO ₃ ) / Cr = 10 to 50
This is because a metal oxide film layer with a higher oxygen bond ratio than the normal oxide state of the metal surface is created while maintaining a very smooth surface state, so that even during continuous production of films, It is possible to produce a cyclic polyolefin film having improved optical properties such as improved releasability (peelability) of a film from an endless support made of Nissan, excellent smooth releasability, and excellent transparency and flatness. it can. In addition, corrosion of the surface of the metal endless support can be prevented, and the corrosion pattern is transferred to the film, eliminating quality defects such as unevenness, and when the surface becomes rough due to corrosion, This prevents the releasability (peelability) of the web from being significantly deteriorated by the anchor effect.

When the (Fe ₂ O ₃ + FeO) / Fe ratio of (i) is less than 5, the corrosion resistance is not much different from that of the untreated one, and the difference in the treatment is partially large. It is not preferable because unevenness is caused by the progress of corrosion. On the other hand, if the (Fe ₂ O ₃ + FeO) / Fe ratio exceeds 50, when something comes into contact with the surface and damages it, it becomes difficult to perform polishing to repair the surface to a smooth surface. Is not preferred.

Further, when the (CrO ₂ + CrO ₃ ) / Cr ratio of (ii) is less than 10, the corrosion resistance is not much different from that of the untreated one, and the difference in the treatment is partially large. It is not preferable because unevenness is caused by the progress of corrosion. On the other hand, if the (CrO ₂ + CrO ₃ ) / Cr ratio exceeds 50, when something comes into contact with the surface and damages the surface, it becomes difficult to perform polishing to restore the surface to a smooth surface. It is not preferable.

  Furthermore, even if the film forming speed is increased, the occurrence of the air entrainment phenomenon is prevented, and the adhesion between the casting film and the endless support is appropriately adjusted, and the peelability of the casting film from the endless support is improved. In order to improve the dope, when casting the dope on the endless support, a liquid containing at least one organic compound contained in the dope is supplied between the endless support and the casting film, and the casting film and It is also preferable to form an intervening film between the endless support.

  As shown in FIG. 7, an intervening film forming apparatus 140 is provided near the casting die 130, and is interposed on the surface of the casting bead 161 which is the flow of the ribbon-shaped dope 160 from the casting die 130 on the endless support side. The film forming liquid 162 is supplied.

  The intervening film forming apparatus 140 has a tank (not shown) for storing the intervening film forming liquid 162, a flow path 140a for this liquid, and a supply port 140b. At the time of casting the dope 160, an appropriate amount of the intervening film forming liquid 162 is supplied from the supply port 140 b along the entire width of the casting bead 161 on the endless support surface side. Thereby, even if the film forming speed is increased, the occurrence of the air entrainment phenomenon in the casting bead 161 can be further prevented. Then, when the casting bead 161 and the intervening film forming liquid 162 reach the casting drum 150, the casting film 170 is formed on the casting drum 150 via the interposing film 163. Thus, if the intervening film 163 exists between the casting drum 150 and the casting film 170, the occurrence of the air entrainment phenomenon can be prevented.

  The intervening film forming liquid 162 is a liquid containing at least one organic compound (solvent) contained in the dope 160, and is a mixture of the above-mentioned raw material solvent and a poor solvent which is not compatible with the polymer contained in the dope 160. It is preferable to prepare it. The intervening film 163 formed between the casting drum 150 and the casting film 170 by such an intervening film forming liquid 162 diffuses toward the casting film 170 over time. Thereby, the adhesion between the casting drum 150 and the casting film 170 does not become too high, so that the casting film 170 can be easily peeled off from the casting drum even with a small peeling stress.

  When the ratio of the solvent contained in the intervening film forming liquid 162 is w (%) regardless of whether the solvent is a good solvent or a poor solvent, and the thickness of the intervening film 163 is t (μm), w and t become t It is preferable to satisfy <−0.05w + 15. Thereby, the intervening film 163 which acts so that the casting film 170 can be easily peeled off from the casting drum 150 can be formed. However, if the intervening film 163 is too thick, the diffusion between the casting film 170 and the intervening film 163 is unlikely to occur, and the intervening film 163 may remain on the casting drum 150. If the intervening film 163 remains on the casting drum 150 in this way, it also has an adverse effect on subsequent casting, and it is not suitable because only a film having a poor surface condition can be manufactured.

  The installation location of the intervening film forming apparatus 140 is not limited to the configuration shown in FIG.

  In order to increase the film production speed, foaming due to entrainment of air is eliminated, film thickness unevenness due to vibration of the casting liquid film from the casting die due to reduced pressure chamber suction air is reduced, and scale dissolution dropped In order to obtain a film with excellent flatness and no transfer failure due to scattering of liquid droplets of excess liquid, a dope is cast on a metal endless support, and a casting film (web When forming the dope, a downwardly-opening vacuum chamber is provided as a means for reducing the pressure from the upstream side of the casting so that the web is formed in close contact with the endless support. In order to prevent the formation of a mustache-like film (scale) at both left and right ends (casting die edge) corresponding to both ends in the width direction of the casting die, a scale dissolving solution is dropped. Preferably comprises a solution liquid drip means. Outside the left and right side walls and the rear wall of the decompression chamber having the main decompression chamber, outer walls are respectively provided at predetermined intervals between these walls, and located outside the left and right both sides and the rear of the decompression chamber. In a preferred embodiment, a sub-vacuum chamber that opens downward is formed, and the pressure in the sub-vacuum chamber is greater than the pressure in the main vacuum chamber in the range of −30 to −300 Pa.

  Further, it is preferable that the gap between the left and right side walls and the rear wall of the decompression chamber having the main decompression chamber and the left and right outer walls and the rear outer wall of the sub decompression chamber opposed thereto is 10 to 300 mm.

  A wall other than the surface in contact with the casting die of the decompression chamber is doubled to form a sub-decompression chamber, and the decompression force of the sub-decompression chamber outside the decompression chamber is larger than the decompression force of the main decompression chamber inside the decompression chamber. By strongly sucking, the flow of suction air from the side to the casting liquid film in the discharge direction of the casting liquid film is blocked, and even if the production speed of the film is increased, the entrained air In addition to eliminating foaming due to entanglement, the stability of the casting liquid film is improved even when the degree of pressure reduction is increased due to an increase in the dope discharge speed accompanying high-speed film formation. The film thickness unevenness in the film transport direction due to the vibration of the film can be reduced, and a film having good smoothness can be produced.

  In addition, during the film formation, the excess amount of the scale solution dropped from the means for dropping the scale solution at the casting die edge to both ends in the width direction of the web at the casting die edge can be suctioned and collected toward the sub-vacuum chamber. The transfer failure due to the scattered droplets of the surplus liquid of the scale dissolving solution dropped does not cause transfer failure, and a film with excellent flatness can be obtained. Therefore, it is possible to produce a thin film with a high production efficiency, excellent quality, and high-speed film formation, which is thin and wide.

  If the gap between the left and right side walls and the rear wall of the decompression chamber having the main decompression chamber and the left and right outer walls and the rear outer wall of the sub decompression chamber opposed thereto is 10 to 300 mm, the decompression chamber is so-called. Internal and external duplexing, the entrained air is relatively strongly sucked from the sub-decompression chamber having a predetermined gap on the outer side of the decompression chamber with a decompression force larger than the decompression force of the main decompression chamber on the inner side of the decompression chamber. Able to reduce the suction air from the side to the edge of the liquid film to achieve stable casting and to remove excess liquid of scale solution blown off from the casting die edge (both right and left ends) The film can be collected in the sub-vacuum chamber having a strong external suction force (decompression force), so that a high-quality film can be stably produced at a high production rate for a long period of time.

  Further, it is preferable that the gas concentration in the vicinity of the casting dope in the decompression chamber is 80% or less.

  This is because when the concentration of gas (mainly vaporized volatile organic solvent) in the air near the casting bead increases and the gas component reaches a desired concentration, it may liquefy, and the liquefied solvent is cast. There is a possibility that the cast film adheres to the bead and the cast film becomes defective. When the pressure of the casting bead is reduced on the side of the endless support contacting surface (hereinafter referred to as the casting bead back surface), the formation of the casting bead is stable, but in this case, gas liquefaction is easy. This may cause a problem that the liquefied solvent adheres to the casting membrane or adheres to the decompression chamber to cause uneven pressure reduction. In such a case, there is a problem that a defect occurs on the surface of the film to be produced, causing optical unevenness, or unevenness in the width direction of the film (hereinafter, referred to as horizontal unevenness). It is improved by setting the gas concentration to 80% or less as shown in FIG.

  That is, by setting the gas concentration to 80% or less, liquefaction of the gas component can be prevented, and it is possible to prevent the gas component from liquefying and causing a failure to adhere to the casting bead. In the film obtained by the above method, the occurrence of optical unevenness and horizontal unevenness is suppressed.

  It is preferable that the pressure reduction degree of the pressure reduction chamber is in a range of -1500 to -200 Pa with respect to the atmospheric pressure. The discharge speed of the dope is preferably in the range of 7 to 40 m / min.

  From the viewpoint of preventing liquefaction, it is also preferable to spray a solvent gas near the casting bead. The ratio of the vapor contained in the solvent gas component is preferably in the range of 5 to 65% by volume, and the solvent is preferably dichloromethane. Further, the solvent is a mixture containing the largest amount of dichloromethane and mixed with a compound that dissolves or disperses the polymer, and it is preferable that the ratio of dichloromethane gas contained in the vapor is 80% by volume or more.

  It is also preferable to use a decompression chamber having a plurality of decompression chambers as the decompression chamber, from the viewpoint that it is possible to suppress the entrainment wind from being applied to the casting bead and to suppress the occurrence of uneven thickness in the film.

  For example, using a decompression chamber having a plurality of decompression chambers for depressurizing the endless support contact surface side of the casting bead, the gap between the decompression chamber and the endless support is set to a range of 0.05 mm or more and 3 mm or less, In the plurality of decompression chambers capable of independently adjusting the degree of decompression, the decompression chamber on the upstream side in the moving direction of the endless support may have a decompression degree lower than that on the downstream side. preferable. The gap between the decompression chamber and the endless support is more preferably in the range of 0.05 to 0.7 mm, and most preferably in the range of 0.05 to 0.5 mm.

  When the maximum value of the absolute pressure of each of the decompression chambers is Pn (Pa), the pressure of each of the decompression chambers is in a range from 0.9 × Pn (Pa) to 1 × Pn (Pa). It is more preferable to adjust the content to a range of 0.98 × Pn (Pa) or more and 1 × Pn (Pa) or less. The number of the decompression chambers is preferably 2 or more and 10 or less, and each of the decompression chambers is preferably provided with an exhaust port.

  In addition, it is preferable that a solvent gas is blown onto the upper part of the casting die, and the solvent gas is sent to the slit outlet while being along the surface of the casting die.

  It is preferable that a nozzle having a slit-shaped blowing port formed long in the width direction of the casting bead is provided at a lower portion of the blowing unit.

  The blower unit is installed downstream of the casting die in the running direction of the endless support and above the endless support. At the lower part of the blowing unit, a nozzle having a slit-shaped blowing port formed long in the width direction of the casting bead is provided, which is a slit outlet from the blowing port, and over the entire area of the casting bead in the width direction. A solvent gas containing the vapor of the solvent used in the preparation of the dope is sent toward the dope, and the concentration is maintained near the exit of the slit so as not to liquefy the solvent gas. In the present embodiment, since dichloromethane is used as a solvent for preparing the dope, a solvent gas containing a vapor obtained by evaporating dichloromethane is sent to the vicinity of the slit outlet.

  The solvent gas contains steam at a rate in the range of 5 to 65% by volume. More preferably, it is in the range of 20 to 65% by volume, particularly preferably in the range of 40 to 65% by volume. In the air in which the solvent gas concentration near the casting bead is maintained at a high level, drying of the casting bead is prevented. For this reason, the dope solidifies in the vicinity of the slit exit and becomes a foreign substance, and is prevented from adhering. Therefore, it is possible to produce a film excellent in surface state without a streak failure or the like.

  In the solution casting method, if the flow rate of the solution is not precisely controlled, the edge of the dope flowing down may be disturbed, or the burrs (excess coating at the edge) may occur at the edge of the slit. There is a problem that it is difficult to apply in a long-term stable state over a wide range.

  In the present invention, when a dope is cast by a casting die on a metal endless support in a method for producing a film by a solution casting method, a solvent is allowed to flow down to both ends of a slit of the casting die, and the solvent is allowed to flow. The inside diameter of the tip of the nozzle on both sides of the casting die to be flown is set to 4 mm or less and 0.5 mm or more, and the solvation parameter (-ΔHD-BF3) of the flowing solvent is 15 kJ / mol to 100 kJ / mol. ] It is preferable to be the following.

  Here, the solvation parameter is P.S. C. Maria, J.M. F. Gal, J Phys. Chem. , 89, 1296 (1985); C. Maria, J.M. F. Gal, J.M. de Franceschi, E.C. Fargin, J.M. Am. Chem. Soc. The standard molar enthalpy [kJ / mol] (-ΔHD-BF3) for 1: 1 complex formation between gaseous BF3 and a donor molecule in a dichloromethane solvent described in Chem., 109, 483 (1987).

  It is preferable that the solvent flowing down the nozzles on both sides of the casting die is, for example, methyl acetate. That is, according to the method for producing a cyclic polyolefin film of the present invention, when a solvent having a large solvation parameter is used, the solubility in the cyclic polyolefin-based resin is reduced, but generation of burrs can be suppressed. Although this factor is not clear, it can be assumed that such a phenomenon occurs because the swelling and dissolution state of the cyclic polyolefin-based resin differ depending on the value of the solvation parameter.

  Further, in the method for producing a cyclic polyolefin film of the present invention, before casting a dope or a resin melt on a metal endless support, the surface of the metal endless support is irradiated with normal-pressure plasma or excimer ultraviolet light. The surface treatment is preferably performed.

  In this case, the integration time of the normal pressure plasma irradiation treatment or the excimer ultraviolet irradiation treatment is preferably 0.1 to 3000 sec, and more preferably 0.5 to 500 sec.

  Here, if the integration time of the normal pressure plasma irradiation treatment or the excimer ultraviolet irradiation treatment is less than 0.1 sec, the surface is not sufficiently modified and the corrosion resistance of the surface is not improved, which is not preferable. On the other hand, if the integration time of the normal-pressure plasma irradiation treatment or the excimer ultraviolet irradiation treatment exceeds 3000 sec, the surface is roughened, which is not preferable.

  According to the present invention, a high-energy surface treatment is performed by a high-energy irradiator (A) composed of a normal-pressure plasma device and an excimer ultraviolet device, and the surface of the metal endless support is smaller than the surface oxide film naturally formed in the atmosphere Then, it is preferable to form a metal oxide film layer having an increased oxygen bond ratio.

  The pressure die used in the method for producing a cyclic polyolefin film of the present invention may be one or more pressure dies installed above a metal endless support. Preferably it is one or two. When two or more dope units are installed, the amount of the dope to be cast may be divided into various ratios for each die, and the dope may be sent to the die at a respective ratio from a plurality of precision metering gear pumps. The temperature of the cyclic polyolefin solution used for casting is preferably from -10 to 55C, more preferably from 25 to 50C. In that case, all of the steps may be the same, or may be different at various points in the steps. If different, the temperature may be a desired temperature immediately before casting.

  The width of the cast can be in the range of 1-4 m, preferably in the range of 1.5-3 m, more preferably in the range of 2-2.8 m. The surface temperature of the metal endless support in the casting step is set in the range of −50 ° C. to the temperature at which the solvent does not boil and foam, more preferably −30 to 100 ° C. A higher temperature is preferable because the drying speed of the web can be increased. However, if the temperature is too high, the web may foam or the flatness may deteriorate. A preferable endless support temperature is appropriately determined at 0 to 100 ° C, and more preferably at 5 to 30 ° C. Alternatively, it is also a preferable method to gel the web by cooling and peel the web from the drum in a state containing a large amount of residual solvent. The method of controlling the temperature of the metal endless support is not particularly limited, and there are a method of blowing hot or cold air, and a method of bringing hot water into contact with the back side of the metal endless support. It is preferable to use hot water because heat is transferred more efficiently, and the time until the temperature of the metal endless support becomes constant is short. When using hot air, in consideration of the temperature drop of the web due to the latent heat of evaporation of the solvent, while using hot air above the boiling point of the solvent, air with a higher temperature than the target temperature may be used while preventing foaming. . In particular, it is preferable to change the temperature of the endless support and the temperature of the drying air during the time from casting to peeling to efficiently perform drying.

  The casting die is preferably a pressure die which can adjust the slit shape of the die portion of the die and can easily make the film thickness uniform. Pressing dies include a coat hanger die and a T-die. In order to increase the film forming speed, two or more pressing dies are provided on a metal endless support, and even if the doping amount is divided and laminated, Good.

  At the time of solution casting, an edge failure called "wafer burr" may occur, but this is caused by a minute defect at the tip of the die. The die defects include minute scratches and dents that occur during die manufacturing and maintenance, and scratches that occur when grinding with a grindstone.

  Therefore, further studies were conducted to develop a means for preventing the occurrence of burrs due to minute defects at the tip of the die. In the method of producing a cyclic polyolefin film by casting from a slot of a solution die dissolved in a die, when the hardness Hv at the tip of the die is 400 or more, when the die is manufactured, at the time of maintenance, at the time of installation, minute scratches, It was found that dents were suppressed and the streak defect in the casting direction was improved until it became difficult to confirm. The hardness (Vickers hardness) represented by Hv is a value obtained by using a diamond pyramid having an apex angle of 136 ° as an indenter, reading the length of the diagonal line of the generated indentation, and dividing the load by the surface area of the dent. .

  Further, in a method for producing a cyclic polyolefin film by casting a solution obtained by dissolving a resin in a solvent from a slot of a die, by setting the surface tension at the tip of the die to 380 μN / cm or more, generation of burrs is prevented, Further, it was found that the streak defect was improved. The surface tension was measured according to JIS K6768, and manufactured by Wako Pure Chemical Industries, Ltd., using a wetting index standard solution, 32 to No. 32 This is a value measured using No. 54.

  Furthermore, in order to prevent the occurrence of burrs, the unevenness of the surface of the lip tip and the corner between the slot face and the flat end face intersecting the slot face are formed into a substantially arc-shaped cross-section to form a curved surface. It has been found that it is necessary that the surface has a small radius of curvature and good solvent wettability, so that it is possible to prevent the burrs at the lip tip and to improve the streak defect.

  The lip tip of the slot, the corner between the slot face and the flat end face that intersects the slot face is formed into a substantially arc-shaped cross section to form a curved surface, and the radius of curvature R of the curved surface is 5 to 50 μm. It is preferable to be within the range.

  The parallelism between a boundary line between the curved surface, the slot surface, and the flat end surface of the tip and a line connecting the center of curvature of the curved surface is set within a range of 1.5 to 15 μm per 1 m in the longitudinal direction of the slot. Is preferred. In addition, the parallelism between a boundary line between the curved surface, the slot surface, and the flat end surface of the tip and a line connecting the center of curvature of the curved surface is set to be equal to 0 of the radius of curvature R per 1 m in the longitudinal direction of the slot. It is preferable to set it to 3 times or less. Further, the parallelism between a boundary line between the curved surface, the slot surface, and the flat end surface of the tip and a line connecting the center of curvature of the curved surface is set in a range of 0.5 to 5 μm per 1 mm in the longitudinal direction of the slot. Is preferable. Furthermore, the parallelism between a boundary line between the curved surface, the slot surface, and the flat end surface of the tip and a line connecting the center of curvature of the curved surface is defined as 0 to 0 of the radius of curvature R per 1 mm in the longitudinal direction of the slot. It is preferable to set it to 1 or less.

  When the surface roughness of the die tip is Ra, the surface roughness Ra in the longitudinal direction of the slot and in a direction perpendicular to the longitudinal direction is preferably in the range of 0.01 to 3 μm.

  After casting the dope from the die onto a metal endless support, if the surface temperature of the rotating roller is high, the effect of promoting gelation of the casting film cannot be sufficiently obtained. In addition, since the dew point at the peeling part is high, dew condensation may occur on the casting film surface at the peeling part, and even if this condensed moisture is dried and volatilized in a later step, clouding occurs on the film surface. There's a problem.

  In order to solve this problem, in the solution casting method used in the present invention, in the rotating roller of the metal endless support, the first rotating roller having a surface temperature of −30 ° C. or more and 6 ° C. or less is used. The casting film toward the second rotating roller is dried by a drying wind, and the casting film is conveyed from the second rotating roller onto the first rotating roller, and then peeled off at a peeling position where the dew point is 0 ° C. or less. Cooling the casting film on the belt toward the first rotating roller by the first rotating roller and the cooling means provided upstream of the peeling position, and adjusting the cooling section up to the peeling position at the position of the cooling means. It is preferable that the temperature of the casting film to be stripped is set to less than 6 ° C., and the cooling roller as the cooling means is brought into contact with the belt surface opposite to the belt surface on which the casting film is formed. By the second The cast film on the belt toward the rotating roller to the first rotary roller is preferably cooled.

  Further, it is preferable that the dew point at the peeling position is set to 0 ° C. or less by adjusting the temperature inside the casting chamber accommodating the first rotating roller and the second rotating roller. In this case, it is preferable that the solvent content on a dry basis at the peeling position of the casting film is in the range of 10 to 200% by mass. That is, since the dew point near the separation position of the casting film is set to 0 ° C. or less, dew condensation is prevented, and the adhesion of moisture to the casting film is suppressed. This eliminates fogging on the surface of the film produced.

  It is also preferable to provide roughened bands at both ends of the surface of the metal endless support from the viewpoint of easy peeling. It is preferable that both the roughened zone and the casting width of the dope from the die overlap by 5 to 30 mm, and the average roughness Rz of the roughened zone is in the range of 0.5 to 2 μm.

  Generally, in the case of an endless support having a completely smooth surface, when peeling the web, the production is often interrupted due to a breakage accident because the both ends are easily torn and easily torn. On the other hand, by providing a roughened zone, the releasability is greatly improved, and no film is generated and no bubbles are generated, which is very effective. The width is a width from the inner side of the doped membrane to 5 to 30 mm to both ends of the endless support so that the casting position may be slightly shifted in the width direction. When the average roughness Rz of the roughened zone is smaller than 0.5 μm, the effect of the roughening is not obtained when Rz is smaller than 0.5 μm, the adhesion is too strong and the peeling is difficult, and when the Rz is larger than 2 μm, the surface is roughened. Adhesion is easy and peeling is difficult. The preferred range of Rz is 0.8 to 1.5 μm.

  In recent years, there has been a demand for higher production speeds and thinner films.However, in order to increase the speed, the temperature of hot air blown to the casting film on the endless support must be increased. There is a problem that the conventional method is inadequate as a measure against foaming because the temperature of the side edge portion of the expanded film rises and foaming is more likely to occur, and as the film becomes thinner, it becomes susceptible to the temperature of the endless support. .

  Therefore, while providing a wind shielding member so as to partition the casting film on the endless support into a central area and a side edge area in the width direction, and blowing hot air to the central area, the width direction of the casting film in the width direction. It is preferable to make the temperature distribution uniform. Cold air may be blown to the side edge area from the inside to the outside in the width direction of the casting film on the endless support to make the temperature distribution in the width direction of the casting film uniform.

  It is also preferable to blow cool air from the inner side to the outer side in the width direction of the casting film on the endless support to make the temperature distribution in the width direction of the casting film uniform.

  The wind shielding member may be provided in a range of 20 to 100 mm, more preferably in a range of 20 to 80 mm, from the side edge of the casting film toward the center thereof in parallel with the side edge. Further, the gap between the wind shielding member and the casting film may be set in a range of 5 to 30 mm, more preferably, in a range of 5 to 15 mm.

  Specifically, the cool air blowing is performed by a blowing duct, and a blowing port of the blowing duct is provided in a range of 20 to 100 mm from a side edge of the casting film to a center part side in parallel with a side edge, and a blowing port is provided. The gap with the casting film is set in the range of 5 to 30 mm, and the cold air is preferably blown to the casting film at an intersection angle of 45 to 90 °, more preferably 60 to 80 °. Further, it is preferable that the cool air has a dew point of −2 ° C. or less and a temperature of 15 to 60 ° C., and blows the cool air at a wind speed of 1 to 10 m / sec.

  It is also preferable to perform so-called initial drying, in which the surface of the casting film immediately after being formed on the endless support is dried using a drying device. As described above, when the initial drying is performed, the evaporation of the solvent from the casting film can be effectively promoted.

  However, in the initial drying, when the drying temperature exceeds the boiling point of the solvent contained in the cast film on the endless support, foaming due to the solvent occurs inside the cast film. In particular, in the vicinity of both end portions of the casting film, heat is easily transmitted from the endless support to the casting film, so that foaming is likely to occur. When foaming occurs inside the casting film in this way, irregularities are generated on the surface of the casting film, and voids are formed inside the casting film. In addition, when drying is performed by sending out drying air adjusted to a predetermined temperature, the drying air causes oblique unevenness and uneven film thickness (thickness unevenness) on the surface of the casting film. Therefore, when such oblique unevenness or uneven thickness (generally referred to as unevenness) or foaming as described above occurs on the surface of the casting film, the flatness of the casting film is significantly reduced. Therefore, only a film having poor flatness can be produced from such a casting film.

  Therefore, a temperature (° C.) within a range of 30 to 160 ° C. is provided from a first air outlet provided to face a metal endless support and having a longitudinal direction in a width direction of the metal endless support. A first drying step of sending the substantially constant drying air to the casting film immediately after being formed while adjusting the static pressure (Pa) to be substantially constant within a range of 50 to 200 Pa; After one drying step, from the second air outlet provided to face the running direction of the endless support, the direction of travel of the endless support is determined according to the residual solvent amount of the casting film. It is preferable to perform a casting film drying method including a second drying step of sending substantially parallel drying air.

  In addition, it is preferable that a partition member is provided inside the first air outlet to divide the endless support into at least three areas in a direction parallel to a running direction of the endless support. In the section of the first blower port, an airflow control member is provided in a section located above the vicinity of both side ends of the casting film, and the amount of dry air to be sent out is adjusted in the width direction of the endless support. Is preferred.

  The first drying treatment is preferably performed while the amount of the residual solvent in the casting film is up to 250% by mass, and the temperature (° C.) is substantially constant within a range of 30 to 160 ° C. from the second air outlet. The drying wind adjusted so that the wind speed (m / sec) is substantially constant within the range of 5 to 20 m / sec may be sent out so as to be parallel to the running direction of the endless support. preferable.

  To improve the releasability of the casting membrane from the metal endless support, a cooling body with a specific temperature range is placed on the surface of the moving endless support that is in contact at the time of peeling, on the side opposite to the dope film release side. By contacting and controlling the amount of the residual solvent at the time of peeling to a specific range, the peelability is improved and the peeling can be favorably performed from the endless support. That is, the amount of the residual solvent at the time of stripping the casting film is controlled to 100% by mass or less, and in the region where the casting film is stripped from the endless support, It is preferable to bring a cooling body having a surface temperature of 10 ° C. or less into contact with the opposite surface.

  The amount of the residual solvent is preferably controlled to 55% or less, and the surface temperature of the cooling body is preferably -5 ° C or less.

  It is preferable that the cooling body also serves as a roller capable of rotating the moving endless support. As a method of controlling the surface temperature of the cooling body, for example, the surface temperature by cooling with a blinch chiller using antifreeze is 10 ° C or less (the upper limit is preferably 5 ° C or less, more preferably 0 ° C or less, particularly (Preferably −5 ° C. or less). The surface temperature of the cooling body is preferably −25 to 5 ° C., more preferably −25 to 0 ° C., and particularly preferably −20 to 0 ° C.

  Further, it is also preferable to set the temperature of the entire metal endless support at -50 to 10 ° C, and to cool the cyclic polyolefin-based resin solution from being cast on the metal endless support to being peeled off. When the speed is represented by (temperature difference / time), it is preferably 3 to 5 (° C./sec).

  At that time, it is preferable to adjust the ratio of the poor solvent in the dope to a range of 2 to 20% by mass from the viewpoint of peelability.

  At the upper end of the casting die, a plurality of supply ports for the cyclic polyolefin-based resin dope are provided, and the dope is preferably supplied to the casting die from the plurality of supply ports into the manifold of the casting die. .

(Laminated casting)
When performing laminating casting such as co-casting, the lip clearance of the casting die is narrowed to increase the shearing of the discharge part, and the locally high concentration (high viscosity) part of the dope causing stick-slip is mixed. In addition, the occurrence of circular deformation can be suppressed. When a multilayer film is formed, the viscosity of the dope that forms the outer layer (the surface layer, the air surface layer and / or the back surface layer, and the endless support surface layer) is reduced, so that the stick-slip itself is weakened and a circular shape is formed. No deformation occurs. Further, there is a predetermined correlation between the lip clearance and the viscosity of the dope for forming the outer layer.

In a solution casting method in which a plurality of dopes containing a polymer and a solvent are co-cast from a casting die to form a multilayer film, the dope of the multilayer film at a temperature T1 (° C.) when the dope is cast. The relationship between the dope viscosity V (Pa · s) forming the front surface or the back surface and the average value C1 (mm) of the lip clearance of the casting die is as follows.
V ≦ −146 × C1 + 219, more preferably V ≦ −135 × C1 + 200,
More preferably, V ≦ −118 × C1 + 175.

  The dope viscosity V (Pa · s) for forming the front or back surface of the multilayer film at a temperature T1 (° C.) at the time of casting the dope is preferably in the range of 5 to 60 Pa · s, more preferably. The range is from 5 to 55 Pa · s, and most preferably from 7 to 40 Pa · s. The average value C1 (mm) of the lip clearance is preferably in the range of 0.9 to 1.5 mm, more preferably in the range of 0.9 to 1.2 mm, and most preferably 0.1 to 1.2 mm. The range is 9 to 1.1 mm. It is preferable that the temperature T1 (° C.) of the dope at the time of casting the dope is in the range of 20 to 38 ° C.

  Further, at least two or more of the dope for the base layer, the dope for the endless support surface layer, and the dope for the air surface layer have different viscosities, and the thickness t1 (μm) of the base layer constituting the casting film and the endless support surface layer It is preferable that the relationship between the thickness t2 (μm) and the thickness t3 (μm) of the air surface layer be t2 ≦ t3 ≦ t1. Further, it is preferable that the ratio of t3 to the thickness of the casting film be 3% or more and 40% or less.

  The relationship among the viscosity η1 (Pa · s) of the dope for the base layer, the viscosity η2 (Pa · s) of the dope for the endless support surface layer, and the viscosity η3 (Pa · s) of the dope for the air surface layer is expressed as η3 ≦ η2. It is preferable that ≦ η1.

  The polymer is preferably a cyclic polyolefin-based resin having a degree of polymerization in the range of 100 to 1,000. Further, η3 preferably satisfies 5 Pa · s ≦ η3 ≦ 30 Pa · s.

  The mass A of the dope for the air surface layer and the mass B of the organic solvent contained in the dope preferably satisfy 16 ≦ {(AB) / A} × 100 ≦ 21.

  The raw material dope is preferably stirred and mixed by an in-line mixer after adding the additive, and the in-line mixer is provided so as to extend in a diameter direction of a pipe through which the raw material dope flows, and has a slit-shaped addition serving as an inlet for the additive. Preferably a mouth is provided.

  The length L of the addition port parallel to the radial direction of the pipe is preferably 20% or more and 80% or less of the inner diameter of the pipe.

  The gap between the slits is preferably 0.1 mm or more and 1/10 mm or less of the inner diameter of the pipe, and the distance D from the addition port to the in-line mixer is preferably 1 mm or more and 250 mm or less. Further, the flow velocity V1 of the additive flowing in the pipe and the flow velocity V2 of the raw material dope preferably satisfy 1 ≦ V1 / V2 ≦ 5.

(Dry)
Drying of the dope on the endless support for the production of the cyclic polyolefin film is generally performed on the surface side of the metal endless support (for example, a drum or a band), that is, the surface of the web on the metal endless support. A method of applying hot air from the back, a method of applying hot air from the back of the drum or band, and contacting a temperature-controlled liquid from the back side opposite to the dope casting surface of the band or drum, and heating the drum or band by heat transfer. Although there is a liquid heat transfer method for controlling the surface temperature, a back liquid heat transfer method is preferable. The surface temperature of the metal endless support before casting may be any number of times as long as it is lower than the boiling point of the solvent used for the dope. However, in order to promote drying and to lose the fluidity on the metal endless support, the temperature should be 1 to 10 ° C. lower than the boiling point of the lowest boiling solvent among the solvents used. It is preferable to set. This is not the case when the casting dope is cooled and peeled off without drying.

(Peeling)
In this step, the web from which the solvent has been evaporated on the metal endless support is peeled off at the peeling position. The peeled web is sent to the next step as a film.

  The temperature at the peeling position on the metal endless support is preferably in the range of 10 to 40C, more preferably in the range of 10 to 30C.

  The residual solvent amount at the time of peeling of the web on the metal endless support at the time of peeling is in the range of 10 to 130% by mass depending on the strength of drying conditions, the length of the metal endless support, and the like. Preferably, peeling is performed in the range of 10 to 100% by mass. However, when peeling is performed at a time when the amount of the residual solvent is larger, if the web is too soft, flatness at the time of peeling is impaired, and unevenness and vertical stripes due to peel tension occur. Therefore, the amount of residual solvent at the time of peeling is determined based on a balance between economic speed and quality.

  The residual solvent amount of the web is defined by the following equation (Z).

Formula (Z)
Residual solvent amount (%) = (mass before heat treatment of web−mass after heat treatment of web) / (mass after heat treatment of web) × 100
Note that the heat treatment at the time of measuring the amount of the residual solvent means performing heat treatment at 115 ° C. for one hour.

  The peeling tension at the time of peeling the metal endless support and the film is usually in the range of 50 to 245 N / m. However, when wrinkles are likely to occur at the time of peeling, the peeling is performed at a tension of 190 N / m or less. Is preferred.

  In the present invention, the temperature at the peeling position on the metal endless support is preferably in the range of −50 to 40 ° C., more preferably in the range of 5 to 40 ° C., and in the range of 5 to 30 ° C. Most preferably, it is within.

  When peeling a dry film from a metal endless support, if the peeling resistance (peeling load) is large, the film is stretched irregularly in the film forming direction, causing optically anisotropic unevenness. In particular, when the peeling load is large, portions that are stretched stepwise in the film forming direction and portions that are not stretched alternately occur, and a distribution occurs in retardation. When the liquid crystal display device is loaded, a linear or band-like unevenness becomes visible. In order to prevent such a problem from occurring, it is preferable to set the peeling load of the film to 2.5 N or less per 1 cm of the film peeling width. The peeling load is more preferably 2 N / cm or less, further preferably 1.8 N or less, particularly preferably 1.5 N or less. When the peeling load is 2.5 N / cm or less, unevenness due to peeling is not recognized at all even in a liquid crystal display device in which unevenness is likely to appear, which is particularly preferable. As a method of reducing the peeling load, there are a method of adding a peeling agent as described above and a method of selecting a solvent composition to be used.

  The peeling load is measured as follows. A dope is dropped on a metal plate having the same material and surface roughness as a metal endless support of a film forming apparatus, spread to a uniform thickness using a doctor blade, and dried. A notch of even width is cut into the film with a cutter knife, the end of the film is peeled off by hand, and the clip is connected to a strain gauge, and the load change is measured while raising the strain gauge obliquely at 45 degrees. The volatile content in the peeled film is also measured. The same measurement is performed several times while changing the drying time, and the peeling load at the same time as the residual volatile matter at the time of peeling in the actual film forming process is determined. As the peeling speed increases, the peeling load tends to increase, and it is preferable to measure at a peeling speed close to actual.

  The preferred concentration of residual volatiles at the time of peeling is 5 to 60% by mass. However, depending on the cyclic polyolefin used, if the residual volatile matter concentration is 30% by mass or more, the film strength is poor, and the film loses its peeling strength and is cut or stretched. In addition, the self-holding force after peeling is poor, and deformation, wrinkles, and knicks are likely to occur. It also causes a distribution in retardation. On the other hand, peeling with a high volatile content has the advantage that the drying speed can be increased and the productivity is improved, which is preferable. Therefore, the more preferable residual volatile matter concentration at the time of peeling is 10 to 55% by mass. Even when the amount of the release agent used is reduced, the release resistance is particularly preferably 15 to 50% by mass at which the release resistance becomes relatively small.

  The stripping speed is preferably 10 m / min or more, and the amount of change in the stripping position at 2 Hz or more is preferably less than 20 mm. In the case where a peeling roller that supports the film immediately after peeling off from the endless support is used, the distance L between the peeling position and the contact position of the film of the peeling roller is 0.1 mm to 100 mm. It is preferable to set the range. It is preferable to adjust the temperature of the endless support in a range of 10 to 40 ° C.

  At this time, it is preferable that the film formation speed is in the range of 10 to 150 m / min. The temperature at the time of peeling is preferably in the range of 5 to 50 ° C.

  In addition, the film immediately after being peeled off from the endless support is a thin buffy film, and the film is thinned in a roller transporting or a tenter transporting process in which both ends of the film are held and transported (hereinafter referred to as ear ends). If the sheet is made thinner, a problem arises in that stable conveyance becomes difficult. Further, if the thickness of the ear end of the film is too large, there may be a case where flakes and the like occur in high-speed film formation.

  Therefore, even if the film is thinned, it is preferable to increase the thickness only at the edge of the film by a method other than the lip clearance adjustment in order to secure transport stability, and separately from the flow path of the die body, A dope flow path for thickness correction of each ear end is provided, and the flow rate of the dope passing therethrough is controlled by an adjustment mechanism different from the clearance adjustment at the tip of the die lip. A preferred method is to feed the film to the edges and to independently control the thickness of only the two ear edges of the film.

  As a production apparatus that can be specifically used, in a film production apparatus in which a dope is cast on an endless support from a die body having a dope flow path, the film is separated into the die separately from the dope flow path. It is provided with a flow path for correcting the thickness at both ends, so that the thickness at both ends of the film can be controlled independently. It is preferable that the apparatus is provided with an adjustment mechanism for adjusting the flow rate of the correction dope passing through the correction channel, and is capable of independently controlling the thickness of both ends of the film. It is preferable that the correction channel has an air vent. Preferably, the correction flow path has a heat retaining mechanism that can be controlled independently of the die main body, and the correction flow path outlet has a die lip from a flow path that is the casting width of the die main body. It is preferably provided between the tip.

  According to the method for producing a film, both end portions of the casting film are thickened, the strength of the film as a whole is increased, and when the thin casting film is peeled off from the endless support, such as peeling residue. Can be suppressed from occurring. In addition, the method of thickening only the both ends of the casting film in this way, separately from the dope flow channel provided in the body of the die, providing the die both ends thickness correction flow channel in the die, The correction dope is supplied from the correction channel, and the thickness of both ends of the film is independently controlled, so that the present invention can be implemented with only a slight improvement to conventional equipment. Therefore, cost can be reduced. In addition, by controlling the flow rate of the dope for correction passing through the flow path for correction by using a mechanism having an adjustment mechanism different from the clearance adjustment at the tip of the die lip, the control of the thickness of the film can be more accurately performed. It can be carried out.

(Atmosphere in the casting process)
In the casting step according to the present invention, at least the oxygen concentration in the casting step is preferably less than 10 vol%, more preferably less than 8 vol%. Further, when the drying step following the casting step is arranged in the same casing as the casting step, the oxygen concentration will be less than 10 vol% even in the drying step. When there is no air permeability between the two, the oxygen concentration may be reduced to less than 10 vol% only in the casting step.

  By setting the oxygen concentration to less than 10 vol% as described above, it is possible to prevent explosion of the organic solvent gas and the like, and it is particularly effective when the concentration of the organic solvent gas in the casting step is high. That is, it is particularly effective when the concentration of the organic solvent gas is 25% or more of the lower explosive limit.

  In order to reduce the oxygen concentration in the casting process to less than 10 vol%, an inert gas such as nitrogen gas or carbon dioxide or a mixture of an inert gas and air and a mixed gas having an oxygen concentration of less than 10 vol% is used. It can be performed by supplying. It is preferable that the oxygen concentration in the casting step is measured by an oxygen concentration meter, and the supply amount of an inert gas or the like is controlled according to the measured value.

(4) Drying / stretching step (4-1. Drying step)
The drying step can be performed by dividing into a preliminary drying step and a main drying step.

  In order to dry the web obtained by peeling from the metal endless support, the web may be dried while being conveyed by a number of rollers arranged vertically or may be dried at both ends of the web like a tenter dryer. May be dried while being transported while fixed with clips.

  The means for drying the web is not particularly limited, and can be generally performed by hot air, infrared rays, a heating roller, a microwave, or the like, but is preferably performed by hot air in terms of simplicity.

  The drying temperature in the web drying step is preferably lower than the glass transition point of the film, and it is effective to perform heat treatment at a temperature of 100 ° C. or higher for a period of 10 to 60 minutes. The drying is performed at a drying temperature in the range of 100 to 200 ° C, more preferably in the range of 110 to 160 ° C.

(4-2. Stretching step)
By subjecting the cyclic polyolefin film of the present invention to a stretching treatment, the orientation of the molecules in the film can be controlled, and the flatness can be improved and the toughness can be obtained. Further, the phase difference can be adjusted to a desired value.

  The stretching operation may be performed in multiple stages. When performing biaxial stretching, simultaneous biaxial stretching may be performed or stepwise may be performed. In this case, stepwise means, for example, that stretching in different stretching directions can be performed sequentially, or that stretching in the same direction is divided into multiple stages, and stretching in different directions is added to any of the stages. Is also possible.

Thus, for example, the following stretching steps are also possible:
・ Stretch in the casting direction → stretch in the width direction → stretch in the casting direction → stretch in the casting direction ・ Stretch in the width direction → stretch in the width direction → stretch in the casting direction → stretch in the casting direction Simultaneous biaxial stretching also includes the case where the film is stretched in one direction and the other is shrunk by relaxing the tension.

  The residual solvent amount at the start of stretching is preferably in the range of 2 to 10% by mass.

  When the amount of the residual solvent is 2% by mass or more, the film thickness deviation is small, and it is preferable from the viewpoint of flatness. When the amount is 10% by mass or less, unevenness on the surface is reduced, and the flatness is improved.

  After the web is peeled off from the metal endless support, the web (film) is dried in a roll drying method (a method in which a large number of rolls arranged vertically are alternately passed through the web and dried) or a tenter method. Is transported while drying, and finally the solvent is dried until the residual solvent amount becomes 0.5% by mass or less.

  Further, the amount of residual solvent contained in the web may be slightly higher in order to obtain a desired retardation value, and in order to impart a high retardation value, 15 to 100% by mass, preferably 20 to 100% by mass. You may have it in the range of 50 mass%.

  One of the methods for producing a cyclic polyolefin film according to the present invention includes a stretching step in which the film is stretched in a direction (TD direction) perpendicular to the transport direction of the film, and includes a heat treatment step downstream of the stretching step. The film temperature is set to a glass transition temperature (Tg) of −50 ° C. or more and Tg + 40 ° C. or less, the roll span of the guide roll in the heat treatment step is set to a range of 50 to 300 mm, and the transport tension of the film is set to 15 to 100 N / m. Heat treatment is performed as a range. Here, the glass transition temperature (Tg) refers to the glass transition temperature of the completed film.

  According to the method for producing a cyclic polyolefin film of the present invention, in a solution casting method, in another step downstream of the stretching step, while suppressing shrinkage in the width direction of the film, the film has a glass transition temperature (Tg). By applying the above temperature, shrinkage of the film in the MD direction (the direction in which the film is conveyed), which could not be achieved with the cellulose ester resin produced by the conventional solution casting method, is promoted, and the retardation in the thickness direction ( In addition to the reduction in Rt), uniformity of the retardation value in the width direction can be ensured, and the haze value of the film can be reduced.

  In the production method of the present invention, the stretching ratio in the stretching in the film transport direction (MD stretching) is preferably 1 to 25%, more preferably 3 to 20%.

  Here, the “stretching ratio (%)” means a value determined by the following equation.

Stretching ratio (%) = 100 × {(length after stretching) − (length before stretching)} / length before stretching The method for stretching the web in the film transport direction is not particularly limited. For example, a method in which a circumferential speed difference is applied to a plurality of rolls, and a longitudinal stretching is performed using the circumferential speed difference between the rolls, and both ends of the web are fixed with clips or pins, and the intervals between the clips and pins are widened in the traveling direction. And a method of extending in the vertical and horizontal directions at the same time and extending in both the vertical and horizontal directions. Of course, these methods may be used in combination. In the so-called tenter method, when the clip portion is driven by the linear drive method, smooth stretching can be performed, and the risk of breakage or the like can be reduced, which is preferable. The stretching in the longitudinal direction is performed using a device having two nip rolls, and the rotational speed of the nip roll on the outlet side is made higher than the rotational speed of the nip roll on the inlet side, so that the cyclic polyolefin film is transported (vertically). Is preferably stretched. By performing such a stretching, the expression of retardation can also be adjusted.

  Another method for producing a cyclic polyolefin film of the present invention similarly includes a stretching step of stretching in a direction (TD direction) perpendicular to the film transport direction, and includes a heat treatment step upstream of the stretching step. Within this, the film temperature is set to a glass transition temperature (Tg) of −50 ° C. or more and a temperature of Tg + 20 ° C. or less, the roll span of the guide roll in the heat treatment step is set to a range of 50 to 300 mm, and the transfer tension of the film is set to 15 to 100 N /. Preferably, the film is subjected to a heat treatment in the range of m, further cooled downstream to a temperature lower than the glass transition temperature (Tg) once from the heat treatment step, and then stretched. According to this method for producing a cyclic polyolefin film, in the solution casting film forming method, after the temperature is raised to a temperature near the glass transition temperature (Tg) in a process upstream of the stretching step, the cooling step is performed again. By stretching while raising the temperature to a temperature near the glass transition temperature (Tg) again, an appropriate combination of in-plane retardation (Ro) and thickness direction retardation (Rt) can be realized, and the film Can also be reduced.

  When the cyclic polyolefin film of the present invention is used, for example, as a retardation film for a VA liquid crystal display device, the in-plane retardation (Ro) is in the range of 45 to 65 nm, and the thickness direction retardation (Rt) is 105. It is preferable that the ratio of the retardation in the thickness direction (Rt) to the in-plane retardation (Ro): Rt / Ro is 1.6 to 2.6.

  According to such a cyclic polyolefin film of the present invention, not only the reduction in retardation in the thickness direction (Rt), but also the uniformity of the retardation value in the width direction can be ensured, and the in-plane retardation ( An appropriate combination of Ro) and the retardation in the thickness direction (Rt) can be realized, and the haze value of the film can be reduced, thereby improving the front contrast of the liquid crystal display panel.

  An example of a stretching step (also referred to as a tenter step) for producing a retardation film will be described with reference to FIG.

  FIG. 8 schematically shows an example of a tenter stretching apparatus 201 preferably used for producing the cyclic polyolefin film of the present invention. In the figure, the tenter stretching device 201 is schematically illustrated, but usually, a large number of clips provided in a single row of a pair of left and right rotary driving devices (ring-shaped chains) 201a and 201b each formed of an endless chain. Of the chains 202a and 202b, the left and right chains 201a and 202b are arranged so that the clips 202a and 202b of the chain forward straight-line transition portion that grip and pull the left and right ends of the film (F) gradually separate in the width direction of the film (F). A track 201b is provided, and the film F is stretched in the width direction.

  In FIG. 8, a process A is a process of gripping the web (film) F peeled and conveyed from an endless support (not shown) by left and right gripping means (clips) 202a and 202b. The web is stretched in the width direction (direction orthogonal to the direction of travel of the web) at a stretching angle as shown in the figure, and in step C, the stretching is completed, and the web is conveyed while being gripped. D is a step of relaxing the web in the width direction.

  It is preferable to provide a slitter for cutting off the end in the web width direction after the web is peeled off from the endless support and before the start of the step B and / or immediately after the step C. In particular, it is preferable to provide a slitter for cutting off the web end just before the start of the step A. When the same stretching is performed in the width direction, especially when comparing the case where the web end is cut off before the start of the process B and the condition where the web end is not cut off, the former shows a more distribution of the optical slow axis (orientation angle). (Also referred to as distribution).

  In the tenter process, it is also preferable to intentionally create sections having different temperatures in order to improve the orientation angle distribution. It is also preferable to provide a neutral zone between different temperature zones so that each zone does not cause interference.

  The stretching operation may be performed in multiple stages, and biaxial stretching is preferably performed in the casting direction and the width direction. When performing biaxial stretching, simultaneous biaxial stretching may be performed or stepwise may be performed. In this case, stepwise means, for example, that stretching in different stretching directions can be performed sequentially, or that stretching in the same direction is divided into multiple stages, and stretching in different directions is added to any of the stages. Is also possible.

  It is particularly preferable that the web peeled from the metal endless support is conveyed while being dried, and further stretched in the width direction by a tenter method in which both ends of the web are gripped by pins or clips. Can be granted. At this time, the film may be stretched only in the width direction, or simultaneously biaxially stretched. The preferred stretching ratio is preferably 1.05 to 2 times, and more preferably 1.15 to 1.5 times. During the simultaneous biaxial stretching, the film may be contracted in the machine direction, or may be contracted to 0.8 to 0.99, preferably 0.9 to 0.99. Preferably, the area is preferably 1.12 to 1.6 times, and more preferably 1.15 to 1.5 times, due to the horizontal stretching and the vertical stretching or shrinkage. This can be determined by a stretching ratio in the longitudinal direction × a stretching ratio in the lateral direction.

  Further, the “stretching direction” in the present invention is usually used in the sense of directly applying a stretching stress when performing a stretching operation, but when the biaxial stretching is performed in multiple stages, the final It may be used in the sense that the draw ratio becomes large (that is, the direction that usually becomes the slow axis).

  The preheating time in step A is preferably long or higher. From the viewpoint of the film temperature uniformity in the width direction and the retardation controllability, the temperature is preferably from 130 to 200C, and more preferably from 3 to 60 seconds.

  The web heating rate in the step B is preferably in the range of 0.5 to 10 ° C./sec in order to improve the orientation angle distribution.

  The stretching time in the step B is preferably short. However, from the viewpoint of the uniformity of the web, the minimum range of the stretching time is specified. Specifically, it is preferably in the range of 1 to 10 seconds, more preferably in the range of 4 to 10 seconds.

In the tenter process, the heat transfer coefficient may be constant or may be changed. The heat transfer coefficient preferably has a heat transfer coefficient in the range of 41.9 to 419 × 10 ³ J / m ² hr. More preferably, in the range of ^{41.9~209.5 × 10 3 J / m 2} hr, and most preferably a range of ^{41.9~126 × 10 3 J / m 2} hr.

  The stretching speed in the width direction in the step B may be constant or may be changed. The stretching speed is preferably from 50 to 2000% / min, more preferably from 100 to 1000% / min, and most preferably from 150 to 800% / min.

  It is preferable to control the stress in the first 10 cm in the step B in order to obtain the effect of the present invention, and it is preferable to control the stress in the range of 100 to 200 N / mm.

  In the tenter process, it is preferable that the temperature distribution in the width direction of the atmosphere is small from the viewpoint of improving the uniformity of the web, and the temperature distribution in the width direction in the tenter process is preferably ± 5 ° C or less, and ± 2 ° C or less. Is more preferable, and the temperature is most preferably within ± 1 ° C. By reducing the temperature distribution, it can be expected that the temperature distribution at the width of the web is also reduced.

  In step D, it is preferable to relax in the width direction. Specifically, it is preferable to adjust the web width so as to be in the range of 95 to 99.5% with respect to the final web width after stretching in the previous step.

  Also, in the present invention, in order to accurately orient the polymer, it is preferable to use a tenter that can independently control the gripping length (the distance from the gripping start to the gripping end) of the web by the tenter's left and right gripping means.

  As a means for controlling the length of the portion holding the left and right ends of the web with the tenter stretching device independently of the left and right to make the grip length of the web different between the left and right, specifically, for example, as shown in FIG. There is something like that.

  FIG. 9 schematically shows an example of a tenter stretching apparatus 201 preferably used in producing a retardation film.

  In the figure, the installation positions of the clip starters 203a, 203b at the grip start positions of the left and right grip means (clips) 202a, 202b of the tenter stretching device 201 are the same for the left and right, and the installation positions of the left and right clip closers 204a, 204b are changed for the left and right. This changes the left and right grip lengths (Xa) and (Xb) of the film F, thereby generating a force that twists the film F in the tenter stretching apparatus 201 and correcting a positional shift due to conveyance other than the tenter stretching apparatus 201. Therefore, even if the transport distance from the peeling to the tenter is increased, the meandering, shearing, and wrinkling of the web can be effectively prevented.

  In the present invention, it is preferable to add a device for preventing meandering of a long film in order to correct wrinkles, frays, distortions, and the like with higher accuracy, and an edge position controller ( It is preferable to use a meandering correction device such as an EPC) or a center position controller (sometimes referred to as a CPC). These devices detect the edge of the film with an air servo sensor or optical sensor, and control the direction of transport of the film based on the information, and the edge of the film and the center in the width direction become a constant transport position. Specifically, as an actuator for the film, a meandering correction is performed by swaying one or two guide rolls or a flat expander roll with a drive left and right (or up and down) with respect to the line direction. Set a pair of small pinch rolls on the left and right (one on the front and back of the film, one on each side of the film), and use this to pinch the film and correct the meandering (Cross guider method). The principle of the meandering correction of these devices is that, when the film is traveling, for example, when going to the left, the former method takes a method in which the roll is tilted so that the film goes to the right, and the latter method uses the right side. A pair of pinch rolls are nipped and pulled to the right. It is preferable to install at least one of these meandering prevention devices between the film peeling point and the tenter stretching device.

  After the treatment in the tenter step, it is preferable to further provide a post-drying step.

  The means for drying the web in this step is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roll, microwaves, or the like, but is preferably performed with hot air in terms of simplicity.

(Diagonal stretching)
The oblique stretching is a process of stretching the formed long film in a direction oblique to the width direction. In the method for manufacturing a long film, the film can be manufactured to any desired length by continuously manufacturing the film. In addition, the manufacturing method of a long stretched film may be such that a long film is formed, then once wound around a core, wound into a roll (also referred to as a raw material), and then supplied to the oblique stretching step. Alternatively, the film may be supplied to the oblique stretching step continuously from the film forming step without winding the film after the film formation. It is preferable to perform the film-forming step and the oblique stretching step continuously since the results of the film thickness and the optical value after the stretching are fed back to change the film-forming conditions and a desired long stretched film can be obtained.

  In the method for producing a long stretched film by oblique stretching, a long stretched film having a slow axis at an angle of more than 0 ° and less than 90 ° with respect to the width direction of the film is produced. Here, the angle with respect to the width direction of the film is an angle in the film plane. Since the slow axis in the plane of the film usually develops in a stretching direction or a direction perpendicular to the stretching direction, such stretching is performed at an angle of more than 0 ° and less than 90 ° with respect to the extending direction of the film. A long stretched film having a slow axis can be produced.

  The angle between the width direction of the elongated stretched film and the slow axis, that is, the orientation angle, can be arbitrarily set to a desired angle within a range of more than 0 ° and less than 90 °.

  An oblique stretching device is used to impart oblique orientation to the long film. The oblique stretching device used in the present embodiment can freely set the orientation angle of the film by variously changing the path pattern of the gripper traveling support tool, and further, the orientation axis of the film extends across the width direction of the film. It is preferable that the film stretching apparatus be capable of uniformly orienting the film to the left and right with high precision and control the film thickness and retardation with high precision.

  FIG. 11 is a schematic diagram for explaining the oblique stretching used in the method for producing a long stretched film of the present embodiment. However, this is an example, and the present invention is not limited to this.

  The running direction (running direction before stretching) D1 of the long film when entering the stretching apparatus is different from the running direction (running direction after stretching) D2 of the long stretched film when unwinding from the stretching apparatus, Is a payout angle θi. The dispensing angle θi can be arbitrarily set to a desired angle within a range of more than 0 ° and less than 90 °.

  At the entrance of the oblong stretching device (a gripping start point at which the gripper grips the long film, and a straight line connecting the gripping start points is indicated by reference numeral A), the both ends of the long film are held at the left and right grippers (a pair of grippers). It is gripped by the gripper pair and travels with the travel of the gripper.

  The gripper pair includes left and right grippers Ci and Co at the entrance of the oblique stretching device, which are opposed in a direction substantially perpendicular to the running direction D1 of the long film (running direction before stretching). The left and right gripper Ci and the gripper Co travel respectively on a left-right asymmetrical path and extend to a position at the end of extension (a grip release point at which the gripper releases gripping, and refer to a straight line connecting the gripping release points). (Shown by B) is released.

  At this time, the left and right gripper Ci and the gripper Co facing each other at the oblique stretching device entrance (position A in the figure) travel on the inner gripper travel support Ri and the outer gripper travel support Ro, respectively. As a result, the gripper Ci that travels on the inner gripper travel support Ri is in a positional relationship that advances with respect to the gripper Co that travels on the outer gripper travel support Ro.

  That is, in a state where the gripper Ci and the gripper Co, which are opposed to the direction substantially perpendicular to the running direction D1 of the long film at the entrance of the oblique stretching device, are at the position B, the gripper Ci and the gripper Co Are inclined by an angle θL with respect to a direction substantially perpendicular to the running direction (running direction after stretching) D2 of the long stretched film.

  With the above operation, the long film is obliquely stretched in the direction of θL. Here, “substantially perpendicular” indicates that the angle is in a range of 90 ± 1 °.

  The stretching apparatus capable of oblique stretching is an apparatus that heats a long film to an arbitrary temperature at which stretching is possible and performs oblique stretching. The stretching apparatus includes a heating zone (heating furnace), a plurality of gripping tools that are paired on both sides for gripping and running both sides of the long film, and gripping tool running for supporting the running of the gripping tool. And a support tool.

  The both ends of the long film sequentially supplied to the entrance (holding start point) of the stretching device are gripped by the gripper, the long film is guided into the heating furnace, and gripped at the outlet of the stretching device (grip release point). Release the long stretched film from the tool. The long stretched film released from the gripper is wound around a core. The gripper running support provided with the gripper has an endless continuous track, and the gripper that has released the gripping of the elongated stretched film at the outlet of the stretching device is sequentially returned to the gripping starting point by the gripper running support. It is supposed to be.

  The gripper running support may be, for example, in a form in which an endless chain whose path is regulated by a guide rail or gear is provided with a gripper, or in a form in which an endless guide rail is provided with a gripper. There may be. That is, in the present invention, the gripper traveling support may be, for example, an endless guide rail provided with an endless chain, or may be an endless guide rail provided with an endless chain. Alternatively, an endless guide rail without a chain may be used. The gripper travels along the path of the gripper travel support itself when the gripper travel support does not include the chain, and travels along the path of the gripper travel support via the chain when the gripper travel support includes the chain. To run. Hereinafter, in the present invention, as an example, a case in which the gripper travels along the path of the gripper travel support will be described.However, the gripper moves the path of the gripper travel support via a chain provided with the gripper. You may run.

  The number of gripping tools provided on each gripping tool travel support tool is not particularly limited, but is preferably the same.

  Note that the gripper running support of the stretching device has an asymmetric shape on the left and right, and the pattern of the path of the gripper running support is determined according to the orientation angle given to the long stretched film to be manufactured, the stretching ratio, and the like. It can be adjusted manually or automatically.

  In the stretching device of the present embodiment, it is preferable that the path of each gripper traveling support can be set freely, and the pattern of the path of the gripper traveling support can be arbitrarily changed.

  The length (full length) of the gripper running support is not particularly limited, and is usually about 10 to 100 m. Further, the total length of the gripper running support on both sides may be the same or different.

  In the embodiment of the present invention, the traveling speed of the gripping device of the stretching device can be appropriately selected, but is preferably 15 to 150 m / min. When the traveling speed of the gripping device of the stretching device is higher than 150 m / min, local stress applied to the edge of the film at the bent portion increases, and wrinkles and shifts occur at the edge of the film. Of the entire width of the obtained film, the effective width obtained as a good product tends to be narrow.

  In the present invention, the traveling speeds of the two gripping tools constituting the gripping tool pair may be the same or different. If there is a difference in running speed between the left and right of the long stretched film at the stretching process outlet, wrinkles at the stretching process outlet may occur, and the speed difference between the left and right gripping tools constituting the gripping tool pair is substantially It is preferably constant in speed.

  In the present invention, it is preferable that the gripper travels at a constant distance from the front and rear grippers.

  In the case where the traveling speeds of the gripping tools constituting the gripping tool pair are set to be uniform, the difference between the traveling speeds of the gripping tools is preferably 1% or less, more preferably 0.5% or less, and still more preferably. Is 0.1% or less. In a general stretching device or the like, there is a speed unevenness that occurs on the order of seconds or less depending on the tooth period of a sprocket (gear) driving a chain, the frequency of a drive motor, and the like. Does not correspond to the speed difference described in the present embodiment.

  In the oblique stretching device used in the present invention, particularly at a position where the conveyance of the long film becomes oblique, a large bending rate is often required for the gripper traveling support which regulates the trajectory of the gripper. In order to avoid interference between the gripping tools due to sharp bending or local stress concentration, it is desirable that the trajectory of the gripping tool bend in an arc at the bent portion.

  At the entrance of the oblique stretching device (the position of the straight line A in FIG. 11), the long film is sequentially gripped at both ends by left and right gripping tools (a pair of gripping tools), and travels with the running of the gripping tools. At the entrance of the oblique stretching device, the pair of gripping tools facing in a direction substantially perpendicular to the running direction D1 of the long film travels on an asymmetrical path, and has a preheating zone, a stretching zone, and a heat fixing zone. Pass through the furnace.

  The preheating zone refers to a section at the entrance of the heating furnace in which the gripping tool that grips both ends travels while maintaining a constant interval.

  The stretching zone refers to a section in which the gap between the grippers holding both ends starts to open and reaches a predetermined interval. In the present embodiment, the film can be stretched in an oblique direction in the stretching zone, but is not limited to the stretching in the oblique direction. It may be stretched in the width direction.

  The heat setting zone refers to a section in which the gripping tools at both ends run parallel to each other during a period in which the distance between the gripping tools after the stretching zone becomes constant again. After passing through the heat setting zone, it may pass through a section (cooling zone) in which the temperature in the zone is set to be equal to or lower than the glass transition temperature Tg ° C. of the cyclic polyolefin resin constituting the long film. At this time, in consideration of the shrinkage of the long stretched film due to cooling, a path pattern that narrows the distance between the opposed grippers in advance may be used.

  For the purpose of adjusting the mechanical physical properties and optical properties of the film, horizontal stretching and longitudinal stretching may be performed as necessary before and after the introduction of the long film into the oblique stretching device.

  The temperature of each zone is the glass transition temperature Tg of the cyclic polyolefin-based resin, the temperature of the preheating zone is in the range of Tg-10 to Tg + 30 ° C, the temperature of the stretching zone is in the range of Tg-10 to Tg + 30 ° C, and the temperature of the cooling zone. Is preferably set in the range of Tg−30 to Tg + 10 ° C.

  In addition, a temperature difference may be provided in the width direction in the stretching zone in order to control thickness unevenness in the width direction. In order to provide a temperature difference in the width direction in the stretching zone, there are known methods such as a method of adjusting the opening degree of a nozzle for sending hot air into a constant temperature chamber so as to make a difference in the width direction, and a method of controlling heating by arranging heaters in the width direction. Can be used. The lengths of the preheating zone, the stretching zone and the heat setting zone can be appropriately selected, and the length of the preheating zone is usually in the range of 100 to 150% and the length of the heat fixing zone is usually 50 to 150% of the length of the stretching zone. The range is 100%.

  The stretching ratio R (W / W0) in the stretching step is preferably in the range of 1.3 to 3.0, more preferably in the range of 1.3 to 2.5. When the stretching ratio is in this range, the thickness unevenness in the width direction is reduced, which is preferable. When the stretching temperature is set so that the stretching temperature is different in the width direction in the stretching zone as necessary, the thickness unevenness in the width direction can be further suppressed. W0 represents the width of the long film before stretching, and W represents the width of the long stretched film after stretching.

  The oblique stretching step of the manufacturing method of the present embodiment will be described more specifically with reference to FIG. FIG. 12 is a schematic diagram of a stretching apparatus used in the manufacturing method of the present embodiment.

  As shown in FIG. 12, the oblique stretching device 401 has, on both sides of the long film F, a gripper traveling support 402 on which a gripper (not shown) for gripping the long film F travels. The gripper traveling support 402 is arranged so that a part thereof passes through the heating furnace 403.

  As described above, the heating furnace 403 is divided into a plurality of zones in the furnace. FIG. 12 illustrates a case where the zone is divided into three zones of a preheating zone, a stretching zone 404, and a heat setting zone. The gripper traveling support 402 has a side wall 406 at least in the extension zone 404.

  The side wall 406 is provided along the gripper running support 402 on both sides in the stretching zone 404. The side wall 406 can block the convection of air generated by the running long film, and can prevent the transfer of heat from the long film F to the extra space. Therefore, the long film F is stretched in a stretching zone in a state where heat is applied sufficiently and uniformly without temperature unevenness. As a result, a variation in the orientation angle of the obtained long film in the width direction is small, and a long stretched film with stable quality can be obtained.

  The method of installing the side wall 406 is not particularly limited, and the side wall 406 can be installed near the gripper travel support 402 or can be provided integrally with the gripper travel support 402. When the side wall 406 is installed in the vicinity of the gripper traveling support 402, it is preferable to stably install the side wall 406 by fixing it to the heating furnace 403 or the installation surface of the gripper traveling support 402. As shown below, the side wall 406 is preferably provided integrally with the gripper travel support 402 from the viewpoint of moving the gripper travel support 402 following the movement thereof.

  When the stretching direction of the oblique stretching device 401 is changed, it is preferable that the side wall 406 moves following the movement of the gripper running support 402.

  In other words, when the stretching angle is changed, the shape, position, and orientation of the side wall 406 (hereinafter, these may be referred to as a shape, etc., together) change according to the shape of the gripper running support 402 before and after the change. Is preferred. As described above, the side wall 406 moves following the movement of the gripper running support 402, so that the shape of the side wall 406 is adjusted according to the path pattern of the gripper running support after the movement. For this reason, regardless of the stretching angle, it is possible to reduce the variation in the orientation angle of the obtained elongated stretched film in the width direction, and to produce a long stretched film from which a stable quality long stretched film can be obtained. it can.

  As described above, the method of causing the side wall 406 to follow the movement of the gripper traveling support 402 is not particularly limited. For example, a clip as shown in FIG. 10 may be used.

  As described above, by forming the side wall 406 integrally with the gripper travel support 402 so as to be able to move following the movement of the gripper travel support 402, the shape and the like of the side wall 406 can be changed. The shape is changed at the same time as the shape of the support 402 is changed. As a result, sufficient and uniform heat is continuously applied to the long film F irrespective of the stretching angle, and as a result, a stable quality long stretched film with small variation in the orientation angle in the width direction is obtained. sell.

  The material forming the side wall 406 is not particularly limited, and the side wall 406 made of resin or metal can be employed. Further, the side wall 406 does not need to be formed by a single member, and may be formed by connecting a plurality of members by a hinge or the like.

  In addition, the surface of the side wall 406 is preferably made of a material having heat insulating properties or covered with the material in order to prevent the transfer of heat from the long film F to the extra space.

  The height of the side wall 406 is not particularly limited, and may be any height that can prevent heat from flowing into and out of the long film F and the extra space in consideration of the internal shape and the like of the heating furnace 403. . In particular, it is preferable that the height of the side wall 406 has such a height that the side wall 406 does not come into contact with the inside of the heating furnace 403 so that the side wall 406 can move following the movement of the gripper running support 402 when the extension angle is changed. .

  The thickness of the side wall 406 is not particularly limited, and may be any thickness that can prevent heat from flowing into and out of the long film F and the extra space. In particular, the thickness of the side wall 406 is such that the bending or rotation of the side wall 406 is not hindered when the side wall 406 moves following the movement of the gripper running support 402 when the extension angle is changed. It is preferred that

  In the manufacturing method of the present embodiment, as shown in FIG. 12, the side wall 406 is provided along at least the gripper traveling support 402 that passes through the extension zone 404. Therefore, even when the stretching angle of the long film F is changed, regardless of the change in the volume or position of the extra space, the long film F to be stretched has sufficient and uniform heat without temperature unevenness. Granted. As a result, in the obtained elongated stretched film, variation in the orientation angle of the elongated film F in the width direction is suppressed regardless of the stretching angle.

  In addition, as shown in FIG. 12, when the side wall 406 is provided only in the stretching zone 404, in the zone where the side wall 406 is not provided, heat from the long film F can move to an extra space. There is. However, as described above, the long film F is only preheated in the preheating zone before the stretching zone, and is only heat set so as not to shrink in the heat setting zone after the stretching zone. Therefore, even if temperature unevenness occurs in the long film F in these zones, the influence on the variation in the orientation angle of the obtained long stretched film in the width direction is small. As a result, according to the manufacturing method of the present embodiment, since the side wall 406 is provided at least in the stretching zone, it is possible to sufficiently reduce the variation in the orientation angle of the obtained elongated stretched film in the width direction.

  Further, as another example of the manufacturing method of the present embodiment, a side wall 406 can be provided along the whole of the gripper running support 402 installed in the heating furnace 403. By providing the side walls 406 in all the zones in the heating furnace 403 as described above, it is possible to more reliably block the heat from flowing into and out of the long film F and the extra space, and run the long film F traveling in the heating furnace 403. The heat can be sufficiently and uniformly applied to the entire surface. Further, even when the stretching angle is changed, sufficient and uniform heat is applied to the running long film F irrespective of changes in the volume and position of the extra space. As a result, the temperature unevenness of the obtained elongated stretched film can be more reliably suppressed, and the variation in the orientation angle of the elongated stretched film in the width direction can be reduced regardless of the stretching angle.

  FIG. 12 shows only a section (hereinafter, this section may be referred to as an outward section) in which the gripper holding the long film F travels, of the gripper travel support 402, and the gripper is A section that travels after releasing the grip of the long film F (hereinafter, this section may be referred to as a backward section) is omitted. The gripper traveling support 402 in the backward section may be disposed in the heating furnace 403 or may be provided outside the heating furnace 403.

  And, for example, when the gripper traveling support 402 in the backward section is provided in the heating furnace 403 and is provided near the gripper traveling support 402 in the forward section, the side wall 406 is May be provided on the gripper traveling support 402 in the forward section, may be provided on the gripper traveling support 402 in the backward section, or may be provided on the gripper traveling support 402 in both sections. That is, the side wall 406 may be arranged at a position where heat transfer from the long film F to the extra space can be blocked. As described above, when the gripper traveling support 402 in the backward section is provided in the heating furnace 403 and is provided in the vicinity of the gripper traveling support 402 in the outward section, the gripper traveling support 402 in the backward section is provided. By providing the gripper running support 402, heat transfer from the long film F to the extra space can be blocked.

(Wet stretching)
The cyclic polyolefin film of the present invention can be subjected to wet stretching on an unstretched film. By such wet stretching, a polymer oriented film having polymer chains oriented can be obtained.

  Wet stretching is a general term for a stretching method using water substantially as a means for softening a film immediately before stretching, wherein water acts as a substantial plasticizer for the main polymer material of the film. ing. It is well known that in order to plasticize a resin film, the film is softened depending on the amount of a plasticizer, and the wet stretching used in the present invention is basically based on this concept.

  As described above, in the production of the film of the present invention, it is important how much the film is softened (plasticized) in water at the time of stretching, and the amount of water contained in the film, that is, the water content is known. This is very important.

[Moisture content]
The water content is the mass fraction (%) of water contained in the film. Actually, when the water content (μg) indicated by the moisture meter is W and the weighed sample amount is F (mg), the water content is (% By mass) = 0.1 × (W / F).

  Considering actually the material of the film of the present invention, the polymer material of the cyclic polyolefin film of the present invention has a water content of about 0.01% at room temperature. Usually, such a cyclic polyolefin film (raw material) is stretched by raising its temperature to a glass transition point (Tg) or so, so that it can be stretched. When the temperature is set to about Tg, for example, 130 ° C., the water content further decreases to 0.001% by mass. In the present invention, the water content of the cyclic polyolefin film (raw material) is adjusted to be in the range of 0.001 to 1% by mass, more preferably 0.001 to 0.5% by mass before the stretching. %, More preferably 0.005 to 0.3% by mass.

  To adjust the water content of the film at the time of stretching to a range of 0.001 to 1% by mass, the glass transition temperature (Tg) of the cyclic polyolefin film is increased from 130 ° C (water content 0.001% by mass) to 75 ° C (water content). 0.005% by mass), and uniform stretching can be performed at a temperature lower than the normal stretching temperature (130 ° C.). The Tg of the cyclic polyolefin film having a water content of 5.5% by mass was obtained by placing water in a silver sealed pan (70 μl), immersing the cyclic polyolefin film, and using a temperature-modulated DSC (TA Instruments DSC2910). It was measured using

  To control the moisture content of the film during stretching, the film may be immersed in water before stretching, or may be conditioned at constant temperature and high humidity, or a combination of these two. You may. When immersed in a water tank, the temperature of water is preferably in the range of 50 to 100 ° C, more preferably in the range of 60 to 95 ° C, and particularly preferably in the range of 70 to 90 ° C. The immersion time is preferably in the range of 5 seconds to 10 minutes, more preferably in the range of 10 seconds to 8 minutes, and particularly preferably in the range of 20 seconds to 6 minutes. When humidity is controlled at a constant temperature and high humidity, the temperature is preferably in the range of 50 to 150 ° C, more preferably in the range of 60 to 140 ° C, and particularly preferably in the range of 70 to 120 ° C. The relative humidity is preferably within a range of 60 to 100%.

  The water used for these immersion and steam aeration may be substantially water. Substantially water refers to water consisting of 60% by mass or more of water, and may contain the following organic solvents, plasticizers, surfactants, and the like in addition to water. Preferred organic solvents include water-soluble organic solvents having 1 to 10 carbon atoms. However, more preferably 90% by mass or more of water is used, and still more preferably 95% by mass or more of water. Most preferably, pure water is used. The water used in the following description may be substantially water.

  The atmosphere during stretching may be any of air, water vapor, and water. The atmosphere in the air at the time of stretching refers to stretching in an atmosphere in which the temperature is controlled and the humidity is not controlled. The stretching temperature is preferably in the range of 50 to 150 ° C, more preferably in the range of 60 to 130 ° C, and particularly preferably in the range of 65 to 110 ° C. The atmosphere in the water vapor at the time of stretching indicates that the film is at a constant temperature and high humidity or that the water vapor is applied to the film. The stretching temperature is preferably in the range of 50 to 150 ° C, more preferably in the range of 60 to 140 ° C, and particularly preferably in the range of 70 to 130 ° C. The relative humidity is preferably in the range of 60 to 100%. By doing so, the water content in the film of the present invention, particularly in the cyclic polyolefin resin, is maintained in the range of 2.0 to 20.0% by mass. When the water content is less than 2.0% by mass, the elongation at break during stretching is small and the film tends to break, and the desired retardation may not be reached.

  The fact that the atmosphere during stretching is water means that the film is stretched while being immersed in a water tank. The temperature of water is preferably in the range of 50 to 100C, more preferably in the range of 60 to 98C, and particularly preferably in the range of 65 to 95C. The immersion time is preferably in the range of 0.5 seconds to 10 minutes, more preferably in the range of 1 second to 8 minutes, and particularly preferably in the range of 1 second to 7 minutes.

  Assuming that the distance between fixing members for fixing the film during stretching is L, the direction perpendicular to the fixing members is W, and the aspect ratio of the film shape during stretching is L / W, the aspect ratio is 0.1 to 10. Is more preferable, the range of 0.1-8.0 is more preferable, and the range of 0.1-6.0 is especially preferable. Here, “at the time of stretching” means the aspect ratio of the film before stretching.

  Maintaining the moisture content immediately after stretching in the range of 0.001 to 1% by mass is essential for uniformly stretching the film. Since the water content of the film is controlled in the range of 0.001 to 1% by mass in the zone immediately before stretching, if the water content is 1.0% by mass or less, the elongation at break becomes small, and the front surface is formed at a desired thickness. Retardation cannot be provided up to the λ / 4 region. Here, the moisture content immediately after stretching refers to the moisture content of the film immediately after the stretching step. Further, after the stretching step, moisture adhering to the film up to the winding site may be removed. Known methods such as an air knife method and a blade method can be used.

(5) Winding Step An example of the winding device used in the present invention is shown in FIGS.

  As shown in FIGS. 13 and 14, the winding device 519 preferably includes a winding unit 551, and further includes a tension control unit 552.

  The winding unit 551 includes a rotation shaft 555, a core holder 556, a turret 557, a motor 558, a shift mechanism 561, and controllers 562 and 563.

  The rotation shaft 555 is arranged so that the longitudinal direction is the B direction. One end in the longitudinal direction of the rotating shaft 555 is rotatably attached to and supported by the turret 557. A motor 558 is connected to the rotating shaft 555, and the rotating shaft 555 is rotated by the motor 558 in the circumferential direction. The controller 562 is connected to the motor 558. When a signal of a target rotation speed of the rotation shaft 555 is input, the controller 562 controls the motor 558 based on the input signal. As a result, the rotation shaft 555 rotates at the target rotation speed.

  A pair of recesses extending in the longitudinal direction are formed on the outer periphery of the rotating shaft 555. A pair of convex portions extending in the longitudinal direction of the core 566 are formed on the inner periphery of the cylindrical core 566 around which the film 527 is wound. The protrusion of the core 566 is engaged by entering the recess of the rotation shaft 555, and the core 566 is set on the rotation shaft 555. As a result, the core 566 rotates integrally with the rotation shaft 555.

  A pair of core holders 556 for holding the core 566 from both ends in the longitudinal direction are provided at both ends in the longitudinal direction of the rotating shaft 555. The core holder 556 is slidable in the longitudinal direction of the rotation shaft 555, and displaces the core 566 in the B direction by sliding.

  A shift mechanism 561 is connected to the core holder 556, and the shift mechanism 561 displaces the core holder 556 along the longitudinal direction of the rotation shaft 555. Due to this displacement, the core 566 is displaced in the B direction.

  The controller 563 is connected to the shift mechanism 561. The controller 563 receives the signals of the target values such as the direction in which the core holder 556 should be moved in the longitudinal direction of the rotary shaft 555, the speed of movement, and the amount of displacement, based on the input signals. The holder 556 is controlled. As a result, the core holder 556 is displaced on the rotating shaft 555 during rotation at a desired timing and at a desired speed with a desired displacement amount.

  The tension control unit 552 preferably includes guide rollers 571 and 572, a dancer roller 573, a shift mechanism 576, and a controller 577.

  The guide rollers 571 and 572 serve as a transport path of the film 527 from the second slitter 518 to the winding unit 551, and support the film 527 so as to guide the film 527 to the winding unit 551. The guide rollers 571 and 572 may be drive rollers having a drive unit, or may be so-called free rollers that rotate by contacting the film 527 being conveyed.

  The dancer roller 573 is disposed between a guide roller 571 and a guide roller 572 that are arranged in the transport direction of the film 527. The film 527 is wound around the dancer roller 573 such that the film surface opposite to the film surface in contact with the guide roller 571 and the guide roller 572 contacts the dancer roller 573.

  The shift mechanism 576 is connected to the dancer roller 573, and displaces the step roller 573 in a direction crossing the film surface. This displacement changes the tension in the longitudinal direction of the film 527. When the signal of the displacement amount of the dancer roller 573 is input, the shift mechanism 576 displaces the dancer roller 573 by a target displacement amount based on the input signal.

  The controller 577 is connected to the shift mechanism 576. When a signal corresponding to the target value of the tension in the longitudinal direction of the film 527 is input, the controller 577 obtains the amount of displacement of the dancer roller 573 based on the input signal, and obtains the obtained displacement. An amount signal is output to shift mechanism 576.

  Preferably, a tension sensor (not shown) for detecting the tension in the longitudinal direction of the film 527 is provided on the downstream guide roller 572. In this case, it is more preferable to provide a calculation unit 578 connected to the controller 577 and the tension sensor of the guide roller 572. When the detection signal of the tension sensor is input, calculation unit 578 obtains a difference between the tension corresponding to the detection signal and the target value of the tension, and if the difference is not 0 (zero), corresponds to the target value of the tension. The signal is output and sent to the controller 577.

  The motor 558 is driven by winding the longitudinal end of the film 527 around the winding core 566 set in the winding unit 551 described above. The guided film 527 is wound by driving of the motor 558. While winding the guided film 527, the core holder 556 is displaced in the B direction by the shift mechanism 561, whereby the core 566 is reciprocated in the B direction. By this reciprocating motion, the guided film 527 is wound around the core 566 while forming a roll in which the welding upper formation region 527w is shifted in the B direction. The region 527w on the welded portion of the film 527 is a region corresponding to the region on the welded portion of the casting film 539 formed on the welded portion 533w of the band 533. The details of the above-formed region 527w will be described later with reference to another drawing.

  The shift mechanism 561 displaces the core holder 556 with a constant amplitude in the B direction, so that the reciprocating motion of the core 566 in the B direction also has a constant amplitude. As a result, the film 527 is wound around the core 566 while the region 527w on the welded portion of the film 527 is shifted at a constant amplitude in the longitudinal direction of the core 566. In the obtained film roll, the formed region 527w on the welded portion is wound while being shifted with a constant amplitude in the width direction of the film 527, and there is no black streak caused by the overlap of the formed region 527w on the welded portion.

  The above-formed region 527w will be described with reference to FIG. As described above, since the casting film 539 is formed in a range extending from one side to the other side 533s of the band 533, the casting film 539 is also formed on the welded portion 533w. The welded portion 533w has a substantially constant width. The width of the welded portion 533w is about 10 mm even when the band 533 is manufactured with extremely high precision. However, depending on the accuracy of the band 533, the width of the welded portion 533w may be uneven in the longitudinal direction or larger than 10 mm. The welded portion 533w is a region formed as a weld bead when a narrow sheet for the side portion 533s and a wide sheet for the central portion 533c, which are raw materials for manufacturing the band 533, are welded. The welded portion 533w can be visually recognized even after post-processing such as polishing after welding.

  In the casting film 539, a region formed on the weld 533w is referred to as a weld upper region 539w. Since the welded portion 533w can be visually identified as described above, the welded portion upper region 539w is specified as a region on the welded portion 533w.

  The casting film 539 is peeled off at the peeling position PP, transported, and subjected to various processes by a first slitter, a first tenter, a second tenter, a second slitter, and the like. Through these processes, tension is applied to the film 527 in the A direction and the B direction, and the side end in the B direction is cut off. Thus, the film 527 elongates in the longitudinal direction, dries and shrinks in the width direction, or is stretched in the width direction and widened after being stripped at the stripping position PP and wound by the winding device. Or narrowed by resection.

  Therefore, the width of the casting film and the width of the film 527 are usually different. Further, the position and width W539 of the upper region 539w in the width direction of the casting film and the position and width W527 of the corresponding region 527w in the width direction of the film 527 are usually different from each other.

  However, even if the welding portion corresponding region 527w is displaced so as to have an amplitude in the width direction of the film 527, the welding portion corresponding region 527w cannot be visually confirmed in the film 527 at the time of winding. Therefore, the welding portion corresponding region 527w at the time of winding may be specified by the following method. Note that, in the present embodiment, the film 527 at the time of winding corresponds to the film 527 at the winding position PW. However, since the drying of the film 527 for a certain period of time before winding is sufficiently advanced, the dimensional change is extremely small. Therefore, a film upstream of the winding position PW may be regarded as the film 527 at the time of winding. The winding position PW is a position at which the film 527 wound around the core 566 contacts the outer peripheral surface of the film 527 wound around the core 566.

  First, marking is performed on the region 539w above the welded portion of the casting film at the stripping position PP. In the following description, this mark is referred to as a casting film mark, and is denoted by reference numeral M539 in FIG. The marking may be performed with an ink or the like having resistance to a solvent. When the casting film mark M539 reaches the winding position PW, the region where the casting film mark M539 is located is specified as the welding portion corresponding region 527w. The mark attached to the specified welded portion corresponding area 527w is referred to as a film mark in the following description, and is denoted by reference numeral M527 in FIG.

  FIG. 15 shows a case where the film mark M527 is larger than the casting film mark M539. However, the film mark M527 may be smaller or may have substantially the same size depending on the conditions of the steps after the peeling. In some cases, the ratio between the width and the length in the longitudinal direction (hereinafter, simply referred to as the “width-to-length ratio”) may change. However, regarding the film mark M527 and the casting film mark M539, it is not necessary to consider the relationship between the size and the ratio between the width and the length, and it is sufficient to detect the width of the film mark M527. The width of the film mark M527 is the width W527 of the welding portion corresponding region 527w.

  In FIG. 15, for convenience of description, the widths of the welded portion 533 w, the upper welded region 539 w, and the formed upper welded region 527 w are exaggerated with respect to the widths of the band 533, the casting film 539, and the film 527. It is drawn large.

  As described above, the welded portion corresponding region 527w is specified, and the film 527 is wound around the core 566 by the winding device 519 while forming a roll in which the welded portion corresponding region 527w is displaced in the B direction. This prevents black streaks from occurring in the film roll.

  Further, it is preferable that the cycle of the displacement of the winding core 566 having the amplitude in the B direction is a time during which the traveling band 533 makes one round. The time required for the band 533 to make one round is the time required for an arbitrary portion of the traveling band 533 to return from the specified position on the traveling path of the band 533 to the specified position. This is the time until the band 533 in the PC returns to the casting position PC again. This time can be determined, for example, by marking an arbitrary portion of the band 533 and measuring the time from the time when the mark passes the casting position PC to the time when the mark passes next time.

  By setting the cycle of the displacement of the core 566 to be the time for the traveling band 533 to make one round, the position of the region 527w on the welded portion of the film 527 is determined by the length obtained in the time for the band 533 to make one round. As a result, a film roll having a displacement amount amplitude in the width direction can be obtained. Thereby, generation of black streaks in the film roll is more reliably prevented. Note that the cycle of the displacement of the core 566 does not have to be strictly the time required for the band 533 to make one round, and a certain effect can be obtained if it is substantially equal to the time required for one round.

  The cycle of displacement of the core 566 can be controlled by the cycle of displacement of the core holder 556. Therefore, when setting the cycle of the displacement of the core 566, the controller 563 may control the shift mechanism 561 based on the input signal when the time for one rotation of the band 533 is input.

  The amplitude of the displacement in the B direction of the welded area 527w may be changed according to the width W527 of the welded area 527w. Specifically, as the width W527 of the welded portion corresponding region 527w is larger, the amplitude of the displacement in the B direction of the welded portion corresponding region 527w is increased. This is particularly effective when the welded portion 533w is on a substantially straight line extending in the longitudinal direction of the band 533. The fact that the welded portion 533w is a substantially straight line extending in the longitudinal direction of the band 533 means that the amplitude of the welded portion 533w in the B direction is within about 2 mm. The amplitude corresponds to a half of the displacement in the B direction.

  When the width W527 of the welded area 527w is constant at about 10 mm, it is effective if the displacement amplitude in the direction B of the welded area 527w is about 10 mm.

When the longitudinal direction of the band 533 corresponds to the cycle, and the welded portion 533w is meandering so as to draw a sine curve (SINE CURVE), the welded portion corresponding region 527w can be associated with the cycle in the longitudinal direction. Meander like drawing a curve. In this case, when the film 527 is caused to synchronize with the sine curve of the welded area 527w and become in phase with the sine curve, the amplitude of the displacement in the B direction of the welded area 527w can be further reduced. Preferred.

  The film size or the like to be wound by the winding device 519 is not particularly limited. For example, the film is preferably a film having a total winding length in the range of 2000 to 10000 m and a width in the range of 500 to 2500 mm. .

  In the winding step, it is preferable to perform a static elimination process. The static elimination process will be described in detail.

  FIG. 16 is a schematic diagram of the present invention from the drying step to the winding step. Between the cooling chamber 607 and the winding chamber 610, static eliminators (blowing type static eliminators) 620, 621, and 622 are provided. Further, the pass rollers 623 and 624 are grounded, and the surface rollers 625 and 626 are provided close to the pass rollers 623 and 624, respectively.

  The film 601 that has exited the drying chamber 605 is neutralized while being cooled to room temperature by the static eliminator 620 in the cooling chamber 607. The static eliminator 620 removes static electricity by directly applying the generated ions to the film 601 using a blower. By installing the static eliminator 620 in the drying chamber 605, the charge potential of the film can be reduced. FIG. 17 is a schematic diagram of the charge elimination processing of the film 601 performed in the cooling chamber 607 by the blower-type charge eliminator 620. As shown in FIG. 17, the blower-type static eliminator 620 generates ions by an ion generator 620b housed in a blower head 620a, sends wind from a blower 620c through a ventilation duct 620e, and removes ion wind from a slit 620d. Release toward the film 601. In order to measure the charging voltage of the film at the time of leaving the drying chamber 605, the pass roller 623 is grounded, and the film 601 that is in contact with the pass roller 623 is measured using a surface voltmeter 625. It is preferable to measure the surface potential. In this case, if the charge has not been removed to a predetermined charging potential based on the measured surface potential, the amount of generated ionic wind is controlled so as to be in an appropriate surface potential, for example, in the range of -10 to +10 V. .

  Further, static elimination is performed on the film 601 that has exited the cooling chamber 607 by using the static eliminator 621. Further, using a knurling roller 609, knurling is applied to both ends of the film 601 by embossing. FIG. 17 illustrates an example in which the static eliminator 621 is provided on the upstream side of the knurling applying roller, but is not limited to that position.

  Next, in the winding chamber 610, the pass roller 624 is grounded, and a surface voltmeter is installed on the film 601 in contact with the pass roller 624, and the surface potential of the film 601 is measured. Then, based on the measured surface potential, the amount of generated ion wind is controlled so as to be in an appropriate surface potential, for example, in a range of -5 to +5 V, and the charge is removed using the charge removing device 622 immediately before winding. , And is wound by a winding roller 611.

  Note that the static eliminators 621 to 623 perform ion elimination by blowing ion wind, but may be neutralized by various known static eliminators. Also, based on the values of the surface potentials measured by the surface voltmeters 625 and 626, each static eliminator is controlled using a controller (not shown) to perform more uniform static elimination. May be omitted, and static elimination may be simply performed by various static eliminators.

  It is also preferable that the cyclic polyolefin film of the present invention be laminated into a laminated film by winding a protective film during winding.

(Protective film)
The protective film is a film that can be attached to and detached from the cyclic polyolefin film. By bonding the protective film to the cyclic polyolefin film, it is possible to prevent the surface of the cyclic polyolefin film from being damaged, and to improve the handling property.

  The arithmetic average roughness Ra of the surface of the protective film opposite to the surface to be bonded to the cyclic polyolefin film is usually 0.2 μm or more, preferably 0.3 μm or more, more preferably 0.5 μm or more. It is 4 μm or less, preferably 1.0 μm or less, more preferably 0.8 μm or less. Usually, the surface of the protective film to be bonded to the cyclic polyolefin film is an adhesive surface. For this reason, usually, the arithmetic average roughness Ra of the non-adhesive surface of the protective film falls within the above range.

  According to the study of the present inventors, the arithmetic average roughness Ra of the surface of the protective film opposite to the cyclic polyolefin film is greatly related to the occurrence of wrinkles and gauge bands of the cyclic polyolefin film roll. Conceivable. When the multilayer film is wound as a cyclic polyolefin film roll, the surface of the multilayer film on the side of the cyclic polyolefin film and the surface of the multilayer film on the protective film are in contact with each other due to the winding of the multilayer film. At this time, the surface roughness of the surface of the multilayer film on the side of the protective film (that is, the surface roughness of the surface of the protective film on the side opposite to the cyclic polyolefin film) is determined by the amount of air entrainment and discharge between the multilayer films. Has a significant effect.

  Specifically, if the surface of the multilayer film on the side opposite to the cyclic polyolefin film is roughened, the amount of air entrained between the multilayer films at the time of winding increases, causing deformation and wrinkles. It will be easier. Further, when the surface roughness of the surface of the multilayer film on the side opposite to the cyclic polyolefin film is rough, the air passage becomes large, and the entrapped air is easily released. Then, when the thickness of the air layer changes due to the escape of air from between the multilayer films, the multilayer film deforms following the change in the thickness, and wrinkles are generated on the cyclic polyolefin film roll. Cheap. Therefore, in the present embodiment, wrinkles are prevented by setting the arithmetic average roughness Ra of the surface of the protective film opposite to the cyclic polyolefin film to be equal to or less than the upper limit of the above range.

  On the other hand, if the surface of the multilayer film on the side opposite to the cyclic polyolefin film becomes smooth, the amount of air entrained between the multilayer films during winding is reduced, and a gauge band is easily generated. Therefore, in the present embodiment, the gauge band is prevented by setting the arithmetic average roughness Ra of the surface of the protective film opposite to the cyclic polyolefin film to be equal to or greater than the lower limit of the above range.

  The composition and layer constitution of the protective film are arbitrary as long as the effects of the present invention are not significantly impaired. For example, the protective film may be a film having a single-layer structure including only one layer, or a film having a multilayer structure including two or more layers. Further, the thickness of the protective film is arbitrary, and may be generally 10 μm or more, preferably 15 μm or more, more preferably 20 μm or more, and usually 80 μm or less, preferably 60 μm or less, more preferably 40 μm or less.

  Among them, the protective film preferably contains a polyolefin-based polymer. When the protective film has a single-layer structure, the layer preferably contains a polyolefin-based polymer. When the protective film has a multilayer structure, at least one layer preferably contains a polyolefin-based polymer. By using a polyolefin-based polymer, molding by coextrusion becomes possible, and the productivity is excellent.

  The protective film is a film having a multilayer structure usually including two or more layers. Preferable examples of the protective film include a film having an adhesive layer and a back layer; a film having an adhesive layer, an intermediate layer and a back layer in this order; and the like. In this case, the surface of the adhesive layer forms the adhesive surface of the protective film.

  Hereinafter, examples of suitable components of the protective film will be described.

(Adhesive layer)
The adhesive layer is located on the surface of the protective film on the side of the cyclic polyolefin film, and is a layer that can adhere to the cyclic polyolefin film. The adhesive layer is formed to include an adhesive, and the protective film can be fixed to the cyclic polyolefin film by the adhesive force of the adhesive.

  Examples of the adhesive include a rubber-based adhesive, an acrylic-based adhesive, a polyvinyl ether-based adhesive, a urethane-based adhesive, and a silicone-based adhesive. One kind of the adhesive may be used alone, or two or more kinds may be used in combination at an arbitrary ratio.

  Among the pressure-sensitive adhesives, a block copolymer represented by the general formula ABA or the general formula AB (where A represents a styrene-based polymer block, and B represents a butadiene polymer) Rubber-based pressure-sensitive adhesive containing a block, an isoprene polymer block, and a polymer block selected from the group consisting of an olefin polymer block obtained by hydrogenating them; an acrylic pressure-sensitive adhesive is preferable.

  In the block copolymer represented by the aforementioned general formula ABA or general formula AB, the styrene-based polymer block A has a weight average molecular weight of 12,000 or more and 100,000 or less, and a glass transition temperature of 20 ° C or more. Are preferred. Further, a polymer block B selected from the group consisting of a butadiene polymer block, an isoprene polymer block, and an olefin polymer block obtained by hydrogenating them, has a weight average molecular weight of 10,000 or more and 300,000 or less, and a glass transition temperature. Is preferably -20 ° C or lower. Further, the mass ratio of the component A and the component B (component A / component B) is preferably 5/95 or more, more preferably 10/90 or more, preferably 50/50 or less, more preferably 30/70. It is as follows.

  Examples of the block copolymer represented by the general formula ABA include styrene-ethylene / propylene-styrene copolymer, styrene-ethylene / butylene-styrene copolymer, and hydrogenated products thereof. Examples of the block copolymer represented by the general formula AB include styrene-ethylene / propylene copolymers, styrene-ethylene / butylene copolymers, and hydrogenated products thereof. it can.

  Examples of acrylic adhesives include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, and octyl. Alkyl (meth) acrylates such as (meth) acrylate, lauryl (meth) acrylate and stearyl (meth) acrylate; alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate; cyclohexyl ( (Meth) acrylamides such as (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, vinyl acetate, (meth) acrylamide, and N-methylol (meth) acrylamide; And the like homopolymers or copolymers. In addition, (meth) acrylate means acrylate and methacrylate, and (meth) acryl means acryl and methacryl.

  The acrylic pressure-sensitive adhesive is preferably used by copolymerizing an acrylic monomer having a functional group. Examples of the acrylic monomer having a functional group include unsaturated acids such as maleic acid, fumaric acid, and (meth) acrylic acid; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, -Hydroxyhexyl (meth) acrylate, dimethylaminoethyl methacrylate, (meth) acrylamide, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, maleic anhydride, and the like. In addition, as the acrylic monomer having a functional group, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

  The acrylic pressure-sensitive adhesive may contain a crosslinking agent as necessary. The cross-linking agent is a compound that undergoes a thermal cross-linking reaction with a functional group present in the copolymer, and finally forms an adhesive layer having a three-dimensional network structure. By including a cross-linking agent, the adhesiveness of the protective film to other layers (intermediate layer, back layer, etc.) in contact with the adhesive layer, the toughness of the protective film, solvent resistance, water resistance, and the like can be improved. . Examples of the crosslinking agent include isocyanate compounds, melamine compounds, urea compounds, epoxy compounds, amino compounds, amide compounds, aziridine compounds, oxazoline compounds, silane coupling agents and the like, and modified products thereof. You may use it suitably. One type of the crosslinking agent may be used alone, or two or more types may be used in combination at an arbitrary ratio.

  From the viewpoint of the crosslinking property and toughness of the pressure-sensitive adhesive layer, it is preferable to use an isocyanate compound and its modified product as the crosslinking agent. The isocyanate compound is a compound having two or more isocyanate groups in one molecule, and is roughly classified into an aromatic compound and an aliphatic compound. Examples of the aromatic isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, naphthalene diisocyanate, tolidine diisocyanate, and paraphenylene diisocyanate. Examples of the aliphatic isocyanate compound include hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, tetramethyl xylene diisocyanate, and xylylene diisocyanate. Furthermore, examples of the modified form of these isocyanate compounds include a biuret form, an isocyanurate form, and a trimethylolpropane adduct form of the isocyanate compound.

  When a cross-linking agent is used, a cross-linking catalyst such as dibutyltin laurate may be included in the adhesive in order to promote the cross-linking reaction.

  The pressure-sensitive adhesive layer may contain a tackifying polymer, if necessary. Examples of the tackifying polymer include, for example, an aromatic hydrocarbon polymer, an aliphatic hydrocarbon polymer, a terpene polymer, a terpene phenol polymer, an aromatic hydrocarbon-modified terpene polymer, a chroman-indene polymer, and a styrene-based polymer. Examples thereof include a polymer, a rosin-based polymer, a phenol-based polymer, and a xylene polymer, and among them, an aliphatic hydrocarbon polymer such as low-density polyethylene is preferable. However, the type of the specific tackifying polymer is appropriately selected from the viewpoint of compatibility with other polymers, the melting point of the resin, and the adhesive strength of the adhesive layer. In addition, as the tackifying polymer, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

  The amount of the tackifying polymer is, for example, 100 parts by mass of the block copolymer, preferably 5 parts by mass or more, preferably 200 parts by mass or less, more preferably 100 parts by mass or less. . When the amount of the tackifying polymer is equal to or more than the lower limit of the above range, the protective film can be prevented from floating or peeling when bonded to the cyclic polyolefin film. In addition, by setting the upper limit or less, the feeding tension of the protective film is suppressed, and wrinkles and scratches during bonding with the cyclic polyolefin film are prevented, and bleed out of the tackifying polymer is prevented to prevent adhesion. Or the adhesion of the layer can be kept high.

  The adhesive layer may contain additives such as a softener, an antioxidant, a filler, and a coloring agent (such as a dye or a pigment), if necessary. One type of additive may be used alone, or two or more types may be used in combination at an arbitrary ratio.

  Examples of the softener include process oil, liquid rubber, and plasticizer.

  Examples of the filler include barium sulfate, talc, calcium carbonate, mica, silica, and titanium oxide.

  The pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer is preferably 0.4 N / cm or more, more preferably 0.6 N / cm or more, with respect to other layers (intermediate layer, back layer, etc.) in contact with the pressure-sensitive adhesive layer in the protective film. cm or less, and more preferably 4 N / cm or less. By setting the adhesive force to be equal to or more than the lower limit of the above range, floating and peeling of the protective film can be prevented when the protective film is bonded to the cyclic polyolefin film. Further, when the thickness is equal to or less than the upper limit, the feeding tension of the protective film can be suppressed, and wrinkles and scratches at the time of lamination with the cyclic polyolefin film can be prevented.

  The thickness of the pressure-sensitive adhesive layer is usually 1.0 μm or more, preferably 2.0 μm or more, and usually 50 μm or less, preferably 30 μm or less. By setting the thickness of the adhesive layer to be equal to or more than the lower limit of the above range, it is possible to increase the adhesive strength and prevent floating and peeling of the protective film when the protective film is bonded to the cyclic polyolefin film. Further, when the content is not more than the upper limit, the adhesive strength can be prevented from being excessively increased, and the feeding tension of the protective film can be suppressed, so that wrinkles and scratches during bonding with the cyclic polyolefin film can be prevented. Further, since the stiffness of the protective film can be prevented from becoming too strong, the handling property of the protective film can be improved.

(Back layer)
The back layer is a layer located on the side opposite to the cyclic polyolefin film with respect to the adhesive layer, and is usually located on the surface of the protective film on the side opposite to the cyclic polyolefin film. This backing layer usually does not adhere to the cyclic polyolefin film. In a protective film having a back layer, the arithmetic average roughness Ra of the exposed surface of the back layer is usually the arithmetic average roughness Ra of the surface of the protective film opposite to the adhesive surface.

  Usually, the back layer is formed of a resin. The polymer contained in the resin forming the back layer may be a homopolymer or a copolymer. Preferable examples include a polyolefin-based polymer.

  The polyolefin-based polymer is a homopolymer or copolymer of a chain olefin, or a copolymer of a chain olefin and a monomer copolymerizable with the chain olefin. Examples thereof include polyethylene, polypropylene, ethylene-propylene copolymer, propylene-α-olefin copolymer, ethylene-α-olefin copolymer, ethylene-ethyl (meth) acrylate copolymer, and ethylene-methyl (meth). A) acrylate copolymer, ethylene-n-butyl (meth) acrylate copolymer, ethylene-vinyl acetate copolymer and the like. Here, examples of the polyethylene include low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene. Examples of the ethylene-propylene copolymer include a random copolymer and a block copolymer. Further, examples of the α-olefin include butene-1, hexene-1, 4-methylpentene-1, octene-1, pentene-1, heptene-1 and the like.

  Among the above-mentioned polyolefin polymers, a polymer selected from the group consisting of polyethylene, polypropylene, ethylene-propylene copolymer, and propylene-α olefin copolymer is preferable, and ethylene-propylene copolymer and propylene-α olefin copolymer are preferable. A polymer (hereinafter, these may be collectively referred to as a “propylene-based copolymer”) is more preferable, and an ethylene-propylene copolymer is particularly preferable.

  One of the above-mentioned polymers may be used alone, or two or more may be used in combination at an arbitrary ratio. Among them, it is preferable to use a combination of a propylene-based copolymer such as an ethylene-propylene copolymer and low-density polyethylene. At this time, it is particularly preferable to combine 60 to 90% by mass of the propylene-based copolymer with 40 to 10% by mass of the low-density polyethylene. As the ethylene content increases, the melting point of the ethylene-propylene copolymer can be lowered. For this reason, from the viewpoint of ease of coextrusion and enabling low-temperature extrusion, the ethylene content of the comonomer is preferably in the range of 3 to 7 mol%. When it is desired to add heat resistance to the back layer, the ethylene content may be reduced and the heat resistance may be appropriately selected so as to obtain a desired heat resistance.

  The melt flow rate of the propylene-based copolymer at 230 ° C. (hereinafter, may be appropriately referred to as “MFR”) is preferably in the range of 5 g / 10 min to 40 g / 10 min. In particular, those having an MFR in the range of 20 g / 10 min to 40 g / 10 min are more preferable because low-temperature extrusion is possible and the surface of the back layer is easily roughened by combining with low-density polyethylene.

  Further, the low-density polyethylene constituting the back layer preferably has an MFR at 190 ° C. of 0.5 g / 10 min to 5 g / 10 min.

Further, the low-density polyethylene preferably has a density of 0.910 g / cm ^{3 to} 0.929 g / cm ³ . When the density of the low-density polyethylene is equal to or more than the lower limit of this range, the surface roughness of the surface of the back layer can be easily adjusted to an appropriate range. In addition, when the amount is not more than the upper limit, detachment of the resin from the protective film due to friction with a roll (for example, a metal roll, a rubber roll, or the like) used for conveyance can be prevented, and generation of white powder can be suppressed.

  The polymer (for example, propylene-based copolymer and low-density polyethylene) contained in the back layer may be different from the polymer contained in the adhesive layer, but it is preferable to use the same polymer.

  In the resin forming the back layer, as long as the effects of the present invention are not significantly impaired, for example, a filler such as talc, stearamide, calcium stearate, a lubricant, an antioxidant, an ultraviolet absorber, a pigment, an antistatic agent, An additive such as a nucleating agent may be included. One type of additive may be used alone, or two or more types may be used in combination at an arbitrary ratio.

  The thickness of the back layer is usually 1/40 or more, preferably 1/20 or more, and usually 1/1 or less, preferably 1/2 or less in a ratio to the thickness of the adhesive layer (adhesive layer / back layer). It is. Thereby, the thickness of the back layer can be prevented from becoming excessively thin as compared with the pressure-sensitive adhesive layer, so that the film formability can be improved and fish eyes can be prevented. Further, since the thickness of the back layer can be prevented from becoming excessively thick as compared with the pressure-sensitive adhesive layer, the feeding tension of the protective film can be suppressed, and wrinkles and scratches during bonding with the cyclic polyolefin can be prevented.

(Intermediate layer)
An intermediate layer may be provided between the adhesive layer and the back layer as needed. The intermediate layer is usually formed of a resin, but is preferably formed of a resin containing a polyolefin-based polymer.

  Examples of the polyolefin polymer contained in the intermediate layer include, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-α-olefin copolymer, polypropylene, ethylene-propylene copolymer (Random copolymer and / or block copolymer), α-olefin-propylene copolymer, ethylene-ethyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer, ethylene-n-butyl (Meth) acrylate copolymer, ethylene-vinyl acetate copolymer and the like can be mentioned. In addition, a polyolefin-type polymer may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios. However, the polyolefin polymer contained in the intermediate layer is preferably a different type of polyolefin polymer than the polymer contained in the adhesive layer and the back layer.

  The intermediate layer may include a material for forming the adhesive layer and a material for forming the back layer as necessary. Normally, when a protective film is produced by a co-extrusion molding method, a portion having an uneven thickness at an end is slit in a slitting step or the like and removed. By using the part thus removed as a raw material for the intermediate layer, the amount of raw material used can be reduced.

  In the intermediate layer, as long as the effects of the present invention are not significantly impaired, for example, fillers such as talc, stearamide, calcium stearate, lubricants, antioxidants, ultraviolet absorbers, pigments, antistatic agents, nucleating agents, etc. May be included. One type of additive may be used alone, or two or more types may be used in combination at an arbitrary ratio.

  The thickness of the intermediate layer is usually in the range of 13 to 70 μm.

(Method of manufacturing protective film)
The protective film may be manufactured, for example, by the following manufacturing methods (i) to (iii).

  (I) A method of co-extruding the material of the adhesive layer, the material of the back layer, and, if necessary, the material of the intermediate layer.

  (Ii) A method of preparing a back layer or an intermediate layer, and applying an adhesive to the prepared layer to form an adhesive layer.

(Iii) A method in which an adhesive layer, a back layer, and, if necessary, an intermediate layer are separately prepared, and the prepared layers are laminated and integrated.

  Among the exemplified production methods, the production method (i) based on the co-extrusion molding method is characterized in that the pressure-sensitive adhesive layer and the back layer or the intermediate layer are firmly adhered to each other, and the adhesive residue on the cyclic polyolefin film hardly occurs. This is particularly preferable because it has advantages such as simplification and low cost. Here, “adhesive residue” refers to a phenomenon in which the pressure-sensitive adhesive remains on the cyclic polyolefin film after the protective film is peeled off. In the protective film produced by the production method (i), a polyolefin polymer such as a branched low-density polyethylene or polypropylene is often used as the back layer. On the other hand, for the adhesive layer, usually, for example, vinyl acetate, linear low-density polyethylene, metallocene linear low-density polyethylene and the like are used. Among them, a linear low-density polyethylene-based pressure-sensitive adhesive is often used rather than a vinyl acetate-based pressure-sensitive adhesive from the viewpoint of avoiding adhesive residue and an increase in adhesion over time.

  Further, in the protective film produced by the production method (ii) by a coating method, polyethylene terephthalate and a polyolefin polymer are usually used as the back layer in many cases, and a rubber-based adhesive and an acrylic-based adhesive are used for the adhesive layer. Is often used. Above all, when there is concern about foreign matter in the protective film, it is preferable to use polyethylene terephthalate rather than a polyolefin polymer for the back layer. In the production method (ii), when the production is performed in a clean room, a high-quality protective film free of foreign matter can be obtained.

  In order for the surface of the protective film opposite to the cyclic polyolefin film to have the above-mentioned arithmetic average roughness Ra, for example, by deforming the surface of the back layer, it has a predetermined arithmetic average roughness Ra Irregularities may be formed. For example, using a shaping roll having irregularities, a nip molding method in which the protective film immediately after extrusion obtained in the co-extrusion molding method is pressed to transfer irregularities to the surface of the back layer; A method of peeling the release film after transferring the unevenness of the release film by pressing with a mold film; a method of cutting fine particles on the surface of the back layer of the protective film by spraying fine particles on the surface of the back layer of the protective film; Is mentioned. The step of deforming the surface of the back layer may be before or after bonding the back layer and the adhesive layer.

  Further, irregularities may be formed on the surface of the back layer by adjusting the composition of the back layer. For example, a method in which fine particles having a predetermined particle size are contained in the rear layer to form irregularities in the rear layer; a method in which the mixing ratio of a material such as a resin forming the rear layer is adjusted to form irregularities in the rear layer; Is mentioned.

  Among the above, since a protective film having no uneven transfer of unevenness can be obtained in a wide width, a nip forming method using a shaping roll having unevenness is preferable, and a protective film using a mirror roll and a shaping roll having unevenness is preferable. Is particularly preferable.

  The surface material of each of the mirror roll and the forming roll includes, for example, metal, rubber, resin, and the like. These are selected so that the desired uneven shape can be transferred to the surface of the back layer of the protective film. However, the hardness of the shaping roll is preferably equal to or greater than the hardness of the mirror roll. Further, for example, the protective film may have a surface property equivalent to that of a mirror roll, and may be narrowed by a resin film or the like that is softer than a forming roll.

  It is preferable that the mirror roll and the shaping roll can be independently temperature-controlled. The temperature of the mirror roll is preferably in the range of 40 to 160 ° C, and the temperature of the forming roll is preferably in the range of 60 to 200 ° C. The temperature of the mirror roll is more preferably in the range of 60 to 130 ° C, and the temperature of the shaping roll is more preferably in the range of 80 to 180 ° C. By setting the temperature of the mirror roll or the shaping roll to a temperature equal to or higher than the lower limit of the above range, uneven transfer of unevenness can be prevented. Further, by setting the temperature of the mirror roll or the shaping roll to the upper limit temperature of the above range or less, it is possible to prevent the protective film from winding around the mirror roll or the shaping roll.

  In the nip forming method, the above-mentioned arithmetic average roughness Ra of the surface of the protective film opposite to the cyclic polyolefin is such that the temperature, the roll speed, and the temperature of the protective film, the mirror roll and the forming roll at the time of pressing are pressed. The pressure at that time and the material of the surfaces of the mirror roll and the forming roll can be adjusted by appropriately selecting them according to the characteristics of the material forming the protective film. Usually, the temperature of the mirror roll and the forming roll is preferably (Tg-60) to (Tg + 20) ° C. with respect to the glass transition temperature (Tg) of the resin forming the back layer.

  The surface of the protective film may be subjected to a surface modification treatment as necessary. Examples of the surface modification treatment include an energy beam irradiation treatment and a chemical treatment.

  Moreover, you may print on the surface of a protective film as needed.

(Lamination)
A multilayer film is obtained by laminating a cyclic polyolefin film and a protective film. At the time of lamination, it is preferable to apply a predetermined amount of tension to the cyclic polyolefin film and the protective film in order to eliminate wrinkles and loosening of the cyclic polyolefin film and the protective film. Further, at the time of bonding, it is preferable to perform bonding while applying pressure using, for example, a nip roll or the like.

  The multilayer film thus produced includes a cyclic polyolefin film and a protective film. Further, in the multilayer film, the cyclic polyolefin film is usually exposed on one surface, and the protective film is exposed on the other surface. At this time, an optional layer may be further provided between the cyclic polyolefin film and the protective film. The optional layer may be a single layer or two or more layers. When there are two or more optional layers, these layers may be the same or different.

  The width of the multilayer film is preferably 1500 mm or more, more preferably 1800 mm or more. Generally, a film roll on which a wide film is wound tends to have wrinkles or gauge bands. However, the multilayer film according to the present embodiment can realize a good winding appearance when wound, while having such a wide width. The upper limit of the width of the multilayer film is usually 2500 mm or less.

(Step of winding a multilayer film)
After obtaining the multilayer film, the multilayer film is wound into a roll to obtain a cyclic polyolefin film roll. Usually, in the step of winding the multilayer film, a winding device including a winding roll and a pressure roller is used. Then, the multilayer film is wound around a winding roll while applying a surface pressure to the multilayer film by pressing with a contact pressure roller to obtain a cyclic polyolefin film roll.

  By winding the multilayer film while applying surface pressure by the contact pressure roller, it is easy to suppress the amount of air entrained in high-speed winding. For this reason, generation of wrinkles can be prevented, and a cyclic polyolefin film roll having a good winding appearance can be manufactured.

  At this time, the pressure P (N / m) of the contact pressure roller satisfies the following equation (4), where Ra (μm) is the arithmetic average roughness of the surface of the protective film opposite to the cyclic polyolefin film. Is preferred.

50 × Ra + 75 ≦ P ≦ 23 × Ra + 160 (4)
As described above, from the viewpoint of preventing wrinkles and gauge bands when winding the multilayer film, it is preferable to suppress and control the amount of air entrained between the overlapping multilayer films. At this time, the amount of entrained air changes depending on the surface roughness of the surface of the protective film opposite to the cyclic polyolefin film. Therefore, the pressure P of the contact pressure roller is preferably set according to the surface roughness of the surface of the protective film opposite to the surface of the cyclic polyolefin film.

  As the surface roughness of the surface opposite to the cyclic polyolefin film of the protective film becomes coarser, the amount of air entrained during winding increases, so that the pressure P of the contact pressure roller is increased and air entrainment is performed. Is preferably suppressed. Furthermore, if the surface roughness of the surface opposite to the cyclic polyolefin film of the protective film is rough, the amount of air entrained at the time of winding increases, so that the amount of air entrained by the change in the pressure P of the contact pressure roller is reduced. The change is also greater. For this reason, compared with the case where the surface roughness of the surface opposite to the cyclic polyolefin film of the protective film is smooth, when the surface roughness of the surface opposite to the cyclic polyolefin film of the protective film is rough, The preferred range of the pressure P of the contact pressure roller becomes narrow. Therefore, the pressure P of the contact pressure roller is in the range of the arithmetic average roughness Ra on the surface of the protective film on the side opposite to the cyclic polyolefin film, and is in a range corresponding to the Ra as in the above formula (4). Is preferred.

  The winding speed of the multilayer film is usually 5 m / min or more, preferably 10 m / min or more, usually 50 m / min or less, preferably 45 m / min or less, more preferably 40 m / min or less. When the winding speed is equal to or higher than the lower limit of the above range, the production efficiency can be increased, and when the winding speed is equal to or lower than the upper limit, the amount of air entrainment can be suppressed.

  The number of windings of the cyclic polyolefin film roll is not limited, but is usually 40 times or more, preferably 60 times or more, and usually 27000 times or less, preferably 13000 times or less.

  Although the outer diameter of the cyclic polyolefin film roll is not limited, it is usually 160 mm or more, preferably 190 mm or more, and usually 2300 mm or less, preferably 1200 mm or less.

  A preferred embodiment of a method for packaging a cyclic polyolefin film roll (roll-shaped film) and a package according to the present invention will be described.

  FIG. 18 is a perspective view showing a roll-shaped film and a packaging material, and FIG. 19 is a perspective view showing a package body obtained by packaging the roll-shaped film with the packaging material.

  As shown in FIG. 18, the roll-shaped film 712 has a cylindrical core 716, and a long film 714 is wound around the core 716 in a roll shape. The width dimension of the core 716 is formed to be larger than the width dimension of the film 714, and the film 714 is wound around a substantially central position in the width direction of the core 716. Therefore, both ends of the roll core 716 of the roll-shaped film 712 protrude from the film 714.

  As described later, the film 714 has at least one photocurable resin layer on its surface.

  Further, the film 714 has minute irregularities also referred to as embossing or knurling at both end positions in the width direction thereof. For the purpose of preventing end face deviation and loosening when winding the film in a roll shape, for example, It is formed in the range of 5 to 50 μm or in the range of 0.05 to 0.3 of the film thickness.

  On the other hand, the packaging material 718 is formed in a cylindrical shape, and its width dimension is formed larger than the width dimension of the film 714. The inner diameter of the packaging material 718 is formed to be larger than the outer diameter of the roll-shaped film 712, so that the packaging material 718 can be covered on the roll-shaped film 712. Note that the packaging material 718 may be a rectangular sheet. In this case, after wrapping the roll-shaped film 712 with the packaging material 718 to form a cylindrical shape, the edge of the packaging material 718 is made of an adhesive tape or the like. It is good to stick and fix with.

  The packaging material 718 whose outer surface has a solar reflectance of 70% or more (based on JIS-R-3106) is used. For example, a packaging material 718 in which an outer surface of polyethylene (PET) is subjected to aluminum evaporation is used. Note that the packaging material 718 only needs to have a solar reflectance of 70% or more, and may be a metal material other than aluminum that has been vapor-deposited or a metal foil such as an aluminum foil. The solar reflectance of the packaging material 718 is more preferably 80% or more, further preferably 90% or more. By forming the package 710 of FIG. 19 using such a packaging material 718, the temperature difference inside the package 710 can be suppressed within 25 ° C., preferably within 20 ° C.

The packaging material 718 preferably has a moisture permeability of 5.4 g / m ² · day or less in a 40 ° C. and 90% RH environment. By using the packaging material 718 having such moisture permeability, the rate of humidity change inside the package 710 can be suppressed to 4% / min or less.

  As shown in FIG. 19, the packaging material 718 configured as described above is covered with a roll-shaped film 712, and rubber bands 720 are externally fitted to both ends thereof. Both ends of the packaging material 718 are fixed to the outer peripheral surface of the core 716 in close contact with the rubber band 720. Thus, a package 710 in which the roll material 712 is wrapped with the packaging material 718 is formed. The method of fixing the packaging material 718 is not limited to the rubber band 720, and may be fixed by attaching the packaging material 718 to the core 716 with an adhesive tape or the like.

  Next, the operation of the package 710 configured as described above will be described. FIGS. 20A and 20B are schematic diagrams illustrating a failure of the roll-shaped film 712 in a conventional package (that is, a package packaged with a packaging material having a solar reflectance of less than 70%). .

  In the case of a conventional package, when sunlight is applied to the package, a temperature difference occurs between the hit side and the non-hit side in the inside of the package, and a humidity difference accompanying the temperature difference occurs. As a result, a difference in thermal expansion or a difference in humidity expansion of the film 714 occurs between the two, and deformation of the roll-shaped film 712 called “beck failure” occurs. As shown in FIG. 20B, the edge failure occurs because the widthwise end of the film 714 is firmly wound by knurls (embosses) 714A, whereas the center portion is loosely wound. This is more likely to occur as the tension during winding is increased. For this reason, conventionally, it is not possible to increase the winding tension in the preceding processing apparatus, and it is not possible to cope with an increase in the length of the film 714 or an increase in the transport speed.

  On the other hand, the package of the present embodiment is packaged with a packaging material 718 having a solar reflectance of 70% or more. Therefore, even when sunlight hits the package 710, most of the sunlight is reflected by the packaging material 718 and is not absorbed by the package 710, so that a temperature difference and a humidity difference occur inside the package 710. Can be prevented. Accordingly, it is possible to prevent the film 714 from being deformed and causing a bellows failure, and to prevent a problem in the package 710 even in the case of the roll-shaped film 714 having a high winding tension. Therefore, according to the present embodiment, the winding tension can be increased in the processing line before packaging, so that the length of the film 714 can be increased and the transport speed can be increased.

  When winding the cyclic polyolefin film around the core, a double-sided tape, a cushioning material, or the like is attached to the core. The double-sided tape is for fixing the leading end of the film to the winding core.

  As shown in FIG. 21, the double-sided tape 831 has a first adhesive layer 831b on the winding core side on one surface (back surface) of a belt-shaped support body 831a made of, for example, PET (polyethylene terephthalate), and the other surface (front surface). A second adhesive layer 831c on the film side is formed. The thickness t02 of the double-sided tape 831 is in the range of 10 to 60 μm, preferably in the range of 10 to 30 μm, and more preferably in the range of 10 to 15 μm. As the double-sided tape 831, for example, Nitto Denko (model: 5601, 5603, 5605, 5606) is used. In each cross-sectional view of FIG. 21 and subsequent figures, if the actual dimensions are displayed, it becomes difficult to distinguish the members such as the film 815, the double-sided tape 831 and the cushioning material 832, and therefore, in each figure, the dimension in the thickness direction is exaggerated. It is displayed.

  The width W02 of the double-sided tape 831 is in the range of 25 to 150 mm, preferably in the range of 40 to 90 mm, and more preferably in the range of 40 to 60 mm. If it is less than 25 mm, the sticking will be defective, and if it exceeds 150 mm, wrinkles are likely to occur on the tape, which are both undesirable.

  Each of the adhesive layers 831b and 831c of the double-sided tape 831 is formed on the entire surface of the support 831a. These adhesive layers 831b and 831c have the same composition and thickness, but may have different compositions and different thicknesses. Although not shown, a release tape is attached to the surface on which the second adhesive layer 831c is formed. The release tape is peeled off before the film 815 is wound after the double-sided tape 831 is attached to the winding core 823 by the first adhesive layer 831b.

  The buffer material 832 is made of, for example, polyester, non-woven fabric, or the like, and is formed to be thinner than the thickness of the film 815 to be wound. And what has elasticity rather than the double-sided tape 831 is used. The cushioning material 832 may not have an adhesive layer itself, and in this case, is attached to the winding core 823 via the double-sided tape 831.

  As shown in FIG. 22, the width W03 of the cushioning material 832 is in the range of 5 to 30 mm, preferably in the range of 8 to 18 mm, and more preferably in the range of 8 to 12 mm. If it is less than 5 mm, poor bonding to the core occurs, and if it is more than 30 mm, it is not possible to improve the appearance of cut edges, which is not preferable. When the width W03 of the cushioning member 832 is determined based on the circumference of the winding core, the width W03 is preferably 2% or less of the circumference of the winding core.

  As shown in FIG. 22, the thickness t03 of the cushioning material 832 varies depending on the number of cushioning materials used. For example, as shown in FIGS. 22 to 25 and FIG. 27 to be described later, when there is one cushioning material 832, 833, the thickness of the film 815 is in the range of 10 to 90%, preferably 25 to 75%. Range, more preferably in the range of 35-65%. When the thickness of the cushioning material 832 is less than 10% or more than 90% of the thickness of the film 815, the effect of improving the cut image is reduced. When there are a plurality of buffer members 841 to 844, the thickness may be gradually reduced from the buffer members 841 to 844 near the film front end 815a. In this case, the difference between the thicknesses of the cushioning members 841 to 844 is desirably suppressed to 5% or more and 30% or less of the thickness of the film 815.

  In the case of the cushioning material 833 having the adhesive layer 833b on at least one surface of the cushioning material main body 833a as in the second embodiment shown in FIG. 24, the cushioning material 833 is directly attached to the winding core 823 without using the double-sided tape 831. Pasted in. In the following embodiments, the same components are denoted by the same reference numerals, and redundant description is omitted.

  FIGS. 25 and 26 show the third embodiment, in which two types of cushioning materials 841 and 842 having different thicknesses are arranged in the winding direction of the film 815. Both the first buffer material 841 near the leading end 815a of the film 815 and the second buffer material 842 far from the leading end 815a have thicknesses t12 and t22 which are less than or equal to the thickness t01 of the polymer film 15, and t12> t22. The widths W12 and W22 of the first buffer material 841 and the second buffer material 842 are in the range of 0.5 to 6.0% of the circumference of the winding core.

  In the third embodiment, since the thicknesses t21 and t22 of the first cushioning material 841 and the second cushioning material 842 are changed in two steps, the bending deformation of the step mark is performed in two steps compared to the first embodiment. , And the length of occurrence of the step trace is shorter than that of the one cushioning material 832 of the first embodiment.

  In the fourth embodiment, instead of the third embodiment shown in FIGS. 25 and 26, as shown in FIG. 27, a cushioning material 843 having adhesive layers 843b and 844b on at least one surface of cushioning material bodies 843a and 844a. , 844. In this case, the cushioning materials 843 and 844 are directly attached to the winding core 823 without using the double-sided tape 831.

  Note that instead of changing the thicknesses t12 and t22 of the cushioning members 841 to 844, the elastic modulus (Young's modulus) of each cushioning member 841 to 844 is changed, or the elastic modulus (Young's modulus) together with the thickness of each of the cushioning members 841 to 844. For example, the amount of compressive deformation of the second cushioning members 842 and 844 moving away from the film leading end 815a may be made larger than the amount of compressive deformation of the first cushioning members 841 and 843. In this case, with the two cushioning materials, the occurrence of a step due to the influence of the leading end of the film is suppressed, and the cut edge image can be further suppressed.

  It is preferable that the relationship between the elastic modulus and the thickness of the cushioning materials 832, 833, 841 to 844 be changed according to the elastic modulus of the film 815 to be wound. For example, when the elastic modulus of the film 815 is Ep and the elastic modulus of the cushioning material is Eb, when Ep ≦ Eb, the thickness of the polymer film is tp, and the thickness of the cushioning material is tb. tp / 2) <tb <tp. When Ep> Eb, tp <tb <2 · tp.

  As shown in FIGS. 21 and 22, the gap G01 from the film front end 815a to the cushioning material 832 is in the range of 0.1 to 20 mm, preferably in the range of 0.1 to 10 mm, and more preferably in the range of 0.1 to 10 mm. ８8 mm. If the thickness is less than 0.1 mm, the film 815 tends to overlap the cushioning material 832.

  As shown in FIG. 23, when the film 815 is wound around the winding core 823 and the next film 815 overlaps the film leading end 815a, the buffer material 832 reduces the influence of the step of the polymer film 815 wound next. . Thus, no extreme bending occurs in the film 815. Thereafter, the next film is wound in the same manner, but in any case, no extreme bending deformation occurs due to the influence of the cushioning material 832, and the occurrence of cut edges is suppressed.

  The attachment of the double-sided tape 831 and the bonding of the leading end of the film with the double-sided tape 831 may be performed manually or by using a film cutting device. In the case of manual operation, a film reservoir (not shown) is provided immediately before the winding device 813. This film reservoir temporarily stores the film 815 for the time required for cutting the film 815 and fixing the film 815 to the core 823, and cuts the film 815 and winds it around the core 823 during the storage. . In the case of automatic operation, the polymer film 815 is cut and fixed to the core 823 using a film cutting device. In this case, the position of the double-sided tape 831 on the winding core 823 is automatically detected, and based on this detection timing, the film 815 is cut, and the cut film tip 815a becomes a predetermined gap G01 with respect to the cushioning material 832. As described above, the leading end of the film is joined to the second adhesive layer 831c.

  Although the double-sided tape 831 and the cushioning materials 832, 833, 841 to 844 are attached to the core 823 in advance, the double-sided tape 831 and the cushioning materials 832, 833, 841 to 841 are attached to the film cutting drum on the film cutting device side. When the film 815 is cut by the film cutting drum, the double-sided tape 831 and the cushioning materials 832, 833, 841 to 844 are attached to the winding core 823, and the film 815 is wound. Good.

  As shown in FIGS. 25 to 27, instead of changing the elastic modulus and thickness of the two cushioning members 841 to 844, the illustration is omitted, but the first end closer to the film front end 815a is provided for one cushioning member. The thickness may be gradually reduced toward the second edge farther from the edge. Also in this case, the film to be wound next by the cushioning material does not undergo extreme bending deformation, and the occurrence of cut-away image is suppressed.

  As shown in FIG. 28, the inclination angle θ1 of the film front end 815a with respect to the film width direction reference line BL1 is preferably in a range of −30 ° <θ1 <30 °, and more preferably in a range of −20 ° <θ1 <20 °. And more preferably in the range of −10 ° <θ1 <10 °. The closer the inclination angle θ1 is to 0 °, the smaller the stress due to the influence of the surface pressure of the film that subsequently overlaps the film front end 815a can be, thereby reducing the appearance of cut edges. As described above, when the leading end 815a of the film 815 is cut at a predetermined inclination angle θ1, the double-sided tape 831 and the cushioning materials 832, 833, 841 to 844 are also set to the same inclination angle in accordance with the inclination angle θ1 of the film leading end 815a. Attach to the winding core 823 at θ1.

  In addition, the width of the film 815 is not particularly limited, but is preferably 600 mm or more, and more preferably 1100 to 2500 mm. Also, the effect is obtained when the width of the film 815 is larger than 2500 mm. The thickness of the film 815 is preferably in the range of 10 to 200 μm, more preferably in the range of 10 to 150 μm, and still more preferably in the range of 15 to 100 μm. The length of the film 815 is preferably 2000 m or more, and more preferably 2500 to 10000 m. Further, the winding radius of the film roll is preferably 450 mm or more, more preferably 650 to 920 mm.

  As shown in FIG. 22, the length L2 of the double-sided tape 831 in the direction of the core of the winding core 823 is not particularly limited, but L2 = (W01-0) mm based on the width W01 of the film 815. (W01-10) mm is preferred.

  The winding core used for winding the cyclic polyolefin film of the present invention preferably satisfies the following formula (1).

E> 0.06 × Aa ³ / I (1)
(E: elastic modulus of the winding core [MPa], A: total mass of the winding core and the film [kg], a: width of the resin film [mm], I: secondary moment of area of the winding core [mm] ⁴ ])
According to the above configuration, the winding core used in the winding step of winding the film into a roll on the winding core has an elastic modulus capable of suppressing bending according to the width and length of the film to be wound. It is. For this reason, a film roll that can suppress the occurrence of horse back deformation even when left for a long time is obtained. Therefore, the obtained film roll can be used as a film in which sticking of films due to horse back deformation is suppressed.

  By using the cyclic polyolefin film of the present invention, it is possible to obtain a film roll having a uniform film thickness and capable of feeding out and supplying a film in which sticking of resin films due to horse back deformation is suppressed.

  The present inventor speculated that the back deformation of the horse in the film roll in which the film was wound on the winding core was caused by the bending of the winding core due to the load of the wound film and the winding core. .

  Therefore, the deflection ν of the winding core will be described below.

  The deflection ν of the take-up core is generally represented by the following equation (2) since the take-up core is held while both ends of the take-up core are supported.

ν = 5ωa ⁴ / 384EI (2)
(Ν: deflection of winding core [mm], ω: load per unit length of winding core [N / mm], a: width of resin film [mm], E: elastic modulus of winding core [MPa] ], I: second moment of area of winding core [mm ⁴ ])
In the above formula (2), the load ω per unit length of the winding core is generally represented by the following formula (3) since the load applied to the winding core is a distributed load.

ω = P / a (3)
(Ω: Load per unit length of winding core [N / mm], P: Load of winding core [N], a: Width of resin film [mm])
Therefore, the bending ν of the winding core is represented by the following equation (4).

ν = 5Pa ³ / 384EI (4)
(Ν: deflection of winding core [mm], P: load of winding core [N], a: width of resin film [mm], E: elastic modulus of winding core [MPa], I: winding core Moment of area [mm ⁴ ])
Next, the inventor paid attention to the fact that the deflection of the winding core is different due to the difference in load based on the width and the winding length of the resin film.

  Therefore, first, the load P of the winding core is a value correlated to the total mass A of the winding core and the resin film in a state where the resin film is wound. Was replaced with Then, as a result of intensive studies on conditions that can sufficiently suppress the occurrence of horse back deformation, the relationship of the above formula (1) was found.

  Therefore, by satisfying the relationship of the above expression (1), the elastic modulus of the winding core is an elastic modulus that can suppress the bending according to the width and the winding length of the resin film to be wound. Therefore, even if the resin film is wound into a roll and left for a long period of time, occurrence of back deformation of the horse can be suppressed.

  In the present embodiment, the elastic modulus of the winding core is defined by the total mass A of the winding core and the resin film, the width a of the resin film, and the second moment of area I of the winding core, as described above. Therefore, it mainly depends on the width and length of the resin film to be wound. For this reason, the elastic modulus of the winding core can be set based on the width and length of the resin film to be wound so that the back deformation of the horse can be sufficiently suppressed. Therefore, the occurrence of back deformation of the horse can be sufficiently suppressed without unnecessarily increasing the manufacturing cost of the winding core, which is preferable. The second moment of area of the winding core is generally a value represented by the following equation (5). The second moment of area is a value that depends on the shape of the winding core, as can be seen from the following equation (5).

^{I = (d2 4 -d1 4)} × π / 64 (5)
(D1: inner diameter of winding core [mm], d2: outer diameter of winding core [mm])
The winding core has only to have an elastic modulus within the above range, and is not particularly limited to a material or the like. For example, it may be made of resin or metal. Among them, those provided with a fiber reinforced resin (FRP) layer containing a resin and a fiber are preferable. Since the fiber reinforced resin layer is a resin layer reinforced with fibers, the elastic modulus can be easily adjusted depending on the strength and content of the contained fibers. Therefore, the elastic modulus of the winding core can be easily adjusted within the above range. The winding core 11 provided with such a fiber reinforced resin layer may be, for example, one composed of only one fiber reinforced resin layer or one obtained by laminating two different fiber reinforced resin layers. It may be one in which three or more different fiber-reinforced resin layers are laminated. Further, a laminate of a fiber reinforced resin layer and a resin layer containing no fiber may be used.

  Further, the shape of the winding core is preferably a cylindrical shape. When the elastic modulus of the winding core is within the above range, a cylindrical shape having a hollow inside is preferable because the weight can be reduced. It is also preferable from the viewpoint that the winding core can be easily mounted on a rotating device. When the shape of the winding core is cylindrical, the thickness of the winding core varies depending on the elastic modulus of the winding core, but is preferably, for example, in the range of 5 to 15 mm.

  Next, a method for manufacturing a wound core including the above-described fiber-reinforced resin layer will be described. The method for producing the winding core is not particularly limited, but it can be produced by, for example, a filament winding method or a sheet winding method. The filament winding method is a method in which a filamentous fiber impregnated with a liquid resin is wound around a predetermined mold, and the resin is dried or cured, and then demolded to form a cylindrical fiber-reinforced resin layer. . The sheet winding method is a method in which a sheet-like fiber (prepreg) impregnated with a liquid resin is wound around a predetermined mold, and the resin is dried or cured. Is formed. More specifically, the following method is used.

  FIG. 29 is a schematic diagram for explaining a method of manufacturing a wound core by a filament winding method. First, the mandrel 931 serving as a mold is attached to the filament winder 932, and the resin that is the raw material of the fiber reinforced resin layer is charged into the resin tank 933. The resin here is a resin solution or a liquid resin before curing. The fiber which is a raw material of the fiber reinforced resin layer is sequentially supplied from a roller 934 around which the fiber is wound by rotating a mandrel 931 by a filament winder 932. Then, the fiber is wound around a mandrel 931 by determining a winding position by a guide 935. At this time, the fiber passes through a resin tank 933 and is impregnated with the resin before being wound around the mandrel 931. By doing so, the resin-impregnated fibers are wrapped around the surface of the mandrel. Then, a fiber-reinforced resin layer is formed on the mandrel by drying or curing the resin. Then, the target molded body is obtained by pulling out the mandrel from the fiber reinforced resin layer.

  FIG. 30 is a schematic diagram for explaining a method of manufacturing a take-up core by a sheet winding method. First, the mandrel 941 as a mold is placed on the support rollers 944 and 945. By rotating the support rollers 944 and 945, the mandrel 941 is rotated. At that time, the touch roller 943 presses the surface of the mandrel 941, and is rotated by the rotation of the mandrel 941. Then, by rotating the mandrel 941 as a mold, as shown in FIG. 30, the film roll (prepreg) 942 is wound around the mandrel 941 while being pressed against the mandrel 941 by the touch roller 943. Then, a fiber-reinforced resin layer is formed on the mandrel by drying or curing the resin. Then, the target molded body is obtained by pulling out the mandrel from the fiber reinforced resin layer.

  As the fiber, any type of fiber material such as a thread, a roving, a woven fabric, a nonwoven fabric, a knitted fabric, a braid, and a cloth can be used. Moreover, as the material, any fiber can be used without particular limitation as long as it is a fiber generally contained in a fiber reinforced resin. For example, glass fiber, carbon fiber, aramid fiber, ceramic fiber and the like can be mentioned. Among these, glass fibers and carbon fibers are preferable, and carbon fibers are more preferable, in that a material having a high elastic modulus can be obtained.

  Further, as the resin, any resin that is generally contained in a fiber-reinforced resin can be used without particular limitation. For example, a polyester resin, an unsaturated polyester resin, an epoxy resin and the like can be mentioned. Among these, a curable resin such as an unsaturated polyester resin or an epoxy resin is preferable in that a wound core stable to heat can be obtained.

  When two or more fiber reinforced layers are stacked, for example, when two different fiber reinforced resin layers are stacked, different fibers and resins may be used for each layer, or the same fiber may be used. You may. Alternatively, two or more kinds of fibers impregnated with resin may be wound and then dried or cured at the same time to form two or more fiber-reinforced layers, or the fibers impregnated with resin may be wound and dried or cured. Thereafter, two or more fiber-reinforced layers may be formed by winding and drying or curing fibers separately impregnated with a resin.

  The method of adjusting the elastic modulus of the winding core is not particularly limited, but can be adjusted by changing the material of the winding core. Further, in the case of a winding core having a fiber reinforced layer, as a fiber to be used, a high-strength fiber such as a carbon fiber or an aramid fiber is used, or the winding amount is increased, or by increasing the fiber content, The elastic modulus can be increased. The elastic modulus can also be adjusted by the resin. Furthermore, in the case where a resin layer containing no fiber is laminated on the surface of the fiber reinforced resin layer, the elastic modulus can be adjusted also by the resin of the surface resin layer. Therefore, by appropriately adjusting the composition of the fiber reinforced resin layer and the surface resin layer, it is possible to adjust the elastic modulus of the winding core within the above elastic modulus range.

(6) Slit Step In the method for producing a cyclic polyolefin film of the present invention, it is preferable to employ a production apparatus in which one to three slit devices are provided at one end of the film per one end of the film.

  In the manufacturing apparatus for manufacturing a cyclic polyolefin film of the present invention, it is preferable that the film slitting device includes a disk-shaped rotating upper blade and a roll-shaped rotating lower blade.

  Here, the disk-shaped rotary blade of the slit device has a diameter of 30 to 300 mm and a thickness of a cut portion of 0.3 to 3 mm, and the material of the rotary blade is made of super steel, super steel. One of steel fine grains, SKD (alloy tool steel) or SKH (high speed tool steel). Further, it is preferable that the toe-in angle of the upper blade is in the range of 30 to 90 degrees.

  The roll-shaped rotary lower blade has a roll diameter in the range of 75 to 200 mm, and the roll material of the rotary lower blade is any of super steel, super steel fine particles, SKD, and SKH.

  In the manufacturing apparatus, the film slitting device may be constituted only by a disk-shaped rotating upper blade. In this case, the disk-shaped rotating upper blade of the slit device has a diameter of 30 to 300 mm and a thickness of a cut portion of 0.3 to 3 mm, and the material of the rotating upper blade is made of super steel, super steel. One of steel fine grains, SKD, and SKH.

  In the present invention, it is preferable that the temperature around the slitter is in the range of 20 to 50 ° C. and the humidity is in the range of 50 to 70% RH.

  Further, in the present invention, it is preferable to provide a suction device in which the periphery of the upper blade is formed as a box and suction is performed at a wind speed of 0.8 to 10 m / sec. In this case, the suction position of the end film is on the downstream side in the base transport direction from the slitting point.

  In the present invention, it is preferable to provide a mechanism for transporting the slit end film (film fragment) to the next trimming step, for example, to provide a mechanism for nip and / or sucking the slit end film. Is preferred. Further, it is preferable to provide a mechanism for nip and / or winding the slit end film.

  Here, it is preferable that the value obtained by dividing the draw ratio, that is, the speed of the nip and / or winding film by the speed of the slit end film, is in the range of 0.8 to 1.5.

  Further, it is preferable that the suction pressure is in a range of −1000 to −100 Pa. And it is preferable to make a nip pressure into the range of 0.1-17 MPa.

  In the production of the cyclic polyolefin film of the present invention, the width of the slit end film is in the range of 20 to 150 mm, and the thickness is in the range of 30 to 150 μm.

  In the present invention, there is also a method in which the transport film is slit after being covered with a masking base.

  The material of the masking base is not particularly limited as long as it can protect the film, and examples thereof include a polyethylene terephthalate (PET) film, a polyethylene (PE) film, and a polypropylene (PP) film.

  Further, it is preferable that the charge amount of the slit end film is in the range of 0 to ± 10 kV. For this reason, it is preferable to provide a static eliminator around the upper blade. As the static eliminator, for example, any one of a static elimination bar, a static elimination blower, and a static elimination thread is used.

  The slit end film (film fragment) is preferably treated with an edge cleaner.

  In addition, it is preferable that the end of the product film after slitting is treated with a web cleaner to remove chips.

  In the production method of the present invention, it is also preferable to take a heating step of heating the formed film by a heating unit.

  In this heating step, first, the film thickness of the film is measured by an in-line film thickness meter. Thereby, for example, the film thickness in which both ends in the width direction are formed thicker than the inside is measured. The reason why the film thickness at both ends in the width direction increases as described above is that a so-called neck-in phenomenon is caused by a force acting on the resin in the width direction when the resin is extruded from the slit of the T-die. It is due to.

  Then, the film whose thickness has been measured is heated by a heat gun. At this time, the control unit calculates an average film thickness t in a range of 10% of the entire width from both ends in the width direction of the film based on the measurement result of the film thickness. It is preferable that a heat gun is set so as to heat at least a part of the film portion H having a thickness of. At the same time, the output of the heat gun is adjusted so that the temperature T of at least a part of the heated film portion H satisfies 80 ≦ T ≦ Tg + 50 [° C.] (Tg: glass transition temperature of resin [° C.]).

  This heating is for relaxing the stress generated at both ends of the film by thermal deformation. More specifically, the transport tension is concentrated on both ends of the film having a large film thickness formed by the above-described neck-in phenomenon when the film is transported by a plurality of rollers. The force that reduces the width) acts to generate stress. The above-mentioned heating is for relaxing this stress. Accordingly, it is possible to suppress the occurrence of vertical wrinkles in the longitudinal direction (transport direction) and minute distortion that cannot be visually confirmed due to the stress. This effect acts more remarkably in the step of transporting the unstretched film for a long time due to the above-mentioned factors of generating stress.

  In addition, this heating is preferably performed before the stretching step in addition to the slitting step, because the occurrence of the above-described vertical wrinkles and distortion can be effectively suppressed. This is because longitudinal wrinkles and distortions are emphasized by stretching in the longitudinal direction of the film in the stretching step. Furthermore, this heating is desirably performed immediately after the resin is cooled and solidified by the cooling roller.

  Further, if the temperature T of the film by this heating is less than 80 ° C., the thermal deformation of the film F is small, and the effect of relaxing the stress is insufficient. There is a possibility that the film is melted and adheres to the roller or breaks in the transport direction. Therefore, by setting the temperature T to 80 ≦ T ≦ Tg + 50 [° C.], the film can be sufficiently thermally deformed while preventing melting of a heated portion. However, the temperature T is more preferably 80 ≦ T ≦ Tg + 30 [° C.], and even more preferably 100 ≦ T ≦ Tg + 10 [° C.].

  Next, at least a part of the heated film portion H is cut and removed (cutting step).

  More specifically, the portion from the heated portion of the film portion H to the end of the film is removed by cutting the film in the longitudinal direction of the film with a rotary cutter of the heating portion. By removing both end portions of the film in this cutting step, it is possible to prevent the occurrence of stress at the both end portions due to subsequent conveyance, so that the occurrence of vertical wrinkles and distortion can be suppressed more reliably. In the cutting step, only the heated portion of the film portion H may be removed, or the entire film portion H may be removed. Further, the cutting step may not be performed.

  Next, the formed and heated film is stretched in the longitudinal direction by a longitudinal stretching machine (stretching step).

  In this stretching step, the film is stretched in the longitudinal direction (the transport direction) by heating the film F with the IR heater and transporting the film by a plurality of rollers driven in such a manner that the peripheral speed is gradually increased in order. I do. At this time, the rollers are driven such that the difference in the peripheral speed between the rollers whose films are heated by the IR heater is the largest.

  Next, the stretched film is wound up by a winder in a winding section.

  According to the above manufacturing method, the film before being stretched in the longitudinal direction is heated at least partially within a predetermined range from both ends in the width direction of the film, so that longitudinal wrinkles and strain in the longitudinal direction are stretched. Before emphasizing, the part where the transport tension is stronger than the inner side in the width direction is thermally deformed, so that the stress causing vertical wrinkles and distortion can be effectively reduced.

  At this time, since at least a part of the film is heated at least partially within a range of 10% of the entire width from both ends in the width direction of the film, the entire film is heated, and unnecessary stretching or change in optical characteristics due to transport tension may occur. In addition, vertical wrinkles and distortion are not generated inside the film outside the above range, and the effective width of the finished cyclic polyolefin film is not reduced.

  Further, since only at least a part of the film portion H having a film thickness equal to or less than the average film thickness t in the above range is heated, that is, the outermost portion of the film F which is formed thickest and has the strongest transport tension is applied. Do not heat. Thereby, it is possible to prevent the film F from being broken due to the extreme end being heated and the film F being partially stretched.

  Further, since at least a part of the film portion H is heated to a temperature T satisfying 80 ≦ T ≦ Tg + 50 [° C.] (Tg: glass transition temperature [° C.] of the cyclic polyolefin resin R), melting of the heated portion is prevented. In this way, it is possible to sufficiently reduce the stress that causes vertical wrinkles and distortion by performing thermal deformation sufficiently.

  As described above, generation of longitudinal wrinkles and distortion in the longitudinal direction can be suppressed.

  In the stretching step, the film is stretched only in the longitudinal direction (transport direction). However, a tenter may be provided downstream of the longitudinal stretching machine, and the tenter may be used to stretch the film in the width direction.

  In addition, the in-line film thickness meter may be either a contact type or a non-contact type. However, a non-contact type using a laser or an X-ray is preferable because of easy measurement in a line. Is preferred.

  Further, the heat gun does not need to heat the film with hot air, but may heat the film while being in contact with a heat roller or the like, or may heat the film by irradiation with an IR heater or the like.

  Further, the rotary cutter need not be a rotary cutter but may be a fixed cutter such as a single-edged cutter.

  In the method for producing a cyclic polyolefin film of the present invention, in the slitting step, preferably, a laser processing step (a step of irradiating a laser beam to process the film, sometimes simply referred to as laser processing hereinafter) is employed. There is little damage to the film, such as melting of the cut portion and poor appearance of the cut portion, and the shape of the cut portion is not disturbed even if the laser intensity fluctuates somewhat. In addition, the step of forming irregularities at both ends in the width direction of the film may be a step of processing by laser irradiation instead of the step of processing with a conventional embossed roller having formed irregularities, so that the predetermined irregular shape can be improved. Can be formed. Also, even if the film thickness specification changes, there is no need to replace it with an embossing roller corresponding to the film thickness as in the past, excessive laser intensity is unnecessary, and damage to the film such as damage to uneven parts is small, In addition, by adjusting the intensity of the laser beam, appropriate embossing can be easily performed, so that the film is excellent in productivity. Further, it is preferable that the irradiation position of the laser beam is made variable and the embossed portion is formed at a predetermined position according to the film width. Thus, by making the irradiation position of the laser beam variable, it is possible to easily form the unevenness of the embossed portion at either the end portion or the center portion in the width direction of the film, and it is possible to form the embossed portion so far. At the time of processing, there is no failure such as minute wrinkles or scratches on the film surface caused by pressing the embossing roller for pressing against the back roller, and the surface property of the film can be dramatically improved.

  Further, the laser processing step is not limited to cutting and embossing as described above, and may be laser processing performed during the film manufacturing process. Laser processing such as processing for roughening the surface or processing for providing grooves and irregularities may be used.

Further, in the present invention, when the laser light in the laser processing step is light in the far infrared region, the compound contained in the film is a compound that absorbs light in the wavelength region of 4 to 25 μm. For example, when the laser light is a CO ₂ laser, the wavelength of the laser light is 9.3 to 10.6 μm, and therefore, a compound absorbing a wavelength in this range is preferable.

  Further, in the present invention, when the laser light in the laser processing step is UV light in the ultraviolet region, the compound contained in the film, or the compound applied to the film surface, the wavelength range of 0.2 to 0.4 μm. It is a compound that absorbs light. For example, as a UV laser, there are a KrF excimer laser (wavelength 0.248 μm), a YAG-FHG laser (wavelength 0.266 μm), a YAG-THG laser (wavelength 0.355 μm), and the like. Absorbing compounds are preferred.

  Further, in the present invention, before the laser processing step, it is preferable that a portion of the film surface to be irradiated with the laser beam contains a compound absorbing the wavelength of the laser beam.

  Examples of the method for containing the component include application and spraying, but other methods may be used, and the means for containing the component is not particularly limited.

  By applying the compound to the laser-irradiated portion, for example, the amount of the compound used can be reduced, and the physical properties (color change, transparency, etc.) of the film area other than the laser-irradiated portion are affected by the compound. Never give. The method for applying the compound to the surface of the film is not particularly limited as long as a layer containing the compound having a required thickness can be formed, and an ink jet method, a roller coating method, or the like can be used.

By the way, laser light means “amplification of light by stimulated emission” (Light Amplif).
Iteration by Stimulated Emission of Radiatio
In the meaning of n), the laser light is classified into the CO ₂ laser light and the UV laser light according to the oscillation wavelength.

  Further, in the present invention, it is also preferable to wind and wind a tape 982 having an embossed or slitted surface at both ends of the film.

  FIG. 31A is a front view of a film roll 942 wound around a tape 982 on which embossed or slitted processing is wound on both ends of the film. FIG. 31 (B) is an enlarged view of a cross section of a portion A surrounded by a circle in FIG. 31 (A).

  Normally, when the film is wound around the winding shaft 934, the tape 982 having an embossed or slitted surface wound around both ends of the substrate Bo is not wound. Therefore, there is a problem that the film is damaged such as a scratch due to dust or winding deviation attached to the film.

  As in the present invention, by winding and winding the tape 982 embossed or slitted at both ends of the film o, it is possible to prevent the film from being damaged due to dust or misalignment. can do.

  FIG. 32 is an enlarged view of the tape 982, and FIG. 32 (A) shows the tape 982 when the tape 982 is sandwiched between the surface of the embossed tape and the film Bo. FIG. 32 (B) shows the surface of the tape subjected to the slit processing and the cross section when the tape 982 is sandwiched between the films Bo. It is a thing.

  By winding and winding an embossed or slitted tape 982 as shown in FIG. 32 around both ends of the film Bo, air can pass through the embossed or slitted tape 982, and the film roll 942. As a result, air can flow into and out of the central portion of the film Bo wound up. Therefore, air can flow into and out of the center of the film Bo wound up as a roll, so that knicks (bends, push marks) and wrinkles can be prevented.

  Here, the thickness X of the tape 982 is preferably 50 μm or more, and the embossing or slitting depth x is preferably in the range of 20 to 50% of the thickness of the tape.

  If the thickness X of the tape is less than 50 μm, the embossing or slit processing of the tape 982 will be crushed by the winding pressure. When the depth x of the embossing or slitting is less than 20% of the thickness X of the tape, the embossing or slitting of the tape is crushed by the winding pressure, and the film wound as the film roll 942 is formed. Air cannot enter or exit the center of Bo. If the depth x of the embossed or slitted portion is larger than 50% of the thickness X of the tape, the strength of the embossed or slitted portion is weak, and the shape processed by the winding pressure is crushed.

  In this manner, by winding and winding the tape 982 having been subjected to embossing or slit processing, it is possible to prevent the film surface and the film from being damaged by dust and the like, and to prevent the occurrence of knicks and wrinkles. can do.

  It is preferable that the film slitting device used in the present invention includes a disk-shaped rotating upper blade and a roll-shaped rotating lower blade.

  Here, the disk-shaped rotary blade of the slit device has a diameter of 30 to 300 mm and a thickness of a cut portion of 0.3 to 3 mm, and the material of the rotary blade is super steel, super steel fine particles, SKD. (Alloy tool steel) or SKH (high-speed tool steel). Further, the toe-in angle of the upper blade is preferably set to 30 to 90 degrees.

  The roll-shaped rotary lower blade preferably has a roll diameter of 75 to 200 mm, and the roll material of the rotary lower blade is preferably any of super steel, super steel fine particles, SKD, and SKH.

  The film slitting device used in the present invention may be constituted only by a disk-shaped rotating upper blade. In this case, the disk-shaped rotary upper blade of the slit device has a diameter of 30 to 300 mm and a thickness of a cut portion of 0.3 to 3 mm, and the material of the rotary upper blade is super steel, super steel fine particles, SKD. Or SKH.

  In the present invention, it is preferable that the temperature around the slitter is 20 to 50 ° C. and the humidity is 50 to 70% RH.

  Further, in the present invention, it is preferable to provide a suction device in which the periphery of the upper blade is formed as a box and suction is performed at a wind speed of 0.8 to 10 m / sec. In this case, the suction position of the end film is on the downstream side in the base transport direction from the slitting point.

  In the present invention, it is preferable to provide a mechanism for transporting the slit end film (film fragment) to the next trimming step, for example, to provide a mechanism for nip and / or sucking the slit end film. Is preferred.

  Further, it is preferable to provide a mechanism for nip and / or winding the slit end film.

  Here, the value obtained by dividing the draw ratio, that is, the speed of the nip and / or the film to be wound, by the speed of the slit end film is preferably 0.8 to 1.5.

  Further, it is preferable to set the suction pressure to -1000 to -100 Pa. And it is preferable to make a nip pressure into 0.1-17 MPa.

(7) Embossing (knurling) step The cyclic polyolefin film of the present invention preferably has embossed regions at both ends in the width direction of the film. The emboss has, in each emboss region, one or more convex rows substantially parallel to the transport direction. The convex rows are formed by forming convex areas intermittently or continuously in the transport direction. In this specification, a convex row in which a convex region is formed intermittently in the transport direction is referred to as an intermittent convex row, and a convex row in which the convex region is formed continuously in the transport direction is referred to as a continuous convex row. Shall be. When the convex array is an intermittent convex array, each individual convex region that intermittently configures the convex array is referred to as a convex region unit.

  The embossed regions at both ends in the width direction of the cyclic polyolefin film of the present invention preferably independently satisfy the following requirements (I) or (II). That is, the embossed regions at both ends may satisfy the requirement of (I), may satisfy the requirement of (II), or the embossed region at one end may satisfy the requirement of (I), and The edge embossed area may satisfy the requirement of (II). When the embossed regions at both ends satisfy the requirement of (I) or satisfy the requirement of (II) in common, the embossed regions at both ends may have symmetry about the center line in the width direction, Alternatively, they may be different from each other within a predetermined range. The embossed regions at both ends preferably satisfy the requirement (I) or the requirement (II) in common, and have symmetry about the center line in the width direction. Hereinafter, the requirements of (I) and (II) will be described in detail, but the description of these requirements is directed to the embossed area at one end. In this specification, when viewed from a direction perpendicular to the film surface, a pattern shape of a convex region included in an emboss region may be referred to as an emboss pattern.

  (I) When the embossed region has only two or more intermittent convex rows, the arrangement of the protruding area units of each intermittent convex row may be changed to any two adjacent ones in the transport direction so as to prevent the escape of entrained air. The control is performed between two convex area units and between any two adjacent convex rows in the width direction.

  In the requirement (I), the embossed region preferably has intermittent convex rows in 2 to 7 rows, more preferably 3 to 5 rows. More specifically, for example, in FIG. 33A, the film has three intermittent convex rows A1 in the emboss area A10 at one end in the width direction in parallel with the transport direction (MD direction). When the convex array is an intermittent convex array as described above, each of the convex regions constituting the intermittent convex array is referred to as a convex area unit, and is indicated by A2 in FIG. All the convex area units A2 in all the intermittent convex rows A1 usually have the same dimensions and are formed repeatedly at regular intervals in the transport direction.

  In the requirement (I), first, the arrangement of the convex area units is controlled between any two adjacent convex area units in the transport direction. More specifically, the distance x (mm) in the transport direction between any two adjacent convex area units A2 in the transport direction in each intermittent convex row A1 (see FIG. 33A) is the length of the convex area unit A2 in the transport direction. It is set to 0.4 or less, particularly 0.01 to 0.4, preferably 0.01 to 0.25 with respect to the thickness y (mm). If the ratio is too large, the air entangled in the film roll is not effectively retained over time, so that sticking, loosening, wrinkling, and breaking of the films cannot be sufficiently suppressed, and the winding deviation cannot be sufficiently suppressed.

  The distance x (mm) in the transport direction between the convex area units A2 is not particularly limited as long as the above ratio is achieved, and is usually in the range of 0.5 to 3 mm, and preferably in the range of 1 to 2 mm.

  The length y (mm) of the convex area unit A2 in the transport direction is not particularly limited as long as the object of the present invention is achieved, and is usually in the range of 3 to 20 mm, and preferably in the range of 5 to 10 mm.

  In the requirement (I), the arrangement of the convex area units is further controlled between any two adjacent convex rows in the width direction. Specifically, for any two adjacent rows in the width direction, any one of the protruding area units in one of the rows is in the transport direction in the other row in the vertical cross-sectional perspective view in the width direction. It arrange | positions so that it may overlap with two adjacent convex area units.

  More specifically, as shown in FIG. 33 (B), any one convex region unit A2a has two convex region units adjacent in the transport direction in adjacent convex rows on the upstream and downstream sides in the transport direction. A2b and A2c are arranged so as to overlap. FIG. 33 (B) shows that, when attention is paid to one convex area unit A2a in the film of FIG. 33 (A), the convex area unit A2c closest to the adjacent convex area unit A2a and the second convex area unit A2c in the adjacent intermittent convex row A1. FIG. 6 is a vertical cross-sectional perspective view in the width direction showing a relationship with a convex region unit A2b close to FIG. In such a vertical cross-sectional perspective view, if any one convex region unit overlaps only one adjacent convex region unit of the intermittent convex row, the air entrained in the film roll is not effectively retained over time. In addition, sticking, loosening, wrinkling and breaking of films cannot be sufficiently suppressed, and winding deviation cannot be sufficiently suppressed.

  In the perspective view perpendicular to the width direction, the overlapping portion of the convex area unit A2a with the upstream convex area unit A2b in the transport direction and the overlapping length with the transport area length Z1 (mm) and the convex area unit A2c on the downstream side in the transport direction. The smaller one of the lengths Z2 (mm) in the transport direction of the portion is 0.3 or more, particularly 0.3 to 0.5, with respect to the length y (mm) in the transport direction of the convex area unit. If the ratio is too small, the air entangled in the film roll is not effectively retained with time, so that sticking, loosening, wrinkling, and folding of the films cannot be sufficiently suppressed, and winding deviation cannot be sufficiently suppressed.

  In the present invention, the above-described relationship in which the convex region unit A2a overlaps with the convex region units A2b and A2c on the upstream side and the downstream side in the transport direction, respectively, is that any one convex region unit in any convex line and any adjacent convex line The condition is satisfied between the convex region unit, the nearest convex region unit, and the second closest convex region unit.

  The convex area unit A2 constituting the intermittent convex row A1 is raised at a predetermined height from an area where no convex area is formed. For example, in FIG. 33B, the convex area unit A2 (A2a, A2b, A2c) is floating at a predetermined height h from the surface A3 of the area where no convex area is formed. The height h is not particularly limited as long as the object of the present invention is achieved, and is usually from 1.5 to 30 μm on average, and preferably from 2 to 20 μm.

  In the embossed region A10, the area ratio of the convex region is in the range of 20% to 80%. If the area ratio of the protruding region is too small, the air entrained by the film roll is not effectively held, so that the effect of suppressing loosening and sticking cannot be obtained. If the area ratio of the convex region is too large, the winding air of the film roll becomes too large, and the loosening of the winding becomes worse.

  The area ratio of the convex region is a ratio of the total area of the convex region unit A2 to the entire area of the emboss region A10. The embossed area A10 is a minimum area divided by a straight line parallel to the transport direction so as to include all the convex areas at one end in the width direction of the film, and is, for example, an area indicated by oblique lines in FIG. is there.

  The distance a between the embossed area A10 and the end face of the film (see FIG. 33C), the width b of the embossed area A10 in the width direction (see FIG. 33C), and the distance between the convex rows adjacent in the width direction. (See FIG. 33C) is not particularly limited as long as the object of the present invention is achieved.

  The distance a is usually 10 mm or less, preferably 5 mm or less.

  The length b is usually in the range of 5 to 30 mm, preferably in the range of 10 to 20 mm.

  The distance c between the convex rows is not particularly limited as long as the area ratio of the convex region is achieved, and is usually in the range of 0.1 to 5 mm, preferably in the range of 0.5 to 2 mm.

  In the cyclic polyolefin film of the present invention, the length in the width direction, the length in the conveyance direction, and the film thickness in the non-embossed region A5 at the center in the width direction are not particularly limited.

  The length in the width direction is usually in the range of 500 to 4000 mm, preferably in the range of 1000 to 3000 mm, and more preferably in the range of 1300 to 3000 mm. Conventionally, the longer the length, the more difficult it is for air to get caught, but because the air escapes with the passage of time, loosening, wrinkles, and problems such as breakage are likely to occur. This is because such problems can be effectively suppressed even if the length is long.

  The length in the transport direction is usually in the range of 500 to 10000 m, preferably in the range of 2000 to 9000 m, and more preferably in the range of 3000 to 8000 m. Conventionally, the longer the length, the greater the amount of air to be entrained, while the air escapes with the lapse of time, so that problems such as loose winding, wrinkles, and breakage are likely to occur. This is because such problems can be effectively suppressed even if the length is long.

  The film thickness in the non-embossed region A5 is usually in the range of 10 to 200 μm, preferably in the range of 20 to 80 μm. The thinner the thickness, the more easily the cyclic polyolefin film is deformed, so that problems such as loose winding, wrinkles, and breakage are likely to occur. This is because it can be suppressed.

  In the emboss pattern shown in FIG. 34A, the convex area unit A2 has a rectangular shape, but is not particularly limited as long as the object of the present invention is achieved. ) Shape, hexagonal shape, cross shape, etc.

  FIGS. 34A to 34C show specific examples of the emboss pattern when the convex region unit A2 has a rhombus shape.

  FIGS. 34 (A) to 34 (C) are the same as FIGS. 33 (A) to 33 (C), respectively, except that the convex region unit A2 has a rhombic shape, and therefore description thereof is omitted. 33 (A) to 33 (C) in FIGS. 34 (A) to 34 (C) are the same as those in FIGS. 33 (A) to 33 (C) except that the shape of the convex region unit A2 is different. It has the same meaning as.

  In FIG. 34C, an area shown by oblique lines is an emboss area A10.

  (II) When the embossed region has one or more continuous convex rows, the embossed area may or may not further have intermittent convex rows. That is, all the convex rows of the embossed region may be composed of only one row or more, preferably 2 to 7 continuous convex examples, or 1 or more rows, preferably 1 to 7 continuous convex rows. It may be composed of rows and one or more rows, preferably 1 to 7 intermittent rows. As a specific example of the former case, for example, emboss patterns shown in FIGS. 35A to 35C can be exemplified. As an embodiment in the latter case, for example, emboss patterns shown in FIGS. 35A to 35C can be exemplified.

  FIGS. 35 (A) to 35 (C) are the same as FIGS. 33 (A) to 33 (C), respectively, except that all the convex rows are continuous convex rows, and therefore description thereof is omitted. I do. 33 (A) to 33 (C) in FIGS. 35 (A) to 35 (C) are the same as those in FIGS. 33 (A) to 33 (C) except that the convex rows are continuous. They have the same meaning.

  FIGS. 36 (A) to 36 (C) are similar to FIGS. 34 (A) to 34 (C) except that the embossed region has one continuous convex row and one intermittent convex row. Since they are the same, their description is omitted. The same reference numerals as in FIGS. 34 (A) to 34 (C) in FIGS. 36 (A) to 36 (C) indicate that the number of convex rows is different and that one convex row is a continuous convex row. 34 (A) to 34 (C).

  In particular, in requirement (II), as in requirement (I), the area ratio of the convex region in the embossed region A10 is in the range of 20 to 80%, and preferably in the range of 30 to 60%. If the area ratio of the convex region is too small, the air entrained by the film roll is not effectively held, so that the effect of suppressing loosening and sticking cannot be obtained. If the area ratio of the convex region is too large, the winding air of the film roll becomes too large, and the loosening of the winding becomes worse.

  The area ratio of the convex region is a ratio of the total area of the convex region unit A2 to the entire area of the emboss region A10. The embossed area A10 is a minimum area divided by a straight line parallel to the transport direction so as to include all the protruded areas at one end in the width direction of the film, and is, for example, a hatched area in FIGS. 34 (C) and 36 (C). This is the area indicated by.

  In the requirement (II), the intermittent convex array that the embossed region may have is not particularly limited, and may be, for example, the same intermittent convex array as in the requirement (I) or the intermittent convex array. Other intermittent convex rows may be used.

  The cyclic polyolefin film of the present invention is formed by other embossed patterns in addition to the intermittent convex rows and / or the continuous convex rows formed substantially parallel to the transport direction in the requirements of the above (I) and (II). It does not prevent the embossed region from having a convex region formed or a randomly (irregularly) formed convex region.

  In the present invention, in the knurling process for forming the embossed portion, the processing temperature of the knurling process is T (° C.), the glass transition temperature of the base film is Tg (° C.), and the time during which the base film is in contact with the emboss ring is s (seconds). ), It is preferable to perform a knurling process under the conditions satisfying the following relational expression to produce a roll-shaped film.

0.75 ≦ (T−Tg) × s ≦ 1.00
The time s (second) during which the base film is in contact with the embossing ring can be changed by changing the film transport speed, the nip width, in other words, the pressing pressure. The nip width and the pressing pressure can be changed by adjusting the hardness of the rubber on the surface of the back roll made of a rubber roll, or by changing the diameter of the emboss ring and the emboss back roll.

  In the above, if the value of (T−Tg) × s is less than 0.75, the embossed height cannot be sufficiently obtained, and the effective knurl in the wound state becomes low. This is not preferable because of the occurrence of unevenness or local deformation in the form of a convex, which does not satisfy the planarity of the film.

  Further, when the value of (T−Tg) × s exceeds 1.00, the emboss height is too large, and as a result, the effective knurl in the wound state is also high. It is not preferable because it is depressed in such a shape and the flatness of the film cannot be maintained. When the temperature during knurling, which is the value of T, is increased, the value of (T−Tg) × s also increases. In this case, the temperature of T is increased until the value of (T−Tg) × s exceeds 1.00. It is not preferable to increase the value because the whisker-like failure occurs.

  Further, in the present invention, it is preferable that cold air of 10 to 20 ° C. be applied to the film discharge side of the embossing marking roller during the knurling process. Here, when knurling is performed, the cold air of 10 to 20 ° C. is applied to the film discharge side of the embossing engraving roller because the resin portion melted by heat is cooled and solidified by cooling the film and the ring immediately after embossing. Therefore, the generation of thread-like foreign matter (whisker-like foreign matter) can be suppressed, and a sufficiently high emboss height can be obtained.

  The cyclic polyolefin film of the present invention preferably has an effective knurl defined by the following formula of the roll-shaped film of 0.5 to 7.0 μm.

Effective knurl = (cross-sectional area of roll of embossed section−cross-sectional area of core) / winding length−average film thickness In the above, if the effective knurl is 0.5 μm or more, the sticking failure between the films does not occur and the convex knurl is formed. The occurrence of local deformation is suppressed, and the flatness as a film is improved. When the effective knurl is 7.0 μm or less, the center of the winding does not dent into a shape like a horse back, and the flatness as a film is improved.

In the cyclic polyolefin film of the present invention, the number of mustache-like foreign matters adhering around the embossed portion of the roll-shaped film is preferably 0 to 50 / cm ² , and is 0 to 20 / cm ² . More preferably, it is more preferably 0 to 10 particles / cm ² .

In the above, the number of whisker-like foreign matter adhering to the embossed portions around the film is preferably as small as possible, and if the number of whisker foreign matter more than 50 / cm ^2, is removed in the cleaning device at the time of processing as a polarizing plate It is not preferable because it cannot be removed completely and enters as a foreign substance between the polarizer and the film and is incorporated into a liquid crystal display, resulting in image defects. The same applies to a case where a coating process such as an anti-reflection treatment or an anti-glare treatment is performed on the surface.

  Here, the height h (μm) of the embossed portion is set in a range of 0.05 to 0.3 times the film thickness H, and the width W is set in a range of 0.005 to 0.02 times the film width L. I do. The embossed portions may be formed on both sides of the film. In this case, the height h1 + h2 (μm) of the embossed portion is set in a range of 0.05 to 0.3 times the film thickness H, and the width W is set in a range of 0.005 to 0.02 times the film width L. . For example, when the film thickness is 40 μm, the height h1 + h2 (μm) of the embossed portion is preferably set in a range of 2 to 12 μm, and the width of the embossed portion is preferably set in a range of 5 to 30 mm.

  The lower limit of the height of the embossed portion is based on the height required to prevent partial adhesion unevenness between the films. On the other hand, the upper limit is higher than this, because the embossed portion is too high. This is because it is deformed into a polygonal shape, and causes a failure.

  As for the width of the embossed portion, it is desirable to reduce the width of the embossed portion because the embossed portion eventually becomes a loss portion. Necessary emboss width.

  However, it is also linked to the height of the above-mentioned embossed portion, and it is necessary to set the embossed portion height x embossed portion width that clears all of the convex shape, pyramid shape, horseback, polygonal shape, and winding failure.

  It is preferable that the film after embossing is wound by the following winding method.

  The winding method includes a straight winding step of winding the film around a core so that the side edges of the film are aligned, and after the straight winding step, the side edges are periodically formed in a certain range with respect to a width direction of the film. It is preferable to include an oscillating winding step of periodically vibrating the film or the core in the width direction of the film so as to shift the film around the core.

  In particular, when the winding length of the film reaches a predetermined switching winding length within a range of 10 to 30% with respect to the total winding length of the film, switching from the straight winding process to the oscillating winding process. Is preferred.

  The film winding device includes a film winding unit that rotates a winding core and winds the film around the winding core, and an oscillating unit that periodically shifts the film on the winding core within a certain range in a width direction of the film. Oscillating portion that vibrates the film or the core in the width direction of the film in conjunction with the winding of the film so as to be wound, and the winding length of the film reaches a predetermined switching winding length. In some cases, it is preferable to include a switching unit that switches the winding of the film from the straight winding to the oscillating winding.

  Hereinafter, the oscillating winding will be described.

  As shown in FIG. 37, the film production line B10 includes a film production device B11 and a winding device B12. The film manufacturing apparatus B11 manufactures a film B13 by a solution casting method. In the solution casting method, first, a dope is prepared using raw materials. Then, the prepared dope is cast on an endless support to form a casting film. When the casting film becomes self-supporting, the casting film is peeled from the endless support. The film B13 is formed by drying the peeled casting film with hot air or the like. The formed film B13 is sent to a winding device B12 via a knurling roller B15. The knurling roller B15 forms minute irregularities on both side edges (ears) in the width direction of the film B13 by embossing or the like. The height of the unevenness formed by the knurling roller is preferably in the range of 0.5 to 20 μm.

  As shown in FIGS. 37 and 38, the winding device B12 includes a winding shaft B19, a core holder B20, a core B21, a turret B22, guide rollers B23, B24, a dancer roller B25, an encoder B27, an oscillating portion B29, It includes a winding motor B30, a controller B31, and a dancer section B32. The film size or the like to be wound by the winding device B12 is not particularly limited. For example, the film is preferably a film having a total winding length in a range of 2000 to 10000 m and a width in a range of 500 to 2500 mm.

  As shown in FIG. 38, the winding shaft B19 is attached to the turret B22 by a cantilever support mechanism. The cantilever support mechanism is a mechanism that supports only one end of the winding shaft B19. A winding core B21 is attached to the winding shaft B19. Both ends of the core B21 are held by the core holder B20 of the winding shaft B19. The core holder B20 is slidably mounted in the axial direction (Y direction) of the winding shaft B19 and is non-rotatably attached to the winding shaft B19. A winding motor B30 is connected to one end of the winding shaft B19, and is configured to rotate the winding shaft B19. With this rotation, the core B21 also rotates, and the film B13 can be wound around the core B21. By winding the film B13, a film roll B38 in which the film B13 is wound in a roll shape is obtained.

  The turret B22 has a shift mechanism B28 attached to the attachment end of the winding shaft B19. The shift mechanism B28 reciprocates the core holder B20 in the axial direction on the winding shaft B19. The shift mechanism B28, the winding shaft B19, and the core holder B20 constitute an oscillating portion B29. By operating the oscillating portion B29, the core holder B20 is reciprocated in the Y direction on the winding shaft B19 by the shift mechanism B28, so that the position of the side edge B13a is in the range of the amplitude Wo every time the film B13 is laminated. Oscillating winding in which the film B13 is wound while being shifted within. When the oscillating portion B29 is not operated, straight winding in which both side edges of the film B13 are aligned can be performed. The switching between the straight winding and the oscillating winding is performed by the controller B31.

  Here, in the oscillating winding, the oscillating width Wo, which is the swing width, can be set arbitrarily, and the amplitude Wo is preferably in the range of 10 to 30 mm. In addition to fixing the value, the value may be gradually increased, decreased, or decreased after the increase.

  The guide rollers B23 and B24 and the dancer roller B25 guide the film B13 from the film manufacturing apparatus B11 in the transport direction (X direction). The dancer roller B25 adjusts the winding tension of the film B13 by moving the film B13 in the vertical direction (Z direction) by the shift mechanism B26. The shift mechanism B26 and the dancer roller B25 constitute a dancer section B32. The encoder B27 transmits an encoder pulse signal to the controller B31 every time the guide roller B24 rotates at a fixed rotation angle. The guide roller B24 may be provided with a tension sensor for measuring the winding tension of the film B13.

  The controller B31 controls driving of the oscillating unit B29, the winding motor B30, and the dancer unit B32. The controller B31 includes a winding information input unit B39, an LUT memory B40, a switching winding length specifying unit B41, a winding length measuring unit B42, and a switching determination unit B43. The winding information input section B39 receives winding information such as the total winding length, thickness, and width of the film B13, the outer diameter of the winding core B21, and the winding tension.

  The LUT memory B40 stores, for each winding information, the winding length (switching winding length) of the film B13 when switching from straight winding to oscillating winding. The winding length at the time of switching is preferably set in advance in the range of 10 to 30% with respect to the total winding length of the film B13, and is more preferably set in the range of 15 to 25% with respect to the entire length of the film B13. I have.

  The winding length at the time of switching is set in the above range for the following reason. As shown in FIG. 39, a graph B50 shows the relationship between the stress generated in the film B13 in the circumferential direction of the core B21 and the winding length. The circumferential stress of the film B13 is obtained based on the rotational torque of the core B21 and the tension of the dancer portion B32. When the rotational torque of the core B21 becomes larger than the tension by the dancer portion B32, the circumferential stress of the film B13 becomes positive, and when the rotational torque of the core B21 becomes smaller than the tension by the dancer portion B32. Becomes negative. As shown in FIG. 40, in the film roll B38 in which the film B13 is wound around the core B21, when a force is applied outward from the point P1 in the circumferential direction, the circumference of the film B13 at the point P1 is increased. The stress in the direction is said to be positive. When a force is applied in the circumferential direction toward the point P2, the circumferential stress at the point P2 of the film B13 is negative.

  The graph B50 in FIG. 39 is obtained in advance from a well-known stress calculation formula based on the tension at the start of winding and the tension at the end of winding of the film B13. The distribution pattern of the stress in the circumferential direction of the film B13 is determined by various values and negative values according to the parameters such as the thickness, width, winding length, and outer diameter of the winding core of each film and the changing state of the winding tension pattern. Are changed, but it is known from the result of film winding up to now that the distribution pattern is almost the same as that of FIG.

  As shown by the graph B50, the circumferential stress of the film B13 is positive (+) at the portion where the winding length on the core B21 side is small in the film roll B38. In FIG. 39, the reference numeral L1 is assigned to the winding length at which the stress decreases from the point where the winding length is 0 and changes to negative (-). Thus, at the beginning of winding, the circumferential stress decreases sharply as the winding length increases. Then, the stress in the circumferential direction further decreases and enters a negative (-) region. In FIG. 39, a reference sign LE is given to a winding length corresponding to completion of winding. In the negative (-) region, the stress in the circumferential direction indicates the minimum value Smin. In FIG. 39, a reference sign Lmin is given to a winding length in which the circumferential stress indicates the minimum value Smin. In the portion where the winding length exceeds Lmin, the circumferential stress gradually increases as the winding length increases, and enters a positive (+) region. A winding length that increases after the circumferential stress exhibits the minimum value Smin and changes to a positive value is denoted by a symbol L2. Here, when the stress in the circumferential direction of the film B13 is in the negative region, the rotation torque of the core B21 becomes larger than the tension of the dancer portion B32, and the film B13 is loosened. The surface pressure (surface pressure) decreases. A graph B51 in FIG. 41 shows a change in surface pressure at both end portions of the film B13 when the film is wound by straight winding, and a graph B52 in FIG. 42 shows a result when the film is wound by oscillating winding. The change in the surface pressure at the left end of the film B13 is shown, and the graph B53 shows the change in the surface pressure at the right end. As shown by the graphs B51 to B53, at the beginning of the winding of the film B13, the decrease in the surface pressure when the film is wound by the straight winding is relatively smaller than the decrease in the surface pressure when the film is wound by the oscillating winding. Note that the left end of the film B13 is the left end in the X direction, and the right end is the right end in the X direction.

  The decrease in the surface pressure at the start of winding the film B13 causes loosening or misalignment of the wound film roll B38. Therefore, as described above, while the surface pressure is reduced at the start of winding the film B13, that is, while the stress in the circumferential direction of the film B13 is in the negative region, the straight winding is performed, and then the winding length becomes the entire winding length. Is switched to the oscillating winding when the range becomes 10% to 30%. Thereby, at the beginning of winding of the film B13, the reduction in surface pressure can be suppressed by winding the film B13 straight, and when the circumferential stress of the film B13 escapes from the negative region, the film is wound by oscillating winding. Thereby, the surface pressure is dispersed in the left-right direction with respect to the width direction of the film B13, and the occurrence of ear extension can be reduced. The switching winding length previously determined as the timing of switching from the straight winding to the oscillating winding may be obtained based on the relationship between the circumferential stress and the winding length as shown in the graph B50 as in the present embodiment. When the winding length of the film B13 reaches the switching winding length thus obtained, the controller B31 switches from straight winding to oscillating winding. The timing for switching from the straight winding to the oscillating winding is more preferable when the winding length is in the range of 15 to 25% of the total winding length.

  Note that when switching from straight winding to oscillating winding when the winding length is 10% or more of the total winding length, the surface pressure sharply decreases at the beginning of winding the film B13 as compared with the case where switching is performed when the winding length is less than 10%. More reliably. For this reason, it is possible to more reliably prevent the film roll B38 from becoming loose or displaced. Further, when switching is performed after the winding length exceeds 30% of the total winding length, the film B13 is wound up by a straight winding even after the circumferential stress of the film B13 escapes from the negative region. In this case, the ear is more likely to be generated in the film roll B38 than in the case where the switching is performed at the time. Therefore, by switching from straight winding to oscillating winding when the winding length is 30% or less of the total winding length, the occurrence of ear extension can be more reliably prevented than when switching is performed after exceeding 30%. .

  The switching-time winding length specifying unit B41 collates the winding information stored in the LUT memory B40 with the winding information input to the winding information input unit B39, and performs switching corresponding to the input winding information. Specify the time volume. The winding length measuring unit B42 measures the winding length of the film B13 wound around the core B21 based on the encoder pulse signal from the encoder B27.

  The switching determination unit B43 determines whether or not the winding length measured by the winding length measurement unit B42 exceeds the switching winding length specified by the switching winding length specification unit B41. When it is determined that the winding length has exceeded the switching winding length, an oscillating winding start signal is transmitted to the oscillating unit B29. When the oscillating unit B29 receives the oscillating winding start signal, the oscillating unit B29 shifts the position of the side edge B13a within the range of the amplitude Wo from the straight winding in which the film B13 is wound so that the side edge B13a of the film is aligned. The winding of the film B13 is changed to the oscillating winding to be wound.

  Next, the operation of the winding device will be described with reference to the flowchart shown in FIG. First, the winding information of the film B13 to be wound is input to the winding information input section B39. The switching-time winding length specifying unit B41 compares the winding information input to the winding information input unit B39 with the winding information stored in the LUT memory B40, and performs switching corresponding to the input winding information. Specify the time volume.

  Then, winding of the film B13 is started by straight winding. At the time of winding, every time the guide roller B24 rotates at a fixed rotation angle, an encoder pulse signal is transmitted from the encoder B27 to the controller B31 at fixed time intervals. Based on the encoder pulse signal, the winding length of the film B13 is measured by the winding length measuring unit B42.

  The switching determination unit B43 sequentially determines whether the winding length measured by the winding length measurement unit B42 exceeds the switching-time winding length. When it is determined that the winding length has exceeded the switching winding length, an oscillating winding start signal is transmitted from the controller B31 to the oscillating unit B29. The oscillating unit B29 that has received the oscillating winding start signal vibrates the winding core B21 with a constant amplitude Wo along the axial direction (Y direction). Thereby, the winding of the film B13 is changed from the straight winding to the oscillating winding.

  When the winding of the film B13 is completed, the film roll B38 is removed from the winding shaft B19. The film roll B38 is transported to various factories by transport means such as a truck. At this time, since the inside of the core of the film roll B38 is formed into a straight winding, there is no loosening of the winding, and the winding of the film roll B38 does not shift even if there is a vibration or the like at the time of conveyance. In addition, since the outside of the core of the film roll B38 is oscillated, occurrence of ear extension is suppressed.

  In the above embodiment, the film B13 is wound by vibrating the core B21 in the width direction of the film B13. However, the method of oscillating winding is not limited to this method, and a known method may be used. For example, the film B13 itself may be vibrated in the width direction without moving the core B21.

(8) Return material collection (trimming process)
The returned material recovery is a process of recovering a portion of the film at the end in the width direction while transporting the film in the slit process (6). For example, the end portion where the trace is left due to being held by the tenter in the stretching step is removed. The cutting and collecting of the ends are usually performed at both ends in the width direction of the film. An appropriate amount of the recovered material is brought into a dissolving step, dissolved in a solvent, and provided for dope preparation.

  The trimming process includes an end cutting step of cutting the end in the width direction of the film and an end collecting step of collecting the cut end.

  In the edge cutting step, the film edge is cut by a fixed cutting means such as a cutter while the film is transported in the transport direction T, and the film body is provided to the next step such as a winding step.

  The length (width) x in the width direction of the cut end is not particularly limited, and such x is specifically, for example, preferably in a range of 30 to 300 mm, particularly preferably in a range of 50 to 130 mm. .

  In the end collecting step, the cut end of the film is collected from the suction port. The suction port usually has a cylindrical shape, especially a cylindrical shape, and suction is performed in a suction direction by a suction device. The suction speed is not particularly limited as long as the object of the present invention is achieved.

  At this stage, when the cut film end is collected from the suction port, the conveying air is supplied from the upstream side and the downstream side in the film conveyance direction toward the opening of the suction port to convey the film end b.・ Assist collection. The supply speed V1 of the transport wind from the upstream side and the supply speed V2 of the transport wind from the downstream side are each independently within a range of 100 to 6000%, preferably 500 to 5500% with respect to the film transport speed. And their ratio V1 / V2 is less than 1, especially in the range from 0.1 to 0.9, preferably in the range from 0.3 to 0.9. As a result, flapping and meandering of the cut end can be suppressed, and the cut and collection of the end can be performed sufficiently smoothly.

  The temperature T1 of the carrier air from the upstream side and the temperature T2 of the carrier air from the downstream side are not particularly limited, and are usually independently independently higher than the ambient temperature by a range of 0 to 50 ° C. By setting the temperatures T1 and T2 independently to be higher than the ambient temperature by a range of 0 to 50 ° C., particularly by a range of 0 to 45 ° C., the shrinkage difference between the support surface side and the non-support surface side at the film edge 80b is reduced. Can be reduced. As a result, meandering of the end portion can be more effectively suppressed, so that end clogging in the suction port and the pipe connected to the suction port can be more sufficiently suppressed. The ambient temperature is the temperature of the ambient atmosphere in which this step is performed, and the temperature at the center in the width direction on the surface of the support of the film in the edge cutting step is used, and can be measured by a non-contact thermometer.

  The temperature T1 of the conveying air is usually in the range of 30 to 170C, and particularly preferably in the range of 30 to 150C.

  The temperature T2 of the conveying air is usually in the range of 30 to 170C, and particularly preferably in the range of 30 to 150C.

  The ambient temperature is usually in the range of 30 to 120C, and particularly preferably in the range of 30 to 100C.

  The transport wind from the upstream side is supplied from the upstream supply device, and the transport wind from the downstream side is supplied from the downstream supply device. When the transport air is heated, the heating is performed by, for example, a hot air heater, a temperature control roll, an IR (infrared) heater, or the like as specific examples of the heating unit.

  The distance L1 between the supply port of the upstream supply device and the opening of the suction port and the distance L2 between the supply port of the downstream supply device and the opening of the suction port are more sufficient to prevent flapping and meandering of the cut end. From the viewpoint of suppressing the temperature, it is preferable that the width is independently 20 to 200 mm, particularly 30 to 180 mm.

  The angle θ1 formed between the supply direction of the conveying air from the upstream side and the suction direction (the conveying direction of the film end in the suction port) and the angle formed between the supply direction of the conveying air from the downstream side and the suction direction are defined by the present invention. It is not particularly limited as long as the object is achieved, and from the viewpoint of more sufficiently suppressing flapping and meandering of the cut end, each is independently in the range of 10 to 90 °, particularly in the range of 30 to 85 °. Is preferred.

  As the upstream supply device and the downstream supply device, those having a circular supply port are usually used.

  The amount of residual solvent in the film subjected to this step, particularly the edge cutting step, is preferably in the range of 0 to 50% by mass, particularly preferably in the range of 0 to 20% by mass. This is because the difference in shrinkage between the support surface side and the non-support surface side at the film end can be more effectively reduced while easily cutting the film end.

≫Materials constituting cyclic polyolefin film≫
Hereinafter, the materials used in the method for producing a cyclic polyolefin film of the present invention will be described in detail.

  The method for producing a cyclic polyolefin film of the present invention is characterized in that a cyclic polyolefin-based resin is dissolved using an organic solvent, and an additive is added for doping. Materials that can be used in the present invention are not limited to the following, and known materials can be appropriately used as constituent elements.

(1) Cyclic polyolefin-based resin Examples of the cyclic polyolefin-based resin according to the present invention include the following (co) polymers.

〔式中、Ｒ^１〜Ｒ^４は、それぞれ独立に、水素原子、炭化水素基、ハロゲン原子、ヒドロキシ基、エステル基、アルコキシ基、シアノ基、アミド基、イミド基、シリル基、又は極性基（すなわち、ハロゲン原子、ヒドロキシ基、エステル基、アルコキシ基、シアノ基、アミド基、イミド基、又はシリル基）で置換された炭化水素基である。ただし、Ｒ^１〜Ｒ^４は、二つ以上が互いに結合して、不飽和結合、単環又は多環を形成していてもよく、この単環又は多環は、二重結合を有していても、芳香環を形成してもよい。Ｒ^１とＲ^２とで、又はＲ^３とＲ^４とで、アルキリデン基を形成していてもよい。ｎとｍは、ｎ＋ｍ＝１、ｎ＝０．２〜１、ｍ＝０〜０．８の関係にある。〕
［１］上記一般式（Ｉ）で表される特定単量体の開環重合体。

[Wherein, R ^{1 to} R ⁴ each independently represent a hydrogen atom, a hydrocarbon group, a halogen atom, a hydroxy group, an ester group, an alkoxy group, a cyano group, an amide group, an imide group, a silyl group, or a polar group ( That is, it is a hydrocarbon group substituted with a halogen atom, a hydroxy group, an ester group, an alkoxy group, a cyano group, an amide group, an imide group, or a silyl group). However, two or more of R ^{1 to} R ⁴ may be bonded to each other to form an unsaturated bond, a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring has a double bond. Or an aromatic ring may be formed. R ¹ and R ² or R ³ and R ⁴ may form an alkylidene group. n and m have a relationship of n + m = 1, n = 0.2 to 1, and m = 0 to 0.8. ]
[1] A ring-opened polymer of the specific monomer represented by the general formula (I).

  [2] A ring-opening copolymer of the specific monomer represented by the general formula (I) and a copolymerizable monomer.

  [3] A hydrogenated (co) polymer of the ring-opened (co) polymer of the above [1] or [2].

  [4] A (co) polymer obtained by cyclizing the ring-opened (co) polymer of the above [1] or [2] by Friedel-Crafts reaction and then hydrogenating it.

  [5] A saturated copolymer of the specific monomer represented by the general formula (I) and an unsaturated double bond-containing compound.

  [6] Addition type (co) of at least one monomer selected from the specific monomer represented by the general formula (I), the vinyl-based cyclic hydrocarbon-based monomer, and the cyclopentadiene-based monomer Polymers and their hydrogenated (co) polymers.

  [7] An alternating copolymer of the specific monomer represented by the general formula (I) and an acrylate.

(Specific monomer)
Specific examples of the specific monomer include the following compounds, but the present invention is not limited to these specific examples.
Bicyclo [2.2.1] hept-2-ene,
Tricyclo [4.3.0.12,5] -8-decene,
Tricyclo [4.4.0.12,5] -3-undecene,
Tetracyclo [4.4.0.12,5.17,10] -3-dodecene,
Pentacyclo [6.5.1.13, 6.02, 7.09, 13] -4-pentadecene;
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-cyanobicyclo [2.2.1] hept-2-ene,
8-methoxycarbonyltetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8-ethoxycarbonyltetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8-n-propoxycarbonyltetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8-isopropoxycarbonyltetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8-n-butoxycarbonyltetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.12,5.17,10] -3-dodecene;
5-ethylidenebicyclo [2.2.1] hept-2-ene,
8-ethylidenetetracyclo [4.4.0.12,5.17,10] -3-dodecene;
5-phenylbicyclo [2.2.1] hept-2-ene,
8-phenyltetracyclo [4.4.0.12,5.17,10] -3-dodecene;
5-fluorobicyclo [2.2.1] hept-2-ene,
5-fluoromethylbicyclo [2.2.1] hept-2-ene,
5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-pentafluoroethylbicyclo [2.2.1] hept-2-ene,
5,5-difluorobicyclo [2.2.1] hept-2-ene,
5,6-difluorobicyclo [2.2.1] hept-2-ene,
5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,5,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5-heptafluoro-iso-propyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene,
8-fluorotetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8-fluoromethyltetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8-difluoromethyltetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8-trifluoromethyltetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8-pentafluoroethyltetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8,8-difluorotetracyclo [4.4.0.12,5.17,10] -3-dodecene,
8,9-difluorotetracyclo [4.4.0.12,5.17,10] -3-dodecene,
8,8-bis (trifluoromethyl) tetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8-methyl-8-trifluoromethyltetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8,8,9-trifluorotetracyclo [4.4.0.12,5.17,10] -3-dodecene,
8,8,9-tris (trifluoromethyl) tetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8,8,9,9-tetrafluorotetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8,8,9,9-tetrakis (trifluoromethyl) tetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8,8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.12,5.17,10] -3-dodecene,
8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.12,5.17,10] -3-dodecene,
8,8,9-trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8,9-difluoro-8-heptafluoroiso-propyl-9-trifluoromethyltetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8-chloro-8,9,9-trifluorotetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.12,5.17,10] -3-dodecene;
8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.12,5.17,10] -3-dodecene and the like can be mentioned.

  These can be used alone or in combination of two or more.

Preferred among the specific monomers are those in which R ¹ and R ³ are a hydrogen atom or a hydrocarbon group having 1 to 10, more preferably 1 to 4, and particularly preferably 1 to 2 in the above general formula (I). R ² and R ⁴ are a hydrogen atom or a monovalent organic group, and at least one of R ² and R ⁴ is a polar group having a polarity other than a hydrogen atom and a hydrocarbon group; And p is an integer of 0 to 3, more preferably m + p = 0 to 4, still more preferably 0 to 2, particularly preferably m = 1 and p = 0. The specific monomer having m = 1 and p = 0 is preferable in that the resulting cyclic polyolefin-based resin has a high glass transition temperature and excellent mechanical strength.

  Examples of the polar group of the specific monomer include a carboxy group, a hydroxy group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, and a cyano group.These polar groups include a linking group such as a methylene group. And may be bonded via In addition, a hydrocarbon group to which a divalent organic group having a polarity such as a carbonyl group, an ether group, a silyl ether group, a thioether group, and an imino group is bonded as a linking group is also exemplified as the polar group. Among these, a carboxy group, a hydroxy group, an alkoxycarbonyl group or an alloxycarbonyl group is preferable, and an alkoxycarbonyl group or an allyloxycarbonyl group is particularly preferable.

Further, a monomer in which at least one of R ² and R ⁴ is a polar group represented by the formula — (CH ₂ ) n COOR is obtained from a cyclic polyolefin resin having a high glass transition temperature, a low hygroscopicity, and various materials. It is preferable in that it has excellent adhesion. In the above formula relating to the specific polar group, R is a hydrocarbon group having 1 to 12, more preferably 1 to 4, particularly preferably 1 to 2 carbon atoms, preferably an alkyl group. In addition, n is usually 0 to 5. However, a smaller value of n is preferable because the glass transition temperature of the obtained cyclic polyolefin-based resin is higher. Further, the specific monomer in which n is 0 is preferable. It is preferable in that the synthesis is easy.

In the above general formula (I), R ¹ or R ³ is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, particularly preferably a methyl group. preferably, in particular, the alkyl group is the above formula - that is coupled to the (CH ₂₎ the same carbon atom and the carbon atom to which specific polar group is bonded, represented by nCOOR is, of the resulting cyclic polyolefin resin This is preferable in that the hygroscopicity can be reduced.

(Copolymerizable monomer)
Specific examples of the copolymerizable monomer include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene.

  The carbon number of the cycloolefin is preferably from 4 to 20, and more preferably from 5 to 12. These can be used alone or in combination of two or more.

  The preferred use range of the specific monomer / copolymerizable monomer is in the range of 100/0 to 50/50 by mass ratio, and more preferably in the range of 100/0 to 60/40.

(Ring-opening polymerization catalyst)
In the present invention, the ring-opening polymerization reaction for obtaining (i) a ring-opening polymer of a specific monomer and (ii) a ring-opening copolymer of a specific monomer and a copolymerizable monomer is performed by metathesis. It is performed in the presence of a catalyst.

The metathesis catalyst includes (a) at least one selected from compounds of W, Mo, and Re; (b) a group IA element (eg, Li, Na, K, etc.) of the Deming periodic table; and a group IIA element (eg, Li, Na, K). , Mg, Ca, etc.), Group IIB elements (eg, Zn, Cd, Hg, etc.), Group IIIA elements (eg, B, Al, etc.), Group IVA elements (eg, Si, Sn, Pb, etc.), or Group IVB A catalyst which is a compound of an element (for example, Ti, Zr or the like) and which is a combination with at least one selected from those having at least one of the element-carbon bond or the element-hydrogen bond. In this case, in order to enhance the activity of the catalyst, an additive (c) described below may be added.

Representative examples of W, Mo or Re compounds suitable as the component (a) include, for example, WCl ₆ , MoCl ₆ , ReOCl _{3 and the} like, JP-A-1-132626, page 8, lower left column, line 6 to page 8, upper right. The compounds described in column, line 17 can be mentioned.

Specific examples of the component (b) include nC ₄ H ₉ Li, (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , (C ₂ H ₅ ) AlCl ₂ , methylalumoxane, LiH, etc., compounds described in JP-A-1-132626, page 8, upper right column, line 18 to page 8, lower right column, line 3 can be exemplified.

  As typical examples of the component (c), which is an additive, alcohols, aldehydes, ketones, amines and the like can be suitably used, and furthermore, JP-A-1-132626, p. The compounds shown in line 16 to page 9, upper left column, line 17 can be used.

  The amount of the metathesis catalyst used is such that the molar ratio of the component (a) to the specific monomer is such that the “component (a): specific monomer” is usually from 1: 500 to 1: 50000, preferably. Is in the range of 1: 1000 to 1: 10000.

  The ratio of the component (a) to the component (b) is such that (a) :( b) is in the range of 1: 1 to 1:50, preferably 1: 2 to 1:30 in terms of metal atom ratio.

  The molar ratio of component (a) to component (c) is such that (c) :( a) is in the range of 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1. You.

(Polymerization reaction solvent)
Examples of the solvent used in the ring-opening polymerization reaction (the solvent constituting the molecular weight modifier solution, the solvent for the specific monomer and / or the metathesis catalyst) include alkanes such as pentane, hexane, heptane, octane, nonane, and decane; Cyclohexanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, Compounds such as halogenated alkanes and aryl halides such as chloroform and tetrachloroethylene; saturated carboxylic acids such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate and dimethoxyethane Ester ethers, dibutyl ether, tetrahydrofuran, and the like can be illustrated ethers such as dimethoxyethane, they can be used alone or in combination. Of these, aromatic hydrocarbons are preferred.

  The amount of the solvent used is such that "solvent: specific monomer (mass ratio)" is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1. You.

(Molecular weight regulator)
The molecular weight of the obtained ring-opened (co) polymer can be controlled by the polymerization temperature, the type of catalyst, and the type of solvent. In the present invention, the molecular weight is controlled by coexisting a molecular weight modifier in the reaction system. I do.

  Here, suitable molecular weight regulators include, for example, α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. Styrene can be mentioned, among which 1-butene and 1-hexene are particularly preferred.

  These molecular weight regulators can be used alone or in combination of two or more.

  The amount of the molecular weight modifier used is 0.005 to 0.6 mol, preferably 0.02 to 0.5 mol, per 1 mol of the specific monomer subjected to the ring-opening polymerization reaction.

  (Ii) In order to obtain a ring-opening copolymer, in the ring-opening polymerization step, a specific monomer and a copolymerizable monomer may be subjected to ring-opening copolymerization, and furthermore, polybutadiene, polyisoprene, etc. In the presence of unsaturated hydrocarbon polymers containing two or more carbon-carbon double bonds in the main chain of conjugated diene compounds, styrene-butadiene copolymers, ethylene-non-conjugated diene copolymers, polynorbornene, etc. The specific monomer may be subjected to ring-opening polymerization.

The ring-opened (co) polymer obtained as described above can be used as it is, but (iii) a hydrogenated (co) polymer obtained by further hydrogenating the polymer has a high impact resistance. Useful as a raw material for

(Hydrogenation catalyst)
The hydrogenation reaction is carried out in a usual manner, that is, a hydrogenation catalyst is added to a solution of the ring-opening polymer, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm is added to the solution at 0 to 200 ° C, preferably 20 to 200 atm. It is performed by operating at ~ 180 ° C.

  As the hydrogenation catalyst, those used in ordinary hydrogenation reactions of olefinic compounds can be used. The hydrogenation catalyst includes a heterogeneous catalyst and a homogeneous catalyst.

  Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst substance such as palladium, platinum, nickel, rhodium and ruthenium is supported on a carrier such as carbon, silica, alumina and titania. Examples of homogeneous catalysts include nickel / triethylaluminum naphthenate, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, and chlorotris (triphenylphosphine) rhodium. , Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium and the like. The form of the catalyst may be powder or granular.

These hydrogenation catalysts are used at a ratio of a ring-opening (co) polymer: hydrogenation catalyst (mass ratio) of 1: 1 × 10 ⁻⁶ to 1: 2.

  As described above, the hydrogenated (co) polymer obtained by hydrogenation has excellent thermal stability, and its properties are degraded by heating during molding and use as a product. There is no. Here, the hydrogenation rate is usually 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition, the hydrogenation rate of the hydrogenated (co) polymer is at least 50%, preferably at least 90%, more preferably at least 98%, most preferably at least 99%, as measured by ¹ H-NMR at 500 MHz. is there. The higher the hydrogenation rate, the more excellent the stability to heat and light becomes, and when the cyclic polyolefin film of the present invention is used as a wave plate, long-term stable characteristics can be obtained.

  The hydrogenated (co) polymer used as the cyclic polyolefin-based resin according to the present invention preferably has a gel content of 5% by mass or less contained in the hydrogenated (co) polymer. It is particularly preferred that the content be 1% by mass or less.

  Further, as the cyclic polyolefin resin according to the present invention, (iv) the ring-opened (co) polymer of the above (i) or (ii) is cyclized by a Friedel-Crafts reaction and then hydrogenated (co) polymer. Can also be used.

(Cyclization by Friedel Craft reaction)
The method for cyclizing the ring-opened (co) polymer of (i) or (ii) by the Friedel-Crafts reaction is not particularly limited, but the acidic compound described in JP-A-50-154399 is used. The known method can be adopted. As the acidic compound, specifically, a Lewis acid such as AlCl ₃ , BF ₃ , FeCl ₃ , Al ₂ O ₃ , HCl, CH ₃ ClCOOH, zeolite, or activated clay, or a Bronsted acid is used.

  The cyclized ring-opened (co) polymer can be hydrogenated similarly to the ring-opened (co) polymer of (i) or (ii).

  Further, as the cyclic polyolefin-based resin of the present invention, (v) a saturated copolymer of the above specific monomer and an unsaturated double bond-containing compound can also be used.

<Unsaturated double bond-containing compound>
Examples of the unsaturated double bond-containing compound include olefin compounds having preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, such as ethylene, propylene and butene.

  The preferred use range of the specific monomer / unsaturated double bond-containing compound is 90/10 to 40/60 by mass ratio, and more preferably 85/15 to 50/50.

  In the present invention, in order to obtain (v) a saturated copolymer of a specific monomer and an unsaturated double bond-containing compound, a usual addition polymerization method can be used.

(Addition polymerization catalyst)
As the catalyst for synthesizing the saturated copolymer (v), at least one selected from a titanium compound, a zirconium compound and a vanadium compound, and an organoaluminum compound as a promoter are used.

  Here, as the titanium compound, titanium tetrachloride, titanium trichloride and the like can be mentioned, and as the zirconium compound, bis (cyclopentadienyl) zirconium chloride and bis (cyclopentadienyl) zirconium dichloride can be mentioned.

Further, as the vanadium compound,
General formula VO (OR) aXb or V (OR) cXd
[Where R is a hydrocarbon group, X is a halogen atom, and 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ (a + b) ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 .Ltoreq. (C + d) .ltoreq.4. ]
Or an electron-donating adduct thereof.

  Examples of the electron donor include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonia, amines, Examples include nitrogen-containing electron donors such as nitriles and isocyanates.

  Further, as the organoaluminum compound as the co-catalyst, at least one selected from compounds having at least one aluminum-carbon bond or aluminum-hydrogen bond is used.

  In the above, for example, when a vanadium compound is used, the ratio of the vanadium compound to the organoaluminum compound is such that the ratio of aluminum atoms to vanadium atoms (Al / V) is 2 or more, preferably 2 to 50, particularly preferably 3 to 20. Range.

  As the solvent for the polymerization reaction used for the addition polymerization, the same solvent as that used for the ring-opening polymerization reaction can be used. Adjustment of the molecular weight of the obtained (v) saturated copolymer is usually performed using hydrogen.

  Further, as the cyclic polyolefin-based resin of the present invention, (vi) an addition type of the above-mentioned specific monomer and one or more monomers selected from vinyl-based cyclic hydrocarbon-based monomers and cyclopentadiene-based monomers Copolymers and their hydrogenated copolymers can also be used.

(Vinyl cyclic hydrocarbon monomer)
Examples of the vinyl cyclic hydrocarbon monomer include, for example, vinyl cyclopentene monomers such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene, 4-vinylcyclopentane, 4-isopropenylcyclopentane, and the like. 5-membered ring hydrocarbon-based monomer such as vinylcyclopentane-based monomer, 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-isopropenylcyclohexene, 2-methyl-4-vinyl Vinylcyclohexene monomers such as cyclohexene and 2-methyl-4-isopropenylcyclohexene; vinylcyclohexane monomers such as 4-vinylcyclohexane and 2-methyl-4-isopropenylcyclohexane; styrene; α-methylstyrene; 2-methylstyrene, 3- Styrene monomers such as styrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-phenylstyrene, p-methoxystyrene, d-terpene, 1-terpene, diterpene, d-limonene, 1- Terpene monomers such as limonene and dipentene; vinylcycloheptene monomers such as 4-vinylcycloheptene and 4-isopropenylcycloheptene; 4-vinylcycloheptane and 4-isopropenylcycloheptane; And vinylcycloheptane-based monomers. Preferred are styrene and α-methylstyrene. These can be used alone or in combination of two or more.

(Cyclopentadiene monomer)
Examples of the cyclopentadiene monomer used for the monomer of the (vi) addition copolymer used in the present invention include cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, and 2-ethylcyclopentadiene. Examples include pentadiene, 5-methylcyclopentadiene, and 5,5-methylcyclopentadiene. Preferred is cyclopentadiene. These can be used alone or in combination of two or more.

  The addition type (co) polymer of at least one kind of monomer selected from the above-mentioned specific monomer, vinyl-based cyclic hydrocarbon-based monomer and cyclopentadiene-based monomer is the above-mentioned (v) specific monomer And an unsaturated double bond-containing compound.

  Further, the hydrogenated (co) polymer of the addition type (co) polymer can be obtained by the same hydrogenation method as the hydrogenated (co) polymer of the (iii) ring-opening (co) polymer. .

  Further, as the cyclic polyolefin-based resin of the present invention, (vii) an alternating copolymer of the above-mentioned specific monomer and acrylate can also be used.

(Acrylate)
(Vii) Examples of the acrylate used in the production of the alternating copolymer of the specific monomer and the acrylate used in the present invention include, for example, methyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate and the like having 1 to 20 carbon atoms. Linear, branched or cyclic alkyl acrylates, glycidyl acrylates, acrylates having 2 to 20 carbon atoms such as 2-tetrahydrofurfuryl acrylate, and aromatic rings having 6 to 20 carbon atoms such as benzyl acrylate An acrylate having a polycyclic structure having 7 to 30 carbon atoms, such as a group-containing acrylate, isobornyl acrylate, and dicyclopentanyl acrylate, may be used.

  In the present invention, (vii) in order to obtain an alternating copolymer of the specific monomer and acrylate, in the presence of a Lewis acid, when the total of the specific monomer and acrylate is 100 mol, usually, The specific monomer is 30 to 70 mol, the acrylate is 70 to 30 mol, preferably the specific monomer is 40 to 60 mol, and the acrylate is 60 to 40 mol, particularly preferably the specific monomer. Radical polymerization is carried out at a ratio of 45 to 55 mol of the body and 55 to 45 mol of the acrylate.

  (Vii) The amount of the Lewis acid used to obtain the alternating copolymer of the specific monomer and the acrylate is 0.001 to 1 mol based on 100 mol of the acrylate. In addition, a known organic peroxide or an azobis-based radical polymerization initiator that generates a free radical can be used, and the polymerization reaction temperature is usually −20 to 80 ° C., preferably 5 to 60 ° C. As the solvent for the polymerization reaction, the same solvent as that used in the ring-opening polymerization reaction can be used.

  In the present invention, the term "alternate copolymer" means that the structural unit derived from the specific monomer is not adjacent, that is, the structural unit derived from the specific monomer is always adjacent to the acrylate. It means a copolymer having a structure as a unit, and does not deny a structure in which acrylate-derived structural units are adjacent to each other.

  The preferred molecular weight of the cyclic polyolefin resin according to the present invention is 0.2 to 5 dl / g, more preferably 0.3 to 3 dl / g, particularly preferably 0.4 to 1.5 dl / g in intrinsic viscosity [η] inh. g, and the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) is 8,000 to 100,000, more preferably 10,000 to 80,000, particularly preferably 12,000 to 50,000, and the weight average molecular weight (Mw). ) Is preferably in the range of 20,000 to 300,000, more preferably 30,000 to 250,000, particularly preferably 40,000 to 200,000.

  Intrinsic viscosity [η] inh, the number average molecular weight and the weight average molecular weight are in the above range, the heat resistance, water resistance, chemical resistance, mechanical properties of the cyclic polyolefin resin and the cyclic polyolefin film of the present invention. Good moldability is obtained.

  The glass transition temperature (Tg) of the cyclic polyolefin resin according to the present invention is usually 110 ° C. or higher, preferably 110 to 350 ° C., more preferably 120 to 250 ° C., and particularly preferably 120 to 220 ° C. When Tg is lower than 110 ° C., it is not preferable because it is deformed by use under high temperature conditions or by secondary processing such as coating and printing. On the other hand, when Tg exceeds 350 ° C., molding becomes difficult, and the possibility of deterioration of the resin due to heat during molding increases.

  As long as the effects of the present invention are not impaired, a specific hydrocarbon-based resin described in, for example, JP-A-9-221577 and JP-A-10-287732, or a known heat-sensitive resin may be used as the cyclic polyolefin-based resin. A plastic resin, a thermoplastic elastomer, a rubbery polymer, organic fine particles, inorganic fine particles, and the like may be blended.

In the cyclic polyolefin-based resin according to the present invention, foreign particles having a particle diameter of 0.5 μm or more are 3 × 10 ⁴ particles / g or less, preferably 1 × 10 ⁴ particles / g or less, more preferably 0.5 × 10 ⁴ particles. / G or less. One in which the amount of foreign particles having a particle size of 0.5 μm or more in the cyclic polyolefin resin is reduced is disclosed in, for example, JP-A-3-57615. The number is at least about 6 × 10 ⁴ / g, which is insufficient to eliminate the generation of foreign particles in ultrasonic cleaning or the like.

  The content of foreign matter in the cyclic polyolefin-based resin can be measured using a light scattering type fine particle detector. The shape of the foreign matter is usually granular, but is not limited thereto. The contents of the foreign matter include not only impurities mixed from the outside, but also all of those which are not compatible with the cyclic polyolefin resin, such as a catalyst residue, a gelled product, and a by-product. Particles having a particle diameter of 0.5 μm or more measured using a light scattering type fine particle detector are regarded as foreign substances. The method for producing a cyclic polyolefin-based resin having a small content of foreign substances having a particle diameter of 0.5 μm or more is not particularly limited. For example, a solution in which a cyclic polyolefin-based resin is dissolved is prepared by: Hereinafter, a method of filtering at least twice with a mechanical filter preferably having a size of 0.3 μm or less, and (2) a method of filtering with a filter having a charge trapping function can be exemplified. Among these methods, the method of (2) using a filtration filter having a charge trapping function has a high ability to remove fine foreign substances, and the filtration by a mechanical filter with openings can remove fine foreign substances that pass through. This is preferable because the generation of foreign matter due to the re-aggregation of the particles is prevented.

  The solution in which the cyclic polyolefin resin is dissolved is usually a polymer-containing solution obtained by (co) polymerizing a cyclic olefin monomer or a vinyl compound copolymerizable with the cyclic olefin monomer, or after a hydrogenation reaction. Is used as it is. The concentration of the polymer-containing solution at the time of filtration is usually in the range of 1 to 40% by mass, preferably in the range of 5 to 35% by mass, and more preferably in the range of 10 to 30% by mass. If the concentration of the polymer-containing solution is too low, it is necessary to treat a large amount of the solvent. Conversely, if the concentration of the solution is too high, the filterability decreases. The concentration of the solution after the polymerization reaction or after the hydrogenation reaction is usually about 10 to 25% by mass, so that the filtration may be performed without concentration or dilution.

  A filter having a charge trapping function is a filter that electrically traps and removes a charged foreign substance, and usually uses a filter medium to which a charge is applied. Generally, a zeta potential filtration filter in which the zeta potential is controlled is used. As the zeta potential filtration filter, generally, for example, cellulose fiber / silica / positive charge modifier (polyamine epichlorohydrin resin, aliphatic polyamine, etc.) described in JP-T-4-504379 A filter in which a positive charge modifying agent is added to a filter medium such as described above is used.

  Other filter media include, for example, a fiber or membrane filter such as polypropylene, polyethylene, and PTFE, a cellulose fiber filter, a glass fiber filter, an inorganic filter such as diatomaceous earth, and a metal fiber filter. Can be Examples of other positive charge modifiers include melamine formaldehyde cationic colloid, inorganic cationic colloid silica, and the like. On the market, a positive charge denaturing filter is sold by Cuno under the trademark "Zetaplus". Filtration with a filtration filter having a charge trapping function is not always high, so that it is usually performed in combination with a mechanical filtration filter. The order of combination is not particularly limited, but is usually a mechanical filtration filter, and then a charge trapping filter.

  The mechanical filtration filter is not particularly limited as long as it is not adversely affected by the solvent. For example, a fiber or membrane filter made of polypropylene, polyethylene, PTFE, etc., a cellulose fiber filter, a glass fiber Filters, inorganic filters such as diatomaceous earth, and metal fiber filters. The diameter of the mechanical filtration filter is not particularly limited, but is usually 10 μm or less, preferably 5 μm or less, more preferably 1 μm or less. These mechanical filtration filters can be used alone or in combination of two or more.

  When a filter having a charge trapping function is not used, this can be achieved by repeating the filtration operation twice or more using a mechanical filtration filter having a diameter of 0.5 μm or less, preferably 0.3 μm or less. The filtrate after filtration is heated under reduced pressure to remove volatile components in a closed system so that foreign substances do not enter from the external environment. For example, in a clean environment such as in a clean room, the cleanness is rated at class 1000. In the following, cooling and pelletizing can be performed in an environment strictly controlled, preferably to class 100 or less.

  In the cyclic polyolefin film of the present invention, it is preferable to use two or more kinds of different cyclic polyolefin-based resins, because the solubility of foreign substances caused by additives increases and the effect of reducing foreign substance failure becomes remarkable. It is presumed that the foreign matter caused by the additive that does not dissolve in one of the cyclic olefins is compatible with the cyclic olefin having a different polarity, so that the foreign matter is significantly reduced.

  When two types are used, the mixing ratio of the secondary cyclic polyolefin resin (B) to the primary cyclic polyolefin resin (A) is preferably in the range of 95: 5 to 50:50 by mass. When three or more types are mixed, the mixing ratio can be appropriately selected depending on the effect.

  As the cyclic polyolefin-based resin described above, commercially available products can be preferably used. Examples of the commercially available products are commercially available from JSR Corporation under the trade names Arton G, Arton F, Arton R, and Arton RX. Zeonor ZF14, ZF16, Zeonex 250 or Zeonex 280 are commercially available from Zeon Corporation, and these can be used.

(2) Cellulose Acylate In the cyclic polyolefin film of the present invention, by adding a very small amount of a cellulose acylate-based resin into the dope, the solubility of foreign substances caused by additives is increased, and the effect of reducing foreign substance failure becomes remarkable. It is presumed that foreign matter caused by additives that do not dissolve in the cyclic polyolefin-based resin is compatible with the highly polar cellulose acylate-based resin, so that the foreign matter is significantly reduced.

  In addition, it is preferable to use a small amount of cellulose acylate in combination with the viewpoint of improving coatability when coating the functional layer on the surface of the film and reducing repelling and uneven coating. Further, by incorporating the cellulose acylate resin, the adhesion to the hard coat substrate is increased, and the hardness as the hard coat film can be increased.

  Particularly preferred cellulose acylates include those having a substitution degree of an acyl group in the range of 2.50 to 2.98, and the acyl group is at least one selected from an acetyl group, a propionyl group and a butyryl group. . Specifically, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose propionate, cellulose butyrate, cellulose acetate propionate butyrate, and the like, and in the present invention, cellulose triacetate, cellulose Acetate propionate and cellulose acetate butyrate are preferred. The degree of substitution of the acetyl group is preferably 1.40 or more. There is no particular limitation on cellulose used as a raw material of cellulose acylate, and cotton linter, wood pulp, kenaf and the like can be used. These may be mixed and used. The ratio of cellulose acylate synthesized from cotton linter is preferably 60% by mass or more, more preferably 85% by mass or more, and most preferably 100% by mass. The method for synthesizing cellulose acylate is not particularly limited. For example, it can be synthesized by the method described in JP-A-10-45804. The method for measuring the degree of substitution of the acyl group can be measured by ASTM-D817-96. The number average molecular weight of the cellulose acylate is preferably in the range of 70,000 to 300,000, and more preferably in the range of 80,000 to 200,000 in order to obtain a preferable mechanical strength as a protective film for a polarizing plate.

(3) Organic thickener In the method for producing a cyclic polyolefin film of the present invention, the following organic thickener described in JP-A-2005-314636 is used in view of improving castability and improving the occurrence of horizontal steps and unevenness. Is preferably added.

  Although the casting method using an organic solvent as in the present invention is very advantageous from the viewpoint of productivity, it is not easy to keep the solvent dry immediately after casting, and surface irregularities are likely to occur. The term "planar unevenness" as used herein refers to streaks caused by poor leveling after casting, unevenness in drying caused by a difference in solvent drying speed, and unevenness in thickness caused by drying air.

  As a means for preventing unevenness while forming a uniform film, a method of preventing flow by increasing the viscosity of a coating solution is considered. It is known to add a thickener such as a polymer in order to increase the viscosity of the dope, but simply increasing the viscosity of the dope deteriorates the leveling property and causes streaks during casting. Connect. As a means for preventing the occurrence of unevenness during drying and the occurrence of streaks during casting, a method of adding a thixotropic additive (hereinafter referred to as a thixotropic agent) to impart thixotropic to the dope is preferable.

for that reason,
[1] It is preferable to use an organic solvent-based thickener comprising a compound represented by the following general formula (1), which satisfies the following condition (a):
General formula (1)
(R) t-Z- (B) s
In the formula, R represents an alkyl group substituted by at least 8 fluorine atoms having 4 or more carbon atoms, Z represents a (t + s) -valent linking group, and B represents a substituted or unsubstituted alkyl group or an aryl group. Or a heterocyclic group. t is an integer from 1 to 6, and s is an integer from 1 to 6.

  In the formula, R represents an alkyl group substituted with at least 8 fluorine atoms having 4 or more carbon atoms, and R may be substituted with at least 8 fluorine atoms, and may be linear, branched, or cyclic. Any structure may be used. Further, it may be further substituted with a substituent other than a fluorine atom, or may be substituted with only a fluorine atom. Examples of the substituent other than a fluorine atom for R include an alkenyl group, an aryl group, an alkoxyl group, a halogen atom other than fluorine, a hydroxy group, an aryloxycarbonyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, and a carbamoyl group. .

  Z represents a (t + s) -valent linking group, and is not particularly limited as long as it links R and B. t is an integer from 1 to 6, and s is an integer from 1 to 6, but preferably t is an integer from 2 to 4, more preferably t is 2 or 3, Preferably, t is 2. Preferably, s is an integer from 1 to 4, and more preferably, s is an integer from 1 to 3.

  As Z, an amino acid derivative is preferably used. The asymmetric carbon of the amino acid in the amino acid derivative may be optically active or racemic. Optically active substances are preferably used.

  B represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group.

<< Condition (a) >>
At any shear rate within the range of 0.01 to 5000 s ⁻¹ , the solution containing the compound represented by the general formula (1) at a concentration of 5% by mass or less with respect to the viscosity η0 of the solvent with respect to the viscosity η0 of the solvent. There is a region where the relative viscosity η1 / η0 of the viscosity η1 is 2 or more. The solvent that can be used here is not particularly limited as long as a desired effect can be obtained, but is preferably toluene, hexane, isopropanol, ethanol, methanol, chloroform, methyl ethyl ketone, 2-methylpentanone, or cyclohexanone. More preferred are toluene, methyl ethyl ketone, 2-methylpentanone and cyclohexanone, and most preferred are methyl ethyl ketone, 2-methylpentanone and cyclohexanone.

  [2] An organic solvent-based thixotropic agent comprising the compound represented by the general formula (1) and satisfying the following condition (b) is preferable.

<< Condition (b) >>
In a solution in which the compound represented by the general formula (1) is contained in the solvent at a concentration of 5% by mass or less, the viscosity η ( _x1 ) at any shear rate _x1 in the range of 0.01 to 5000 s ⁻¹ . The value η ( _x1 ) / η ( _x2 ) for the viscosity η ( _x2 ) at the shear rate _x2 where _x2 / _x1 ≧ 10 is 1.5 or more.

  [3] The compound represented by the general formula (1) is represented by the following general formula (2), [1] or [2], wherein the organic solvent-based thickener or thixotropic agent is used. It is preferred that

In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group, but at least one of R ₁ and R ₂ represents an alkyl group substituted with at least 8 or more fluorine atoms. R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or a substituent, T ₁ , T ₂ and L ₁ each independently represent a divalent linking group or a single bond, and k is 0 or 1. . B represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group.

  [4] The organic solvent-based thickener according to any one of [1] to [3], wherein the compound represented by the general formula (1) is represented by the following general formula (3). It is preferably an agent or a thixotropic agent.

In the formula, R ₁ and R ₂ each independently represent an alkyl group substituted by at least 8 fluorine atoms having 4 or more carbon atoms. B represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. T ₃ and _{T 4} are each independently -O -, - S- or _{-NR 23} - represents a. R ₂₃ represents a hydrogen atom or a substituent, L ₁ represents a divalent linking group or a single bond, and k is 0 or 1.

  [5] The organic solvent-based thickening according to any one of [1] to [4], wherein the compound represented by the general formula (1) is represented by the following general formula (4). It is preferably an agent or a thixotropic agent.

In the formula, A ₁ and A ₂ each independently represent a fluorine atom or a hydrogen atom. The integer n ₁₁ and _{n 21} each independently Less than _{six, n 12} and _{n 22} each independently represents a 3-12 integer. T ₃ and _{T 4} are each independently -O -, - S- or _{-NR 23} - represents a. R ₂₃ represents a hydrogen atom or a substituent, and L ₁ represents a divalent linking group or a single bond. B represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, and k is 0 or 1.

  Specific examples of the compounds represented by the general formulas (1) to (4) are preferably selected from the compounds described in paragraphs [0083] to [0089] of JP-A-2005-314636. The content of the fluorine-containing compound is not particularly limited, but is usually 0.01 to 10% by mass (% by mass based on the total mass of the dope) in the dope, preferably 0.01 to 5% by mass, and more preferably 0 to 5% by mass. 0.01 to 2.5% by mass. Further, the fluorine-containing compound may contain only one kind or a plurality of kinds.

(4) Matting agent (fine particles)
The fine particles used in the present invention are usually used as an additive of the film, and in order to improve the poor slipperiness of the film surface, it is effective to impart unevenness to the film surface, and it is effective to use an organic or inorganic material. It is used to reduce the adhesiveness by adding fine particles of a substance to increase the roughness of the film surface and to form a so-called mat.

  However, as the surface becomes rougher, the haze increases and the transparency decreases, so that the average particle size and content are limited. The fine particles used in the present invention have an average particle size of 1 to 1000 nm, preferably 1 to 100 nm, more preferably 3 to 50 nm.

  When the fine particles are added to various films and used, the content in the film is in the range of 0.03 to 1% by mass irrespective of spherical or irregular fine particles with respect to 100% by mass of the film. Is in the range of 0.03 to 0.60% by mass, more preferably in the range of 0.03 to 0.5% by mass.

  The haze range of the cyclic polyolefin film containing fine particles in the present invention is preferably 2.0% or less, more preferably 1.2% or less, and particularly preferably 0.5% or less. The preferred static friction coefficient of the cyclic polyolefin film to which the fine particles are added is 1.5 or less, and particularly preferably 1.0 or less. When the coefficient of static friction is 1.5 or less, the cyclic polyolefin film does not generate crevices or wrinkles during winding in film formation and processing, and therefore, the wound appearance is impaired by the crevices or wrinkles, or is unfavorable due to crevices or wrinkles. There is no problem that uniform tension is applied to the cyclic polyolefin film, and unintended non-uniform optical characteristics are generated on the film surface.

  The coefficient of static friction is measured between the same materials, and specifically, is measured according to the method described in Examples.

  The fine particles to be used are not particularly limited as long as they are usually used for a film, and two or more of these fine particles can be used as a mixture. Examples of the fine particles include inorganic compounds and polymer compounds. As the inorganic compound, for example, barium sulfate, manganese colloid, titanium dioxide, strontium barium sulfate, silicon dioxide, and the like, there are fine powders of inorganic substances, such as synthetic silica obtained by a wet method or gelation of silicic acid, etc. Titanium dioxide (rutile type or anatase type) generated by silicon dioxide or titanium slag and sulfuric acid, and the like. Further, it can also be obtained by pulverizing an inorganic substance having a relatively large particle size, for example, 20 μm or more, and then performing classification (vibration filtration, air classification, etc.). As the inorganic fine particles, those containing silicon are preferable in that turbidity is reduced and haze of the film can be reduced. Fine particles such as silicon dioxide are often subjected to a surface treatment with an organic substance, but such particles are preferable because the surface haze of the film can be reduced. Preferred organic substances for the surface treatment include halosilanes, alkoxysilanes, silazanes, siloxanes, and the like.

  Examples of the polymer compound include polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate, starch, and the like, and pulverized and classified products thereof. Alternatively, a polymer compound synthesized by a suspension polymerization method, a polymer compound formed into a spherical shape by a spray drying method, a dispersion method, or the like, or an inorganic compound can be used.

  Further, a polymer compound which is one or more polymers of the monomer compounds described below may be formed into particles by various means. Specific examples of the monomer compound of the high molecular compound include acrylic acid ester, methacrylic acid ester, itaconic acid diester, crotonic acid ester, maleic acid diester, and phthalic acid diesters. Ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylhexyl, 2-chloroethyl, cyanoethyl, 2-acetoxyethyl, dimethylaminoethyl, benzyl, cyclohexyl, furfuryl, phenyl, 2-hydroxyethyl, 2-ethoxyethyl, glycidyl, ω -Methoxy polyethylene glycol (number of added moles: 9);

  Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate, and the like. No. Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene.

  Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, trifluoromethylstyrene, and vinyl. Benzoic acid methyl ester and the like can be mentioned.

  Examples of acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, phenylacrylamide, dimethylacrylamide and the like; methacrylamides, for example, methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacryl Amides, tert-butyl methacrylamide, etc .; allyl compounds such as allyl acetate, allyl caproate, allyl laurate, allyl benzoate, etc .; vinyl ethers such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethyl Aminoethyl vinyl ether and the like; vinyl ketones such as methyl vinyl Tones, phenyl vinyl ketone, methoxyethyl vinyl ketone and the like; vinyl heterocyclic compounds such as vinyl pyridine, N-vinyl imidazole, N-vinyl oxazolidone, N-vinyl triazole, N-vinyl pyrrolidone and the like; unsaturated nitriles such as , Acrylonitrile, methacrylonitrile and the like; polyfunctional monomers such as divinylbenzene, methylenebisacrylamide, ethylene glycol dimethacrylate and the like.

  Further, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate (eg, monoethyl itaconate, etc.); monoalkyl maleate (eg, monomethyl maleate, etc .; styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl) Sulfonic acid, acryloyloxyalkylsulfonic acid (eg, acryloyloxymethylsulfonic acid); methacryloyloxyalkylsulfonic acid (eg, methacryloyloxyethylsulfonic acid); acrylamidoalkylsulfonic acid (eg, 2-acrylamido-2-methylethane) Methacrylamidoalkylsulfonic acid (such as 2-methacrylamido-2-methylethanesulfonic acid); acryloyloxyalkyl phosphate (such as sulfonic acid); These acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions.Other monomeric compounds include US Pat. No. 3,459,790. And Nos. 3,438,708, 3,554,987, 4,215,195, 4,247,673, and JP-A-57-205735, and the like. Specific examples of the crosslinkable monomer include N- (2-acetoacetoxyethyl) acrylamide and N- (2- (2-acetoacetoxyethoxy) ethyl) acrylamide.

  These monomer compounds may be used as polymer particles polymerized alone or as copolymer particles obtained by polymerizing a plurality of monomers. Among these monomer compounds, acrylic esters, methacrylic esters, vinyl esters, styrenes, and olefins are preferably used. In the present invention, particles having a fluorine atom or a silicon atom as described in JP-A Nos. 62-14647, 62-17744, and 62-17743 may be used.

  Among these, the particle compositions preferably used are polystyrene, polymethyl (meth) acrylate, polyethyl acrylate, poly (methyl methacrylate / methacrylic acid = 95/5 (molar ratio), and poly (styrene / styrene sulfonic acid = 95/5 ( Mole ratio), polyacrylonitrile, poly (methyl methacrylate / ethyl acrylate / methacrylic acid = 50/40/10), silica, and the like.

Further, as the fine particles used in the present invention, particles having a reactive (especially gelatin) group described in JP-A-64-77052 and EP-A-307855 can be used. Further, a large amount of a group which is soluble in an alkaline or acidic state can be contained. The fine particles contain an inorganic compound or a high molecular compound, and preferably have an average primary particle size in the range of 10 ⁻³ to 10 μm. The average primary particle size is more preferably in the range of 10 ⁻³ to 10 μm, further preferably in the range of 0.005 to 5 μm, and particularly preferably in the range of 0.01 to 3 μm. Further, the fine particles are preferably silicon dioxide fine particles.

(Organic solvent used for fine particle dispersion)
The organic solvent used in the preparation of the fine particle dispersion is not particularly limited as long as the fine particles are dispersed and the dispersion can be prepared. The organic solvent used in the present invention is, for example, a chlorinated solvent such as dichloromethane or chloroform, a solvent selected from chain hydrocarbons having 3 to 12 carbon atoms, cyclic hydrocarbons, aromatic hydrocarbons, esters, ketones and ethers. Is preferred. Esters, ketones, and ethers may have a cyclic structure. Examples of chain hydrocarbons having 3 to 12 carbon atoms include hexane, octane, isooctane, decane, and the like. Examples of the cyclic hydrocarbon having 3 to 12 carbon atoms include cyclopentane, cyclohexane, decalin and derivatives thereof. Examples of the aromatic hydrocarbon having 3 to 12 carbon atoms include benzene, toluene, and xylene. Examples of the esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate. Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone. Examples of the ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolan, tetrahydrofuran, anisole and phenetole. Examples of the organic solvent having two or more types of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol, and 2-butoxyethanol. As the organic solvent used in the method for preparing a fine particle dispersion of the present invention, one kind of organic solvent may be used alone, or two or more kinds of organic solvents may be mixed and used at an arbitrary ratio.

  When dispersing the fine particles, if the amount of the organic solvent is small, sufficient dispersion cannot be performed, an aggregate is generated, and a foreign substance failure is caused. Conversely, when the amount of the organic solvent is large, the dispersion of the fine particles is excellent, but a large amount of the dispersion is prepared, which is not preferable in terms of handling in production. Therefore, the amount of the organic solvent used is preferably in the range of 1000 to 100,000 parts by mass, more preferably in the range of 1500 to 40000 parts by mass, and more preferably in the range of 2000 to 20,000 parts by mass, based on 100 parts by mass of the fine particles. It is particularly preferable to set the range.

(Dispersant)
Next, the dispersant used in the present invention will be described. When a fine particle dispersion and a dope are mixed in-line, if a dispersion having a low viscosity is used, it is difficult to add a dope having a high viscosity due to a difference in viscosity due to a difference in viscosity, and mixing is not successful. This problem is solved by dissolving the dispersant in the dispersion and slightly increasing the viscosity. Therefore, a resin is usually used as the dispersant. It is preferable that the viscosity of the dope and the dispersion is equal when only mixing is considered, but the viscosity of the fine particle dispersion is 0.7 mPa · s or more in consideration of the dispersibility as a fine particle dispersion and the simplicity of handling. Is preferably, and more preferably 1 mPa · s or more. On the other hand, if the weight average molecular weight of the dispersant is too large to increase the viscosity, poor solubility of the dispersant and poor filterability are caused. For this reason, the weight average molecular weight of the dispersant is preferably in the range of 10,000 to 500,000, more preferably in the range of 10,000 to 300,000, and more preferably in the range of 30,000 to 30,000 in order to prepare a dispersion having excellent solubility and filterability that does not lose strength to the dope. A range of 200,000 is more preferred.

  It is preferable to use a cyclic polyolefin-based resin as a dispersant, and to further disperse the fine particles in the presence of the dispersant. This is preferable from the viewpoint of improving the compatibility between the fine particle dispersion and the dope when preparing the dope, improving the stability of the dispersed fine particles when the dope is cast, and forming a dope without agglomerates. .

(5) Nitrogen-containing heterocyclic compound The cyclic polyolefin film of the present invention preferably contains the following nitrogen-containing heterocyclic compound in order to control optical performance such as retardation. The nitrogen-containing heterocyclic compound is a nitrogen-containing heterocyclic compound having a molecular weight in the range of 100 to 800, and is particularly preferably a compound having a structure represented by the following general formula (A1). By using a compound having a structure represented by the following general formula (A1) together with a cyclic polyolefin-based resin, for example, when a polarizing plate is used in a liquid crystal display device, the occurrence of phase difference fluctuation due to environmental humidity fluctuation is suppressed. In addition, it is possible to suppress a reduction in contrast and uneven color. Further, it can function as a phase difference increasing agent.

  It is a preferable range that the molecular weight is in the range of 250 to 450 from the viewpoints of the effect of suppressing the fluctuation of the phase difference due to the fluctuation of the humidity and the generation of flying objects.

(Compound having a structure represented by the general formula (A1))

In the general formula (A1), A ₁ , A ₂ and B each independently represent an alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2- A cycloalkyl group (cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Among these, an aromatic hydrocarbon ring or an aromatic heterocyclic ring is preferable, and a 5- or 6-membered aromatic hydrocarbon ring or an aromatic heterocyclic ring is particularly preferable.

  The structure of the 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring is not limited, and examples thereof include a benzene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a 1,2,3-triazole ring, , 4-triazole ring, tetrazole ring, furan ring, oxazole ring, isoxazole ring, oxadiazole ring, isoxadiazole ring, thiophene ring, thiazole ring, isothiazole ring, thiadiazole ring, isothiadiazole ring and the like. .

The 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring represented by A ₁ , A ₂ and B may have a substituent. As the substituent, for example, a halogen atom ( Fluorine atom, chlorine atom, bromine atom, iodine atom, etc., alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group, etc.), cycloalkyl Group (cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), alkenyl group (vinyl group, allyl group, etc.), cycloalkenyl group (2-cyclopenten-1-yl, 2-cyclohexen-1-yl group, etc.) ), Alkynyl group (ethynyl group, propargyl group, etc.), aromatic hydrocarbon ring group (phenyl group, p-tolyl group, naphthyl group, etc.), aromatic heterocyclic group (2 Pyrrole, 2-furyl, 2-thienyl, pyrrole, imidazolyl, oxazolyl, thiazolyl, benzimidazolyl, benzoxazolyl, 2-benzothiazolyl, pyrazolinone, pyridyl, pyridinone, 2- Pyrimidinyl group, triazine group, pyrazole group, 1,2,3-triazole group, 1,2,4-triazole group, oxazole group, isoxazole group, 1,2,4-oxadiazole group, 1,3,4 -Oxadiazole, thiazole, isothiazole, 1,2,4-thiodiazole, 1,3,4-thiadiazole, etc.), cyano, hydroxy, nitro, carboxy, alkoxy (methoxy) Ethoxy group, isopropoxy group, tert-butoxy group, n-octyloxy group, 2-meth Xyethoxy group, etc.), aryloxy group (phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group, etc.), acyloxy group (formyloxy group, Acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group, etc., amino group (amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenyl) Amino), acylamino (formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, etc.), alkyl and arylsulfonylamino (methylsulfonylamino, butylsulfonylamino, phenyl) Sulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group, etc., mercapto group, alkylthio group (methylthio group, ethylthio group, n-hexadecylthio group, etc.), arylthio group (phenylthio group) , P-chlorophenylthio group, m-methoxyphenylthio group, etc.), sulfamoyl group (N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N -Acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N'-phenylcarbamoyl) sulfamoyl group, etc.), sulfo group, acyl group (acetyl group, pivaloylbenzoyl group, etc.), carbamoyl group (carbamoyl group) Group, N-methylcarbamoyl group, N, N-di Chi-carbamoyl, N, N-di -n- octylcarbamoyl group, and each group such as N- (methylsulfonyl) carbamoyl group).

In the general formula (A1), A ₁ , A ₂ and B may represent a benzene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a 1,2,3-triazole ring or a 1,2,4-triazole ring. This is preferable because a cyclic polyolefin film having excellent optical property fluctuation effects and excellent durability can be obtained.

In the formula (A1), T ₁ and T ₂ each preferably independently represent a pyrrole ring, a pyrazole ring, an imidazole ring, a 1,2,3-triazole ring, or a 1,2,4-triazole ring. . Among these, a pyrazole ring, a triazole ring or an imidazole ring are particularly excellent in the effect of suppressing the fluctuation of the phase difference with respect to humidity fluctuation, and are preferable because a resin composition having excellent durability is obtained. It is particularly preferred that there is. The pyrazole ring, 1,2,3-triazole ring or 1,2,4-triazole ring or imidazole ring represented by T ₁ and T ₂ may be a tautomer. Specific structures of a pyrrole ring, a pyrazole ring, an imidazole ring, a 1,2,3-triazole ring or a 1,2,4-triazole ring are shown below.

In the formula, * represents a bonding position to L ₁ , L ₂ , L ₃ or L ₄ in the general formula (A1). R ⁵ represents a hydrogen atom or a non-aromatic substituent. Examples of the non-aromatic substituent represented by R ⁵ include the same groups as the non-aromatic substituent among the substituents that A ₁ may have in the general formula (A1). When the substituent represented by R ⁵ is a substituent having an aromatic group, A ₁ and T ₁ or B and T ₁ are easily twisted, and A ₁ , B and T ₁ form an interaction with the cyclic polyolefin. This makes it difficult to suppress variations in optical characteristics. In order to enhance the effect of suppressing fluctuations in optical characteristics, R ⁵ is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom. .

In the general formula (A1), T ₁ and T ₂ may have a substituent. Examples of the substituent include a substituent which A ₁ and A ₂ in the general formula (A1) may have. Similar groups can be mentioned.

In the general formula (A1), L ₁ , L ₂ , L _3, and L ₄ each independently represent a single bond or a divalent linking group, and are 5-membered or 6-membered via 2 or less atoms. Membered aromatic hydrocarbon rings or aromatic heterocycles are connected. The term “via two or less atoms” means the minimum number of atoms existing between the connected substituents among the atoms constituting the connecting group. The divalent linking group having 2 or less linking atoms is not particularly limited, but includes an alkylene group, an alkenylene group, an alkynylene group, O, (C = O), NR, S, and (O = S = O). A divalent linking group selected from the group consisting of: or a combination of two divalent linking groups. R represents a hydrogen atom or a substituent. Examples of the substituent represented by R include an alkyl group (e.g., a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, an n-octyl group, a 2-ethylhexyl group), a cycloalkyl group ( Cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), aromatic hydrocarbon ring group (phenyl group, p-tolyl group, naphthyl group, etc.), aromatic heterocyclic group (2-furyl group, 2-thienyl) Group, 2-pyrimidinyl group, 2-benzothiazolyl group, 2-pyridyl group and the like), cyano group and the like. The divalent linking group represented by L ₁ , L ₂ , L ₃ and L ₄ may have a substituent, and the substituent is not particularly limited. For example, A in the general formula (A1) _{The same} groups as the substituents that ₁ and A ₂ may have can be mentioned.

In the general formula (A1), L ₁ , L ₂ , L ₃ and L ₄ represent a resin having a structure represented by the general formula (A1) having high planarity, and thus a resin that adsorbs water. Interaction and the fluctuation of optical properties are suppressed, so that a single bond or O, (C = O) -O, O- (C = O), (C = O) -NR or NR- (C = O) is preferable, and a single bond is more preferable.

In the general formula (A1), n represents an integer of 0 to 5. When n represents an integer of 2 or more, a plurality of A ₂ , T ₂ , L ₃ , and L ₄ in the general formula (A1) may be the same or different. The larger the value of n, the stronger the interaction between the compound having the structure represented by the general formula (A1) and the resin that adsorbs water, and the better the effect of suppressing fluctuations in optical characteristics. Excellent compatibility with resin that adsorbs water. For this reason, n is preferably an integer of 1 to 3, and more preferably an integer of 1 to 2.

<Compound having a structure represented by General Formula (A2)>
The compound having a structure represented by the general formula (A1) is preferably a compound having a structure represented by the general formula (A2).

(In the formula, A ₁ , A ₂ , T ₁ , T ₂ , L ₁ , L ₂ , L ₃ and L ₄ are respectively A ₁ , A ₂ , T ₁ , T ₂ , L ₂ in the general formula (A1). _{1, L} 2, _{L 3} and .A ₃ and _{T 3 L 4} as synonymous, the .L ₅ and _{L 6} represent the same group as _{a 1} and _{T 1,} respectively, in the general formula (A1), the general .m representing the same groups as _{L 1} in formula (A1) represents an integer of 0 to 4.)
m is preferably an integer of 0 to 2, and more preferably an integer of 0 to 1, since the smaller the value of m, the better the compatibility with cellulose acylate.

<Compound having a structure represented by General Formula (A1.1)>
The compound having a structure represented by the general formula (A1) is preferably a triazole compound having a structure represented by the following general formula (A1.1).

_(Wherein, A 1, B, _{L 1} and _{L 2,} .k representing the _A 1, B, the same group as _{L 1} and _{L 2} in formula (A1) represents an integer of 1 to 4 .T ₁ represents a 1,2,4-triazole ring.)
Further, the triazole compound having a structure represented by the general formula (A1.1) is preferably a triazole compound having a structure represented by the following general formula (A1.2).

  (In the formula, Z represents a structure of the following general formula (A1.2a). Q represents an integer of 2 to 3. At least two Zs represent at least one Z substituted with a benzene ring. Bonds to the ortho or meta position.)

(In the formula, R ¹⁰ represents a hydrogen atom, an alkyl group or an alkoxy group. P represents an integer of 1 to 5. * represents a bonding position with a benzene ring. T ₁ is a 1,2,4-triazole ring. Represents.)
The compound having a structure represented by the general formula (A1), (A2), (A1.1) or (A1.2) may form a hydrate, a solvate or a salt. In the present invention, the hydrate may contain an organic solvent, and the solvate may contain water. That is, "hydrate" and "solvate" include mixed solvates containing both water and organic solvents. Salts include acid addition salts formed with inorganic or organic acids. Examples of inorganic acids include, but are not limited to, hydrohalic acids (such as hydrochloric acid, hydrobromic acid), sulfuric acid, phosphoric acid, and the like. Examples of the organic acid include acetic acid, trifluoroacetic acid, propionic acid, butyric acid, oxalic acid, citric acid, benzoic acid, alkylsulfonic acid (such as methanesulfonic acid), and allylsulfonic acid (benzenesulfonic acid, 4-toluene). Sulfonic acid, 1,5-naphthalenedisulfonic acid, etc.), and the like, but is not limited thereto. Of these, hydrochloride, acetate, propionate and butyrate are preferred.

  Examples of salts include those in which the acidic moiety present in the parent compound is a metal ion (eg, an alkali metal salt, such as a sodium or potassium salt, an alkaline earth metal salt, such as a calcium or magnesium salt, an ammonium salt, an alkali metal ion, an alkaline earth metal salt). And salts formed when adjusted with an organic base (ethanolamine, diethanolamine, triethanolamine, morpholine, piperidine, etc.) by a metal ion or an aluminum ion, and the like. Not limited. Of these, sodium salts and potassium salts are preferred.

  Examples of the solvent contained in the solvate include any of common organic solvents. Specifically, alcohols (eg, methanol, ethanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, t-butanol), esters (eg, ethyl acetate), hydrocarbons (eg, toluene, hexane) , Heptane), ether (eg, tetrahydrofuran), nitrile (eg, acetonitrile), ketone (acetone), and the like. Preferably, it is a solvate of alcohol (eg, methanol, ethanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, t-butanol). These solvents may be reaction solvents used in the synthesis of the compound, solvents used in crystallization purification after synthesis, or a mixture thereof.

  Further, two or more kinds of solvents may be simultaneously contained, or a form containing water and a solvent (for example, water and an alcohol (for example, methanol, ethanol, t-butanol, etc.)) may be used.

  In addition, even if the compound having the structure represented by the general formula (A1), (A2), (A1.1) or (A1.2) is added in a form not containing water, a solvent, or a salt, Hydrates, solvates or salts may be formed in the resin composition or cyclic polyolefin film of the invention.

  The molecular weight of the compound having the structure represented by the general formula (A1), (A2), (A1.1) or (A1.2) is not particularly limited, but the smaller the compound, the better the compatibility with the resin and the larger. Since the effect of suppressing the fluctuation of the optical value with respect to the change in the environmental humidity is higher, the value is preferably from 150 to 2,000, more preferably from 200 to 1500, and even more preferably from 300 to 1,000.

  Further, the nitrogen-containing heterocyclic compound according to the present invention is more preferably a compound having a structure represented by the following general formula (A3).

(Wherein A represents a pyrazole ring, Ar ₁ and Ar ₂ each represent an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and may have a substituent. R ₁ is a hydrogen atom, an alkyl group, an acyl group. , A sulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group, q represents an integer of 1-2, and n and m represent an integer of 1-3.)
The aromatic hydrocarbon ring or the aromatic heterocyclic ring represented by Ar ₁ and Ar ₂ may be the 5- or 6-membered aromatic hydrocarbon ring or the aromatic heterocyclic ring described in formula (A1), respectively. preferable. Examples of the substituent for Ar ₁ and Ar ₂ include the same substituents as those described for the compound having the structure represented by the general formula (A1).

Specific examples of R ₁ include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), an alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl) Group, 2-ethylhexyl group, etc.), acyl group (acetyl group, pivaloylbenzoyl group, etc.), sulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, etc.), alkyloxycarbonyl group (eg, methoxycarbonyl group), And an aryloxycarbonyl group (for example, a phenoxycarbonyl group and the like).

  q represents an integer of 1-2, and n and m represent an integer of 1-3.

  Hereinafter, specific examples of the compound having a 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring used in the present invention will be described. Among them, a compound having a structure represented by the general formula (A1), (A2), (A1.1), (A1.2) or a compound having a structure represented by the general formula (A3). preferable. The compound having a 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring that can be used in the present invention is not limited at all by the following specific examples. As described above, the following specific examples may be tautomers and may form hydrates, solvates or salts.

  Next, a method for synthesizing a compound having a structure represented by the general formula (A1) will be described.

  The compound having the structure represented by the general formula (A1) can be synthesized by a known method. In the compound having a structure represented by the general formula (A1), a compound having a 1,2,4-triazole ring may be any material, and may be a nitrile derivative or an imino ether derivative and a hydrazide derivative. A reaction method is preferred. As the solvent used in the reaction, any solvent may be used as long as it does not react with the raw materials, but an ester type (eg, ethyl acetate, methyl acetate, etc.), an amide type (dimethylformamide, dimethylacetamide, etc.), an ether type (Eg, ethylene glycol dimethyl ether), alcohols (eg, methanol, ethanol, propanol, isopropanol, n-butanol, 2-butanol, ethylene glycol, ethylene glycol monomethyl ether, etc.), and aromatic hydrocarbons (eg, toluene, xylene, etc.) ), Water. The solvent used is preferably an alcohol solvent. These solvents may be used as a mixture.

  The amount of the solvent to be used is not particularly limited, but is preferably in the range of 0.5 to 30 times, more preferably 1.0 to 25 times the mass of the hydrazide derivative used. Yes, particularly preferably within the range of 3.0 to 20 times the amount.

  When reacting the nitrile derivative with the hydrazide derivative, a catalyst may not be used, but it is preferable to use a catalyst to accelerate the reaction. As the catalyst to be used, an acid or a base may be used. Examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, acetic acid and the like, preferably hydrochloric acid. The acid may be diluted with water and added, or may be added by blowing gas into the system. Examples of the base include inorganic bases (potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, potassium hydroxide, sodium hydroxide, etc.) and organic bases (sodium methylate, sodium ethylate, potassium methylate, potassium ethylate, Sodium butyrate, potassium butyrate, diisopropylethylamine, N, N'-dimethylaminopyridine, 1,4-diazabicyclo [2.2.2] octane, N-methylmorpholine, imidazole, N-methylimidazole, pyridine and the like) Any of these may be used. As the inorganic base, potassium carbonate is preferable, and as the organic base, sodium ethylate, sodium ethylate, and sodium butyrate are preferable. The inorganic base may be added as it is as a powder, or may be added in a state of being dispersed in a solvent. The organic base may be added in a state of being dissolved in a solvent (for example, a 28% methanol solution of sodium methylate).

  The amount of the catalyst used is not particularly limited as long as the reaction proceeds, but is preferably in the range of 1.0 to 5.0 moles, more preferably 1.05 to 3.0 times, based on the formed triazole ring. It is preferably in the range of 0 moles.

  When reacting the imino ether derivative with the hydrazide derivative, it is not necessary to use a catalyst, and the desired product can be obtained by heating in a solvent.

  There are no particular restrictions on the method of adding the starting materials, solvent and catalyst used in the reaction, and the catalyst may be added last, or the solvent may be added last. It is also preferable to disperse or dissolve the nitrile derivative in a solvent, add a catalyst, and then add a hydrazide derivative.

  The temperature of the solution during the reaction may be any temperature as long as the reaction proceeds, but is preferably in the range of 0 to 150 ° C, and more preferably in the range of 20 to 140 ° C. The reaction may be performed while removing generated water.

  Although any method may be used for the treatment of the reaction solution, when a base is used as a catalyst, it is preferable to neutralize the reaction solution by adding an acid. Examples of the acid used for neutralization include hydrochloric acid, sulfuric acid, nitric acid and acetic acid, and acetic acid is particularly preferred. The amount of the acid used for the neutralization is not particularly limited as long as the pH of the reaction solution is in the range of 4 to 9, but is preferably 0.1 to 3 times, particularly preferably 1 to 3 times the mol of the base used. , 0.2-1.5 moles.

  As a method for treating the reaction solution, when extracting with a suitable organic solvent, a method of washing the organic solvent with water after extraction, and then concentrating the solution is preferable. The appropriate organic solvent referred to herein is a water-insoluble solvent such as ethyl acetate, toluene, dichloromethane, or ether, or a mixed solvent of the water-insoluble solvent and tetrahydrofuran or an alcohol solvent, preferably Ethyl acetate.

  When the compound having the structure represented by the general formula (A1) is crystallized, there is no particular limitation, but a method of crystallizing by adding water to the neutralized reaction solution or a method represented by the general formula (A1) It is preferable to neutralize and crystallize an aqueous solution in which a compound having the structure to be dissolved is dissolved.

  For example, Exemplified Compound 1 can be synthesized according to the following scheme.

(Synthesis of Exemplified Compound 1)

  77.3 g (75.0 mmol) of benzonitrile, 34.0 g (25.0 mmol) of benzoylhydrazine, and 107.0 g (77.4 mmol) of potassium carbonate were added to 350 ml of n-butanol, and the mixture was stirred at 120 ° C. for 24 hours under a nitrogen atmosphere. did. The reaction solution was cooled to room temperature, the precipitate was filtered, and the filtrate was concentrated under reduced pressure. 20 ml of isopropanol was added to the concentrate, and the precipitate was collected by filtration. The precipitate collected by filtration was dissolved in 80 ml of methanol, 300 ml of pure water was added, and acetic acid was added dropwise until the pH of the solution reached 7. The precipitated crystals were collected by filtration, washed with pure water, and dried by blowing at 50 ° C. to obtain 38.6 g of Exemplified Compound 1. The yield was 70% based on benzoylhydrazine.

The ¹ H-NMR spectrum of the obtained Exemplified Compound 1 is as follows.

¹ H-NMR (400 MHz, solvent: heavy DMSO, standard: tetramethylsilane) δ (ppm): 7.56 to 7.48 (6H, m), 7.62 to 7.61 (4H, m)
(Synthesis of Exemplified Compound 6)
Exemplary compound 6 can be synthesized according to the following scheme.

  2.5 g (19.5 mmol) of 1,3-dicyanobenzene, 7.9 g (58.5 mmol) of benzoylhydrazine and 9.0 g (68.3 mmol) of potassium carbonate were added to 40 ml of n-butanol, and the mixture was heated at 120 ° C. under a nitrogen atmosphere. For 24 hours. After cooling the reaction solution, 40 ml of pure water was added, and the mixture was stirred at room temperature for 3 hours. The precipitated solid was separated by filtration and washed with pure water. Water and ethyl acetate were added to the obtained solid to carry out liquid separation, and the organic layer was washed with pure water. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude crystals were purified by silica gel chromatography (ethyl acetate / heptane) to obtain 5.5 g of Exemplified Compound 6. The yield was 77% based on 1,3-dicyanobenzene.

The ¹ H-NMR spectrum of the obtained Exemplified Compound 6 is as follows.

¹ H-NMR (400 MHz, solvent: heavy DMSO, standard: tetramethylsilane) δ (ppm): 8.83 (1H, s), 8.16 to 8.11 (6H, m), 7.67 to 7 .54 (7H, m)
(Synthesis of Exemplified Compound 176)
Exemplary compound 176 can be synthesized according to the following scheme.

  80 g (0.67 mol) of acetophenone and 52 g (0.27 mol) of dimethyl isophthalate were added to 520 ml of dehydrated tetrahydrofuran, and 52.3 g (1.34 mol) of sodium amide was gradually added dropwise with stirring under ice-water cooling under a nitrogen atmosphere. . After stirring for 3 hours under ice-water cooling, the mixture was stirred for 12 hours under water cooling. After the reaction solution was neutralized by adding concentrated sulfuric acid, pure water and ethyl acetate were added thereto to carry out liquid separation, and the organic layer was washed with pure water. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Methanol was added to the obtained crude crystals, followed by suspension washing to obtain 55.2 g of Intermediate A.

  55 g (0.15 mol) of the intermediate A was added to 300 ml of tetrahydrofuran and 200 ml of ethanol, and 18.6 g (0.37 mol) of hydrazine monohydrate was added dropwise little by little while stirring at room temperature. After the dropwise addition, the mixture was heated under reflux for 12 hours. Pure water and ethyl acetate were added to the reaction solution to carry out liquid separation, and the organic layer was washed with pure water. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude crystals were purified by silica gel chromatography (ethyl acetate / heptane) to obtain 27 g of Exemplified Compound 176.

The ¹ H-NMR spectrum of the obtained exemplary compound 176 is as follows. In addition, in order to avoid complicating the chemical shift due to the presence of the tautomer, the measurement was performed by adding a few drops of trifluoroacetic acid to the measurement solvent.

¹ H-NMR (400 MHz, solvent: heavy DMSO, standard: tetramethylsilane) δ (ppm): 8.34 (1H, s), 7.87 to 7.81 (6H, m), 7.55 to 7 .51 (1H, m), 7.48 to 7.44 (4H, m), 7.36 to 7.33 (2H, m), 7.29 (1H, s)
Other compounds can be synthesized by the same method.

<How to Use Compound Having Structure Represented by General Formula (A1)>
The compound having a structure represented by the general formula (A1) used in the present invention can be contained in the cyclic polyolefin film in an appropriate amount by adjusting the amount thereof. It is preferably contained in an amount of 1 to 10% by mass, particularly preferably 0.5 to 5% by mass. Within this range, the fluctuation of the phase difference depending on the change of the environmental humidity can be reduced without impairing the mechanical strength of the cyclic polyolefin film of the present invention.

  As a method of adding the compound having the structure represented by the general formula (A1), the compound may be added as a powder to the resin forming the cyclic polyolefin film, and after dissolving in a solvent, forming the cyclic polyolefin film. May be added to the resin.

(6) Organic Ester The following organic esters are preferably used as the plasticizer in the cyclic polyolefin film of the present invention from the viewpoint of moldability and dimensional stability.

  The organic ester is preferably a compound having a melting point in the range of −60 to 120 ° C. and having a 1% mass reduction temperature Td1 in the range of 100 to 350 ° C. by differential thermogravimetry. Preferably, there is. The organic ester is not particularly limited, but the organic ester is preferably at least one selected from sugar esters, polycondensed esters, and polyhydric alcohol esters. It is preferable that the ester does not contain a nitrogen atom in the structure.

(Measurement of melting point of organic ester)
The melting point was measured using a differential thermal / thermogravimetric simultaneous measurement apparatus manufactured by Seiko Instruments, EXSTAR6220TG / DTA. The melting point was determined from the endothermic and exothermic peaks when 10 mg of the sample compound was placed in an aluminum pan and the temperature was changed to 30 to 350 ° C and 350 to 30 ° C at 10 ° C / min. When a compound having a melting point of 0 ° C. or lower was measured, the melting point was determined at 5 ° C./min from endothermic and exothermic peaks at −50 to 30 ° C. and 30 to −50 ° C.

  In order to exhibit the effects of the present invention, the organic ester used in the present invention needs to have a melting point within the range of -60 to 120C, and preferably within the range of -45 to 90C.

  When the melting point of the organic ester is in the range of −60 to 120 ° C., it is scattered in the production line and easily liquefied after being cooled. .

(Measurement of 1% mass loss temperature of organic ester)
The measurement of the 1% mass reduction temperature Td1 of the organic ester is performed by, for example, putting 10 mg of the sample compound in an aluminum pan using an EXSTAR6200TG / DTA simultaneous thermal / thermogravimetric measuring device manufactured by Seiko Instruments Inc. at 100 ° C. at 50 ° C./min. After heating to 40 ° C, the mass was monitored while the temperature was raised to 400 ° C at a rate of 10 ° C / min. I do. In addition, the measurement is performed under dry air (dew point −30 ° C.).

  In order to exhibit the effects of the present invention, the organic ester used in the present invention preferably has a 1% mass reduction temperature in the range of 100 to 300 ° C, more preferably in the range of 200 to 270 ° C. .

  When the 1% mass reduction temperature of the organic ester is 100 ° C. or more, the viscosity when liquefied after scattering and cooling is appropriate, and the bulk of the scattered matter of the nitrogen-containing heterocyclic compound can be reduced. When the% mass reduction temperature is 350 ° C. or lower, an amount necessary for reducing the bulkiness of the scattered matter of the nitrogen-containing heterocyclic compound is scattered, and a sufficient effect can be obtained.

  Hereinafter, sugar esters, polycondensation esters, and polyhydric alcohol esters will be described as organic esters preferably used in the present invention.

  In the present invention, a compound having the above melting point and 1% mass reduction temperature Td1 within the range of the present invention can be appropriately selected and used from the following preferable organic esters.

(6-1) Sugar Ester As the sugar ester used in the present invention, a sugar having at least one but not more than 12 pyranose rings or furanose rings and having all or a part of the OH groups of the structure esterified is provided. It is preferably an ester.

  The sugar ester used in the present invention is a compound containing at least one of a furanose ring and a pyranose ring, and may be a monosaccharide or a polysaccharide in which 2 to 12 sugar structures are linked. The sugar ester is preferably a compound in which at least one of the OH groups of the sugar structure is esterified. In the sugar ester according to the present invention, the average degree of ester substitution is preferably in the range of 4.0 to 8.0, more preferably in the range of 5.0 to 7.5.

  The sugar ester used in the present invention is not particularly limited, and includes a sugar ester represented by the following general formula (B).

General formula (B)
(HO) _m -G- (OC (= O) -R ² ) _n
In the general formula (B), G represents a monosaccharide or disaccharide residue, R ² represents an aliphatic group or an aromatic group, and m represents a direct bond to the monosaccharide or disaccharide residue. to have a total number of hydroxy groups, n is bonded directly to the residue of the monosaccharide or disaccharide - (O-C (= O ) -R 2) is the sum of the number of groups, 3 ≦ m + n ≦ 8, and n ≠ 0.

The sugar ester having the structure represented by the general formula (B) is a single type of sugar in which the number (m) of hydroxy groups and the number (n) of-(OC (= O) -R ² ) groups are fixed. It is difficult to isolate as a compound, and it is known that a compound in which several types of components having different m and n in the formula are mixed is obtained. Therefore, the performance as a mixture in which the number (m) of hydroxy groups and the number (n) of — (OC (＝ O) —R ² ) groups are changed is important. In the case of the cyclic polyolefin film of the present invention, And a sugar ester having an average ester substitution degree in the range of 5.0 to 7.5.

  In the above general formula (B), G represents a monosaccharide or disaccharide residue. Specific examples of the monosaccharide include allose, altrose, glucose, mannose, gulose, idose, galactose, talose, ribose, arabinose, xylose, and lyxose.

  Hereinafter, specific examples of the compound having a monosaccharide residue of a sugar ester represented by the general formula (B) are shown, but the present invention is not limited to these exemplified compounds.

  Further, specific examples of the disaccharide residue include, for example, trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, isotrehalose, and the like.

  Hereinafter, specific examples of the compound having a disaccharide residue of a sugar ester represented by the general formula (B) are shown, but the present invention is not limited to these exemplified compounds.

In the general formula (B), R ² represents an aliphatic group or an aromatic group. Here, the aliphatic group and the aromatic group may each independently have a substituent.

Further, in the general formula (B), m is the total number of hydroxy groups directly bonded to the monosaccharide or disaccharide residue, and n is directly bonded to the monosaccharide or disaccharide residue. The total number of-(OC (= O) -R ² ) groups. It is necessary that 3 ≦ m + n ≦ 8, and it is preferable that 4 ≦ m + n ≦ 8. Also, n ≠ 0. Incidentally, when n is 2 or more, - (O-C (= O) -R 2) groups may be different or may be equal to each other.

The aliphatic group in the definition of R ² may be linear, branched, or cyclic, preferably has 1 to 25 carbon atoms, more preferably has 1 to 20 carbon atoms, and has 2 carbon atoms. To 15 are particularly preferred. Specific examples of the aliphatic group include, for example, methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, n-butyl, iso-butyl, tert-butyl, amyl, iso-amyl, tert-amyl, n- Examples include hexyl, cyclohexyl, n-heptyl, n-octyl, bicyclooctyl, adamantyl, n-decyl, tert-octyl, dodecyl, hexadecyl, octadecyl, and didecyl.

Further, the aromatic group in the definition of R ² may be an aromatic hydrocarbon group may be an aromatic heterocyclic group, more preferably an aromatic hydrocarbon group. The aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, and more preferably has 6 to 12 carbon atoms. Specific examples of the aromatic hydrocarbon group include, for example, rings such as benzene, naphthalene, anthracene, biphenyl, and terphenyl. As the aromatic hydrocarbon group, a benzene ring, a naphthalene ring and a biphenyl ring are particularly preferred. As the aromatic heterocyclic group, a ring containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom is preferable. Specific examples of the heterocycle, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, Each ring includes isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzotriazole, tetrazaindene and the like. As the aromatic heterocyclic group, a pyridine ring, a triazine ring and a quinoline ring are particularly preferred.

  Next, preferred examples of the sugar ester represented by the general formula (B) are shown below, but the present invention is not limited to these exemplified compounds. The following exemplified compounds all have a melting point and a 1% mass loss temperature Td1 within the scope of the present invention.

  The sugar ester may contain two or more different substituents in one molecule, contain an aromatic substituent and an aliphatic substituent in one molecule, and contain two or more different aromatic substituents. Two or more different aliphatic substituents contained in one molecule may be contained in one molecule.

  It is also preferable that two or more sugar esters are mixed and contained. It is also preferable to simultaneously contain a sugar ester containing an aromatic substituent and a sugar ester containing an aliphatic substituent.

<Synthesis example: Synthesis example of sugar ester represented by general formula (B)>
Hereinafter, an example of the synthesis of a sugar ester that can be suitably used in the present invention will be described.

34.2 g (0.1 mol) of sucrose, 180.8 g (0.8 mol) of benzoic anhydride, and pyridine were placed in a four-headed kolben equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas inlet tube. Was charged, and the temperature was raised while bubbling nitrogen gas from a nitrogen gas inlet tube with stirring to carry out an esterification reaction at 70 ° C. for 5 hours. Next, the pressure inside the Kolben was reduced to 4 × 10 ² Pa or less, and excess pyridine was distilled off at 60 ° C. Then, the pressure inside the Kolben was reduced to 1.3 × 10 Pa or less, and the temperature was raised to 120 ° C. to obtain anhydrous benzoic acid. Most of the acid and benzoic acid formed were distilled off. Then, 1 L of toluene and 300 g of a 0.5% by mass aqueous solution of sodium carbonate were added, and the mixture was stirred at 50 ° C. for 30 minutes, and then allowed to stand to separate a toluene layer. Finally, 100 g of water was added to the separated toluene layer, and the mixture was washed with water at room temperature for 30 minutes. Then, the toluene layer was separated, and toluene was distilled off at 60 ° C. under reduced pressure (4 × 10 ² Pa or less). A mixture of compounds A-1, A-2, A-3, A-4 and A-5 was obtained. When the obtained mixture was analyzed by HPLC and LC-MASS, A-1 was 7% by mass, A-2 was 58% by mass, A-3 was 23% by mass, A-4 was 9% by mass, A-5. Was 3% by mass, and the average ester substitution degree of the sugar ester was 6.57. A part of the obtained mixture was purified by silica gel column chromatography to obtain 100% pure A-1, A-2, A-3, A-4 and A-5, respectively.

  The amount of the sugar ester is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 1 to 15% by mass, based on the cyclic polyolefin resin.

(6-2) Polycondensed ester In the cyclic polyolefin film of the present invention, it is preferable to use a polycondensed ester having a structure represented by the following general formula (C) as an organic ester, because of its dimensional stability against temperature and humidity changes. Preferred from a viewpoint.

  The polycondensed ester is preferably contained in the cyclic polyolefin film of the present invention in the range of 1 to 30% by mass, and more preferably in the range of 5 to 20% by mass, due to its plastic effect.

General formula (C)
_{B 3 - (G 2 -A)} n -G 2 -B 4
In the formula (C), B ₃ and B ₄ each independently represent an aliphatic or aromatic monocarboxylic acid residue or a hydroxy group. G ₂ is an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue or a carbon number of 6 to 12 carbon atoms represents an oxyalkylene glycol residue having 4 to 12. A represents an alkylenedicarboxylic acid residue having 4 to 12 carbon atoms or an aryldicarboxylic acid residue having 6 to 12 carbon atoms. n represents an integer of 1 or more.

In the present invention, the polycondensation ester is a polycondensed ester having a repeating unit obtained by reacting a dicarboxylic acid and a diol, A represents a carboxylic acid residue in the polycondensed ester, G ₂ is an alcohol residue Represent.

  The dicarboxylic acid constituting the polycondensed ester is an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid, and is preferably an aromatic dicarboxylic acid. The dicarboxylic acid may be one type or a mixture of two or more types. In particular, it is preferable to mix aromatics and aliphatics.

  The diol constituting the polycondensed ester is an aromatic diol, an aliphatic diol or an alicyclic diol, preferably an aliphatic diol, and more preferably a diol having 1 to 4 carbon atoms. The diol may be one kind or a mixture of two or more kinds.

  Among them, a dicarboxylic acid containing at least an aromatic dicarboxylic acid and a repeating unit obtained by reacting a diol having 1 to 8 carbon atoms are preferable, and a dicarboxylic acid containing an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid is preferably used. And a repeating unit obtained by reacting a diol having 1 to 8 carbon atoms.

  Both ends of the polycondensed ester molecule may or may not be sealed.

  Specific examples of the alkylenedicarboxylic acid constituting A in the general formula (C) include 1,2-ethanedicarboxylic acid (succinic acid), 1,3-propanedicarboxylic acid (glutaric acid), and 1,4-butanedicarboxylic acid. (Adipic acid), 1,5-pentanedicarboxylic acid (pimelic acid), and a divalent group derived from 1,8-octanedicarboxylic acid (sebacic acid). Specific examples of the alkenylene dicarboxylic acid constituting A include maleic acid and fumaric acid. Specific examples of the aryldicarboxylic acid constituting A include 1,2-benzenedicarboxylic acid (phthalic acid), 1,3-benzenedicarboxylic acid, 1,4-benzenedicarboxylic acid, and 1,5-naphthalenedicarboxylic acid. No.

  A may be a single type or a combination of two or more types. Among them, A is preferably a combination of an alkylenedicarboxylic acid having 4 to 12 carbon atoms and an aryldicarboxylic acid having 8 to 12 carbon atoms.

G ₂ in the general formula (C) represents a divalent group derived from an alkylene glycol having 2 to 12 carbon atoms, a divalent group derived from an aryl glycol having 6 to 12 carbon atoms, or a carbon atom. It represents a divalent group derived from oxyalkylene glycol of the formulas 4 to 12.

Examples of the divalent group derived from an alkylene glycol having 2 to 12 carbon atoms in G _2, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1 , 3-Butanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (Neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-diene) Methylol heptane), 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanedio , 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol and the like. Divalent groups.

Examples of the divalent group derived from an aryl glycol having 6 to 12 carbon atoms in G _2, 1,2-dihydroxybenzene (catechol), 1,3-dihydroxybenzene (resorcinol), 1,4-dihydroxy Includes divalent groups derived from benzene (hydroquinone) and the like. Examples of the divalent group derived from oxyalkylene glycol having 4 to 12 carbon atoms in G are derived from diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and the like. Includes divalent groups.

G ₂ is, 1 be a kind, two or more kinds may be combined. Among them, _{G 2} is preferably a divalent group derived from an alkylene glycol having 2 to 12 carbon atoms, more preferably 2 to 5, 2 to 4 is most preferred.

B ₃ and B ₄ in the general formula (C) are each a monovalent group derived from an aromatic ring-containing monocarboxylic acid or an aliphatic monocarboxylic acid, or a hydroxy group.

  The aromatic ring-containing monocarboxylic acid in the monovalent group derived from the aromatic ring-containing monocarboxylic acid is a carboxylic acid containing an aromatic ring in the molecule, and is not limited to the one in which the aromatic ring is directly bonded to the carboxy group, Also included are those in which an aromatic ring is bonded to a carboxy group via an alkylene group or the like. Examples of the monovalent group derived from an aromatic ring-containing monocarboxylic acid include benzoic acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, paratoluic acid, dimethylbenzoic acid, ethylbenzoic acid, and normal propylbenzoic acid And monovalent groups derived from aminobenzoic acid, acetoxybenzoic acid, phenylacetic acid, 3-phenylpropionic acid and the like. Above all, benzoic acid and paratoluic acid are preferred.

  Examples of monovalent groups derived from aliphatic monocarboxylic acids include monovalent groups derived from acetic acid, propionic acid, butanoic acid, caprylic acid, caproic acid, decanoic acid, dodecanoic acid, stearic acid, oleic acid, and the like. Groups are included. Among them, a monovalent group derived from an alkyl monocarboxylic acid having 1 to 3 carbon atoms in the alkyl portion is preferable, and an acetyl group (a monovalent group derived from acetic acid) is more preferable.

  The weight average molecular weight of the polycondensed ester used in the present invention is preferably in the range of 500 to 3,000, and more preferably in the range of 600 to 2,000. The weight average molecular weight can be measured by the aforementioned gel permeation chromatography (GPC).

  Hereinafter, specific examples of the polycondensed ester having a structure represented by the general formula (C) are shown, but the invention is not limited thereto. The following exemplified compounds all have a melting point and a 1% mass loss temperature Td1 within the scope of the present invention.

  Hereinafter, specific synthesis examples of the above-described polycondensed ester will be described.

<Polycondensed ester P1>
180 g of ethylene glycol, 278 g of phthalic anhydride, 91 g of adipic acid, 610 g of benzoic acid, and 0.191 g of tetraisopropyl titanate as an esterification catalyst were charged into a 2 L four-necked flask equipped with a thermometer, a stirrer, and a cooling tube. The temperature is gradually increased while stirring in a nitrogen stream until the temperature reaches 230 ° C. A dehydration condensation reaction was performed while observing the degree of polymerization. After the reaction was completed, unreacted ethylene glycol was distilled off under reduced pressure at 200 ° C. to obtain a polycondensed ester P1. The acid value was 0.20 and the number average molecular weight was 450.

<Polycondensed ester P2>
251 g of 1,2-propylene glycol, 103 g of phthalic anhydride, 244 g of adipic acid, 610 g of benzoic acid, and 0.191 g of tetraisopropyl titanate as an esterification catalyst were prepared. The flask is charged, and the temperature is gradually increased while stirring in a nitrogen stream until the temperature reaches 230 ° C. A dehydration condensation reaction was performed while observing the degree of polymerization. After the reaction was completed, unreacted 1,2-propylene glycol was distilled off under reduced pressure at 200 ° C. to obtain the following polycondensed ester P2. The acid value was 0.10 and the number average molecular weight was 450.

<Polycondensed ester P3>
330 g of 1,4-butanediol, 244 g of phthalic anhydride, 103 g of adipic acid, 610 g of benzoic acid, and 0.191 g of tetraisopropyl titanate as an esterification catalyst were placed in a 2 L four-necked port equipped with a thermometer, a stirrer, and a cooling pipe. The flask is charged, and the temperature is gradually increased while stirring in a nitrogen stream until the temperature reaches 230 ° C. A dehydration condensation reaction was performed while observing the degree of polymerization. After completion of the reaction, unreacted 1,4-butanediol was distilled off at 200 ° C. under reduced pressure to obtain a polycondensed ester P3. The acid value was 0.50 and the number average molecular weight was 2,000.

<Polycondensed ester P4>
251 g of 1,2-propylene glycol, 354 g of terephthalic acid, 610 g of benzoic acid, and 0.191 g of tetraisopropyl titanate as an esterification catalyst were charged into a 2 L four-necked flask equipped with a thermometer, a stirrer, and a slow cooling tube. The temperature is gradually raised with stirring until the temperature reaches 230 ° C in an air current. A dehydration condensation reaction was performed while observing the degree of polymerization. After completion of the reaction, unreacted 1,2-propylene glycol was distilled off under reduced pressure at 200 ° C. to obtain a polycondensed ester P4. The acid value was 0.10 and the number average molecular weight was 400.

<Polycondensed ester P5>
251 g of 1,2-propylene glycol, 354 g of terephthalic acid, 680 g of p-toroic acid, and 0.191 g of tetraisopropyl titanate as an esterification catalyst were charged into a 2 L four-necked flask equipped with a thermometer, a stirrer, and a cooling tube for cooling. The temperature is gradually increased while stirring in a nitrogen stream until the temperature reaches 230 ° C. A dehydration condensation reaction was performed while observing the degree of polymerization. After completion of the reaction, unreacted 1,2-propylene glycol was distilled off under reduced pressure at 200 ° C. to obtain the following polycondensed ester P5. The acid value was 0.30 and the number average molecular weight was 400.

<Polycondensed ester P6>
180 g of 1,2-propylene glycol, 292 g of adipic acid, and 0.191 g of tetraisopropyl titanate as an esterification catalyst were charged into a 2 L four-necked flask equipped with a thermometer, a stirrer, and a slow cooling tube, and were charged in a nitrogen stream. The temperature is gradually raised with stirring until the temperature reaches 200 ° C. A dehydration condensation reaction was performed while observing the degree of polymerization. After completion of the reaction, unreacted 1,2-propylene glycol was distilled off under reduced pressure at 200 ° C. to obtain a polycondensed ester P6. The acid value was 0.10 and the number average molecular weight was 400.

<Polycondensed ester P7>
180 g of 1,2-propylene glycol, 244 g of phthalic anhydride, 103 g of adipic acid, and 0.191 g of tetraisopropyl titanate as an esterification catalyst are charged into a 2 L four-necked flask equipped with a thermometer, a stirrer, and a slow cooling tube. The temperature is gradually increased while stirring in a nitrogen stream until the temperature reaches 200 ° C. A dehydration condensation reaction was performed while observing the degree of polymerization. After completion of the reaction, unreacted 1,2-propylene glycol was distilled off under reduced pressure at 200 ° C. to obtain a polycondensed ester P7. The acid value was 0.10 and the number average molecular weight was 320.

<Polycondensed ester P8>
251 g of ethylene glycol, 244 g of phthalic anhydride, 120 g of succinic acid, 150 g of acetic acid, and 0.191 g of tetraisopropyl titanate as an esterification catalyst were charged into a 2 L four-necked flask equipped with a thermometer, a stirrer, and a slow cooling tube. The temperature is gradually increased with stirring until the temperature reaches 200 ° C in an air stream. A dehydration condensation reaction was performed while observing the degree of polymerization. After the reaction was completed, unreacted ethylene glycol was distilled off under reduced pressure at 200 ° C. to obtain a polycondensed ester P8. The acid value was 0.50 and the number average molecular weight was 1200.

<Polycondensed ester P9>
The polycondensed ester P9 having an acid value of 0.10 and a number average molecular weight of 315 was obtained by the same production method as that for the polycondensed ester P2, but changing the reaction conditions.

(6-3) Polyhydric alcohol ester The cyclic polyolefin film of the present invention preferably contains a polyhydric alcohol ester.

  The polyhydric alcohol ester is a compound comprising an ester of a dihydric or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. Preferred are aliphatic polyhydric alcohol esters having 2 to 20 valences.

  The polyhydric alcohol preferably used in the present invention is represented by the following general formula (D).

General formula (D)
R ₁₁ - _{(OH) n}
Here, R ₁₁ represents an n-valent organic group, n represents a positive integer of 2 or more, and an OH group represents an alcoholic and / or phenolic hydroxy group.

  Examples of preferred polyhydric alcohols include, for example, the following, but the present invention is not limited thereto.

  Adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol, mannitol, 3-methylpentane Examples thereof include 1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, and xylitol.

  Particularly, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable.

  The monocarboxylic acid used for the polyhydric alcohol ester is not particularly limited, and known aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, aromatic monocarboxylic acids, and the like can be used. It is preferable to use an alicyclic monocarboxylic acid or an aromatic monocarboxylic acid from the viewpoint of improving moisture permeability and retention.

  Preferred examples of the monocarboxylic acid include the following, but the present invention is not limited thereto.

  As the aliphatic monocarboxylic acid, a fatty acid having a linear or side chain having 1 to 32 carbon atoms can be preferably used. The number of carbon atoms is more preferably 1 to 20, and particularly preferably 1 to 10. It is preferable to include acetic acid because compatibility with cellulose acetate is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid.

  Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanoic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachiic acid, behenic acid, lignoceric acid, serotinic acid, heptacosanoic acid, montanic acid, melisic acid, and raccelic acid, undecylenic acid, and olein And unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid and arachidonic acid.

  Preferred examples of alicyclic monocarboxylic acids include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof.

  Examples of preferable aromatic monocarboxylic acids include benzoic acid such as benzoic acid and toluic acid, in which 1 to 3 alkoxy groups such as an alkyl group, a methoxy group or an ethoxy group are introduced into a benzene ring, biphenylcarboxylic acid, Aromatic monocarboxylic acids having two or more benzene rings, such as naphthalenecarboxylic acid and tetralincarboxylic acid, and derivatives thereof can be given. Particularly, benzoic acid is preferred.

  The molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably in the range of 300 to 1500, and more preferably in the range of 350 to 750. A larger molecular weight is preferred because it is less likely to volatilize, and a smaller one is preferred in terms of moisture permeability and compatibility with cellulose acylate.

  The carboxylic acid used for the polyhydric alcohol ester may be one type or a mixture of two or more types. Further, all the OH groups in the polyhydric alcohol may be esterified, or some of them may be left as OH groups.

  Hereinafter, specific compounds of the polyhydric alcohol ester will be exemplified. The following exemplified compounds all have a melting point and a 1% mass loss temperature Td1 within the scope of the present invention.

  The polyhydric alcohol ester used in the present invention is preferably contained in the range of 0.5 to 5% by mass relative to the cyclic polyolefin film, more preferably in the range of 1 to 3% by mass, and more preferably 1 to 3% by mass. It is particularly preferred that the content be in the range of 2% by mass.

  The polyhydric alcohol ester used in the present invention can be synthesized according to a conventionally known general synthesis method.

(7) Other plasticizers (7-1) Acrylic resin The acrylic resin compound represented by the following general formula (E) and having an average molecular weight (Mw) in the range of 1,000 to 30,000 is a cyclic polyolefin-based compound according to the present invention. It is preferably used from the viewpoint of high compatibility with the resin and improvement in heat resistance.

General formula (E)
_{- [CH 2 -C (-R 1} ) (- CO 2 R 2)] m - [CH 2 -C (-R 3) (- CO 2 R 4 -OH) -] n
(Wherein, R ₁ , R ₃ are H or CH ₃ , R ₂ , R ₄ are CH ₂ or C ₂ H ₄ or C ₃ H ₆ , m and n each represent a repeating unit)
Since the compound represented by formula (E) used in the present invention has a weight average molecular weight in the range of 1,000 to 30,000, it is considered that the compound is between an oligomer and a low molecular weight polymer.

  The compound represented by formula (E) is preferably a polymer obtained by copolymerizing one of the following ethylenically unsaturated monomers Xa and one of the following ethylenically unsaturated monomers Xb.

-(Xa) _m- (Xb) _n- (m and n represent a repeating unit)
The monomers as monomer units constituting the compound represented by formula (E) are listed below, but are not limited thereto.

  Examples of the ethylenically unsaturated monomer Xa include methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s-, t-), pentyl acrylate ( n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n-, i-), nonyl acrylate (n-, i-), myristyl acrylate (n-, i-), acrylic acid (2-ethylhexyl), acrylic acid (ε-caprolactone), acrylic acid (2-ethoxyethyl), etc., or the above acrylate is a methacrylate Can be mentioned. Among them, preferred are methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and propyl methacrylate (i-, n-).

  The ethylenically unsaturated monomer Xb is preferably an acrylic acid or a methacrylic acid ester, for example, acrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic acid (3-hydroxypropyl), acrylic acid (4 -Hydroxybutyl), acrylic acid (2-hydroxybutyl), or those obtained by replacing these acrylic acids with methacrylic acid, preferably acrylic acid (2-hydroxyethyl) and methacrylic acid (2-hydroxyethyl). ), Acrylic acid (2-hydroxypropyl) and acrylic acid (3-hydroxypropyl).

  The molar composition ratio m: n of Xa and Xb is preferably in the range of 99: 1 to 65:35, and more preferably in the range of 95: 5 to 75:25.

  When the molar composition ratio of Xa is large, the compatibility with the cyclic polyolefin resin is improved, but the heat resistance of the film is reduced. If the molar composition ratio of Xb is large, the above compatibility becomes poor. If the molar composition ratio of Xb exceeds the above range, haze tends to occur during film formation, and it is preferable to optimize these and determine the molar composition ratio of Xa and Xb.

  The weight average molecular weight of the compound represented by formula (E) is in the range of 1,000 to 30,000, and more preferably 8,000 to 25,000.

  When the weight average molecular weight is 1,000 or more and 30,000 or less, compatibility with the resin is further improved without evaporation or volatilization, which is preferable.

  The weight average molecular weight can be measured by the following method.

(Weight average molecular weight measurement method)
The weight average molecular weight Mw was measured using gel permeation chromatography. The measurement conditions are as follows.

Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko KK)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (GL Science)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 500 to 1,000,000 A calibration curve with 13 samples was used. Thirteen samples are used at approximately equal intervals.

  In order to synthesize the compound represented by the general formula (E), it is difficult to control the molecular weight by ordinary polymerization, and it is desirable to use a method that can make the molecular weight as uniform as possible by a method that does not increase the molecular weight too much. Examples of such a polymerization method include a method using a peroxide polymerization initiator such as cumene peroxide or t-butyl hydroperoxide, a method using a polymerization initiator in a larger amount than ordinary polymerization, and a mercapto compound in addition to the polymerization initiator. Using a chain transfer agent such as benzene or carbon tetrachloride, a method using a polymerization terminator such as benzoquinone or dinitrobenzene in addition to the polymerization initiator, and further JP-A-2000-128911 or JP-A-2000-344823. And a method of performing bulk polymerization using a compound having one thiol group and a secondary hydroxy group as described in (1), or a polymerization catalyst using the compound and an organometallic compound in combination. In particular, a compound having a thiol group and a secondary hydroxy group in the molecule is used as a chain transfer agent. The polymerization method of use is preferred.

  In this case, the terminal of the compound represented by the general formula (E) has a hydroxy group and a thioether derived from the polymerization catalyst and the chain transfer agent. The compatibility between the compound represented by formula (E) and the polymer resin having an alicyclic structure can be adjusted by the terminal residue.

  The polymerization temperature is usually from room temperature to 130 ° C., preferably from 50 to 100 ° C. The molecular weight can be controlled by adjusting the temperature or the polymerization reaction time.

  The hydroxy value of the compound represented by formula (E) is preferably 30 to 150 [mgKOH / g].

(Method for measuring hydroxy value)
This measurement conforms to JIS K 0070 (1992). The hydroxy value is defined as the number of mg of potassium hydroxide required to neutralize acetic acid bound to the hydroxy group when 1 g of a sample is acetylated. Specifically, a sample Xg (about 1 g) is precisely weighed in a flask, and 20 ml of an acetylating reagent (20 ml of acetic anhydride to which 400 ml of pyridine has been added) is accurately added. Attach an air condenser to the mouth of the flask, and heat in a glycerin bath at 95 to 100 ° C.

  After 1 hour and 30 minutes, the mixture was cooled, and 1 ml of purified water was added from an air condenser to decompose acetic anhydride into acetic acid. Next, titration is performed with a 0.5 mol / L potassium hydroxide ethanol solution using a potentiometric titrator, and the inflection point of the obtained titration curve is defined as the end point. Further, as a blank test, titration is performed without any sample, and the inflection point of the titration curve is determined.

  The hydroxy value is calculated by the following equation.

Hydroxy group value = {(BC) × f × 28.05 / X} + D
(Where B is the amount of the 0.5 mol / L potassium hydroxide ethanol solution used for the blank test (ml), and C is the amount of the 0.5 mol / L potassium hydroxide ethanol solution used for the titration (ml). , F is a factor of a 0.5 mol / L potassium hydroxide ethanol solution, D is an acid value, and 28.05 is １ ／ of 56.11 of 1 mol of potassium hydroxide.)
The compound represented by the general formula (E) needs to be contained in the cyclic polyolefin-based resin in an amount of 0.1 to 30% by mass, preferably 1 to 25% by mass, more preferably 3 to 20% by mass, Particularly preferably, it is 5 to 15% by mass.

(7-2) Phosphate ester A phosphate ester can be used for the cyclic polyolefin film of the present invention. Examples of the phosphate ester include a triaryl phosphate ester, a diaryl phosphate ester, a monoaryl phosphate ester, an arylphosphonic acid compound, an aryl phosphine oxide compound, a condensed aryl phosphate ester, a halogenated alkyl phosphate ester, and a halogen-containing condensed phosphoric acid. Esters, halogen-containing condensed phosphonic esters, halogen-containing phosphites and the like can be mentioned.

  Specific examples of the phosphoric acid ester include triphenyl phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenylphosphonic acid, tris (β-chloroethyl) phosphate, and tris (dichlorophosphate). Propyl) phosphate, tris (tribromoneopentyl) phosphate and the like.

(7-3) Glycolic Acid Esters In the present invention, glycolic acid esters (glycolate compounds) can be used as one kind of polyhydric alcohol esters.

  The glycolate compound applicable to the present invention is not particularly limited, but alkylphthalylalkyl glycolates can be preferably used.

  Examples of the alkylphthalylalkyl glycolates include, for example, methylphthalylmethyl glycolate, ethylphthalylethyl glycolate, propylphthalylpropyl glycolate, butylphthalylbutyl glycolate, octylphthalyloctyl glycolate, and methylphthalyl Ethyl glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl Glycolate, butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl glycolate, octyl phthalyl methyl glycolate, octyl phthalate Ethyl glycolate and the like, preferably ethyl phthalyl ethyl glycolate.

(8) Ultraviolet absorber The cyclic polyolefin film of the present invention preferably contains an ultraviolet absorber from the viewpoint of improving light resistance. The ultraviolet absorber is intended to improve the light resistance by absorbing ultraviolet light having a wavelength of 400 nm or less. In particular, the transmittance at a wavelength of 370 nm is preferably in the range of 2 to 30%, more preferably 4 to 30%. -20%, more preferably 5-10%.

  The ultraviolet absorber preferably used in the present invention is a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber or a triazine-based ultraviolet absorber which is a nitrogen-containing heterocyclic compound, and particularly preferably a benzotriazole-based ultraviolet absorber and benzophenone. It is a system ultraviolet absorber.

  For example, 5-chloro-2- (3,5-di-sec-butyl-2-hydroxylphenyl) -2H-benzotriazole, (2-2H-benzotriazol-2-yl) -6- (linear and branched Chain dodecyl) -4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxybenzophenone, etc., and tinuvin 109, tinuvin 171, tinuvin 234, tinuvin 326, tinuvin 327, tinuvin 328, There are tinuvins such as tinuvin 928, all of which are commercially available products of BASF Japan Ltd. and can be preferably used. Of these, halogen-free ones are preferred.

  In addition, discotic compounds such as compounds having a 1,3,5-triazine ring are also preferably used as an ultraviolet absorber.

  The cyclic polyolefin film of the present invention preferably contains two or more ultraviolet absorbers.

  As the ultraviolet absorber, a polymer ultraviolet absorber can also be preferably used, and particularly, a polymer type ultraviolet absorber described in JP-A-6-148430 is preferably used. Further, it is preferable that the ultraviolet absorber does not have a halogen group.

  Addition method of ultraviolet absorber, methanol, ethanol, alcohol such as butanol or methylene chloride, methyl acetate, acetone, organic solvent such as dioxolane or a mixed solvent thereof, or added to the dope, Alternatively, it may be directly added to the dope composition.

  Those that do not dissolve in an organic solvent such as inorganic powders are dispersed in an organic solvent and cellulose acylate using a dissolver or a sand mill, and then added to the dope.

  The amount of the ultraviolet absorber used is not uniform depending on the type of the ultraviolet absorber, the use conditions, and the like. However, when the dry film thickness of the cyclic polyolefin film is 15 to 50 μm, the amount is 0.5 to 10 with respect to the cyclic polyolefin film. The range of mass% is preferable, and the range of 0.6 to 4% by mass is more preferable.

(9) Antioxidant The antioxidant is also called a deterioration inhibitor. When an electronic device or the like is placed in a state of high humidity and high temperature, the cyclic polyolefin film may deteriorate.

  The antioxidant has, for example, a role of delaying or preventing the cyclic polyolefin film from being decomposed by the residual amount of the solvent in the cyclic polyolefin film, such as halogen or a phosphoric acid-based plasticizer, or the like. It is preferable to include it in the cyclic polyolefin film.

  As such an antioxidant, a hindered phenol compound is preferably used. For example, 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octa Sil-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide) 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxy) Benzyl) -isocyanurate and the like.

  Particularly, 2,6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3 -(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferred. Further, for example, a hydrazine-based metal deactivator such as N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine or tris (2,4-di- A phosphorus-based processing stabilizer such as (t-butylphenyl) phosphite may be used in combination.

  The amount of these compounds to be added is preferably in the range of 1 ppm to 1.0% by mass relative to the cyclic polyolefin film, and more preferably in the range of 10 to 1000 ppm.

(10) Phase difference controlling agent In order to improve the display quality of an image display device such as a liquid crystal display device, a phase difference controlling agent is added to a cyclic polyolefin film or an alignment film is formed to provide a liquid crystal layer, and a polarizing plate is provided. By compounding the phase difference derived from the protective film and the liquid crystal layer, the cyclic polyolefin film can be provided with optical compensation ability.

  Examples of the retardation controlling agent include an aromatic compound having two or more aromatic rings as described in European Patent No. 911656A2, and a rod-shaped compound described in JP-A-2006-2025. Further, two or more aromatic compounds may be used in combination. The aromatic ring of the aromatic compound is preferably an aromatic hetero ring including an aromatic hetero ring in addition to the aromatic hydrocarbon ring. Aromatic heterocycles are generally unsaturated heterocycles. Among them, a 1,3,5-triazine ring described in JP-A-2006-2026 is preferable.

  Note that the compound having the structure represented by the general formula (A1) also functions as a phase difference controlling agent. Therefore, the compound having the structure represented by the general formula (A1) can provide both functions of controlling the phase difference and suppressing the optical value fluctuation with respect to the humidity fluctuation with one compound.

  The addition amount of these retardation control agents is preferably in the range of 0.5 to 20% by mass, and more preferably in the range of 1 to 10% by mass, based on 100% by mass of the cyclic polyolefin resin. More preferred.

(11) Peeling Accelerators Many additives that reduce the peeling resistance of the cyclic polyolefin film have a remarkable effect on surfactants, and preferred releasing agents are phosphate ester surfactants, carboxylic acids or carboxylic acids. Salt-based surfactants, sulfonic acid or sulfonate-based surfactants, and sulfate-based surfactants are effective. Further, a fluorine-based surfactant in which a part of the hydrogen atoms bonded to the hydrocarbon chain of the surfactant is replaced with a fluorine atom is also effective. The release agent is exemplified below.
_{RZ-1 C 8 H 17 O} -P (= O) - (OH) 2
_{RZ-2 C 12 H 25 O} -P (= O) - (OK) 2
_{RZ-3 C 12 H 25 OCH} 2 CH 2 O-P (= O) - (OK) 2
_{RZ-4 C 15 H 31 (} OCH 2 CH 2) 5 O-P (= O) - (OK) 2
_{RZ-5 {C 12 H 25} O (CH 2 CH 2 O) 5} 2 -P (= O) -OH
_{RZ-6 {C 18 H 35} (OCH 2 CH 2) 8 O} 2 -P (= O) -ONH 4
_{RZ-7 (t-C 4} H 9) 3 -C 6 H 2 -OCH 2 CH 2 O-P (= O) - (OK) 2 RZ-8 (iso-C 9 H 19 -C 6 H 4 - _{O- (CH 2 CH 2 O)} 5 -P (= O) - (OK) (OH)
_{RZ-9 C 12 H 25 SO} 3 Na
_{RZ-10 C 12 H 25 OSO} 3 Na
_RZ-11 C ₁₇ H 33 COOH
_{RZ-12 C 17 H 33 COOH} · N (CH 2 CH 2 OH) 3
_{RZ-13 iso-C 8 H} 17 -C 6 H 4 -O- (CH 2 CH 2 O) 3 - (CH 2) 2 SO 3 Na
_{RZ-14 (iso-C 9} H 19) 2 -C 6 H 3 -O- (CH 2 CH 2 O) 3 - (CH 2) 4 SO 3 Na
RZ-15 triisopropyl naphthalenesulfonic acid sodium RZ-16 tri -t- butyl naphthalene sulfonate sodium _{RZ-17 C 17 H 33 CON} (CH 3) CH 2 CH 2 SO 3 Na
_{RZ-18 C 12 H 25 -C} 6 H 4 SO 3 · NH 4
The addition amount of the release accelerator is preferably 0.05 to 5% by mass, more preferably 0.1 to 2% by mass, and most preferably 0.1 to 0.5% by mass, based on the cyclic polyolefin resin.

(12) Rubber Particles In order to improve the flexibility of the cyclic polyolefin film and enhance the handleability, it is preferable to blend rubber elastic particles with the cyclic polyolefin-based resin. The rubber elastic body particles are particles containing a rubber elastic body, and may be particles composed of only the rubber elastic body or particles having a multilayer structure having a layer of the rubber elastic body. Examples of the rubber elastic body include an olefin elastic polymer, a diene elastic polymer, a styrene-diene elastic copolymer, and an acrylic elastic polymer. Above all, an acrylic elastic polymer is preferable from the viewpoint of the surface hardness, light resistance and transparency of the cyclic polyolefin film.

  The acrylic elastic polymer is preferably a polymer mainly composed of alkyl acrylate, and may be a homopolymer of alkyl acrylate, or may be 50% by mass or more of alkyl acrylate and a monomer other than alkyl acrylate. It may be a copolymer with 50% by mass or less of a monomer. As the alkyl acrylate, those having 4 to 8 carbon atoms in the alkyl group are usually used. Examples of monomers other than alkyl acrylates include alkyl methacrylates such as methyl methacrylate and ethyl methacrylate, styrene-based monomers such as styrene and alkyl styrene, and acrylonitrile and methacrylonitrile. Monofunctional monomers such as unsaturated nitriles; alkenyl esters of unsaturated carboxylic acids such as allyl (meth) acrylate and methallyl (meth) acrylate; dialkenyl esters of dibasic acids such as diallyl maleate; Examples include polyfunctional monomers such as unsaturated carboxylic acid diesters of glycols such as alkylene glycol di (meth) acrylate.

  The rubber elastic particles containing the acrylic elastic polymer are preferably particles having a multilayer structure having a layer of the acrylic elastic polymer, and a polymer mainly composed of alkyl methacrylate on the outside of the acrylic elastic polymer. Or a three-layer structure having a polymer layer mainly composed of alkyl methacrylate inside an acrylic elastic polymer. In addition, examples of the monomer composition of the polymer mainly composed of alkyl methacrylate constituting the layer formed on the outside or inside of the acrylic elastic polymer include the alkyl methacrylate described above as an example of the acrylic resin. This is the same as the example of the monomer composition of the main polymer. The acrylic rubber elastic particles having such a multilayer structure can be produced, for example, by the method described in JP-B-55-27576.

  As the rubber elastic body particles, those having a number average particle diameter of 10 to 300 nm of the rubber elastic body contained therein can be used. Thereby, when the cyclic polyolefin film is laminated on the polarizing film using the adhesive, the cyclic polyolefin film can be made hard to peel off from the adhesive layer. The number average particle size of the rubber elastic body is preferably 50 nm or more and 250 nm or less.

  The cyclic polyolefin film preferably has a flexural modulus (JIS K7171) of 1500 MPa or less from the viewpoint of the flexibility of the cyclic polyolefin-based resin. This flexural modulus is more preferably 1300 MPa or less, and still more preferably 1200 MPa or less. The flexural modulus varies depending on the type and amount of the rubber elastic particles in the cyclic polyolefin film, and, for example, as the content of the rubber elastic particles increases, the flexural modulus generally decreases.

  In addition, the use of the acrylic elastomeric polymer particles having the two-layer structure generally results in a smaller bending elastic modulus and the simpler elastic rubber particles than the use of the acrylic elastic polymer particles having the three-layer structure as the rubber elastic particles. The use of the acrylic elastic polymer particles having a layer structure generally results in a lower flexural modulus. In addition, as the average particle size of the rubber elastic body in the rubber elastic body particles is smaller or the amount of the rubber elastic body is larger, the bending elastic modulus generally becomes smaller. Therefore, it is preferable to adjust the type and amount of the acrylic resin and rubber elastic particles within the above-described predetermined range so that the flexural modulus becomes 1500 MPa or less.

  When the cyclic polyolefin film has a multilayer structure, the content of each layer of the rubber elastic material particles and the compounding agent may be different from each other. For example, a layer containing an ultraviolet absorber and / or an infrared absorber and a layer containing no ultraviolet absorber and / or an infrared absorber may be laminated with this layer interposed therebetween. Further, the content of the ultraviolet absorbent in the layer of the cyclic polyolefin-based resin composition is higher than the content of the ultraviolet absorbent in the layer of the cyclic polyolefin-based resin containing no rubber elastic particles or the composition thereof. Specifically, the former is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, and the latter is preferably 0 to 1% by mass, more preferably 0 to 0.5% by mass. %, Whereby ultraviolet rays can be efficiently blocked without deteriorating the color tone of the polarizing plate, and a decrease in the degree of polarization during long-term use can be prevented.

物 Physical properties of cyclic polyolefin film≫
(1) Thickness of Cyclic Polyolefin Film The thickness of the completed (after drying) cyclic polyolefin film of the present invention varies depending on the purpose of use, but is usually in the range of 5 to 500 μm, preferably in the range of 10 to 150 μm. The thickness is preferably 20 to 110 μm for a display device, and particularly preferably 20 to 60 μm in consideration of recent thinning.

  The thickness of the film is adjusted so that the desired thickness and the thickness distribution according to the present invention are obtained, the solid content concentration in the dope, the slit gap of the die cap, the extrusion pressure from the die, the metal support speed, and the like. Can be adjusted. The width of the cyclic polyolefin film obtained as described above is preferably in the range of 0.5 to 4 m, more preferably in the range of 0.6 to 3 m, and still more preferably 0.8 to 2.5 m. The length is preferably wound in the range of 100 to 10,000 m per roll, more preferably in the range of 500 to 9000 m, and still more preferably in the range of 1000 to 8000 m.

(2) Optical Properties of Cyclic Polyolefin Film Preferred optical properties of the cyclic polyolefin film of the present invention vary depending on the use of the film. In the case of a polarizing plate protective film, the in-plane retardation (Ro) is preferably 10 nm or less, more preferably 5 nm or less. The thickness direction retardation (Rt) is also preferably 50 nm or less, more preferably 35 nm or less, and particularly preferably 10 nm or less.

  When a cyclic polyolefin film is used as an optical compensation film (retardation film), the range of Ro or Rt varies depending on the type of the retardation film, and there are various needs, but 0 nm ≦ Ro ≦ 100 nm, 40 nm ≦ Rt ≦ 400 nm. It is preferred that For the TN mode, 0 nm ≦ Ro ≦ 20 nm, 40 nm ≦ Rt ≦ 80 nm, and for the VA mode, 20 nm ≦ Ro ≦ 80 nm, 80 nm ≦ Rt ≦ 400 nm are more preferable, and particularly preferable ranges for the VA mode are 30 nm ≦ Ro ≦ 75 nm, 120 nm ≦ Rt. ≦ 250 nm, 50 nm ≦ Ro ≦ 75 nm, 180 nm ≦ Rt ≦ 250 nm when compensating with one retardation film, 30 nm ≦ Ro ≦ 60 nm, 80 nm ≦ Rt when compensating with two retardation films In the case of a VA-mode compensation film, a value of ≤140 nm is more preferable in terms of the color shift during black display and the viewing angle dependence of contrast.

  The optical properties of the cyclic polyolefin film of the present invention can be realized by appropriately adjusting the process conditions such as the polymer structure to be used, the type and amount of additives, the stretching ratio, and the residual volatile matter at the time of peeling. For example, by adjusting the amount of the residual solvent at the time of peeling within the range of 40 to 85% by mass, the retardation Rt in the thickness direction can be widely controlled to 180 to 300 nm. In general, the larger the amount of the residual solvent at the time of peeling, the smaller the Rt, and the smaller the amount of the residual solvent at the time of peeling, the larger the Rt. For example, by shortening the drying time on a metal endless support and increasing the amount of residual solvent at the time of peeling, the plane orientation can be relaxed and Rt can be lowered freely, and by adjusting the process conditions, It is possible to exhibit various retardations according to various uses.

(Retardation, Ro, Rt)
In the present specification, Ro and Rt respectively represent an in-plane retardation and a retardation in a thickness direction at a wavelength λ. Ro is measured using KOBRA 21ADH (manufactured by Oji Scientific Instruments) by irradiating light having a wavelength of λ nm in the normal direction of the film. Rt was measured by injecting light having a wavelength of λ nm from a direction inclined by + 40 ° with respect to the normal direction of the film using the above-mentioned Ro and the in-plane slow axis (determined by KOBRA 21ADH) as an inclined axis (rotation axis). A retardation value and a retardation value measured by injecting light having a wavelength of λ nm from a direction inclined by −40 ° with respect to the normal direction of the film with the in-plane slow axis as an inclined axis (rotation axis) are measured. KOBRA 21ADH is calculated based on the retardation value measured in the direction. Here, as the assumed value of the average refractive index, a value from a catalog of various optical films and a polymer handbook (John Wiley & Sons, Inc.) can be used. If the value of the average refractive index is not known, it can be measured with an Abbe refractometer. By inputting the assumed value of the average refractive index and the film thickness, KOBRA 21ADH calculates nx, ny, and nz, and calculates retardation based on the following equations (i) and (ii).

Formula _{(i): Ro = (n} x -n y) × d (nm)
Formula _{(ii): Rt = {(} n x + n y) / 2-n z} × d (nm)
(Wherein, Ro represents a plane retardation value of the film, Rt represents the retardation value in the thickness direction of the film. Further, d represents the thickness of the optical film (nm), n _x is represents the maximum refractive index in the plane of the film, also referred to as a slow axis direction of the refractive index .n _y represents a refractive index in the direction perpendicular to the slow axis in the film plane, n _z is the film in the thickness direction , Which are measured values at a wavelength of 590 nm.)
(3) Total Light Transmittance and Haze The cyclic polyolefin film of the present invention is characterized by having high transparency, but has a total light transmittance measured after humidity control in an environment of 23 ° C. and 55% RH. It is at least 80%, preferably at least 85%, more preferably at least 90%, particularly preferably at least 95%. The total light transmittance can be measured in accordance with JIS 7573 “Plastics—How to determine total light transmittance and total light reflectance”.

  Further, the haze of the cyclic polyolefin film of the present invention is preferably less than 1%, more preferably less than 0.5%. By setting the haze to less than 1%, there is an advantage that the transparency of the film becomes higher and the film can be more easily used as a film for optical use. The measurement is performed using a haze meter (1001DP type, manufactured by Nippon Denshoku Industries Co., Ltd.) after adjusting the humidity of the sample film in an environment of 23 ° C. and 55% RH for 5 hours or more.

(4) Equilibrium Water Content The cyclic polyolefin film of the present invention preferably has an equilibrium water content at 25 ° C. and a relative humidity of 60% of 3% or less, more preferably 1% or less. By setting the equilibrium water content to 3% or less, it is easy to cope with a change in humidity, and the optical characteristics and dimensions are more unlikely to change.

  The equilibrium water content was determined by leaving the sample film in a room conditioned at 23 ° C. and 20% relative humidity for 4 hours or more, and then left in a room conditioned at 23 ° C. and 80% RH for 24 hours. The water is dried and vaporized at a temperature of 150 ° C. using a meter (for example, Model CA-20 manufactured by Mitsubishi Chemical Corporation), and then quantified by the Karl Fischer method.

≫Applications of cyclic polyolefin film≫
The cyclic polyolefin film of the present invention is a display device such as an optical film such as a polarizing plate protective film or a retardation film for a liquid crystal display or an organic electroluminescence display, a base film for a touch panel or a gas barrier base film. It can be suitably used for a substrate film, a substrate film for a nanoimprint, a substrate film for a flexible electronic circuit, and the like.

  Hereinafter, a description will be given of a polarizing plate protective film, a polarizing plate, a liquid crystal display device, an organic electroluminescence display device, and a gas barrier film, which are typical applications.

(1) Polarizing Plate Protective Film and Polarizing Plate The polarizing plate is subjected to surface treatment as appropriate using the cyclic polyolefin film of the present invention as a polarizing plate protective film, and at least a polarizer using a water paste or an active energy ray-curable adhesive. It is preferable to be stuck on one side of. The cyclic polyolefin film of the present invention can be similarly bonded to a surface of the polarizer opposite to the surface to which the cyclic polyolefin is bonded.

  Further, it is also preferable that a cellulose acylate film having an optical compensation function of the liquid crystal cell is bonded to the polarizer on the opposite surface using a water paste or an active energy ray-curable adhesive. The cyclic polyolefin film of the present invention is preferable from the viewpoint of making it possible to further reduce the fluctuation of the phase difference with respect to the temperature and humidity of the cellulose acylate film and to provide a polarizing plate which is stable against environmental changes and has excellent visibility.

When the polarizing plate is used as a polarizing plate on the viewing side, the film on the viewing side of the polarizing plate is preferably provided with a hard coat layer, an antiglare layer, an antireflection layer, an antistatic layer, an antifouling layer, or the like. (Polarizer)
A polarizer, which is a main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction, and a typical polarizer currently known is a polyvinyl alcohol-based polarizing film. Polyvinyl alcohol-based polarizing films include those obtained by dyeing a polyvinyl alcohol-based film with iodine and those obtained by dyeing a dichroic dye.

  As the polarizer, a polarizer obtained by forming a film of an aqueous solution of polyvinyl alcohol and uniaxially stretching and dyeing the film, or dyeing the film and then uniaxially stretching the film, and then preferably performing a durability treatment with a boron compound can be used. The thickness of the polarizer is preferably from 2 to 30 μm, and particularly preferably from 2 to 15 μm.

  Further, the content of an ethylene unit described in JP-A-2003-248123, JP-A-2003-342322, and the like is 1 to 4 mol%, the degree of polymerization is 2000 to 4000, and the degree of saponification is 99.0 to 99.99 mol%. Of ethylene-modified polyvinyl alcohol is also preferably used. Among them, an ethylene-modified polyvinyl alcohol film having a hot water cutting temperature of 66 to 73 ° C is preferably used. A polarizer using this ethylene-modified polyvinyl alcohol film is excellent in polarization performance and durability performance, and has little color unevenness, and is particularly preferably used for a large-sized liquid crystal display device.

<Laminated film type polarizer>
Further, the polarizing plate is preferably a thin film, and the thickness of the polarizer is particularly preferably in the range of 2 to 15 μm, from the viewpoint of achieving both the strength of the polarizing plate and thinning.

  As such a thin-film polarizer, a laminated film-type polarizer is produced by a method described in JP-A-2011-100161, JP-A-46991205, JP-A-4751581, and JP-A-4804589. Is preferred.

  As an example, it is preferable to use a thin film laminated film type polarizer (polarizing laminated film) manufactured by the following steps from the viewpoint of reducing the overall thickness of the polarizing plate and reducing its weight.

(Manufacturing method of polarizing laminated film)
The method for producing a polarizing laminated film used in the present invention includes the following steps.
(A) a laminating step of forming a polyvinyl alcohol-based resin layer on one surface of a base film in which a rubber component is dispersed in a thermoplastic resin to obtain a laminated film;
(B) a stretching step of uniaxially stretching the laminated film to obtain a stretched film,
(C) a dyeing step of dyeing the polyvinyl alcohol-based resin layer of the stretched film with a dichroic dye to obtain a dyed film;
(D) a polyvinyl alcohol-based resin layer of the dyed film is immersed in a solution containing a crosslinking agent to form a polarizer layer, and a crosslinking step of obtaining a crosslinked film; and (e) a drying step of drying the crosslinked film. To explain the process,
(A) Lamination Step In this step, a film in which a rubber component is dispersed (blended and dispersed) in a thermoplastic resin is used as a base film, and a polyvinyl alcohol-based resin layer is formed on one surface of the base film to obtain a laminated film. Is preferred.

(Base film)
The thermoplastic resin serving as the base of the base film is preferably a thermoplastic resin having excellent transparency, mechanical strength, thermal stability, stretchability and the like. Specific examples of such a thermoplastic resin include, for example, a chain polyolefin resin; a cyclic polyolefin resin; a (meth) acrylic resin; a polyester resin; a cellulose acylate resin; a polycarbonate resin; Resins; vinyl acetate resins; polyarylate resins; polystyrene resins; polyether sulfone resins; polysulfone resins; polyamide resins; polyimide resins; and mixtures or copolymers thereof.

  The rubber component dispersed in the thermoplastic resin is a resin component having rubber elasticity, and is usually uniformly dispersed as rubber particles in the thermoplastic resin. By mixing and dispersing the rubber component, the tear strength of the base film, and thus the stretched film, can be improved. The rubber component is not particularly limited as long as it is a resin having rubber elasticity. However, from the viewpoint of compatibility with the thermoplastic resin, the rubber component is preferably composed of a resin of the same type or similar to the thermoplastic resin used.

  For example, when the thermoplastic resin is a linear polyolefin-based resin, the rubber component can be a copolymer of two or more monomers selected from ethylene and α-olefin. In this case, the content (polymerization ratio) of each monomer constituting the copolymer is preferably less than 90% by mass, and more preferably less than 80% by mass.

  When the thermoplastic resin is a (meth) acrylic resin, it is preferable to contain, as a rubber component, an acrylic polymer having rubber elasticity from the viewpoint of compatibility. The acrylic polymer is preferably a polymer mainly composed of an alkyl acrylate, and may be a homopolymer of an alkyl acrylate, or 50% by mass or more of an alkyl acrylate and 50% by mass or less of another monomer. And a copolymer of

  The compounding amount of the rubber component is preferably 5 to 50% by mass of the thermoplastic resin, more preferably 10 to 45% by mass. If the amount of the rubber component is too small, a sufficient effect of improving the tear strength tends to be hardly obtained, and if the amount of the rubber component is too large, the handleability of the base film tends to decrease.

  The method of dispersing the rubber component in the thermoplastic resin is not particularly limited. For example, a method in which a separately prepared thermoplastic resin and a rubber component (rubber particles) are kneaded and dispersed by a plast mill or the like, or the same reaction is performed during the preparation of the thermoplastic resin. A reactor blending method in which a rubber component is also prepared in a container to obtain a thermoplastic resin in which the rubber component is dispersed can be used. The reactor blending method is advantageous in improving the degree of dispersion of the rubber component.

(Polyvinyl alcohol resin layer)
Examples of the polyvinyl alcohol-based resin forming the polyvinyl alcohol-based resin layer include polyvinyl alcohol resins and derivatives thereof. Derivatives of polyvinyl alcohol resins include polyvinyl formal, polyvinyl acetal, etc., and polyvinyl alcohol resins such as olefins such as ethylene and propylene, unsaturated carboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, and alkyl esters of unsaturated carboxylic acids. And those modified with acrylamide and the like. Among these, it is preferable to use a polyvinyl alcohol resin.

  The polyvinyl alcohol-based resin is preferably a completely saponified product. The range of the degree of saponification is preferably in the range of 80.0 to 100.0 mol%, more preferably in the range of 90.0 to 99.5 mol%, and still more preferably 94.0 to 99.0. Mol% range.

  If necessary, additives such as a plasticizer and a surfactant may be added to the polyvinyl alcohol-based resin described above. As the plasticizer, polyols and condensates thereof can be used, and examples thereof include glycerin, diglycerin, triglycerin, ethylene glycol, propylene glycol, and polyethylene glycol. The amount of the additive is not particularly limited, but is preferably 20% by mass or less of the polyvinyl alcohol-based resin.

  Examples of the method of applying a polyvinyl alcohol-based resin solution to a base film include a wire bar coating method, a reverse coating method, a roll coating method such as a gravure coating method, a spin coating method, a screen coating method, a fountain coating method, a dipping method, and a spray method. And other known methods. The drying temperature is, for example, in the range of 50 to 200C, and preferably in the range of 60 to 150C. The drying time is, for example, in the range of 2 to 20 minutes.

  The thickness of the polyvinyl alcohol-based resin layer in the laminated film is preferably 3 μm or more and 50 μm or less, more preferably 5 μm or more and 45 μm or less. If it is less than 3 μm, it will be too thin after stretching and the dyeing properties will be remarkably deteriorated. If it exceeds 50 μm, the obtained polarizing laminate film will be thick.

  The thickness of the polyvinyl alcohol-based resin layer as a polarizer used in the present invention, from the viewpoint of thinning and strength as a polarizer, flexibility, from the viewpoint of the following thickness after stretching treatment is in the range of 2 to 15 μm. Is preferred.

(B) Stretching Step This step is a step of uniaxially stretching a laminated film including a base film and a polyvinyl alcohol-based resin layer to obtain a stretched film. The stretching ratio of the laminated film can be appropriately selected according to the desired polarization characteristics, but is preferably in the range of 5 to 17 times, more preferably 5 to 8 times with respect to the original length of the laminated film. Within range.

  The stretching is preferably longitudinal stretching in which stretching is performed in the longitudinal direction (film transport direction) of the laminated film. Examples of the longitudinal stretching method include an inter-roller stretching method, a compression stretching method, and a stretching method using a tenter. In addition, the uniaxial stretching is not limited to the longitudinal stretching process, and may be oblique stretching or the like.

(C) Dyeing Step This step is a step of dyeing the polyvinyl alcohol resin layer of the stretched film with a dichroic dye to obtain a dyed film. Examples of the dichroic dye include iodine and organic dyes. Examples of the organic dye include Red BR, Red LR, Red R, Pink LB, Rubin BL, Bordeaux GS, Sky Blue LG, Lemon Yellow, Blue BR, Blue 2R, Navy RY, Green LG, Violet LB, Violet B, Black H, Black B, Black GSP, Yellow 3G, Yellow R, Orange LR, Orange 3R, Scarlet GL, Scarlet KGL, Congo Red, Brilliant Violet BK, Supra Blue G, Supra Blue GL, Supra Orange GL, Direct Sky Blue, Direct First Orange S, First Black, etc. can be used. These dichroic substances may be used alone or in combination of two or more.

  When iodine is used as the dichroic dye, it is preferable to further add an iodide to the iodine-containing dyeing solution since the dyeing efficiency can be further improved. Examples of the iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and tin iodide. Titanium and the like can be mentioned.

(D) Cross-linking step In this step, a cross-linking treatment is performed on the polyvinyl alcohol-based resin layer of the dyed film obtained by dyeing with a dichroic dye, and the cross-linked film having the polyvinyl alcohol-based resin layer as a polarizer layer is obtained. This is the step of obtaining. The crosslinking step can be performed, for example, by immersing the dyed film in a solution containing a crosslinking agent (crosslinking solution). As the cross-linking agent, a conventionally known substance can be used. For example, boron compounds such as boric acid and borax, glyoxal, glutaraldehyde and the like can be mentioned. These may be used alone or in combination of two or more.

(E) Drying step The obtained crosslinked film is usually dried after washing. Thereby, a polarizing laminated film is obtained. Washing can be performed by immersing the crosslinked film in pure water such as ion-exchanged water or distilled water. The water washing temperature is usually in the range of 3 to 50 ° C, preferably in the range of 4 to 20 ° C. The immersion time is usually in the range of 2 to 300 seconds, preferably 5 to 240 seconds. For washing, a washing treatment with an iodide solution and a water washing treatment may be combined, and a solution in which a liquid alcohol such as methanol, ethanol, isopropyl alcohol, butanol, or propanol is appropriately blended may be used.

  As a drying method, any appropriate method (for example, natural drying, blast drying, and heat drying) can be adopted. For example, the drying temperature in the case of heat drying is usually in the range of 20 to 95 ° C., and the drying time is usually about 1 to 15 minutes.

  The polarizing laminated film includes a polarizer layer composed of a polyvinyl alcohol-based resin layer on which a dichroic dye is adsorbed and oriented, and can be used as a polarizing plate itself. As a preferred embodiment of the present invention, after forming the polarizing laminate film by the above process, by peeling the polyvinyl alcohol layer of the polarizing laminate film from the base film, the polyvinyl alcohol layer is used as a polarizer. That is. According to this method, the thickness of the polarizer layer can be reduced to 15 μm or less, so that a thin polarizer can be obtained. Further, the polarizer used in the present invention has excellent polarization performance and durability.

(Preparation of polarizing plate)
The polarizing plate can be manufactured by a general method. It is preferable that the polarizer side of the cyclic polyolefin film of the present invention is subjected to a surface treatment, and is bonded to a polarizer produced by dipping and stretching in an iodine solution using the following active energy ray-curable adhesive. When a cellulose acylate film is used on the surface opposite to the surface on which the cyclic polyolefin film is bonded, the cellulose acylate film is subjected to alkali saponification treatment, and at least one surface of the polarizer is completely saponified. It is preferable to bond together using a modified polyvinyl alcohol aqueous solution (water paste). Another polarizing plate protective film can be bonded to the other surface.

  For example, commercially available cellulose acylate films (e.g., Konica Minolta Tac KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC6UY, KC6UA, KC4UY, KC4UE, KC8UE, KC8U-HUCH, HXA-X, H-X, H-A, H-A, H-C, H-A, H-A, H-A, H-A, H-A, H-A, H-C KC8UXW-RHA-NC and KC4UXW-RHA-NC (all manufactured by Konica Minolta Inc.) are preferably used.

[Active energy ray-curable adhesive]
Further, in the polarizing plate, it is preferable that the cyclic polyolefin film of the present invention and the polarizer are bonded with an active energy ray-curable adhesive.

  As the active energy ray-curable adhesive, the following ultraviolet-curable adhesive is preferably used.

  In the present invention, by applying an ultraviolet curable adhesive to the bonding between the cyclic polyolefin film and the polarizer, a polarizing plate having high strength and excellent flatness can be obtained even in a thin film.

<Composition of UV-curable adhesive>
As an ultraviolet-curable adhesive composition for a polarizing plate, a photo-radical polymerization type composition using photo-radical polymerization, a photo-cation polymerization type composition using photo-cation polymerization, and a combination of photo-radical polymerization and photo-cation polymerization Hybrid compositions are known.

  As the photoradical polymerization type composition, a specific ratio of a radical polymerizable compound containing a polar group such as a hydroxy group or a carboxy group and a radical polymerizable compound not containing a polar group described in JP-A-2008-09329 are included. Compositions) are known. In particular, the radical polymerizable compound is preferably a compound having a radically polymerizable ethylenically unsaturated bond. Preferred examples of the compound having an ethylenically unsaturated bond capable of undergoing radical polymerization include a compound having a (meth) acryloyl group. Examples of the compound having a (meth) acryloyl group include an N-substituted (meth) acrylamide compound, a (meth) acrylate compound, and the like. (Meth) acrylamide means acrylamide or methacrylamide.

  Further, as the cationic photopolymerizable composition, (α) cationic polymerizable compound, (β) cationic photopolymerization initiator, and (γ) wavelength longer than 380 nm as disclosed in JP-A-2011-028234. UV-curable adhesive compositions containing each component of a photosensitizer exhibiting a maximum absorption of the above-mentioned light and (δ) a naphthalene-based photosensitizer. However, other UV-curable adhesives may be used.

(I) Pretreatment Step The pretreatment step is a step of performing an easy adhesion treatment on the surface of the cyclic polyolefin film to be adhered to the polarizer. Examples of the easy adhesion treatment include a corona treatment and a plasma treatment.

(Application process of UV curable adhesive)
In the step of applying the UV-curable adhesive, the UV-curable adhesive is applied to at least one of the bonding surfaces of the polarizer and the cyclic polyolefin film. When an ultraviolet-curable adhesive is directly applied to the surface of a polarizer or a cyclic polyolefin film, the application method is not particularly limited. For example, various wet coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used. Further, a method in which an ultraviolet-curable adhesive is cast between the polarizer and the cyclic polyolefin film, and then pressure is applied with a roller or the like to uniformly spread the adhesive is used.

(Ii) Laminating Step After the application of the ultraviolet-curable adhesive by the above-mentioned method, it is processed in the laminating step. In this bonding step, for example, when an ultraviolet curable adhesive is applied to the surface of the polarizer in the previous application step, the cyclic polyolefin film is superposed thereon. In the case of applying a UV curable adhesive to the surface of the cyclic polyolefin film first, a polarizer is superposed thereon. When an ultraviolet curable adhesive is cast between the polarizer and the cyclic polyolefin film, the polarizer and the cyclic polyolefin film are superposed in this state. Usually, in this state, pressure is applied between both sides of the cyclic polyolefin film by a pressure roller or the like. As the material of the pressure roller, metal, rubber, or the like can be used. The pressure rollers arranged on both sides may be made of the same material or different materials.

(Iii) Curing Step In the curing step, an uncured ultraviolet-curable adhesive is irradiated with ultraviolet rays to irradiate a cationically polymerizable compound (for example, an epoxy compound or an oxetane compound) or a radically polymerizable compound (for example, an acrylate compound or acrylamide). An ultraviolet-curable adhesive layer containing an organic compound and the like is cured, and the polarizer and the cyclic polyolefin film are bonded to each other via the ultraviolet-curable adhesive. When laminating a cyclic polyolefin film on one side of a polarizer, the active energy ray may be irradiated from either the polarizer side or the cyclic polyolefin film side. In addition, when laminating the cyclic polyolefin film on both sides of the polarizer, irradiate ultraviolet rays in a state where the cyclic polyolefin film is laminated on both sides of the polarizer via an ultraviolet-curable adhesive, respectively, and the ultraviolet curable It is advantageous to cure the adhesive simultaneously.

As the irradiation condition of the ultraviolet ray, any appropriate condition can be adopted as long as it can cure the ultraviolet curable adhesive applied to the present invention. Preferably the dose of ultraviolet rays in the range of 50~1500mJ / cm ² in accumulated light quantity, and even more preferably in the range of 100 to 500 mJ / cm ^2.

  When the manufacturing process of the polarizing plate is performed in a continuous line, the line speed depends on the curing time of the adhesive, but is preferably in the range of 1 to 500 m / min, more preferably in the range of 5 to 300 m / min, and still more preferably in the range of 10 to 300 m / min. The range is 100 m / min. When the line speed is 1 m / min or more, productivity can be ensured, or damage to the cyclic polyolefin film can be suppressed, and a polarizing plate having excellent durability can be manufactured. When the line speed is 500 m / min or less, the curing of the ultraviolet-curable adhesive is sufficient, and the ultraviolet-curable adhesive layer having the desired hardness and excellent adhesiveness can be formed.

(Functional layer)
In the cyclic polyolefin film of the present invention, an antireflection layer, a light scattering layer, a hard coat layer, an antistatic layer and the like can be provided as functional layers.

<Anti-reflective layer>
It is preferable to provide a functional film such as an anti-reflection layer on the transparent protective film disposed on the opposite side of the polarizing plate from the liquid crystal cell. An antireflection layer in which at least a light scattering layer and a low refractive index layer are laminated in this order on a cyclic polyolefin film, or a medium refractive index layer, a high refractive index layer, and a low refractive index layer are laminated in this order on a cyclic polyolefin film. An antireflection layer is preferably used.

(Anti-reflection layer provided with a light scattering layer and a low refractive index layer)
It is preferable that the mat particles are dispersed in the light scattering layer, and the refractive index of the material other than the mat particles of the light scattering layer is preferably in the range of 1.50 to 2.00. Is preferably in the range of 1.35 to 1.49. The light scattering layer may have both the antiglare property and the hard coat property, may be a single layer, or may be composed of a plurality of layers, for example, two to four layers.

  The antireflection layer has, as its surface unevenness, a center line average roughness Ra of 0.08 to 0.40 μm, a 10-point average roughness Rz of 10 times or less of Ra, an average peak-to-valley distance Sm of 1 to 100 μm, Designed so that the standard deviation of the height of the convex portion from the part is 0.5 μm or less, the standard deviation of the average peak-to-valley distance Sm with respect to the center line is 20 μm or less, and the surface with a tilt angle of 0 to 5 degrees is 10% or more. By doing so, sufficient anti-glare properties and a uniform matte feeling visually are achieved, which is preferable.

Further, the ratio of the minimum value to the maximum value of the reflectance in the range of a ^* value −2 to 2, b ^* value −3 to 3, and 380 to 780 nm when the color of the reflected light under the C light source is 0.5 is 0.5. When it is 0.99, the color of the reflected light becomes neutral, which is preferable. Further, when the b ^* value of the transmitted light under the C light source is 0 to 3, the yellow color of white display when applied to a display device is reduced, which is preferable.

  Further, when a standard deviation of the luminance distribution when the luminance distribution is measured on the film by inserting a grid of 120 × 40 μm between the surface light source and the antireflection film is 20 or less, the present invention is applied to a high definition panel. It is preferable because glare when a cyclic polyolefin film is applied is reduced.

  The anti-reflection layer can suppress the reflection of external light and improve the visibility by setting the optical characteristics of the anti-reflection layer to 2.5% or less for specular reflectivity, 90% or more for transmittance, and 70% or less for 60 degree glossiness. Therefore, it is preferable. In particular, the specular reflectance is more preferably 1% or less, most preferably 0.5% or less. Haze 20 to 50%, internal haze / total haze value (ratio) 0.3 to 1, reduction in haze value after formation of low refractive index layer from haze value up to light scattering layer within 15%, comb width 0 By setting the transmitted image clarity at 0.5 mm to 20 to 50% and the transmittance ratio of vertical transmitted light / transmittance in a direction inclined at 2 degrees from vertical to 1.5 to 5.0, glare on a high-definition LCD panel can be prevented, and characters can be prevented. The reduction of blurs such as is achieved, which is preferable.

(Low refractive index layer)
The refractive index of the low refractive index layer of the antireflection film is preferably in the range of 1.20 to 1.49, and more preferably in the range of 1.30 to 1.44. Further, it is preferable that the low refractive index layer satisfies the following formula from the viewpoint of lowering the reflectance.

(M / 4) × 0.7 <n1d1 <(m / 4) × 1.3
In the formula, m is a positive odd number, n1 is the refractive index of the low refractive index layer, and d1 is the thickness (nm) of the low refractive index layer. Λ is a wavelength and is a value in a range of 500 to 550 nm.

  The material for forming the low refractive index layer will be described below.

  The low refractive index layer preferably contains a fluorine-containing polymer as a low refractive index binder. As the fluoropolymer, a fluoropolymer which is crosslinked by heat or ionizing radiation having a dynamic friction coefficient of 0.03 to 0.20, a contact angle to water of 90 to 120 °, and a sliding angle of pure water of 70 ° or less is preferable. When the antireflection film is mounted on an image display device, the lower the peeling force with a commercially available adhesive tape, the easier it is to peel off after attaching a seal or memo, preferably 500 gf or less, more preferably 300 gf or less, and more preferably 100 gf or less. Most preferred.

  Also, the higher the surface hardness measured by the microhardness tester, the less likely it is to be scratched, preferably 0.3 GPa or more, more preferably 0.5 GPa or more.

  Examples of the fluorine-containing polymer used for the low refractive index layer include hydrolysis and dehydration condensates of perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane). And a fluorine-containing copolymer containing a fluorine-containing monomer unit and a structural unit for imparting crosslinking reactivity as a constituent component.

  Specific examples of the fluorinated monomer include, for example, fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc. ), Partially or completely fluorinated alkyl ester derivatives of (meth) acrylic acid (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)), and fully or partially fluorinated vinyl ethers. , Preferably perfluoroolefins, and particularly preferably hexafluoropropylene from the viewpoints of refractive index, solubility, transparency, availability and the like.

  Structural units for imparting crosslinking reactivity include structural units obtained by polymerization of a monomer having a self-crosslinkable functional group in the molecule, such as glycidyl (meth) acrylate and glycidyl vinyl ether, carboxy group, hydroxy group, and amino group , A monomer having a sulfo group or the like (eg, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc.) Structural units, or structural units in which a cross-linking reactive group such as a (meth) acryloyl group is introduced into these structural units by a polymer reaction (for example, they can be introduced by a method such as making acrylic acid chloride act on a hydroxy group) But It is below.

  In addition to the above-mentioned fluorine-containing monomer unit and the constituent unit for imparting crosslinking reactivity, a monomer containing no fluorine atom can be appropriately copolymerized from the viewpoint of solubility in a solvent, transparency of a film, and the like. There is no particular limitation on the monomer units that can be used in combination, and for example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylates (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2) -Ethylhexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyltoluene, α-methylstyrene, etc.), vinyl ethers (methyl Vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tert-butylacrylamide, N Cyclohexyl acrylamide), methacrylamides, and acrylonitrile derivatives. As described in JP-A-10-25388 and JP-A-10-147739, a curing agent may be appropriately used in combination with the above polymer.

(Light scattering layer)
The light-scattering layer is generally formed for the purpose of contributing to the film light diffusibility due to surface scattering and / or internal scattering and hard coating properties for improving the scratch resistance of the film. Therefore, it is generally formed to include a binder for imparting a hard coat property, mat particles for imparting a light diffusing property, and an inorganic filler for increasing the refractive index, preventing crosslinking shrinkage, and increasing the strength as necessary. Is done. The thickness of the light-scattering layer is preferably in the range of 1 to 10 μm, more preferably 1.2 to 6 μm, from the viewpoint of imparting a hard coat property and suppressing the occurrence of curl and deterioration of brittleness.

  The binder of the scattering layer is preferably a polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a polymer having a saturated hydrocarbon chain as a main chain. Further, the binder polymer preferably has a crosslinked structure. As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer is preferable. As the binder polymer having a saturated hydrocarbon chain as a main chain and having a crosslinked structure, a (co) polymer of a monomer having two or more ethylenically unsaturated groups is preferable. In order to make the binder polymer have a high refractive index, an aromatic ring or a monomer containing at least one atom selected from a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom in the structure of the monomer is used. You can also choose.

  Examples of the monomer having two or more ethylenically unsaturated groups include esters of a polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di ( (Meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropanetri (meth) acrylate, trimethylolethanetri (meth) acrylate, dipentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-c Roxanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), the above-mentioned modified ethylene oxide, vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4 -Divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide. Two or more of the above monomers may be used in combination.

  Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinylnaphthalene, vinylphenylsulfide, 4-methacryloxyphenyl-4'-methoxyphenylthioether, and the like. Two or more of these monomers may be used in combination.

  Polymerization of these monomers having an ethylenically unsaturated group can be carried out by irradiation with ionizing radiation or heating in the presence of a photoradical initiator or a thermal radical initiator.

  Therefore, a coating liquid containing a monomer having an ethylenically unsaturated group, a photoradical initiator or a thermal radical initiator, mat particles and an inorganic filler is prepared, and the coating liquid is applied on a transparent support, and then ionized radiation or heat is applied. To form an anti-reflection film by the polymerization reaction. Known photo-radical initiators and the like can be used.

  The polymer having a polyether as a main chain is preferably a ring-opened polymer of a polyfunctional epoxy compound. Ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator.

  Therefore, a coating solution containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, a mat particle and an inorganic filler is prepared, and the coating solution is applied on a transparent support and then polymerized by ionizing radiation or heat. By curing, an anti-reflection film can be formed.

  Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinkable functional group is introduced into the polymer using a monomer having a crosslinkable functional group, and the reaction of the crosslinkable functional group A crosslinked structure may be introduced into the binder polymer.

  Examples of the crosslinkable functional group include an isocyanate group, an epoxy group, an aziridine group, an oxazoline group, an aldehyde group, a carbonyl group, a hydrazine group, a carboxy group, a methylol group, and an active methylene group. Vinyl sulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of a decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not show a reaction immediately but may show a reactivity as a result of decomposition.

  These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after application.

  In the light scattering layer, for the purpose of imparting anti-glare properties, mat particles having a size larger than the filler particles and having an average particle size in the range of 1 to 10 μm, preferably 1.5 to 7.0 μm, for example, particles of an inorganic compound or Preferably, resin particles are contained.

Specific examples of the mat particles include particles of inorganic compounds such as silica particles and TiO ₂ particles; and resin particles such as acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles. No. Of these, crosslinked styrene particles, crosslinked acryl particles, crosslinked acrylstyrene particles, and silica particles are preferred. The shape of the mat particles can be either spherical or irregular.

  Further, two or more kinds of mat particles having different particle diameters may be used in combination. It is possible to provide anti-glare properties with matte particles having a larger particle diameter, and to impart another optical property with matte particles having a smaller particle diameter.

  Further, the particle size distribution of the above matte particles is most preferably monodisperse, and the closer the particle diameters of the respective particles are to the same, the better. For example, when particles having a particle size larger than 20% or more than the average particle size are defined as coarse particles, the ratio of the coarse particles is preferably 1% or less of the total number of particles, more preferably 0.1%. Or less, more preferably 0.01% or less. Mat particles having such a particle size distribution are obtained by classification after a usual synthesis reaction, and fine particles having a more preferable distribution can be obtained by increasing the number of times of classification and increasing the degree thereof.

The above-mentioned mat particles are contained in the light-scattering layer such that the amount of the mat particles in the formed light-scattering layer is preferably in the range of 10 to 1000 mg / m ² , more preferably in the range of 100 to 700 mg / m ² . The particle size distribution of the mat particles is measured by the Coulter counter method, and the measured distribution is converted into a particle number distribution.

  In order to increase the refractive index of the light-scattering layer, in addition to the above matte particles, an oxide of at least one metal selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony is used. In addition, it is preferable that an inorganic filler having an average particle diameter of 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less is contained.

  Conversely, in order to increase the refractive index difference from the matting particles, it is also preferable to use silicon oxide in the light scattering layer using the high refractive index matting particles in order to keep the refractive index of the layer low. The preferred particle size is the same as the above-mentioned inorganic filler.

Specific examples of the inorganic filler used for the light scattering layer include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and SiO _{2 and the} like. TiO ₂ and ZrO ₂ are particularly preferred in terms of increasing the refractive index. The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treating agent having a functional group capable of reacting with a binder species on the filler surface is preferably used. The addition amount of these inorganic fillers is preferably in the range of 10 to 90% of the total mass of the light scattering layer, more preferably in the range of 20 to 80%, and particularly preferably in the range of 30 to 75%. is there. Note that such a filler does not scatter because the particle diameter is sufficiently smaller than the wavelength of light, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

  The bulk refractive index of the mixture of the binder and the inorganic filler in the light scattering layer is preferably in the range of 1.48 to 2.00, and more preferably in the range of 1.50 to 1.80. In order to set the refractive index in the above range, the types and the proportions of the binder and the inorganic filler may be appropriately selected. How to select can be easily known experimentally in advance.

  The light-scattering layer is coated with a fluorine-based or silicone-based surfactant or both to form an antiglare layer in order to secure surface uniformity such as uneven coating, uneven drying, and point defects. Preferably, it is contained in the composition. In particular, a fluorine-based surfactant is preferably used because the effect of improving surface defects such as uneven application of the antireflection film, uneven drying, and point defects appears with a smaller addition amount. The purpose is to increase productivity by giving high-speed coating suitability while improving surface uniformity.

<Anti-reflection layer in which a middle refractive index layer, a high refractive index layer, and a low refractive index layer are laminated in this order>
An antireflection film having at least a middle refractive index layer, a high refractive index layer, and a low refractive index layer (outermost layer) on a film is designed to have a refractive index satisfying the following relationship. Is preferred. Refractive index of high refractive index layer> refractive index of medium refractive index layer> refractive index of transparent support> refractive index of low refractive index layer. Further, a hard coat layer may be provided between the transparent support and the middle refractive index layer. Further, it may be composed of a medium refractive index hard coat layer, a high refractive index layer and a low refractive index layer (for example, JP-A-8-122504, JP-A-8-110401, JP-A-10-300902, JP-A-2002-243906, JP-A-2000-111706 and the like). Further, each layer may be provided with another function, for example, an antifouling low refractive index layer and an antistatic high refractive index layer (eg, JP-A-10-206603, JP-A-2002-2002). -243906 and the like).

  The haze of the antireflection film is preferably 5% or less, more preferably 3% or less. The strength of the film is preferably H or more in a pencil hardness test according to JIS K5400, more preferably 2H or more, and most preferably 3H or more.

(High refractive index layer and medium refractive index layer)
The layer having a high refractive index of the antireflection film is preferably composed of a curable film containing at least an inorganic compound ultrafine particle having a high refractive index having an average particle diameter of 100 nm or less and a matrix binder.

  Examples of the inorganic compound fine particles having a high refractive index include inorganic compounds having a refractive index of 1.65 or more, and preferably those having a refractive index of 1.9 or more. For example, oxides such as Ti, Zn, Sb, Sn, Zr, Ce, Ta, La, and In, and composite oxides containing these metal atoms can be given.

  In order to obtain such ultrafine particles, the surface of the particles must be treated with a surface treating agent (for example, silane coupling agents and the like: JP-A-11-295503, JP-A-11-153703, JP-A-2000-9908). , An anionic compound or an organic metal coupling agent: JP-A-2001-310432, etc.) and a core-shell structure having high-refractive-index particles as cores (: JP-A-2001-166104, JP-A-2001-310432, etc.) ) And specific dispersants (for example, JP-A-11-153703, U.S. Pat. No. 6,210,858) and the like.

  As a material for forming the matrix, conventionally known thermoplastic resins, curable resin films and the like can be mentioned.

  Furthermore, a polyfunctional compound-containing composition having at least two radically polymerizable and / or cationically polymerizable groups, and a composition containing an organometallic compound having a hydrolyzable group and a partial condensate thereof At least one composition chosen is preferred. For example, the compositions described in JP-A-2000-47004, JP-A-2001-315242, JP-A-2001-31871, JP-A-2001-296401 and the like can be mentioned.

  Further, a curable film obtained from a colloidal metal oxide obtained from a hydrolytic condensate of a metal alkoxide and a metal alkoxide composition is also preferable. For example, it is described in JP-A-2001-293818.

  The refractive index of the high refractive index layer is generally in the range of 1.70 to 2.20. The thickness of the high refractive index layer is preferably in the range of 5 nm to 10 μm, more preferably in the range of 10 nm to 1 μm. The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably in the range of 1.50 to 1.70. Further, the thickness is preferably in the range of 5 nm to 10 μm, and more preferably in the range of 10 nm to 1 μm.

(Low refractive index layer)
In the above configuration, the low refractive index layer is formed by sequentially laminating the high refractive index layer. The low refractive index layer preferably has a refractive index in the range of 1.20 to 1.55, and more preferably 1.30 to 1.50.

  It is preferable to construct as an outermost layer having scratch resistance and stain resistance. As a means for greatly improving the scratch resistance, it is effective to impart slipperiness to the surface, and a conventionally known means of a thin film layer formed by introducing silicone or fluorine can be applied.

  The refractive index of the fluorine-containing compound is preferably in the range of 1.35 to 1.50. More preferably, it is in the range of 1.36 to 1.47. Further, the fluorine-containing compound is preferably a compound containing a fluorine atom in the range of 35 to 80% by mass and having a crosslinkable or polymerizable functional group. For example, paragraph numbers [0018] to [0026] of JP-A-9-222503, paragraph numbers [0019] to [0030] of JP-A-11-38202, and paragraph numbers of JP-A-2001-40284. [0027] to [0028] and compounds described in JP-A-2000-284102 and the like.

  The silicone compound is a compound having a polysiloxane structure, and preferably contains a curable functional group or a polymerizable functional group in a polymer chain and has a crosslinked structure in the film. Examples thereof include reactive silicones (eg, Silaplane (manufactured by Chisso Corporation) and polysiloxanes containing silanol groups at both ends (JP-A-11-258403).

  The crosslinking or polymerization reaction of the fluorine-containing and / or siloxane polymer having a crosslinking or polymerizable group is carried out simultaneously with or after the application of a coating composition for forming an outermost layer containing a polymerization initiator, a sensitizer and the like. It is preferable to carry out by light irradiation or heating.

  Further, a sol-gel cured film that cures an organometallic compound such as a silane coupling agent and a specific fluorinated hydrocarbon group-containing silane coupling agent by a condensation reaction in the presence of a catalyst is also preferable.

  For example, a polyfluoroalkyl group-containing silane compound or a partially hydrolyzed condensate thereof (JP-A-58-142958, JP-A-58-147483, JP-A-58-147484, JP-A-9-157584, and JP-A-11-157584) -106704), silyl compounds containing a fluorine-containing long chain poly (perfluoroalkyl ether) group (JP-A-2000-117902, JP-A-2001-48590, JP-A-2002-2002). No. 53804) and the like.

  The low refractive index layer has a primary particle average diameter of 1 to 150 nm such as a filler (for example, silicon dioxide (silica), or fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride)) as an additive other than the above. Low refractive index inorganic compounds, organic fine particles described in paragraphs [0020] to [0038] of JP-A-11-3820, a silane coupling agent, a slipping agent, a surfactant and the like.

  When the low-refractive-index layer is located below the outermost layer, the low-refractive-index layer may be formed by a vapor phase method (a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, or the like). The coating method is preferable because it can be manufactured at low cost. The thickness of the low refractive index layer is preferably in the range of 30 to 200 nm, more preferably in the range of 50 to 150 nm, and most preferably in the range of 60 to 120 nm.

<Other layers of antireflection layer>
Further, a hard coat layer, a forward scattering layer, a primer layer, an antistatic layer, an undercoat layer, a protective layer, and the like may be provided.

(Hard coat layer)
The hard coat layer is usually provided on the surface of the transparent support in order to impart physical strength to the transparent protective film provided with the antireflection layer. In particular, it is preferably provided between the transparent support and the high refractive index layer. The hard coat layer is preferably formed by a crosslinking reaction of a light and / or heat curable compound or a polymerization reaction. The curable functional group is preferably a photopolymerizable functional group, and the hydrolyzable functional group-containing organometallic compound is preferably an organic alkoxysilyl compound.

  Specific examples of these compounds include those similar to those exemplified for the high refractive index layer. Specific examples of the constituent composition of the hard coat layer include those described in JP-A-2002-144913, JP-A-2000-9908, and WO 00/46617.

  The high refractive index layer can also serve as a hard coat layer. In such a case, it is preferable that fine particles are finely dispersed by using the method described for the high refractive index layer, and the fine particles are contained in the hard coat layer.

  The hard coat layer may also serve as an anti-glare layer (described later) provided with an anti-glare function (anti-glare function) by containing particles having an average particle diameter in the range of 0.2 to 10 μm.

  The thickness of the hard coat layer can be appropriately designed depending on the application. The thickness of the hard coat layer is preferably in the range of 0.2 to 10 μm, more preferably in the range of 0.5 to 7 μm.

The strength of the hard coat layer is preferably at least H, more preferably at least 2H, most preferably at least 3H in a pencil hardness test according to JIS K5400. In a Taber test according to JIS K5400, it is preferable that the amount of wear of the test piece before and after the test is small.

(Antistatic layer)
When an antistatic layer is provided, it is preferable to impart conductivity with a volume resistivity of 10 ⁻⁸ Ω · cm ⁻³ or less. A volume resistivity of 10 ⁻⁸ Ω · cm ⁻³ can be provided by using a hygroscopic substance, a water-soluble inorganic salt, a certain surfactant, a cationic polymer, an anionic polymer, colloidal silica, or the like. There is a problem that dependency is large and sufficient conductivity cannot be ensured at low humidity. Therefore, a metal oxide is preferable as the conductive layer material. It is preferable to use an uncolored metal oxide as the conductive layer material because the coloring of the entire film is suppressed. As a metal forming a metal oxide without coloring, Zn, Ti, Al, In, Si, Mg, Ba, Mo, W, or V can be given, and a metal oxide containing this as a main component can be used. preferable. Specific examples include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , V ₂ O _{5 and the} like, or a composite oxide thereof. Particularly, ZnO, TiO ₂ and SnO ₂ are preferable. Examples of containing heteroatoms include additives such as Al and In for ZnO, addition of Sb, Nb, and halogen element for SnO ₂ , and addition of Nb and TA for TiO ₂ . The addition is effective. Further, as described in JP-B-59-6235, a material in which the above-mentioned metal oxide is adhered to other crystalline metal particles or fibrous materials (for example, titanium oxide) may be used. The volume resistance value and the surface resistance value are different physical properties and cannot be simply compared. However, in order to secure a conductivity of 10 ⁻⁸ Ω · cm ⁻³ or less in terms of the volume resistance, it is necessary to use the conductive property. It is sufficient that the layer has a surface resistance of about 10 ⁻¹⁰ Ω / □ or less, and more preferably 10 ⁻⁸ Ω / □.

(2) Liquid crystal display device By using a polarizing plate to which the cyclic polyolefin film of the present invention is bonded for a liquid crystal display device, various liquid crystal display devices excellent in visibility can be manufactured.

  The polarizing plate can be used for liquid crystal display devices of various driving systems such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, and OCB. Preferably, it is a VA (MVA, PVA) type liquid crystal display device.

  In a liquid crystal display device, two polarizing plates, a polarizing plate on the viewing side and a polarizing plate on the backlight side, are usually used. However, a polarizing plate having the cyclic polyolefin film of the present invention may be used as both polarizing plates. Preferably, it is also preferably used as a polarizing plate on one side. In particular, the polarizing plate provided with the cyclic polyolefin film of the present invention is preferably used as a polarizing plate on the viewing side that directly touches the external environment, in which case, a retardation film such as a cellulose acylate film is disposed on the liquid crystal cell side. Is preferred.

  Further, as the polarizing plate on the backlight side, a polarizing plate not provided with the cyclic polyolefin film of the present invention can be used. In this case, both surfaces of the polarizer can be used, for example, a commercially available cellulose acylate film (for example, Konica Minolta Tac KC8UX, KC5UX, KC4UX, KC8UCR3, KC4SR, KC4BR, KC4CR, KC4DR, KC4FR, KC4KR, KC8UY, KC6UY, KC4UY, KC4UE, KC8UE, KC8U-HA, KC2UK, AUCK, AUCK, AUCK, AA FUJITAC T40UZ, FUJITAC T60UZ, FUJITAC T80UZ, FUJITAC TD80UL, FUJITAC TD60UL, FUJITAC TD40UL, FUJITAC R02, FUJITAC Click R06, or produced by Fujifilm Corp., etc.) bonded combined polarizing plate is preferably used.

  Further, as the polarizing plate on the backlight side, the cyclic polyolefin film of the present invention is used on the liquid crystal cell side of the polarizer, and the above-mentioned commercially available cellulose acylate film, polyester film, acrylic film, or polycarbonate film is pasted on the opposite surface. A combined polarizing plate can also be preferably used.

  By using the polarizing plate, it is possible to obtain a liquid crystal display device having excellent visibility such as uneven display and front contrast even in a large-screen liquid crystal display device having a screen of 30 inches or more.

(3) Organic Electroluminescent Display Device and Element The polarizing plate provided with the cyclic polyolefin film of the present invention can be preferably used for an organic electroluminescent display device as well as a liquid crystal display device. For example, by stretching the cyclic polyolefin film of the present invention in the oblique direction at an angle of 45 ° with respect to the transport direction described above, a polarizer having an absorption axis in the transport direction, and laminating with a roll-to-roll to form a circularly polarizing plate. When manufactured and the circularly polarizing plate is used for an organic electroluminescence display device, a display device with high visibility can be obtained.

  Further, the cyclic polyolefin film of the present invention is preferably used as a flexible substrate of an organic electroluminescence device, and in that case, it is preferable to apply the film as a gas barrier film described later.

  Regarding the specific layer structure, members, manufacturing method, and the like of the organic EL element, JP-A-2011-238355, JP-A-2013-077585, JP-A-2013-187090, JP-A-2013-229202, The details are described in JP-A-2013-232320 and JP-A-2014-026853, and can be referred to.

(4) Gas barrier film It is preferable to form an inorganic or organic film or a hybrid film of both on the surface of the cyclic polyolefin film of the present invention and use it as a gas barrier film.

The gas barrier property was determined by a method according to JIS K 7129-1992, and the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)%) was 0.01 g / (m ² · 24 h). It is preferable that the film has the following gas barrier layer. Further, the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻³ ml / (m ² · 24 h · atm). hereinafter, the water vapor permeability is preferably a film having a ^{1 × 10 -5 g / (m} 2 · 24h) or less of the high gas barrier properties.

  The method for forming the gas barrier layer applicable to the present invention is not particularly limited. For example, a sputtering method (for example, magnetron cathode sputtering, flat-plate magnetron sputtering, two-pole AC flat-plate magnetron sputtering, two-pole AC rotary magnetron sputtering, etc.) , Evaporation method (for example, resistance heating evaporation, electron beam evaporation, ion beam evaporation, plasma-assisted evaporation, etc.), thermal CVD method, catalytic chemical vapor deposition (Cat-CVD), capacitively coupled plasma CVD (CCP-CVD) Chemical vapor deposition such as photo-CVD, plasma CVD (PE-CVD), epitaxial growth, atomic layer growth, and reactive sputtering.

  Further, the inorganic gas barrier layer may include an organic layer containing an organic polymer. That is, the inorganic gas barrier layer may be a laminate of an inorganic layer containing an inorganic material and an organic layer.

  The organic layer is formed, for example, by applying an organic monomer or oligomer to a resin substrate to form a layer, followed by polymerization and polymerization using, for example, an electron beam device, a UV light source, a discharge device, or other suitable device. It can be formed by crosslinking if necessary. It can also be formed, for example, by depositing an organic monomer or organic oligomer capable of flash evaporation and radiation crosslinking, and then forming a polymer from the organic monomer or organic oligomer. Coating efficiency can be improved by cooling the resin substrate.

  Examples of the method for applying the organic monomer or organic oligomer include roll coating (for example, gravure roll coating) and spray coating (for example, electrostatic spray coating). Examples of the laminate of the inorganic layer and the organic layer include, for example, the laminate described in WO2012 / 003198 and WO2011 / 013341.

  In the case of a laminate of an inorganic layer and an organic layer, the thickness of each layer may be the same or different. The thickness of the inorganic layer is preferably in the range of 3 to 1000 nm, more preferably in the range of 10 to 300 nm. The thickness of the organic layer is preferably in the range of 100 nm to 100 μm, more preferably in the range of 1 to 50 μm.

  Furthermore, after a coating solution containing an inorganic precursor such as polysilazane or tetraethyl orthosilicate (TEOS) is wet-coated on a support, a modification process is performed by irradiation with vacuum ultraviolet light or the like to form an inorganic gas barrier layer. The inorganic gas barrier layer is also formed by metal plating on a resin substrate, film metallization technology such as bonding a metal foil to a resin substrate, or the like.

  In the case of a laminate of an inorganic layer and an organic layer, the thickness of each layer may be the same or different. The thickness of the inorganic layer is preferably in the range of 3 to 1000 nm, more preferably in the range of 10 to 300 nm. The thickness of the organic layer is preferably in the range of 100 nm to 100 μm, more preferably in the range of 1 to 50 μm.

  Furthermore, after a coating solution containing an inorganic precursor such as polysilazane or tetraethyl orthosilicate (TEOS) is wet-coated on a support, a modification process is performed by irradiation with vacuum ultraviolet light or the like to form an inorganic gas barrier layer. The inorganic gas barrier layer is also formed by metal plating on a resin substrate, film metallization technology such as bonding a metal foil to a resin substrate, or the like.

  Hereinafter, an example of an inorganic gas barrier layer formed using a plasma CVD method will be described.

  From the viewpoint of productivity, the inorganic gas barrier layer is preferably formed on the surface of the cyclic polyolefin film of the present invention by a roll-to-roll method. Further, an apparatus that can be used when the inorganic gas barrier layer is manufactured by such a plasma CVD method is not particularly limited, but includes at least a pair of film forming rollers, a plasma power supply, and a pair of components. It is preferable that the apparatus be configured to be capable of discharging between the film rollers. For example, when a manufacturing apparatus shown in FIG. 44 is used, the apparatus is manufactured by a roll-to-roll method while utilizing a plasma CVD method. It is also possible to do.

  Hereinafter, a method for forming an inorganic gas barrier layer by a plasma CVD method will be described in more detail with reference to FIG. FIG. 44 is a schematic diagram showing an example of a production apparatus that can be suitably used for producing an inorganic gas barrier layer.

  44 includes a delivery roller C32, transport rollers C33, C34, C35, and C36, film forming rollers C39 and C40, a gas supply pipe C41, a power supply C42 for plasma generation, and a film forming roller. Magnetic field generators C43 and C44 installed inside C39 and C40, and a winding roller C45 are provided.

  In such a manufacturing apparatus C31, at least the film forming rollers C39 and C40, the gas supply pipe C41, the power supply C42 for plasma generation, and the magnetic field generators C43 and C44 are arranged in a vacuum chamber not shown. Have been.

  Further, in such a manufacturing apparatus C31, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.

  In such a manufacturing apparatus C31, each of the film forming rollers is connected to the plasma generation power source C42 so that the pair of film forming rollers (film forming rollers C39 and C40) can function as a pair of counter electrodes. It is connected. Therefore, in such a manufacturing apparatus C31, it is possible to discharge to the space between the film forming roller C39 and the film forming roller C40 by supplying electric power from the power source C42 for plasma generation. Plasma can be generated in the space between the film roller C39 and the film formation roller C40.

  When the film forming roller C39 and the film forming roller C40 are also used as electrodes as described above, their materials and designs may be appropriately changed so that they can be used as electrodes.

  Further, in such a manufacturing apparatus C31, it is preferable that the pair of film forming rollers (film forming rollers C39 and C40) be arranged such that their central axes are substantially parallel on the same plane. By arranging a pair of film forming rollers (film forming rollers C39 and C40) in this manner, the film forming rate can be doubled.

  According to such a manufacturing apparatus C31, the inorganic gas barrier layer C4 (dry gas barrier layer) can be formed on the surface of the resin substrate C2 by the CVD method, and the resin substrate is formed on the film forming roller C39. Since the inorganic gas barrier layer component can be deposited on the surface of the resin substrate C2 also on the film forming roller C40 while depositing the inorganic gas barrier layer component on the surface of C2, the inorganic gas barrier layer component can be deposited on the surface of the resin substrate C2. The inorganic gas barrier layer C4 can be efficiently formed.

  Inside the film forming rollers C39 and C40, magnetic field generators C43 and C44, which are fixed so as not to rotate even when the film forming roller rotates, are provided, respectively.

  The magnetic field generators C43 and C44 provided on the film forming rollers C39 and C40 respectively include a magnetic field generator C43 provided on one film forming roller C39 and a magnetic field generator C44 provided on the other film forming roller C40. It is preferable to arrange the magnetic poles so that the magnetic field lines do not extend between them and the respective magnetic field generators C43 and C44 form a substantially closed magnetic circuit. By providing such magnetic field generators C43 and C44, it is possible to promote the formation of a magnetic field in which the lines of magnetic force swell near the opposing surfaces of the film forming rollers C39 and C40, and the plasma is converged on the swelling portion. This is advantageous in that film formation efficiency can be improved.

  Further, the magnetic field generators C43 and C44 provided on the film forming rollers C39 and C40 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generator C43 and the other magnetic field generator C44 are different from each other. It is preferable to arrange the magnetic poles so that the magnetic poles facing each other have the same polarity. By providing such magnetic field generators C43 and C44, the respective magnetic field generators C43 and C44 do not straddle the magnetic field generator on the roller side where the lines of magnetic force are opposed to each other. A racetrack-shaped magnetic field can be easily formed near the roller surface facing the (discharge area), and the plasma can be focused on the magnetic field, so a wide resin wound along the roller width direction This is excellent in that the inorganic gas barrier layer C4, which is a deposition film, can be efficiently formed using the substrate C2.

  Known rollers can be appropriately used as the film forming rollers C39 and C40. As such film forming rollers C39 and C40, those having the same diameter are preferably used from the viewpoint that a thin film can be formed more efficiently.

  Further, the diameter of such film forming rollers C39 and C40 is preferably in the range of 300 to 1000 mmφ, particularly preferably in the range of 300 to 700 mmφ from the viewpoint of discharge conditions, chamber space, and the like. When the diameter of the film-forming roller is 300 mmφ or more, the plasma discharge space does not become small and the productivity does not deteriorate, and the total heat of the plasma discharge can be prevented from being applied to the resin substrate C2 in a short time. This is preferable because damage to the substrate C2 can be reduced. On the other hand, if the diameter of the film-forming roller is 1000 mmφ or less, it is preferable because practicality can be maintained in the apparatus design including the uniformity of the plasma discharge space.

  In such a manufacturing apparatus C31, the resin substrate C2 is disposed on a pair of film forming rollers (film forming rollers C39 and C40) such that the surfaces of the resin substrate C2 face each other. By arranging the resin substrate C2 in this way, the resin existing between the pair of film-forming rollers is generated when the plasma is generated by discharging the space between the film-forming rollers C39 and C40. The respective surfaces of the substrate C2 can be simultaneously formed.

  That is, according to the manufacturing apparatus C31, the inorganic gas barrier layer component is deposited on the surface of the resin substrate C2 on the film forming roller C39 by the plasma CVD method, and the inorganic gas barrier layer is further formed on the film forming roller C40. Since the barrier layer component can be deposited, the inorganic gas barrier layer C4 can be efficiently formed on the surface of the resin substrate C2.

  As the delivery roller C32 and the transport rollers C33 to C36 used in the manufacturing apparatus C31, known rollers can be used as appropriate. The winding roller C45 may be any roller capable of winding the sealing substrate C1 having the inorganic gas barrier layer C4 formed on the resin substrate C2, and is not particularly limited. be able to.

  Further, as the gas supply pipe C41 and the vacuum pump (not shown), those capable of supplying or discharging a source gas or the like at a predetermined speed can be appropriately used.

  Further, the gas supply pipe C41 serving as a gas supply means is preferably provided in one of the opposing spaces (discharge area; film formation zone) between the film formation roller C39 and the film formation roller C40. The pump is preferably provided in the other of the opposed spaces. By arranging the gas supply pipe C41 as the gas supply means and the vacuum pump as the vacuum evacuation means in this manner, the film formation gas is efficiently supplied to the space between the film formation roller C39 and the film formation roller C40. This is excellent in that the film formation efficiency can be improved.

  Further, as the plasma generation power source C42, a power source of a known plasma generation device can be appropriately used. Such a plasma generation power supply C42 supplies electric power to the film-forming roller C39 and the film-forming roller C40 connected thereto, thereby enabling these to be used as a counter electrode for discharging. As such a plasma generation power supply C42, a power supply (such as an AC power supply) capable of alternately reversing the polarities of a pair of film forming rollers can be used because plasma CVD can be performed more efficiently. It is preferable to use it.

  In addition, since such a plasma generation power source C42 can perform plasma CVD more efficiently, the applied power can be in the range of 100 W to 10 kW, and the AC frequency is 50 Hz. More preferably, the frequency can be set to 500 kHz.

  Further, as the magnetic field generators C43 and C44, known magnetic field generators can be appropriately used. Further, as the resin substrate C2, in addition to the resin substrate used in the present invention, a substrate on which an inorganic gas barrier layer C4 is formed in advance can be used. As described above, by using the resin substrate C2 on which the inorganic gas barrier layer C4 is formed in advance, it is possible to increase the thickness of the inorganic gas barrier layer C4.

  By using such a manufacturing apparatus C31 shown in FIG. 44, for example, the type of the raw material gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming rollers C39 and C40, and the The inorganic gas barrier layer C4 can be manufactured by appropriately adjusting the transport speed.

  That is, using the manufacturing apparatus C31 shown in FIG. 44, a discharge is generated between the pair of film-forming rollers C39 and C40 while supplying a film-forming gas (raw material gas or the like) into the vacuum chamber. (Source gas and the like) are decomposed by the plasma, and an inorganic gas barrier layer C4 is formed by a plasma CVD method on the surface of the resin substrate C2 on the film forming roller C39 and on the surface of the resin substrate C2 on the film forming roller C40. You. At this time, a racetrack-shaped magnetic field is formed near the roller surface facing the opposing space (discharge region) along the length direction of the roller shafts of the film forming rollers C39 and C40, and the plasma converges to the magnetic field. In such a film formation, the resin substrate C2 is transported by the delivery roller C32, the film formation roller C39, and the like, thereby enabling a continuous film formation process of a roll-to-roll method. An inorganic gas barrier layer C4 is formed on the surface.

  As the film formation gas (source gas or the like) supplied from the gas supply pipe C41 to the opposed space, a source gas, a reaction gas, a carrier gas, and a discharge gas can be used alone or in combination of two or more. The source gas in the film forming gas used for forming the inorganic gas barrier layer C4 can be appropriately selected and used according to the material of the formed inorganic gas barrier layer C4.

  As such a source gas, for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, and hexamethyldisilane , Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy Examples include silane and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferred from the viewpoint of properties such as handleability of the compound and gas barrier properties of the obtained inorganic gas barrier layer C4. . These organosilicon compounds can be used alone or in combination of two or more. Examples of the organic compound gas containing carbon include methane, ethane, ethylene, and acetylene. As the organic silicon compound gas or the organic compound gas, a suitable source gas is selected according to the type of the inorganic gas barrier layer C4.

  In addition, a reactive gas may be used as a deposition gas in addition to a source gas. As such a reaction gas, a gas which becomes an inorganic compound such as an oxide or a nitride by reacting with a source gas can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. As a reaction gas for forming a nitride, for example, nitrogen or ammonia can be used. These reaction gases can be used alone or in combination of two or more. For example, when an oxynitride is formed, a reaction gas for forming an oxide and a nitride are used for forming a nitride. Can be used in combination.

  As the film forming gas, a carrier gas may be used as needed to supply the source gas into the vacuum chamber. Further, as a film forming gas, a discharge gas may be used as necessary to generate plasma discharge. As such a carrier gas and a discharge gas, known gases can be used as appropriate, and for example, a rare gas such as helium, argon, neon, or xenon, or hydrogen can be used.

  When such a film forming gas contains a source gas and a reaction gas, the ratio between the source gas and the reaction gas is a reaction ratio theoretically necessary for completely reacting the source gas and the reaction gas. It is preferable that the ratio of the reaction gas is not excessively higher than the ratio of the gas amounts. When the ratio of the reaction gas is not excessively large, the formed inorganic gas barrier layer C4 is excellent in that excellent gas barrier properties and bending resistance can be obtained. When the film-forming gas contains an organic silicon compound and oxygen, the amount is preferably not more than the theoretical amount of oxygen necessary to completely oxidize the whole amount of the organic silicon compound in the film-forming gas.

Hereinafter, in the production of the inorganic gas barrier layer C4 using the apparatus shown in FIG. 44, hexamethyldisiloxane (organosilicon compound, HMDSO, (CH ₃ ) ₆ Si ₂ O) as a raw material gas as a film forming gas; A preferred example of the case where a silicon-oxygen based thin film is manufactured using a material containing oxygen (O ₂ ) as a reaction gas will be described. This will be described in more detail.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a raw material gas and oxygen (O ₂ ) as a reaction gas is reacted by plasma CVD to form a silicon-oxygen-based gas. When a thin film is prepared, a reaction represented by the following reaction formula (1) occurs by the film forming gas, and silicon dioxide is generated.

Reaction formula (1)
_{(CH 3) 6 Si 2 O} + 12O 2 → 6CO 2 + 9H 2 O + 2SiO 2
In such a reaction, the amount of oxygen required to completely oxidize 1 mole of hexamethyldisiloxane is 12 moles. Therefore, when oxygen is contained in the film forming gas in an amount of 12 mol or more with respect to 1 mol of hexamethyldisiloxane and completely reacted, a uniform silicon dioxide film is formed.

  For this reason, in the present invention, when forming the inorganic gas barrier layer, the oxygen content is determined based on the stoichiometric amount with respect to 1 mol of hexamethyldisiloxane so that the reaction of the above reaction formula (1) does not proceed completely. It is preferred that the ratio be less than 12 moles.

  In the actual reaction in the plasma CVD chamber, the raw material hexamethyldisiloxane and the oxygen of the reaction gas are supplied from the gas supply unit to the film formation region to form a film. Even if the (flow rate) is 12 times the molar quantity (flow rate) of the raw material hexamethyldisiloxane, the reaction cannot actually proceed completely, and the oxygen content is reduced. It is considered that the reaction is completed only when a large excess is supplied as compared with the stoichiometric ratio (for example, in order to completely oxidize by CVD and obtain silicon oxide, the molar amount (flow rate) of oxygen is changed to hexamethyldiamine as a raw material. The molar amount (flow rate) of siloxane may be about 20 times or more.)

  Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane as a raw material is preferably 12 times or less (more preferably 10 times or less), which is the stoichiometric ratio. . By including hexamethyldisiloxane and oxygen at such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the inorganic gas barrier layer, and the resulting sealing substrate It is possible to exhibit excellent gas barrier properties and bending resistance.

  In addition, from the viewpoint of application to a flexible substrate for a device requiring transparency such as an organic EL element or a solar cell, the molar amount of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas. The lower limit of (flow rate) is preferably larger than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane, and more preferably larger than 0.5 times.

  Further, the pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted depending on the type of the source gas and the like, but is preferably in the range of 0.5 to 50 Pa.

  Further, in such a plasma CVD method, in order to discharge between the film forming roller C39 and the film forming roller C40, an electrode drum (installed on the film forming rollers C39 and C40) connected to the plasma generating power source C42. ) Can be appropriately adjusted according to the type of the source gas, the pressure in the vacuum chamber, and the like, and cannot be said unconditionally, but should be in the range of 0.1 to 10 kW. Is preferred. When the applied power is 0.1 kW or more, the generation of particles can be sufficiently suppressed. On the other hand, when the applied power is 10 kW or less, the amount of heat generated at the time of film formation can be suppressed. An increase in the temperature of the resin substrate surface can be suppressed. Therefore, the resin substrate is excellent in that wrinkles can be prevented from being generated during film formation without losing heat.

  The transfer speed (line speed) of the resin substrate C2 can be appropriately adjusted according to the type of the source gas, the pressure in the vacuum chamber, and the like, but is preferably in the range of 0.25 to 100 m / min. More preferably, it is within the range of 0.5 to 20 m / min. When the line speed is 0.25 m / min or more, generation of wrinkles due to heat on the resin substrate can be effectively suppressed. On the other hand, when it is 100 m / min or less, it is excellent in that a sufficient layer thickness as an inorganic gas barrier layer can be secured without impairing productivity.

  As described above, as a more preferable aspect of the present embodiment, the inorganic gas barrier layer used in the present invention is formed by a plasma CVD method using a plasma CVD apparatus (roll-to-roll method) having a counter roller electrode shown in FIG. Is to form a film. This is because when mass-produced using a plasma CVD apparatus having a counter roller electrode (roll-to-roll method), it has excellent flexibility (flexibility) and mechanical strength, particularly durability when transported by roll-to-roll. This is because it is possible to efficiently produce an inorganic gas barrier layer that is compatible with gas barrier performance. Such a manufacturing apparatus is also excellent in that it can easily and inexpensively mass-produce sealing substrates used for solar cells, electronic components, and the like, which are required to have durability against temperature changes.

  Next, the inorganic gas barrier layer formed by modifying the layer containing polysilazane will be described in detail.

The polysilazane used for forming the inorganic gas barrier layer used in the present invention is a polymer having a silicon-nitrogen bond, and SiO ₂ , Si ₃ N having a bond such as Si—N, Si—H, and NH. ₄ and both intermediate solid solutions are ceramic precursor inorganic polymers such as SiO _x N _y , and preferably have a structure represented by the following general formula (P).

General formula (P)
- _{[- Si (R 1) (R} 2) -N (R 3) - ] _n -
In the general formula (P), R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group. R ₁ , R ₂ and R ₃ may be the same or different from each other.

  In the general formula (P), n is an integer, and is preferably determined so that the polysilazane having the structure represented by the general formula (P) has a number average molecular weight of 150 to 150,000 g / mol.

In the present invention, from the viewpoint of the denseness of the obtained inorganic gas barrier layer as a film, perhydropolysilazane (PHPS) in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms is particularly preferred.

  It is presumed that perhydropolysilazane has a linear structure and a ring structure centered on a 6- and 8-membered ring. Its molecular weight is a number average molecular weight (Mn) of about 600 to 2,000 (in terms of polystyrene), is a liquid or solid substance, and differs depending on the molecular weight.

  Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and a commercially available product can be used as it is as a coating solution for forming a polysilazane layer. Examples of commercially available polysilazane solutions include NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140 and the like manufactured by AZ Electronic Materials Co., Ltd. Is mentioned.

  The solvent for preparing a coating solution containing polysilazane (hereinafter, also simply referred to as a coating solution containing polysilazane) is not particularly limited as long as it can dissolve polysilazane, and water and water which easily react with polysilazane are used. An organic solvent that does not contain a reactive group (for example, a hydroxy group or an amine group) and is inert to polysilazane is preferable, and an aprotic organic solvent is more preferable.

  Specifically, as the solvent for preparing the polysilazane-containing coating solution, aprotic solvents, for example, pentane, hexane, cyclohexane, toluene, xylene, solvesso, aliphatic hydrocarbons such as turbene, alicyclic hydrocarbons , Hydrocarbon solvents such as aromatic hydrocarbons, halogenated hydrocarbon solvents such as methylene chloride and trichloroethane, esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl ethyl ketone, and aliphatics such as dibutyl ether, dioxane and tetrahydrofuran Ethers such as ethers and alicyclic ethers (eg, tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes)) and the like can be mentioned. The solvent is selected depending on the purpose such as the solubility of polysilazane and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.

  The concentration of polysilazane in the polysilazane-containing coating solution is not particularly limited, and varies depending on the intended thickness of the inorganic gas barrier layer and the pot life of the coating solution, but is preferably in the range of 0.1 to 30% by mass. Preferably it is in the range of 0.5 to 20% by mass, more preferably in the range of 1 to 15% by mass.

  The polysilazane-containing coating liquid preferably contains a catalyst together with polysilazane in order to promote the modification to silicon oxynitride. As the catalyst applicable to the present invention, a basic catalyst is preferable, and particularly, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, Amine catalysts such as N ', N'-tetramethyl-1,3-diaminopropane, N, N, N', N'-tetramethyl-1,6-diaminohexane; Pt compounds such as Pt acetylacetonate; propion Pd compounds such as acid Pd; metal catalysts such as Rh compounds such as Rh acetylacetonate; and N-heterocyclic compounds. Among them, it is preferable to use an amine catalyst. At this time, the concentration of the catalyst to be added is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.2 to 5% by mass, and further preferably 0.5% by mass, based on polysilazane. ２2% by mass. By setting the catalyst addition amount within this range, excessive silanol formation due to rapid progress of the reaction, a decrease in film density, an increase in film defects, and the like can be avoided.

  In the polysilazane-containing coating solution, the following additives can be used as needed. For example, cellulose ethers, cellulose esters (eg, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate, etc.), natural resins (eg, rubber, rosin resin, etc.), synthetic resins (eg, polymerized resins, etc.), condensation Resins (eg, aminoplasts, especially urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, polysiloxanes, etc.).

  As a method for applying the polysilazane-containing coating solution, a conventionally known appropriate wet coating method is adopted. Specific examples include a spin coating method, a die coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method. Can be

    The coating thickness can be set appropriately according to the purpose. For example, the coating thickness after drying is preferably about 10 nm to 10 μm, more preferably in the range of 15 nm to 1 μm, and still more preferably in the range of 20 to 500 nm. If the layer thickness of the polysilazane layer is 10 nm or more, sufficient gas barrier properties can be obtained, and if it is 10 μm or less, stable coating properties can be obtained when forming the polysilazane layer, and high light transmittance can be realized. .

  The reforming treatment refers to a reaction in which part or all of a polysilazane compound is converted into silicon oxide or silicon oxynitride.

This makes it possible to form an inorganic thin film at a level that allows the inorganic gas barrier layer to contribute to exhibiting gas barrier properties (water vapor permeability of 1 × 10 ⁻³ g / (m ² · day) or less) as a whole.

  Specifically, a heat treatment, a plasma treatment, an active energy ray irradiation treatment, or the like can be given. Above all, treatment by irradiation with active energy rays is preferable from the viewpoint that the modification can be performed at a low temperature and the degree of freedom in selecting the type of the base material is high.

(Heat treatment)
Examples of the heat treatment method include, for example, a method in which a substrate is brought into contact with a heating element such as a heat block to heat a coating film by heat conduction, a method in which an environment in which a coating film is placed by an external heater using a resistance wire or the like, Examples thereof include a method using light in an infrared region such as an IR heater, but are not limited thereto. In the case of performing the heat treatment, a method capable of maintaining the smoothness of the coating film may be appropriately selected.

  The temperature for heating the coating film is preferably in the range of 40 to 250 ° C, more preferably in the range of 60 to 150 ° C. The heating time is preferably in the range of 10 seconds to 100 hours, and more preferably in the range of 30 seconds to 5 minutes.

(Plasma treatment)
In the present invention, as a plasma treatment that can be used as the reforming treatment, a known method can be used, and preferably, an atmospheric pressure plasma treatment or the like can be used. Atmospheric-pressure plasma CVD, in which plasma CVD is performed near atmospheric pressure, does not require pressure reduction and has high productivity compared with plasma CVD under vacuum. Under a high pressure condition, that is, under the atmospheric pressure, as compared with the condition of the ordinary CVD method, the average free path of the gas is very short, so that a very uniform film can be obtained.

  In the case of the atmospheric pressure plasma treatment, as the discharge gas, nitrogen gas or an atom belonging to Group 18 of the long-periodic table, specifically, helium, neon, argon, krypton, xenon, radon, or the like is used. Of these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferred because of its low cost.

(Active energy ray irradiation treatment)
As the active energy ray, for example, an infrared ray, a visible ray, an ultraviolet ray, an X-ray, an electron beam, an α-ray, a β-ray, a γ-ray, or the like can be used, but an electron beam or an ultraviolet ray is preferable, and an ultraviolet ray is more preferable. Ozone and active oxygen atoms generated by ultraviolet rays (synonymous with ultraviolet light) have high oxidizing ability and can form a gas barrier layer having high density and insulating properties at a low temperature.

  In the ultraviolet irradiation treatment, any commonly used ultraviolet ray generator can be used.

  In the method for producing an inorganic gas barrier layer used in the present invention, a coating film containing a polysilazane compound from which moisture has been removed is modified by irradiation with ultraviolet light. Ozone and active oxygen atoms generated by ultraviolet rays have high oxidizing ability and can form a silicon oxide film or a silicon oxynitride film having high density and insulating properties at a low temperature.

By this ultraviolet light irradiation, O ₂ and H ₂ O contributing to the formation of ceramics, an ultraviolet absorber, and polysilazane itself are excited and activated. Then, the formation of the excited polysilazane into a ceramic is promoted, and the resulting ceramic film becomes dense. Irradiation with ultraviolet light is effective even if it is performed at any time after the formation of the coating film.

  For the vacuum ultraviolet light irradiation treatment in the present invention, any commonly used ultraviolet ray generator can be used. In addition, the ultraviolet light referred to in the present invention generally refers to ultraviolet light including electromagnetic waves having a wavelength of 10 to 200 nm, which is called vacuum ultraviolet light.

  It is preferable to set the irradiation intensity and the irradiation time of the vacuum ultraviolet light within a range where the resin substrate carrying the layer containing the polysilazane compound before the modification is not damaged.

For example, using a lamp of 2 kW (80 W / cm × 25 cm), the substrate-ultraviolet light is applied so that the intensity of the substrate surface is in the range of ²⁰ to 300 mW / cm ² , preferably in the range of 50 to 200 mW / cm ^2. By setting the distance between the irradiation lamps, irradiation can be performed for 0.1 second to 10 minutes.

  In general, when the temperature of the support during the ultraviolet irradiation treatment is 150 ° C. or higher, in the case of a resin film or the like, the characteristics of the support are impaired, such as the support being deformed or its strength being deteriorated. Become. However, in the case of a film having a high heat resistance such as a cyclic polyolefin, a modification treatment at a higher temperature is possible. Therefore, there is no general upper limit for the temperature of the support at the time of the ultraviolet irradiation, and a person skilled in the art can appropriately set the temperature depending on the type of the resin substrate. There is no particular limitation on the atmosphere in which the ultraviolet light is irradiated, and the irradiation may be performed in the air.

  Examples of means for generating such ultraviolet rays include, but are not particularly limited to, metal halide lamps, high-pressure mercury lamps, low-pressure mercury lamps, xenon arc lamps, carbon arc lamps, excimer lamps, and UV light lasers. In addition, when irradiating the generated polysilazane layer to the polysilazane layer before the modification, from the viewpoint of improving efficiency and achieving uniform irradiation, the polysilazane before the modification is reflected from the reflector from the ultraviolet ray from the source. It is desirable to irradiate the layer.

  UV irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the resin substrate used. When the resin substrate having the coating layer containing the polysilazane compound is in the form of a long film, the substrate is formed by continuously irradiating ultraviolet rays in a drying zone provided with an ultraviolet ray source as described above while transporting the resin substrate. can do. The time required for ultraviolet irradiation depends on the composition and concentration of the resin substrate and the coating layer containing the polysilazane compound, but is generally 0.1 second to 10 minutes, preferably 0.5 second to 3 minutes.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
In the present invention, the most preferred modification treatment method is treatment by vacuum ultraviolet irradiation (excimer irradiation treatment).

  When irradiating with vacuum ultraviolet light (VUV), it is preferable to use a dry inert gas as a gas other than oxygen, and it is particularly preferable to use a dry nitrogen gas from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rates of the oxygen gas and the inert gas introduced into the irradiation chamber, and changing the flow rate ratio.

  Specifically, the method for modifying the layer containing the polysilazane compound before the modification in the present invention is treatment by irradiation with vacuum ultraviolet light. The treatment by irradiation with vacuum ultraviolet light uses light energy of 100 to 200 nm, which is larger than the interatomic bonding force in the polysilazane compound, and preferably uses light energy of a wavelength of 100 to 180 nm. In this method, a silicon oxide film is formed at a relatively low temperature by promoting an oxidation reaction with active oxygen or ozone while directly cutting by only the action. A rare gas excimer lamp is preferably used as a vacuum ultraviolet light source required for this.

In addition, since rare gas atoms such as Xe, Kr, Ar, and Ne do not chemically bond to form molecules, they are called inert gas. However, atoms of a rare gas (excited atoms) whose energy has been obtained by discharge or the like can combine with other atoms to form a molecule. When the rare gas is xenon,
e + Xe → e + Xe ^*
Xe ^* + Xe + Xe → Xe ₂ ^* + Xe
Xe ₂ ^* → Xe + Xe + hν (172 nm)
When the excited excimer molecule Xe ₂ ^* transitions to the ground state, it emits 172 nm excimer light (vacuum ultraviolet light).

  A feature of the excimer lamp is that the radiation is concentrated at one wavelength and almost no light other than necessary light is emitted, so that the efficiency is high. Also, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking is possible.

In vacuum ultraviolet irradiation step, preferably the illumination of the vacuum ultraviolet rays in the coated surface to receive the coating film containing a polysilazane compound is in the range of ^{1mW / cm 2 ~10W / cm 2} , in the range of 30~200mW / cm ² Is more preferable, and more preferably within a range of 50 to 160 mW / cm ² . If it is 1 mW / cm ² or more, sufficient reforming efficiency can be obtained. If it is 10 W / cm ² or less, abrasion of the coating film is less likely to occur, and the resin substrate is less likely to be damaged.

Irradiation energy amount of the VUV in the layer containing a polysilazane compound is preferably in the range of 10 to 10000 mJ / cm ^2, more preferably in the range of 100~8000mJ / cm ^2, it is 200~6000mJ / cm ² More preferably, it is particularly preferably in the range of 500 to 5000 mJ / cm ² . If 10 mJ / cm ² or more sufficient reforming efficiency is obtained, 10000 mJ / cm ² or less value, if cracks and the resin substrate thermal deformation hardly occurs in.

  Further, when irradiating vacuum ultraviolet light (VUV), the oxygen concentration is preferably in the range of 300 to 10000 vol ppm (1 vol%), more preferably 500 to 5000 vol ppm. By adjusting the oxygen concentration within such a range, it is possible to prevent the formation of an inorganic gas barrier layer containing an excessive amount of oxygen and to prevent the gas barrier property from deteriorating.

  In order to obtain excimer light emission, a method using a dielectric barrier discharge is known. Dielectric barrier discharge is a technique in which a gas space is arranged between both electrodes via a dielectric (in the case of an excimer lamp, transparent quartz), and a high-frequency high voltage of several tens of kHz is applied to the electrodes to prevent lightning generated in the gas space. It is a discharge similar to a very fine micro discharge.

  As a method for efficiently obtaining excimer light emission, an electrodeless electric field discharge is also known in addition to the dielectric barrier discharge. The electrodeless electric field discharge is a discharge due to capacitive coupling, and is also called an RF discharge. The lamp, the electrodes and the arrangement thereof may be basically the same as the dielectric barrier discharge, but the high frequency applied between the two electrodes is turned on at several MHz. In the electrodeless electric field discharge, a spatially and temporally uniform discharge can be obtained.

  The Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, a very small amount of oxygen can generate radical oxygen atom species and ozone at a high concentration. Further, it is known that the energy of light having a short wavelength of 172 nm to dissociate the bond of an organic substance has a high ability. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the coating layer containing the polysilazane compound can be modified in a short time. Therefore, compared to low-pressure mercury lamps emitting at wavelengths of 185 nm and 254 nm and plasma cleaning, the process time and equipment area required for high throughput are reduced, and irradiation of organic materials, plastic substrates, resin films, etc., which are easily damaged by heat, is performed. It is possible.

  In addition, since the excimer lamp has a high light generation efficiency, it can be turned on by inputting low power. In addition, since long-wavelength light that causes a temperature rise due to light is not emitted and energy of a single wavelength is irradiated in the ultraviolet region, the surface temperature of the irradiation target is suppressed from rising. Therefore, it is suitable for irradiating a sealing substrate made of a resin film such as polyethylene terephthalate which is considered to be easily affected by heat.

The layer formed by the above-described coating is formed by modifying at least a part of the polysilazane in the step of irradiating the coating film containing the polysilazane compound with vacuum ultraviolet rays, so that the layer as a whole has a composition of SiO _x N _y C _z . A silicon-containing film containing the indicated silicon oxynitride is formed.

  The film composition can be measured by measuring the atomic composition ratio using an XPS (X-ray Photoelectron Spectroscopy) surface analyzer. Alternatively, the silicon-containing film can be cut to measure the cut surface by measuring the atomic composition ratio with an XPS surface analyzer.

Further, the film density can be set appropriately according to the purpose. For example, the film density of the silicon-containing film is preferably in the range of 1.5 to 2.6 g / cm ³ . Within this range, the denseness of the film is improved, and the deterioration of the gas barrier property and the deterioration of the film under high temperature and high humidity conditions can be prevented.

  Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. In the examples, “parts” or “%” is used, but “parts by mass” or “% by mass” is used unless otherwise specified.

Example 1
<Preparation of cyclic polyolefin film 101>
With reference to the description in Japanese Patent No. 4585947, the following cyclic polyolefin film was produced.

<Synthesis of cyclic polyolefin polymer P-1>
100 parts by mass of purified toluene and 100 parts by mass of norbornene carboxylic acid methyl ester were charged into a reactor. Next, 25 mmol% of ethylhexanoate-Ni dissolved in toluene (based on the weight of the monomer), 0.225 mol% of tri (pentafluorophenyl) boron (based on the weight of the monomer), and 0.25 mol% of triethylaluminum dissolved in toluene (based on the weight of the monomer) ) Was charged into the reactor. The reaction was carried out for 18 hours while stirring at room temperature. After completion of the reaction, the reaction mixture was poured into excess ethanol to form a polymer precipitate. The polymer (P-1) obtained by purifying the precipitate was dried under vacuum at 65 ° C. for 24 hours.

<Preparation of dope D-1>
The following composition was put into a mixing tank, stirred to dissolve each component, and then filtered through a filter paper having an average pore diameter of 34 μm and a sintered metal filter having an average pore diameter of 10 μm to prepare a dope.

Cyclic polyolefin polymer P-1 150 parts by mass Dichloromethane 380 parts by mass Methanol 70 parts by mass Next, the following composition containing the cyclic polyolefin solution (dope) prepared by the above method was charged into a disperser, and a fine particle dispersion (M-1) was added. ) Was prepared.

Fine particles (Aerosil R812: manufactured by Nippon Aerosil Co., Ltd.
(Primary average particle diameter: 7 nm, apparent specific gravity 50 g / L) 4 parts by mass Dichloromethane 76 parts by mass Methanol 10 parts by mass 10 parts by mass of cyclic polyolefin solution (dope D-1) 10 parts by mass 100 parts by mass of the above cyclic polyolefin solution (dope D-1) Then, 0.75 parts by mass of the fine particle dispersion liquid (M-1) was mixed to prepare a dope for film formation. The dope was cast on a film forming line, dried on a metal support until the dope was self-supporting, stripped off as a web, and introduced into a tenter.

  The residual solvent of the web at the time of introduction into the tenter was 5 to 15% by mass. The film was conveyed without stretching in the width direction at a stretching ratio of 0% and a temperature in the tenter of 140 ° C. in the tenter. Immediately after the tenter was released, the film was roll-transported at a tension of 100 N / m and dried at 140 ° C., and the film was wound up with a winding length of 4000 m to produce a cyclic polyolefin film 101. The dry thickness of the film at this time was 40 μm.

<Preparation of cyclic polyolefin film 102>
<Fine particle addition liquid 1>
Fine particles (Aerosil R812: manufactured by Nippon Aerosil Co., Ltd.
(Primary average particle diameter: 7 nm, apparent specific gravity 50 g / L) 4 parts by mass Dichloromethane 48 parts by mass Ethanol 48 parts by mass The above components were stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton-Gaulin.

  Further, dispersion was performed with an attritor so that the particle size of the secondary particles became a predetermined size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle-added liquid 1.

  Next, a main dope 1 having the following composition was prepared. First, methylene chloride was added to the pressure dissolution tank at a flow rate of 400 kg / min and ethanol at a flow rate of 20 kg / min. Three minutes after the start of the addition of the solvent, ARTON G7810 manufactured by JSR Corporation was charged into the pressure dissolution tank with stirring at 200 kg / min. Further, 15 minutes after the start of the introduction of the solvent, the fine particle addition liquid 1 was introduced, heated to 80 ° C., and completely dissolved while stirring. The heating temperature was increased from room temperature by 5 ° C./min, dissolved for 30 minutes, and then decreased by 3 ° C./min.

The dope viscosity was 10,000 CP, and the water content was 0.50%. Azumi filter paper No. No. manufactured by Azumi Filter Paper Co., Ltd. Using 244 (filtration accuracy 0.005 mm) at a filtration flow rate of 300 L / m ² · h and a filtration pressure of 1.0 × 10 ⁶ Pa, main dope 1 was prepared.

<Composition of main dope 1>
100 parts by mass of ARTON G7810 manufactured by JSR Corporation 200 parts by mass of dichloromethane 200 parts by mass of ethanol 10 parts by mass of fine particle additive liquid 3 parts by mass Purified toluene 0.004 part by mass The above is charged into a sealed main dissolving vessel 1 and dissolved with stirring. Thus, a dope was prepared.

  The prepared dope was cast on a stainless steel endless support (belt) at a flow rate of 1000 L / hr. At that time, casting was performed while dropping dichloromethane at the casting end.

  The solvent was evaporated at a drying temperature of 40 ° C. until the amount of the residual solvent in the cast web became 30% by mass, and then peeled off from the stainless steel endless support at a peeling tension of 130 N / m. The amount of the residual solvent was adjusted to 5% by mass while drying the peeled web, and stretched 20% in the width direction using a tenter while applying heat at 160 ° C. The stretching speed was 200% / min.

  Next, drying was completed while transporting the drying zone with a large number of rollers at a temperature of 140 ° C. for 20 minutes. The transport tension was 100 N / m.

  Both ends of the dried film are slit by a slit device having rotating teeth by 100 mm, embossed under the following conditions, and the obtained film is wound around a core using a touch roll at 25 ° C. and 60% RH. Was. The winding tension was 10 kg / m of initial tension and 8 kg / m of final winding tension.

(Embossing conditions)
Processing temperature: 250 ° C
Processing pressure: 0.5MPa
Processing width: 10mm (both ends of film)
Working height: 5μm
Emboss opposed roll: made of metal As described above, a cyclic polyolefin film 102 having a film width of 1.5 m, a dry film thickness of 40 μm, and a winding length of 4000 m was obtained.

<Preparation of cyclic polyolefin film 103>
A cyclic polyolefin film 103 was produced in the same manner as in the production of the cyclic polyolefin film 102 except that 0.1 part by mass of toluene was added to the main dope 1 to prepare a dope.

<Preparation of cyclic polyolefin film 104>
In the production of the cyclic polyolefin film 102, a cyclic polyolefin film 104 was produced in the same manner except that 0.3 parts by mass of toluene was added to the main dope 1 to prepare a dope.

<Preparation of cyclic polyolefin film 105>
A cyclic polyolefin film 105 was produced in the same manner as in the production of the cyclic polyolefin film 102 except that 0.003 parts by mass of toluene was added to the main dope 1 to prepare a dope.

<Preparation of cyclic polyolefin film 106>
A cyclic polyolefin film 106 was produced in the same manner as in the production of the cyclic polyolefin film 102 except that 0.35 parts by mass of toluene was added to the main dope 1 to prepare a dope.

<Preparation of cyclic polyolefin film 107>
In the production of the cyclic polyolefin film 102, 0.0004 parts by mass of triacetyl cellulose (TAC: degree of acetyl group substitution 2.85, weight average molecular weight 250,000) was added to the main dope 1, and Ti928 (manufactured by BASF Japan Ltd.) 2 A cyclic polyolefin film 107 was produced in the same manner except that a dope was prepared by adding parts by mass.

<Preparation of cyclic polyolefin film 108>
In the preparation of the cyclic polyolefin film 102, 0.04 parts by mass of triacetyl cellulose (TAC: degree of acetyl group substitution 2.85, weight average molecular weight 250,000) was added to the main dope 1 and Ti928 (manufactured by BASF Japan Ltd.) 2 A cyclic polyolefin film 108 was produced in the same manner except that a dope was prepared by adding parts by mass.

<Preparation of cyclic polyolefin film 109>
In the production of the cyclic polyolefin film 102, 0.3 parts by mass of triacetyl cellulose (TAC: degree of acetyl group substitution 2.85, weight average molecular weight 250,000) was added to the main dope 1 and Ti928 (manufactured by BASF Japan Ltd.) 2 A cyclic polyolefin film 109 was produced in the same manner except that a dope was prepared by adding parts by mass.

<Production of cyclic polyolefin film 110>
In the preparation of the cyclic polyolefin film 102, 0.35 parts by mass of triacetyl cellulose (TAC: degree of acetyl group substitution 2.85, weight average molecular weight 250,000) was added to the main dope 1 and Ti928 (manufactured by BASF Japan Ltd.) 2 A cyclic polyolefin film 110 was produced in the same manner except that a dope was prepared by adding parts by mass.

<Preparation of cyclic polyolefin film 111>
In the production of the cyclic polyolefin film 102, 0.00003 parts by mass of triacetyl cellulose (TAC: degree of acetyl group substitution 2.85, weight average molecular weight 250,000) was added to the main dope 1 and Ti928 (manufactured by BASF Japan Ltd.) 2 A cyclic polyolefin film 111 was produced in the same manner except that a dope was prepared by adding parts by mass.

<Preparation of cyclic polyolefin film 112>
In the production of the cyclic polyolefin film 102, 50 parts by mass of ARTON G7810 manufactured by JSR Corporation and 50 parts by mass of ARTON R5000 manufactured by JSR Corporation were used instead of 100 parts by mass of ARTON G7810 manufactured by JSR Corporation of the main dope 1. Further, a cyclic polyolefin film 112 was produced in the same manner except that dope was prepared by adding 2 parts by mass of Ti928 (manufactured by BASF Japan K.K.).

<Preparation of cyclic polyolefin film 113>
In producing the cyclic polyolefin film 102, instead of 100 parts by mass of ARTON G7810 manufactured by JSR Corporation of the main dope 1, ARTON G7810 manufactured by JSR Corporation was used.
40 parts by mass, 30 parts by mass of ARTON R5000 manufactured by JSR Corporation, 30 parts by mass of ARTON RX4500 manufactured by JSR Corporation, and 2 parts by mass of Ti928 (manufactured by BASF Japan Ltd.) were added to prepare a dope. Produced a cyclic polyolefin film 113 in the same manner.

<Preparation of cyclic polyolefin film 114>
A cyclic polyolefin film 114 was produced in the same manner as in the production of the cyclic polyolefin film 112 except that 5 parts by mass of the polycondensed ester P7 was added to prepare a dope, and the film thickness was adjusted to 30 μm.

<Preparation of cyclic polyolefin film 115>
In the production of the cyclic polyolefin film 113, instead of 40 parts by mass of ARTON G7810 manufactured by JSR Corporation, 30 parts by mass of ARTON R5000 manufactured by the company, and 30 parts by mass of ARTON RX4500 manufactured by the company, 50 parts by mass of ARTON G7810 manufactured by the company and ARTON manufactured by the company are used. Using 50 parts by mass of RX4500 and adding a sugar ester; BzSc (benzyl saccharose: a mixture of compounds a1 to a4 described in Chemical formula 92), the average degree of ester substitution = 5.57 parts by mass to prepare a dope, Was adjusted to 20 μm to produce a cyclic polyolefin film 115 in the same manner.

<Preparation of hard coat film>
A hard coat layer was applied on the surfaces of the cyclic polyolefin films 107 to 111 prepared above by the following procedure.

On the surface A (the surface not in contact with the casting belt) of the above-prepared cyclic polyolefin film 107, a material obtained by filtering the following hard coat layer composition 1 with a polypropylene filter having a pore diameter of 0.4 μm was used using an extrusion coater. After drying at a constant rate drying section temperature of 50 ° C. and a declining rate drying section temperature of 50 ° C., the irradiation section is performed using an ultraviolet lamp while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less. The coating layer was cured at an illuminance of 100 mW / cm ² and an irradiation amount of 0.2 J / cm ² to form a hard coat layer having a dry film thickness of 2.5 μm. Similarly, a hard coat layer was formed on the cyclic polyolefin films 108 to 111.

(Hard coat layer composition 1)
Pentaerythritol tri / tetraacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) 70 parts by mass Trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.) 30 parts by mass ( Photopolymerization initiator)
Irgacure 184 (manufactured by BASF Japan K.K.) 6 parts by mass (additive)
Optool DAC (fluorine compound, manufactured by Daikin Industries, Ltd.) 2 parts by mass (solvent)
20 parts by mass of propylene glycol monomethyl ether 30 parts by mass of methyl acetate 70 parts by mass of methyl ethyl ketone <Preparation of polarizing plate>
[Preparation of Polarizer 1]
A polyvinyl alcohol film having a thickness of 70 μm was swollen with water at 35 ° C. The obtained film was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and further immersed in a 45 ° C. aqueous solution composed of 3 g of potassium iodide, 7.5 g of boric acid and 100 g of water. . The obtained film was uniaxially stretched under the conditions of a stretching temperature of 55 ° C. and a stretching ratio of 5 times. The uniaxially stretched film was washed with water and dried to obtain a polarizer 1 having a thickness of 15 μm.

[Preparation of UV-curable adhesive liquid 1]
After mixing the following components, the mixture was defoamed to prepare an ultraviolet-curable adhesive liquid 1. The triarylsulfonium hexafluorophosphate was blended as a 50% propylene carbonate solution, and the solid content of the triarylsulfonium hexafluorophosphate is shown below.

3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 45 parts by mass Eporide GT-301 (alicyclic epoxy resin manufactured by Daicel Chemical) 40 parts by mass 1,4-butanediol diglycidyl ether 15 parts by mass Triarylsulfonium hexafluorophosphate 2.3 parts by mass 9,10-dibutoxyanthracene 0.1 part by mass 1,4-diethoxynaphthalene 2.0 parts by mass [Preparation of retardation film 1]
(Preparation of fine particle dispersion diluent)
10 parts by mass of Aerosil R812 (manufactured by Nippon Aerosil Co., Ltd., primary average particle diameter: 7 nm, apparent specific gravity 50 g / L) and 90 parts by mass of ethanol were mixed by stirring with a dissolver for 30 minutes, and then a high-pressure disperser, Menton-Gaulin. To prepare a fine particle dispersion.

  88 parts by mass of dichloromethane was added to the obtained fine particle dispersion while stirring, and the mixture was diluted by stirring and mixing with a dissolver for 30 minutes. The obtained solution was filtered through a polypropylene wind cartridge filter TCW-PPS-1N manufactured by Advantech Toyo Co., Ltd. to obtain a fine particle dispersion diluent.

(Preparation of in-line additive solution)
To 100 parts by mass of dichloromethane, 36 parts by mass of the prepared fine particle dispersion and diluent were added with stirring, and further stirred for 30 minutes. Then, 6 parts by mass of diacetyl cellulose (acetyl substitution degree 2.35, Mn = 90000, (Mw = 152000, Mw / Mn = 1.7) was added with stirring, and the mixture was further stirred for 60 minutes. The obtained solution was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to obtain an in-line additive liquid. The filter medium used had a nominal filtration accuracy of 20 μm.

(Preparation of main dope)
The following components were charged into a closed container and completely dissolved while heating and stirring. Azumi Filter Paper No. No. manufactured by Azumi Filter Paper Co., Ltd. Filtration at 24 gave the main dope.

<Composition of main dope>
81 parts by mass of diacetyl cellulose (degree of acetyl group substitution: 2.35, Mn = 90000, Mw = 152000, Mw / Mn = 1.7) Polyhydric alcohol ester (compound represented by formula (D)): Exemplified compound 2-10
2 parts by mass sugar ester; BzSc (benzyl saccharose: mixture of compounds a1 to a4 described in Chemical formula 92), average degree of ester substitution = 5.5 7 parts by mass Polycondensation ester: polycondensation represented by general formula (C) Ester: P8 5 parts by mass Retardation regulator: compound represented by general formula (A1) Exemplary compound 6 described in Chemical formula 12 3 parts by mass Dichloromethane 430 parts by mass Methanol 11 parts by mass Main dope of 100 parts by mass; 5 parts by mass of the in-line additive liquid was sufficiently mixed with an in-line mixer (Toray static type in-tube mixer Hi-Mixer, SWJ) to obtain a dope.

(Film forming process)
The obtained dope was uniformly cast on a stainless steel band support using a belt casting apparatus under the conditions of a dope liquid temperature of 35 ° C., a width of 1.5 m, and a final film thickness of 40 μm. . The organic solvent in the obtained dope film was evaporated on the stainless band support until the residual solvent amount became 100% by mass to form a web, and then the web was peeled from the stainless band support. After the obtained web was further preliminarily dried at 110 ° C. for 10 minutes, the web was stretched with a tenter at 160 ° C. to 1.2 times the original width in the TD direction. The residual solvent amount of the web at the start of stretching was 2.0% by mass. After stretching with a tenter, relaxation was performed at 130 ° C. for 5 minutes, and then the web was transported through a number of transport rollers at a temperature of 130 ° C. and a transport speed of 20 m / min.

  The obtained film is slit into a 1.5 m width, knurling is performed on both ends of the film with a width of 10 mm and a height of 5 μm, and the film is wound around a core with an inner diameter of 15.24 cm at an initial tension of 220 N / m and a final tension of 110 N / m. A retardation film 1 having a length of 4000 m and a length of 40 μm and containing long diacetyl cellulose was obtained.

<Preparation of Polarizing Plate 101>
The polarizing plate 101 was manufactured according to the following method.

  First, the retardation film 1 prepared above was used as a retardation film, and the surface thereof was subjected to a corona discharge treatment. The conditions for the corona discharge treatment were a corona output intensity of 2.0 kW and a line speed of 18 m / min. Next, the above prepared ultraviolet curable adhesive liquid 1 is applied to the corona discharge treated surface of the film retardation film 1 with a bar coater so that the film thickness after curing becomes about 3 μm, and the ultraviolet curable adhesive is applied. A layer was formed. The polarizer (thickness: 15 μm) side prepared above was bonded to the obtained ultraviolet-curable adhesive layer.

  Next, a corona discharge treatment was performed using the cyclic polyolefin film 101 produced above. The conditions of the corona discharge treatment were a corona output intensity of 2.0 kW and a speed of 18 m / min.

  Next, the ultraviolet curable adhesive liquid 1 prepared above is applied to the corona discharge treated surface of the cyclic polyolefin film 101 with a bar coater so that the cured film thickness is about 3 μm, and the ultraviolet curable adhesive layer is formed. Was formed.

  A polarizer bonded to one side of the retardation film 1 is bonded to this ultraviolet-curable adhesive layer, and a cyclic polyolefin film 101 / ultraviolet-curable adhesive layer / polarizer / ultraviolet-curable adhesive layer / A laminate in which the retardation film 1 was laminated was obtained. At that time, lamination was performed so that the slow axes of the cyclic polyolefin film 101 and the retardation film 1 and the absorption axis of the polarizer were orthogonal to each other.

Ultraviolet rays were irradiated from both sides of this laminate using an ultraviolet irradiation device with a belt conveyor (the lamp used was a D bulb manufactured by Fusion UV Systems) so that the integrated light amount became 750 mJ / cm ^2. Was cured to produce a polarizing plate 101 having a total thickness of 95 μm.

<Preparation of Polarizing Plates 102 to 115>
Polarizing plates 102 to 115 were produced using cyclic polyolefin films 102 to 115 in the same manner as the production of polarizing plate 101.

<Production of liquid crystal display device>
Using a commercially available VA type liquid crystal display device (SONY 40 type display KLV-40J3000), the polarizing plate bonded to the viewing side of the liquid crystal cell was peeled off, and the polarizing plates 101 to 115 produced above were placed on the liquid crystal cell side. The liquid crystal display devices 101 to 115 were produced by laminating such that the retardation film 1 was disposed on the surface of. At this time, a liquid crystal display device was manufactured by laminating the polarizing plates manufactured so that the absorption axis of the polarizing plate was in the same direction as the absorption axis of the polarizing plate bonded in advance.

≪Evaluation≫
(1) Evaluation of cyclic polyolefin film (bright spot foreign matter)
The number of bright spot foreign matters in the cyclic polyolefin film was measured by the following method.

(Method of measuring bright spot foreign matter on film)
Two polarizing plates are arranged in an orthogonal state (crossed Nicols) to block transmitted light, and the prepared film sample is placed between the two polarizing plates. The polarizing plate used was a glass protective plate. Light was irradiated from one side, and the number of bright spot foreign substances having a major axis of 10 μm or more per 100 cm ² was counted by an optical microscope (50 times) from the opposite side. The smaller the number of bright spot foreign substances, the better the characteristics.

(Haze)
The haze of the prepared cyclic polyolefin film was measured with a haze meter (Model 1001DP, manufactured by Nippon Denshoku Industries Co., Ltd.) after adjusting the humidity of the sample film in an environment of 23 ° C. and 55% RH for 5 hours or more. The haze is preferably less than 0.5 to less than 1.0%, more preferably less than 0.5%.

(Coefficient of friction)
Before the stretching step in the film forming process, a film sample is taken when the residual solvent is 5 to 30% by mass, and the film surface is measured according to JIS K7125 (1999): (Plastic-film and sheet friction coefficient test method). The coefficient of static friction was measured.

(2) Evaluation of Hard Coat Layer The pencil hardness of the surface of the hard coat layer was measured.

  Specifically, using a test pencil specified by JIS-S6006, in accordance with a pencil hardness evaluation method specified by JIS-K5400, a predetermined surface is repeatedly scratched five times with a pencil of each hardness using a weight of 500 g, and a scratch is generated. The hardness until the book was formed was measured. The pencil hardness is preferably 2H or more, more preferably 3H or more.

(3) Evaluation of polarizing plate and liquid crystal display device (Evaluation of point defects)
The polarizing plate produced above was incorporated into a liquid crystal display device, and the light and dark appearing as dots or planes when displaying black was visually observed and ranked according to the following criteria.

◎: Dark field uniform throughout without any light leakage. 明: Very slightly dark and light is partially observed.: Slightly dark and light is recognized as a whole, but there is no practical problem. Brightness and darkness are recognized. If the value is Δ or more, it can be put to practical use.

  Table 1 shows the obtained evaluation results.

  The cyclic polyolefin films 102 to 104 produced by the method for producing a cyclic polyolefin film of the present invention are superior to the cyclic polyolefin films 101 and 105 of the comparative examples in the number of foreign matters, haze, and point defects of the liquid crystal display device. I understood that.

  As for 106, which is 0.35 parts by mass of toluene, the solvent volatilization was somewhat slow, and the drying step was slightly long.

  Moreover, the cyclic polyolefin films 107 to 109 to which 0.0004 to 0.3 parts by mass of cellulose triacetate (TAC) were added, compared with the cyclic polyolefin films 110 and 111 of the comparative examples, the number of foreign substances, haze, and In addition to being excellent in point defects, the hardness after application of the hard coat was also excellent.

  The cyclic polyolefin films 112 to 115 using two or more kinds of cyclic polyolefin-based resins had a high effect of suppressing foreign substances and were excellent in haze and point defects.

Example 2
The cyclic polyolefin films 102 to 104, 106 to 109, 112, and 113 of the present invention produced in Example 1 were used as base films (supports) of gas barrier films.

<Preparation of gas barrier film 201>
(Support)
The cyclic polyolefin film 102 produced in Example 1 was used as a resin film support.

  The gas barrier film is produced by forming the anti-bleed layer on one side and the smooth layer on the other side by the following forming method while conveying the support at a speed of 20 m / min. A laminated gas barrier film having a roll shape was obtained.

(Formation of bleed-out prevention layer)
On one surface of the support, a UV-curable organic / inorganic hybrid hard coat material OPSTAR Z7535 manufactured by JSR Corporation is applied, and is applied with a wire bar so that the film thickness after drying is 4 μm. After drying, the composition was cured at 500 mJ / cm ² using a high-pressure mercury lamp in an air atmosphere to form a bleed-out preventing layer.

(Formation of smooth layer)
Subsequently, on the opposite surface of the support, a UV-curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation was applied, and then applied with a wire bar so that the film thickness after drying was 4 μm. After drying for 3 minutes, it was cured at 500 mJ / cm ² using a high-pressure mercury lamp in an air atmosphere to form a smooth layer.

  At this time, the maximum sectional height Rt (p) was 18 nm. The maximum cross-sectional height Rt (p) is calculated from the cross-sectional curve of the irregularities continuously measured with a detector having a stylus having a very small tip radius with an AFM (atomic force microscope). This is the average roughness related to the amplitude of fine irregularities measured many times in a section where the measurement direction is 30 μm.

(Preparation of gas barrier layer)
Next, the following polysilazane coating solution is prepared on the smooth layer of the film provided with the above-mentioned smooth layer and bleed-out preventing layer, and then the concentration is adjusted by diluting with dehydrated dibutyl ether to obtain a 23 ° C., 50% RH environment. After application under the above conditions, the film was dried at 80 ° C. for 1 minute (the atmosphere in the process was adjusted to a dew point of 10 ° C.) to form a polysilazane layer having a thickness of 150 nm after drying.

(Polysilazane coating solution)
Aquamica NN120-20 (Perhydropolysilazane, AZ Electronic Materials Co., Ltd., 20% by mass dibutyl ether solution)
(Reforming treatment A)
The coating sample was modified under the following conditions to form a first gas barrier layer. The dew point temperature during the reforming treatment was -8 ° C.

(Reforming equipment)
Excimer irradiator MODEL manufactured by M.D.COM Co., Ltd .: MECL-M-1-20
0, a wavelength of 172 nm, and a sample fixed on a Xe operating stage with a lamp-filled gas was subjected to a reforming treatment under the following conditions.

(Reforming conditions)
Excimer light intensity 120 mW / cm ² (172 nm)
Distance between sample and light source 3mm
Stage heating temperature 25 ℃
Oxygen concentration in the irradiation device 1000ppm (0.1%)
Actual excimer irradiation time 5 seconds Further, the concentration of the polysilazane compound coating solution was adjusted by diluting the solution with dehydrated dibutyl ether, and then applied at 23 ° C. and 50% RH environment. The atmosphere was adjusted to a dew point of 10 ° C.) and dried to form a polysilazane layer such that the film thickness after drying was 90 nm.

(Reforming treatment B)
The sample coated with the second coating layer was subjected to a modification treatment at an integrated light amount of 500 mJ / cm ² and a stage heating temperature (substrate temperature at the time of VUV irradiation) of 25 ° C. to form a second gas barrier layer. The dew point temperature at the time of the modification treatment was −8 ° C. to obtain a gas barrier film 201.

(Reforming equipment)
Same as reforming treatment A.

(Reforming conditions)
Excimer light intensity 120 mW / cm ² (172 nm)
Distance between sample and light source 3mm
Oxygen concentration in the irradiation device 1000ppm (0.1%)
Reciprocating transfer of sample at a stage moving speed of 10 mm / sec <Preparation of gas barrier films 202 to 209>
Gas barrier films 202 to 209 were produced in the same manner except that the support was changed to the cyclic polyolefin films 103, 104, 106 to 109, 112, and 113 in the production of the gas barrier film 201.

≫Evaluation of gas barrier film≫
(Measurement of water vapor transmission rate)
<Water vapor transmission rate measurement device>
Evaporator: Vacuum evaporator JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humic Chamber IG47M
(raw materials)
Metal that corrodes by reacting with moisture: calcium (granular)
Water vapor impermeable metal: Aluminum (φ3-5mm, granular)
(Preparation of cell for evaluating water vapor barrier property)
Using a vacuum deposition device (JEOL vacuum deposition device JEE-400), mask portions other than the portions to be deposited (9 locations of 12 mm × 12 mm) of the gas barrier films 201 to 209 before attaching the transparent conductive film. , Metal calcium was deposited.

  Thereafter, the mask was removed in a vacuum state, and aluminum was evaporated from another metal evaporation source on one entire surface of the sheet. After sealing with aluminum, the vacuum is released, and immediately, in a dry nitrogen gas atmosphere, face the aluminum sealing side with a 0.2 mm-thick quartz glass via a UV curable resin for sealing (manufactured by Nagase ChemteX). Then, the cell for evaluation was produced by irradiating with ultraviolet rays.

  The obtained sample in which both sides were sealed was stored under high temperature and high humidity of 60 ° C. and 90% RH, and based on the method described in JP-A-2005-283561, the moisture permeated into the cell based on the corrosion amount of metallic calcium. The amount was calculated.

(Rank evaluation)
5: less than 1 × 10 ⁻⁴ g / m ² / day 4: 1 × 10 ⁻⁴ g / m ² / day or more and less than 1 × 10 ⁻³ g / m ² / day 3: 1 × 10 ⁻³ g / day m ² / day or more and less than 1 × 10 ⁻² g / m ² / day 2: 1 × 10 ⁻² g / m ² / day or more and less than 1 × 10 ⁻¹ g / m ² / day 1: 1 × 10 ^-1 g / m ² / day or more In the rank evaluation, a practical range is rank 3 or more.

(Heat resistance test of gas barrier film)
The gas barrier films 201 to 209 immediately after the preparation were each stored for 7 days in an environment of 85 ° C., and thereafter the water vapor transmission rate was measured in the same manner as described above to evaluate deterioration (durability) due to heat.

(Durability test of gas barrier film)
Deterioration (durability) of the gas barrier properties after repeating bending the gas barrier films 201 to 209 immediately after production at an angle of 180 degrees 100 times so that each has a curvature of a radius of 10 mm, as described above. Was evaluated by water vapor transmission rate.

  As a result of the above evaluations, the cyclic polyolefin film of the present invention showed a rank of 3 or more for all evaluation items, and was confirmed to be an excellent support for a gas barrier film.

Example 3
The cyclic polyolefin films 102 to 104, 106 to 109, 112, and 113 of the present invention produced in Example 1 were used as a base film (support) for a touch panel.

(Preparation of transparent substrate)
The following coating liquid for a hard coat layer was applied to both surfaces of the cyclic polyolefin films 102 to 104, 106 to 109, 112 and 113 by a die coater to form a coating film to be a hard coat layer. The coating film was dried at 70 ° C., and while being purged with nitrogen so that the atmosphere had an oxygen concentration of 1.0% by volume or less, using an ultraviolet lamp, the illuminance of the irradiated portion was 300 mW / cm ² , and the irradiation amount was 0.1%. The coating film was cured at ³ J / cm ² , and further subjected to heat treatment at 130 ° C. for 5 minutes in a heat treatment zone to produce transparent substrates 301 to 309. The cured hard coat layers each had a thickness of 5 μm.

(Preparation of hard coat layer coating solution)
The following constituent materials were mixed, stirred, and dissolved to prepare a hard coat layer coating solution.

Hard coating layer coating solution Pentaerythritol tetraacrylate 30 parts by mass Dipentaerythritol hexaacrylate 60 parts by mass Dipentaerythritol pentaacrylate 50 parts by mass Irgacure 184 (manufactured by BASF Japan) 5 parts by mass Irgacure 907 (BASF Japan Ltd.) 5 parts by mass ZX-212 (fluorine-siloxane graft polymer, manufactured by T & K Toka)
5 parts by mass Sea Hostar KEP-50 (powder silica particles, average particle size 0.47 to 0.61 μm, manufactured by Nippon Shokubai Co., Ltd.) 24.3 parts by mass propylene glycol monomethyl ether 20 parts by mass Methyl acetate 40 parts by mass methyl ethyl ketone 60 Parts by mass (production of conductive film 301)
On one surface of the transparent substrate 301, an intermediate layer (thickness: 25 nm) is formed by evaporation using the following compound 1, and subsequently, an electrode layer (8 nm in thickness) made of silver (Ag) is formed by evaporation. did. Subsequently, a surface protective layer (thickness: 30 nm) made of titanium oxide (TiO ₂ ) was formed by an evaporation method. Thus, a conductive film 301 having a transparent electrode having a three-layer structure of an intermediate layer, a transparent conductive layer, and a surface protective layer was produced.

At this time, first, the transparent substrate 301 was fixed to a substrate holder of a commercially available vacuum evaporation apparatus. Compound 1 was placed in a tantalum resistance heating boat. These substrate holders and the heating boat were attached to a first vacuum tank of a vacuum evaporation apparatus. In addition, silver (Ag) was put in a tungsten resistance heating boat, and was mounted in a second vacuum chamber. Further, titanium oxide (TiO ₂ ) was put in a tantalum resistance heating boat, and was mounted in a third vacuum chamber.

Next, after reducing the pressure in the first vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing each compound was energized and heated, and was placed on the transparent substrate 301 at a deposition rate of 0.1 to 0.2 nm / sec. An intermediate layer 13 having a thickness of 25 nm was provided.

Next, the transparent substrate 301 on which the film was formed up to the intermediate layer was transferred to a second vacuum chamber while keeping the vacuum, and the pressure in the second vacuum chamber was reduced to 4 × 10 ⁻⁴ Pa. did. Thus, a transparent conductive layer made of silver having a thickness of 8 nm was formed at a deposition rate of 0.1 to 0.2 nm / sec.

Next, the transparent substrate 301 on which the intermediate layer and the electrode layer were formed was transferred to a third vacuum chamber while keeping the vacuum, and the pressure in the third vacuum chamber was reduced to 4 × 10 ⁻⁴ Pa, and then titanium oxide (TiO ₂ ) was charged. The heating boat was energized and heated. Thus, a surface protective layer made of titanium oxide (TiO ₂ ) having a thickness of 30 nm was formed at a deposition rate of 0.1 to 0.2 nm / sec.

  Through the above steps, a conductive film 301 having a laminated structure of an intermediate layer, a transparent conductive layer on the intermediate layer, and a surface protective layer was obtained.

  The thickness of the deposited film is described in J. A. Woollam Co. Inc. Was measured using a VB-250 type VASE ellipsometer manufactured by Toshiba Corporation.

(Production of conductive films 302 to 309)
Similarly to the conductive film 301, the conductive films 302 to 309 were produced using the cyclic polyolefin films 103, 104, 106 to 109, 112, and 113, respectively.

≫Evaluation of each sample≫
Regarding the produced conductive films 301 to 309, the bending resistance, the interference unevenness, and the deterioration of the table specific resistance after wet heat durability were measured.

(Bending resistance)
The bending resistance of the produced conductive film was evaluated according to the method specified in JIS K5400. In the evaluation of the bending resistance, a stainless steel rod having a diameter of 10 mm was used for winding the conductive film sample.

  The rank of the electrode layer was evaluated as described below.

◎: No change was observed.: Slightly deformed, but no problem occurred in practical use. ：: Fine cracks occurred in the electrode layer. X: Cracks occurred in the electrode layer (uneven color).
The touch panel of the iPad (registered trademark) (a 9.7-inch IPS liquid crystal tablet computer manufactured by Apple Inc.) is removed, and the produced conductive film is put through a 25-μm double-sided adhesive tape (baseless tape MO-300C manufactured by Lintec). Then, they were bonded so that the conductive layer faced the display surface. White was displayed on the display, and the display surface was observed through polarized sunglasses at an angle of 45 °.

  As a result of the test, rank evaluation was performed as follows.

: No color unevenness was observed at all ○: Slight color unevenness was observed, but there was no practical problem △: Color unevenness was observed ×: Very deep rainbow-like color unevenness was observed (moist heat) Surface resistance deterioration due to durability)
After leaving the sample for which the surface resistivity was measured in an environment of a temperature of 60 ° C. and a relative humidity of 90% RH for 300 hours, arbitrary 10 points of the surface resistivity were measured, and the average value was measured after the wet heat endurance of the sample. The surface resistivity was used.

  As a result of the test, rank evaluation was performed as follows.

[Surface resistance degradation] = [(Surface resistivity after wet heat durability)-(Surface resistivity before wet heat durability)] / [Surface resistivity before wet heat durability]
◎: Surface resistance deterioration is less than ± 10% ○: Surface resistance deterioration is ± 10% or more and less than ± 20% △: Surface resistance deterioration is ± 20% or more and less than ± 30% × : The surface resistance deterioration is ± 30%. When the above evaluations were performed, those using the cyclic polyolefin film of the present invention were evaluated as ○ or more in all cases, and excellent support of a conductive film for a touch panel was obtained. I confirmed my body. Among them, a conductive film using the cyclic polyolefin films 107 to 109 containing a trace amount of cellulose acylate was found to be a film for a touch panel which is hardly damaged even after various tests as a result of surface observation.

Example 4
The cyclic polyolefin films 102 to 104, 106 to 109, 112, and 113 of the present invention produced in Example 1 were used as substrate films (supports) for flexible organic electroluminescence devices, respectively.

  Transparent conductive films 401 to 409 were prepared by forming a thin film on the film in the order of a clear hard coat layer (both surfaces), a moisture-proof film (both surfaces), and a transparent conductive film (one surface).

<Preparation of clear hard coat layer>
The following coating composition for a hard coat layer is coated on a cyclic polyolefin film 102 by an extrusion coater so as to have a thickness of 3 μm, then dried in a drying unit set at 80 ° C. for 1 minute, and then irradiated with ultraviolet light at 120 mW / cm ² . It was formed by irradiation.

(Clear hard coat layer coating composition)
Dipentaerythritol hexaatalylate dimer 60 parts by mass Dipentaerythritol hexaatalylate dimer 20 parts by mass Dipentaerythritol hexaatalylate trimer or higher component 20 parts by mass Dimethoxybenzophenone 4 parts by mass Ethyl acetate 50 parts by mass Part Methinole ethyl ketone 50 parts by weight Isopropyl alcohol 50 parts by weight <Preparation of moisture-proof film>
As the plasma discharge device, a parallel plate type electrode was used, the substrate film was placed between the electrodes, and a mixed gas was introduced to form a thin film.
The following electrodes were used. A 200 mm × 200 mm × 2 mm stainless steel plate is coated with a high-density, high-adhesion alumina sprayed film, and then a solution obtained by diluting tetramethoxysilane with ethyl acetate is applied and dried, and then cured by ultraviolet irradiation to perform a sealing treatment. Further, the surface of the dielectric material thus coated was polished and smoothed, and processed so that the surface roughness Ra became 5 μm. An electrode was prepared in this way and grounded (grounded). On the other hand, as an application electrode, a plurality of hollow square pure titanium pipes each coated with the same dielectric material under the same conditions as described above were produced to form an opposing electrode group.

The power source used for plasma generation is a high frequency power source JRF-10000 manufactured by JEOL Ltd., supplying a voltage of 13.56 MHz and a power of 5 W / cm ² , and a mixed gas having the following composition between the electrodes. Shed.

Inert gas: 99.3% by volume of argon
Reactive gas 1: 0.5% by volume of hydrogen
Reactive gas 2: 0.3% by volume of tetraethoxysilane
Atmospheric pressure plasma treatment was performed on the clear hard coat layer of the cyclic polyolefin film 101 provided with the clear hard coat layer under the above-mentioned reaction gas and reaction conditions to produce a silicon oxide film having a thickness of 18 nm as a moisture-proof film.

<Preparation of transparent conductive film>
Except that the supply power was changed to 12 W / cm ² , the mixture gas was changed to the following composition under the same atmospheric pressure plasma conditions as the formation of the moisture-proof film, and a transparent conductive film was produced.

Inert gas: 98.69% by volume of helium
Reactive gas 1: 0.05% by volume of hydrogen
Reactive gas 2: indium acetylacetonate 1.2% by volume
Reactive gas 3: 0.05% by volume of dibutyltin diacetate
Reactive gas 4: 0.01% by volume of tetraethoxysilane
Atmospheric pressure plasma treatment is performed on the silicon oxide layer of the cyclic polyolefin film 101 provided with the clear hard coat layer and the silicon oxide layer according to the above reaction gas and reaction conditions to form a tin-doped indium oxide film (ITO film) as a transparent conductive film. The transparent conductive film 401 was manufactured (thickness: 110 nm).

<Transparent conductive films 402 to 409>
In the same manner as the transparent conductive film 401, the transparent conductive films 402 to 409 were produced using the cyclic polyolefin film films 103, 104, 106 to 109, 112, and 113.

  The following evaluations were performed on the transparent conductive films 401 to 409 thus obtained.

≪Evaluation≫
(Transmissivity)
The measurement was performed using TURBIDITY METER T2600DA manufactured by Tokyo Denshoku.

(Evaluation of moisture permeability)
The moisture permeability was measured under the conditions described in JIS Z-0208 (40 ° C., 90% RH).

  The measurement was also performed after a series of 10 cooling cycles of heating at 180 ° C. for 1 hour and then cooling at room temperature for 1 hour.

(Specific resistance)
It was determined by a four-terminal method according to JIS R-1637. In addition, Mitsubishi Chemical Lorester cyclic polyolefin film GP and MCP-T600 were used for the measurement.

  As a result of the above evaluations, it was confirmed that the cyclic polyolefin film of the present invention was an excellent conductive film support.

<Method of manufacturing organic EL element>
The transparent conductive film was used as the transparent conductive film 1, and a transparent conductive film (positive electrode) was patterned thereon. Thereafter, the substrate was subjected to ultrasonic cleaning using a neutral detergent, acetone and ethanol, and then pulled out from boiling ethanol and dried. Next, after the surface of the transparent conductive film was subjected to ultrasonic cleaning, N, N-diphenyl-m-tolyl-4,4'-diamine-1,1'-biphenyl (TPD) was deposited in a vacuum deposition apparatus at a deposition rate of 0.2 nm /. Vapor deposition was performed to a thickness of 55 nm in seconds to form a hole injection transport layer.

Further, Alq ₃ : tris (8-quinolinolato) aluminum was vapor-deposited at a vapor deposition rate of 0.2 nm / sec to a thickness of 50 nm to form an electron-injection-transport luminescent layer. Next, a negative electrode was formed to a thickness of 200 nm by a DC sputtering method using a sputtering apparatus and using an Al.Su alloy (Su: 10 at%) as a target. At this time, Ar was used as the sputtering gas, the gas pressure was 3.5 Pa, and the distance between the target and the substrate (Ts) was 9.0 cm. The input power was 1.2 W / cm ² .

Finally, SiO ₂ was sputtered to a thickness of 200 nm to obtain an organic EL device as a protective layer. In this organic EL device, two parallel stripe-shaped negative electrodes and eight parallel stripe-shaped electrodes are orthogonal to each other, and 2 × 2 mm vertical and horizontal element units (pixels) are arranged at an interval of 2 mm from each other. , 16 pixels.

When the organic EL device thus obtained was driven at 9 V, the transparent conductive films 401 to 409 using the cyclic polyolefin film of the present invention had a luminance of 350 cd / m ² or more.

  According to the present invention, it is possible to provide an excellent transparent film for a display substrate such as an organic EL display having a high glass transition temperature and a low linear expansion coefficient, or a touch panel.

Example 5
The cyclic polyolefin films 102 to 104, 106 to 109, 112, and 113 of the present invention produced in Example 1 were used as base films (supports) for nanoimprinting.

(Mold production by laser interference exposure)
A resist is applied by spin coating on a quartz glass substrate (1.2 mm thick, 70 mm square). As the resist material, a positive resist that removes the resist in the exposed portion is used.

  Using a liquid immersion exposure optical system, a fine pattern is drawn on the resist. The immersion exposure optical system uses an ultraviolet laser (wavelength: 266 nm) to irradiate two light beams at an inclination of 15 degrees with respect to the normal direction of the quartz glass substrate to form first interference fringes on the resist. Is exposed. As a laser light source, "MBD266 made by Coherent" is used. Next, the quartz glass substrate is rotated 90 degrees to form a second interference fringe orthogonal to the first interference fringe, and a second exposure is performed. In the first exposure and the second exposure, development is performed so that only a portion where bright portions of interference fringes intersect remains. Through the above process, a resist was formed on the quartz glass substrate in which holes having a pitch of 300 nm and a depth of 150 nm were regularly arranged. A fine hole structure (pitch: 300 nm, depth: 150 nm) with a drawing size of 50 mm square was formed in quartz glass by dry etching.

(Release treatment of quartz glass substrate)
Chlorine tridecafluoro-1,1,2,2-tetrahydrooctyl trichlorosilane is a fluorine resin-containing silane coupling agent _{[CF 3 - (CF 2)} 5 -CH 2 -CH 2 SiCl 3] In the quartz glass The mold was surface-treated to form a fluororesin chemisorption film on the surface of the fine shape.

(Preparation of liquid composition)
Polymethyl methacrylate (PMMA) was prepared as a resin, and dissolved in toluene to prepare a liquid composition. The mass ratio between the resin and the solvent was 1/20 (5%).

(Application of liquid composition)
The liquid crystal composition was applied on a quartz glass substrate with a wet thickness of 80 μm using a wire bar.

(Lamination of film)
Within 5 seconds after the application of the liquid composition, the cyclic polyolefin films 102 to 104, 106 to 109, 112 and 113 were adhered to the applied liquid composition, respectively.

(Dry)
The laminate was dried at room temperature for 55 seconds with the quartz glass substrate coated with the liquid composition and the cyclic polyolefin film bonded together.

(Release)
After drying, when the film was released, a pillar shape having a pitch of 300 nm and a height of 150 nm was transferred onto the film. Observation of the surface with a scanning microscope revealed that the pitch and height had excellent uniformity.

  As described above, the cyclic polyolefin films 102 to 104, 106 to 109, 112, and 113 of the present invention prepared in Example 1 are excellent for use as a base film (support) for nanoimprint.

Example 6
The cyclic polyolefin films 102 to 104, 106 to 109, 112, and 113 of the present invention produced in Example 1 were used as base films (supports) for flexible electronic circuits.

(Production of substrate 1 with anchor layer)
<Synthesis of polymerizable compound 1 having an ethylenically unsaturated group>
According to the following procedure, polymerizable compound 1 having an ethylenically unsaturated group as a polymerizable group was synthesized.

  20 ml of ethylene glycol diacetate, 7.43 g of hydroxyethyl acrylate, 32.08 g of cyanoethyl acrylate were added to a 500 ml three-necked flask, and the temperature was raised to 80 ° C., and the oil-soluble azo polymerization initiator was added therein. A mixture of 0.737 g of V-601 (dimethyl-2,2'-azobis (2-methylisopropionate)) and 20 ml of ethylene glycol diacetate was added dropwise over 4 hours. Allowed to react for hours.

  0.32 g of di-tert-butylhydroquinone, 1.04 g of Neostan U-600 (bismuth octylate, manufactured by Nitto Kasei), and Karenz AOI (acroxyethyl isocyanate, Showa) as a photocurable resin additive were added to the reaction solution. 21.87 g and 22 g of ethylene glycol diacetate were added and reacted at 55 ° C. for 6 hours. Thereafter, 4.1 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was carried out with water, and a solid substance was taken out to obtain a polymerizable compound 1 having a nitrile group as an interactive group.

  Polymerizable compound 1 was a repeating unit containing a polymerizable group (ethylenically unsaturated group): a repeating unit containing a nitrile group = 22: 78 (molar ratio). The molecular weight was Mw = 820,000 (Mw / Mn = 3.4) in terms of polystyrene.

<Preparation of anchor layer coating liquid 1>
10 parts by mass of the polymerizable compound 1 prepared above and 90 parts by mass of acetonitrile were mixed and stirred to prepare an anchor layer coating solution 1 having a solid content of 10% by mass.

<Formation of anchor layer 1>
After using the cyclic polyolefin film 102 prepared in Example 1 as a substrate and subjecting its surface to oxygen plasma treatment, the anchor layer coating liquid 1 was spin-coated so that the film thickness after drying would be 1.0 μm. Coated and dried at 80 ° C. for 30 minutes.

<Curing treatment of anchor layer 1>
Subsequently, using a UV irradiation lamp (model number: UVF-502S, lamp: UXM-501MD) manufactured by Sanaga Electric Co., Ltd., irradiation power of 1.5 mW / cm ² (Ultraviolet integrated light meter UIT150 manufactured by Ushio Inc.) — Light receiving sensor UVD-S254 And the irradiation power was measured under the condition that the integrated light amount was 500 mJ / cm ² , and the anchor layer 1 was cured. This curing condition is referred to as condition A.

  After the anchor layer 1 cured under the above condition A was isolated and subjected to an extraction treatment in an acetone solution at 25 ° C. for 12 hours, the mass of the anchor layer before the treatment was changed to W1 (g), and the anchor layer after the acetone extraction was extracted. When the mass of was determined to be W2 (g), the gel fraction was determined by the following equation. As a result of the measurement, the gel fraction of the anchor layer 1 was 93%.

Gel fraction (%) = (W2 / W1) × 100
<< Making of metal pattern >>
[Production of Metal Pattern 1]
Using the substrate 1 with the anchor layer manufactured as described above, a metal pattern 1 was manufactured according to the following metal pattern forming process.

(Metal pattern forming process)
1: Step of applying catalyst ink 2: Drying step 3: Surface treatment step 4: Activation step 5: Electroless plating step 6: Electroplating step (1: Step of applying catalyst ink)
<Preparation of catalyst ink 1>
The following additives were mixed to prepare Catalyst Ink 1.

Catalyst precursor for electroless plating: palladium acetate 0.05% by mass
79.95% by mass of ethylene diacetate
t-butyl alcohol 20% by mass
<Application of catalyst ink 1>
The catalyst ink 1 prepared above was subjected to pattern drawing of lines and spaces of 75 μm, 100 μm, 150 μm, and 200 μm on the anchor layer of the substrate 1 with the anchor layer formed using an ink jet recording head. Was prepared.

  The used inkjet recording head used was a 512S head manufactured by Konica Minolta, which can eject ink droplets of 4 pl size in a piezo method.

(2: drying process)
After the application of the catalyst ink 1, warm air at 50 ° C. was blown onto the surface to which the catalyst ink was applied for 10 minutes to dry the surface.

(3: Surface treatment step)
The dried sample 1 was subjected to a surface treatment method according to the following method.

<Surface treatment method>
The sample 1 was immersed in a 10% by mass solution of a nonionic surfactant-containing plating conditioner (trade name: PC-321, manufactured by Meltac Inc.) at 60 ° C. for 5 minutes to perform a surface treatment.

  As a result of measuring the contact angles of the surface-treated sample 1 and the untreated sample with water, it was confirmed that the contact angle was reduced by 20% or more due to the surface treatment.

(4: Activation step)
Next, the surface-treated sample 1 was immersed in the following activating solution at 35 ° C. for 10 minutes to perform an activating treatment.

<Activation liquid>
Either reflected light or transmitted light emitted from the opposite surface is photographed and measured.

Alcup MRD2-A (Uemura Kogyo) 18ml
Alcup MRD2-C (made by Uemura Industries) 60ml
The volume was adjusted to 1000 ml with pure water.

(5: Electroless plating process)
After adjusting the pH of the following electroless copper plating solution to 13.0 with sodium hydroxide, the sample 1 subjected to the activation treatment at a temperature of 50 ° C. A copper plating layer having a thickness of 0.2 μm was formed.

<Electroless copper plating solution>
Melplate CU-5100A (Meltex) 60ml
Melplate CU-5100B (Meltex) 55ml
Melplate CU-5100C (Meltex) 20ml
Melplate CU-5100M (Meltex) 40ml
The volume was adjusted to 1000 ml with pure water.

  The electroless copper plating solution has a copper concentration of 2.5% by mass, a formalin concentration of 1% by mass, and an ethylenediaminetetraacetic acid (EDTA) concentration of 2.5% by mass.

(6: electroplating process)
The sample 1 subjected to the electroless plating was immersed in an electroplating bath, and electroplated at a current density of 1.5 A / dm ² using a copper plate as an anode to form a copper film of about 15 μm. 1 was produced.

<Preparation of electroplating bath>
Copper sulfate pentahydrate 60g
190g of sulfuric acid
Chloride ion 50mg
Copper Gream PCM (Meltex) 5ml
The volume was adjusted to 1000 ml with pure water.

  In the same manner as in the above steps, the cyclic polyolefin films 103, 104, 106 to 109, 112, and 113 were used as base films (supports) for flexible electronic circuits.

《Evaluation of metal pattern》
The following evaluations were performed for each of the prepared metal patterns.

[Evaluation of plating quality]
The drawn 75 μm, 100 μm, 150 μm, and 200 μm line and space patterns of the samples processed up to the electroless plating step of each metal pattern were visually observed, and the image quality was evaluated according to the following criteria.

：: The line and space pattern after the completion of the electroless plating has no abnormal deposition outside the printed portion, and has good quality without any decrease in plating gloss or cracks. In the space pattern, abnormal deposition outside the printed area slightly occurs, but no decrease in plating gloss or cracks are observed. ×: Abnormal deposition outside the printed area in the line & space pattern after electroless plating is completed. In this case, any one of reduction in the gloss of the plating and generation of cracks has occurred.

[Evaluation of durability (adhesion resistance) under high temperature and high humidity environment]
After storing each of the prepared metal patterns in a high-temperature and high-humidity environment of 80 ° C. and 90% RH for 7 days, immediately heat-treat them on a hot plate at 240 ° C. and 260 ° C. to obtain a substrate and a copper plating pattern. The adhesion between the layers (the presence or absence of blisters) was visually observed, and the durability (adhesion resistance) was evaluated according to the following criteria.

：: No blistering was observed between the substrate and the copper plating pattern even when heated to 260 ° C. on the hot plate. Δ: Between the substrate and the copper plating pattern even when heated to 240 ° C. on the hot plate. No blistering was observed, but some blistering was observed when heated at 260 ° C. ×: When heated to 240 ° C on a hot plate, blistering was clearly observed between the substrate and the copper plating pattern. As a result of performing the above evaluation, all of the samples in which the metal patterns were prepared using the cyclic polyolefin films 102 to 104, 106 to 109, 112, and 113 of the present invention were evaluated as Δ to 、, and excellent flexible electronic devices were obtained. It was found to be a substrate film (support) for circuits.

Example 7
The cyclic polyolefin films 102 to 104, 106 to 109, 112, and 113 of the present invention produced in Example 1 were used as a base film (support) of a medium for preventing forgery.

(Preparation of coating liquid AL-1 for alignment layer)
The following composition was prepared and filtered with a polypropylene filter having a pore size of 30 μm, and used as a coating liquid for alignment layer AL-1.

<Coating liquid composition for alignment layer>
Polyvinyl alcohol (PVA205, manufactured by Kuraray Co., Ltd.) 3.21% by mass
Polyvinylpyrrolidone (Luvitec K30, manufactured by BASF Japan Ltd.)
1.48 mass%
Distilled water 52.10% by mass
43.21% by mass of methanol
(Preparation of alignment layer coating liquid AL-2)
The following composition was prepared and filtered through a polypropylene filter having a pore size of 30 μm, and used as a coating liquid for alignment layer AL-2.

<Coating liquid AL-2 composition for alignment layer>
Liquid crystal aligning agent (AL-1-1) 1.0% by mass
99.0% by mass of tetrahydrofuran

(Preparation of coating liquid LC-1 for optically anisotropic layer)
After preparing the following composition, the composition was filtered through a polypropylene filter having a pore size of 0.2 μm, and used as a coating liquid LC-1 for an optically anisotropic layer.

  LC-1-1 is a liquid crystal compound having two reactive groups. One of the two reactive groups is an acryl group which is a radical reactive group, and the other is an oxetane group which is a cationic reactive group. is there.

<Coating liquid composition for optically anisotropic layer>
32.88% by mass of polymerizable liquid crystal compound (LC-1-1)
Horizontal alignment agent (LC-1-2) 0.05% by mass
Cationic photopolymerization initiator (CPI100-P, manufactured by San Apro Corporation) 0.66% by mass
Polymerization control agent (IRGANOX1076, manufactured by BASF Japan Ltd.)
0.07% by mass
46.34% by mass of methyl ethyl ketone
Cyclohexanone 20.00% by mass

(Preparation of coating liquid LC-2 for optically anisotropic layer)
After preparing the following composition, the composition was filtered through a polypropylene filter having a pore size of 0.2 μm, and used as a coating liquid LC-1 for an optically anisotropic layer.

<Coating liquid LC-1 composition for optically anisotropic layer>
Diacrylate liquid crystal compound (Paliocolor LC242 (trade name, manufactured by BASF Japan Ltd.))
31.53% by mass
Photopolymerization initiator (IRGACURE907 (trade name, manufactured by BASF Japan Ltd.))
0.99 mass%
Alkylthioxanthone (Kayacure DETX-S (trade name, manufactured by Nippon Kayaku Co., Ltd.)) 0.33% by mass
Fluorosurfactant (MegaFac F-176PF (trade name, manufactured by DIC Corporation))
0.15% by mass
67.00% by mass of methyl ethyl ketone
(Preparation of Additive Layer OC-1)
After the following composition was prepared, it was filtered through a polypropylene filter having a pore size of 0.2 μm, and used as a transfer adhesive layer coating liquid OC-1. As the radical photopolymerization initiator RPI-1, 2-trichloromethyl-5- (p-styrylstyryl) 1,3,4-oxadiazole was used. The following composition is the amount used as the solution.

<Coating liquid composition for additive layer>
Binder (MH-101-5, manufactured by Fujikura Kasei Co., Ltd.) 7.63% by mass
0.49% by mass of radical photopolymerization initiator (RPI-1)
Surfactant 0.03% by mass
(Mega Fuck F-176PF, manufactured by DIC Corporation)
91.85% by mass of methyl ethyl ketone
(Production of birefringence pattern production material P-1)
Aluminum was vapor-deposited on the cyclic polyolefin film 102 to a thickness of 60 nm to produce a support having a reflective layer. The coating liquid for alignment layer AL-1 was applied to the aluminum-deposited surface using a wire bar and dried. The dry film thickness was 0.5 μm. After rubbing the alignment layer, the coating liquid LC-1 for an optically anisotropic layer was applied using a wire bar, dried at a film surface temperature of 90 ° C. for 2 minutes to obtain a liquid crystal phase, and then 160 W under air. UV irradiation was performed using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) to fix the orientation state, thereby forming an optically anisotropic layer having a thickness of 4.5 μm. The illuminance of the ultraviolet rays used at this time was 500 mW / cm ² in the UV-A region (integration of wavelengths from 320 to 400 nm), and the irradiation amount was 500 mJ / cm ² in the UV-A region. The retardation of the optically anisotropic layer was 400 nm and was a polymer solid at 20 ° C. Finally, a coating liquid OC-1 for an additive layer is applied on the optically anisotropic layer and dried to form an additive layer having a thickness of 0.8 μm, and the birefringence pattern builder P-1 of Example 1 is obtained. Produced.

(Anti-counterfeit medium A: birefringent pattern patterned by retardation)
Digital exposure machine P-1 by laser scanning exposure, as shown in FIG. 45 at (INPREX IP-3600H, produced by Fujifilm ^{Corp.), 0mJ / cm 2, 8mJ} / cm 2, the exposure amount of 25 mJ / cm ² Was used to perform pattern exposure with a roll-to-roll. In the figure, the exposure amount is 0 mJ / cm ² of the area indicated by solid color, exposure so that the exposure amount of the region indicated exposure region illustrated by horizontal lines 8 mJ / cm ^2, a vertical line is 25 mJ / cm ² did. Thereafter, the article P-2 having a birefringence pattern was manufactured by using a far-infrared heater continuous furnace and heating by roll-to-roll so that the film surface temperature was 210 ° C. for 20 minutes. When a polarizing plate (HLC-5618, manufactured by Sanlitz Co., Ltd.) was held over the article P-2, the birefringence pattern applied to the article P-2 was confirmed when the polarizing plate was held in a predetermined direction. Was. FIG. 46 is an enlarged view of a pattern observed through the polarizing plate on the article P-2. In the figure, a two-color pattern is observed, in which the aluminum foil in the ground has a silver color, while the lattice portion has a dark blue or light blue color, and the hatched portions have a yellow or orange color.

(Anti-counterfeit medium B :: Birefringent pattern with patterned optical axis)
Aluminum was vapor-deposited on the cyclic polyolefin film 102 to a thickness of 60 nm. Next, the coating liquid for alignment layer AL-2 was applied on aluminum using a wire bar and dried. The dry film thickness was 0.1 μm.

A photomask A shown in FIG. 47 is arranged on the obtained organic film, and an ultraviolet irradiator (HOYA) is used.
Light emitted from ultraviolet light emitted from CANDEO OPTRONICS (trade name: EXECURE3000) is passed through a linear polarizing plate at an intensity of 100 mW / cm ² (365 nm) from a direction perpendicular to the support. Irradiated for seconds. At this time, the polarizing plate was arranged such that the azimuth of the absorption axis of the linear polarizing plate was 0 ° with respect to the long side of the photomask.

  Subsequently, the photomask was changed in order of B, C, and D shown in FIG. 47, and the polarizers were set such that the absorption axes of the linear polarizers were 45 °, 90 °, and 135 ° with respect to the long side of the photomask, respectively. , And similarly irradiated with ultraviolet rays.

Next, the coating liquid LC-2 for an optically anisotropic layer was applied using a wire bar, dried at a film surface temperature of 105 ° C. for 2 minutes to obtain a liquid crystal phase, and then air-cooled at 160 mW / cm ² under air. A metal halide lamp (manufactured by Eye Graphics Co., Ltd.) is used to irradiate ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 400 mJ / cm ² to fix the orientation state thereof, and to form an optically anisotropic layer having a thickness of 0.9 μm. The forgery prevention medium B having the pattern shown in the plan view of FIG. 48 was produced.

  As shown in FIG. 48, the slow axes of the characters A12, B13, C14, and the background 15 of the forgery prevention medium B were 0 °, 45 °, 90 °, and 135 ° with respect to the long side, respectively. The retardation in each of these regions was 135 nm (λ / 4).

(Production Example 1)
The forgery prevention medium A was treated with a surface modification device MEIR-5-600 (manufactured by MD Eximer). Thereafter, letters and designs were letterpress printed using UV161 black, red, indigo and yellow (manufactured by T & K). Thereafter, dry lamination was performed using Suncut PL Syn 7LK (manufactured by Lintec Co., Ltd., front retardation = 5 nm, film thickness 50 μm) to produce a forgery prevention medium of Production Example 1.

(Production Example 2)
A forgery prevention medium of Production Example 2 was produced in the same manner as in Production Example 1, except that the forgery prevention medium A was changed to the forgery prevention medium B.

(Production Example 3)
A forgery prevention medium of Production Example 3 in the same manner as in Production Example 1, except that Sancut PL Shin 7LK (Lintec Co., Ltd., front retardation = 5 nm, film thickness 50 μm) whose surface was sandblasted was used as a laminate film. Was prepared.

(Production Example 4)
Using LUXEL JET UV250GT (manufactured by FUJIFILM Corporation), variable information was printed on the forgery prevention medium of Production Example 1 with KI ink. Thus, the forgery prevention medium of Production Example 4 was produced.

(Production Example 5)
The forgery prevention medium A was treated with a surface modification device MEIR-5-600 (manufactured by MD Eximer). Thereafter, printing was performed with KI ink using LUXEL JET UV250GT (manufactured by FUJIFILM Corporation). Thereafter, dry lamination was performed using Suncut PL Syn 7LK (manufactured by Lintec Co., Ltd., front retardation = 5 nm, film thickness 50 μm) to produce a forgery prevention medium of Production Example 5.

(Production Example 6)
The forgery prevention medium A was treated with a surface modification device MEIR-5-600 (manufactured by MD Eximer). Thereafter, letters and designs were letterpress printed using UV Flexo 500 ink, red, indigo, and yellow (manufactured by T & K). Thereafter, dry lamination was performed using Suncut PL Syn 7LK (manufactured by Lintec Co., Ltd., front retardation = 5 nm, film thickness 50 μm) to produce a forgery prevention medium of Production Example 6.

(Production Example 7)
The forgery prevention medium A was treated with a surface modification device MEIR-5-600 (manufactured by MD Eximer). Thereafter, the characters and the designs were screen printed. Thereafter, dry lamination was performed using Suncut PL Syn 7LK (manufactured by Lintec Co., Ltd., front retardation = 5 nm, film thickness 50 μm) to produce a forgery prevention medium of Production Example 6.

(Production Example 8)
A forgery prevention medium of Production Example 8 was produced in the same manner as in Production Example 1, except that KES25N Matt PL Syn 7LK (manufactured by Lintec Corporation, front retardation = 33 nm, film thickness 25 μm) was used as a laminate film.

(Production Example 9)
As a laminated film, an adhesive (trade name: Z2-25, Panac Co., Ltd.) is laminated to triacetyl cellulose (trade name: TDP, manufactured by FUJIFILM Corporation, front retardation = 1 nm, film thickness: 60 μm). A forgery prevention medium of Production Example 9 was prepared in the same manner as in Production Example 1 except that the anti-counterfeit medium was used.

  Similarly, the cyclic polyolefin films 103, 104, 106 to 109, 112, and 113 were used as a base film (support) of a medium for preventing forgery.

  Each of the anti-counterfeit media of Production Examples 1 to 9 was excellent in the latent image visibility, and the print was not peeled off by the tape adhesion test or the abrasion resistance test, and the durability was excellent. Therefore, it was found that the cyclic polyolefin film of the present invention can be preferably used as a base film (support) of a medium for preventing forgery.

DESCRIPTION OF SYMBOLS 1 Dissolution pot 3, 6, 12, 15 Filter 4, 13 Stock tank 5, 14 Liquid feed pump 8, 16 Conduit 10 Ultraviolet absorbent charging pot 20 Confluence pipe 21 Mixer 30 Die 31 Endless support 32 Web 33 Peeling position 34 Tenter device 35 Roller drying device 36 Conveyance roller 37 Winding device 41 Charging tank 42 Stock tank 43 Pump 44 Filtration device 100 Main filtration device 102 Ultrafiltration device 103 Stationary tank (stock tank)
104 Dope flow pipe (flow pipe)
105 Pump 106 Diluent solvent tank 107 Solvent injection pipe 108 Pipe 110 Casting die 111 Endless support 112 Peeling roll 113 Open / close valve 114 Open / close valve 115 Open / close valve 116 Open / close valve 117 Open / close valve 118 Solvent discharge pipe 119 Solvent reuse return pipe

Claims (5)

A method for producing a cyclic polyolefin film, at least,
Dissolving a cyclic polyolefin-based resin using an organic solvent, adding an additive to prepare a dope, followed by filtration, and adjusting the content of foreign substances having a major axis of 10 μm or more as a finished film to 5 pieces / 100 cm ² or less,
The content of toluene in the dope is in the range of 0.001 to 0.1% by mass,
Casting the dope on an endless support,
Drying the cast dope and peeling off from the endless support to form a web,
Drying and stretching the peeled web, and winding the stretched web as a roll,
A method for producing a cyclic polyolefin film, comprising: A method for producing a cyclic polyolefin film, at least,
The cyclic polyolefin resin is dissolved using an organic solvent, in preparing the dope by adding additives, further adding toluene as organic solvent, the organic solvent other than toluene content of the toluene in the dope And by adding the above-mentioned additives, the content is adjusted within the range of 0.001 to 0.1% by mass and then filtered, and the content of foreign substances having a major axis of 10 μm or more as a finished film is adjusted to 5 pieces / 100 cm ² or less. Process,
Casting the dope on an endless support ,
Drying the cast dope and peeling off from the endless support to form a web,
Drying and stretching the peeled web; and
Winding the stretched web as a roll,
Method for producing a ring-like polyolefin film you characterized by having a. A method for producing a cyclic polyolefin film, at least,
When the cyclic polyolefin-based resin is dissolved using an organic solvent and an additive is added to prepare a dope, a cellulose acylate is further added as an additive, and the content of the cellulose acylate in the dope is adjusted to the organic solvent. By adding the above-mentioned additives other than cellulose acylate or cellulose acylate, the content is adjusted to be in the range of 0.0001 to 0.1% by mass and then filtered. Adjusting to ² or less,
Casting the dope on an endless support,
Drying the cast dope and peeling off from the endless support to form a web,
Drying and stretching the peeled web; and
Winding the stretched web as a roll,
Method for producing a ring-like polyolefin film you characterized by having a.   The method for producing a cyclic polyolefin film according to claim 1, wherein two or more kinds of the cyclic polyolefin-based resin are used. Before Ki添 pressurizing agent, a nitrogen-containing heterocyclic compounds, organic esters, and method for producing a cyclic polyolefin film according to claim 1, characterized in that at least one selected from the matting agent.

Images