JP2009082890A - Manufacturing method for optical resin film and hard coat film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for an optical resin film which comprises forming a functional layer that has an excellent adhesiveness and a fast drying property and causes no change in the physical and chemical properties of a substrate on the substrate, and also to provide a hard coat film and an antireflection film which are manufactured by the manufacturing method. <P>SOLUTION: In the manufacturing method for the optical resin film, at least one functional layer is formed by coating a coating liquid for forming the functional layer which contains a solvent having 5%-80% of a total mass and a permeability of ≥1g/(cm<SP>2</SP>×min) to the resin film and contains a reactive curable resin having 20-70 mass% of the total mass using the resin film having at least two phases each having a different volume occupation ratio by voids sequentially in a thickness direction. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing an optical resin film, and a hard coat film and an antireflection film produced by the production method. More specifically, the present invention relates to a method for producing an optical resin film using resin films having phases in which the volume occupancy of pores sequentially differs in the thickness direction, and a hard coat film and an antireflection film produced by this production method.

  In recent years, various displays have been used in various applications such as portable devices, personal computers, monitors, and televisions. Among them, liquid crystal displays are widely used from small products for portable devices to recently large-sized products such as monitors and televisions. An antistatic layer for providing an antistatic function as a protective film on the outermost member of the liquid crystal display device, a hard coat layer for improving surface hardness or imparting scratch resistance, and an anticurl for preventing curling In order to improve the visibility of a layer, an image, or a character, an optical resin film having various functions such as an antiglare layer, an antireflection layer, and an antiglare antireflection layer is used. These functional layers are provided by coating a coating liquid having various additives and resins for imparting various functions.

  For example, in JP 2001-264508 A and JP 2003-121620 A, a hard coat layer containing antiglare fine particles is provided in a smooth support film, and an antireflection layer is provided thereon. An antireflective film is described.

  Thus, when a functional layer is coated on a transparent resin film, particularly when a laminated structure is formed such that a hard coat layer or an antireflection layer is further coated thereon, cracks are generated or scratches occur in various processes. Occurrence etc. were seen and sometimes became a problem. In particular, when a polarizing plate is produced using these optical resin films, there has been a problem that productivity is remarkably impaired due to failure such as peeling or cracking of the hard coat layer during subsequent cutting and punching.

  In order to give various functions, fine particles may be added to the lower layer. For example, when the lower layer is an antistatic layer, conductive fine particles are added. Adhesion between the added fine particles and the lower layer binder may be a problem, and the peeling and cracking may be increased.

  Further studies have been made on these peelings. For example, when a hard coat layer is provided on a specific cellulose ester film substrate, it can swell or dissolve in the substrate to improve the adhesion of the hard coat layer. A method of providing an intermediate layer formed by coating a coating composition, in which the ratio of the solvent to the entire coating composition solvent is 20 to 95% by volume, is known (for example, Patent Document 1). However, the method described in Patent Document 1 has the following drawbacks, although improved adhesion is recognized. 1) Since the base material is dissolved and penetrated, it takes time to dry, which is one of the factors that hinder the improvement of productivity. 2) Since the residence time of the solvent that has permeated into the base material becomes long, there is a risk that components in the base material are separated and the physicochemical properties of the base material are changed.

From such a situation, a manufacturing method of an optical resin film that forms a functional layer that has excellent adhesion on the base material, quick drying, and does not change the physicochemical properties of the base material, and manufactured by this manufacturing method Development of a hard coat film and an antireflection film that have been developed is desired.
JP 2005-70744 A

  The present invention has been made in view of the above circumstances, and its purpose is to form a functional layer on a substrate with excellent adhesion, quick drying, and without changing the physicochemical properties of the substrate. Another object of the present invention is to provide a method for producing an optical resin film, and a hard coat film and an antireflection film produced by the production method.

  The above object of the present invention has been achieved by the following constitution.

1. Using a resin film having at least two phases with different volume occupancy rates due to pores in the thickness direction, 5% of the total mass of a solvent having a permeability of 1 g / (cm ² · min) or more to the resin film Optically characterized in that at least one functional layer is formed by applying a functional layer forming coating solution containing ~ 80% and containing 20% by mass to 70% by mass of a reactive curable resin. A method for producing a resin film.

  2. 2. The optical resin as described in 1 above, wherein the phase has a first phase and a second phase, and the first phase is on a surface on which the resin layer of the second phase is applied. A method for producing a film.

  3. 2. The volume occupancy ratio of the voids due to the pores of the first phase is 5% to 20%, and the volume occupancy ratio of the voids due to the voids of the second phase is 0% to 1% The manufacturing method of the resin film for optics of description.

  4). 2 or 3 above, wherein the thickness of the first phase is 60% to 99% of the total thickness of the resin film, and the thickness of the second phase is 1% to 40% of the total thickness of the resin film. The manufacturing method of the resin film for optics as described in any one of.

  5). 3. The method for producing an optical resin film as described in 2 above, wherein the third phase is provided on a surface opposite to the surface on which the first phase of the second phase is formed.

  6). 6. The method for producing an optical resin film as described in 5 above, wherein the volume occupancy ratio of the voids due to the holes of the third phase is 5% to 20%.

  7. The thickness of the first phase is 40% to 60% of the total thickness of the resin film, the thickness of the second phase is 1% to 20% of the total thickness of the resin film, and the thickness of the third phase is The method for producing an optical resin film as described in 5 or 6 above, which is 40% to 60% of the total thickness of the resin film.

  8). 8. The method for producing an optical resin film according to any one of 1 to 7, wherein the resin layer is formed on a first phase.

  9. The method for producing an optical resin film as described in any one of 1 to 8 above, wherein the pores are 80% or more of the pores and the maximum diameter is distributed in a range of 1.0 nm to 1000 nm. .

  10. 10. The method for producing an optical resin film according to any one of 1 to 9, wherein the resin film has a thickness of 40 μm to 80 μm and the functional layer has a thickness of 4 μm to 16 μm.

  11. 11. The method for producing an optical resin film according to any one of 1 to 10, wherein the resin film is produced by a solution casting method.

  12 A hard coat film produced by the method for producing an optical resin film described in any one of 1 to 11 above.

  A method for producing an optical resin film having excellent adhesion on a substrate, quick drying, and forming a functional layer without changing the physicochemical properties of the substrate, and a hard coat produced by this production method A film and an antireflection film can be provided, and productivity can be improved.

  The embodiment of the present invention will be described with reference to FIGS. 1 to 4, but the present invention is not limited to this.

  FIG. 1 is a schematic cross-sectional view of an optical resin film produced by the production method of the present invention. Fig.1 (a) is a schematic sectional drawing of the optical resin film which has a functional layer manufactured using the resin film which has two phases from which the volume occupation rate by a void | hole differs. FIG.1 (b) is a schematic sectional drawing of the optical resin film which has a functional layer manufactured using the resin film which has three phases from which the volume occupation rate by a void | hole differs.

  Description will be made with reference to an optical resin film having the functional layer shown in FIG. In the figure, 1a indicates 1a having a functional layer. The optical resin film 1a includes a resin film 2 that is a base material and a functional layer 3. The resin film 2 has a first phase 2a and a second phase 2b having different volume occupancy rates of voids due to holes. The resin film 2 will be described in detail with reference to FIG. The functional layer 3 only needs to be provided at least on the first phase 2a side, and can be appropriately selected as necessary.

  O indicates the thickness of the functional layer 3. The thickness O is preferably 4 μm to 16 μm in consideration of adhesion, the amount of solvent during coating, the reaction rate and speed of the curing reaction, and the like.

  P indicates the thickness of the resin film 2. The thickness P is preferably 40 μm to 80 μm in consideration of productivity, physical strength, film thickness after processing, and the like.

  Q indicates the thickness of the first phase 2a. The thickness Q is preferably 60% to 99% with respect to the thickness P of the resin film 2 in consideration of the permeation rate of the solvent, physical strength, and the like.

  R represents the thickness of the second phase 2b. The thickness R is preferably 1% to 40% with respect to the thickness P of the resin film 2 in consideration of the solvent penetration rate, physical strength, and the like.

  The description will be given with respect to an optical resin film having the functional layer shown in FIG. In the figure, 1b represents an optical resin film having a functional layer. The optical resin film 1b has a structure including a resin film 4 as a base material and a functional layer 5. The resin film 4 has a first phase 4a, a second phase 4b, and a third phase 4c, which have different product occupation ratios of voids due to holes. The third phase 4c is formed on the surface opposite to the surface on which the first phase 4a of the second phase 4b is formed.

  The resin film 4 will be described in detail with reference to FIG. The functional layer 5 only needs to be provided at least on the first phase 4a side, and can be appropriately selected as necessary.

  S indicates the thickness of the functional layer 5. The thickness S is preferably 4 μm to 16 μm in consideration of physical strength, optical characteristics, curing reaction rate, and the like.

  T indicates the thickness of the resin film 4. The thickness T is preferably 40 μm to 80 μm in consideration of productivity, physical strength, film thickness after processing, and the like.

  U represents the thickness of the first phase 4a. The thickness U is preferably 40% to 60% with respect to the thickness T of the resin film 4 in consideration of the solvent penetration rate, physical strength, and the like.

  V indicates the thickness of the second phase 4b. The thickness V is preferably 1% to 20% with respect to the thickness T of the resin film 4 in consideration of the permeation rate of the solvent, physical strength, and the like.

  W represents the thickness of the third phase 4c. The thickness W is preferably 40% to 60% with respect to the thickness T of the resin film 4 in consideration of the solvent penetration rate, physical strength, and the like.

  The optical resin film having the structure shown in FIGS. 1 (a) and 1 (b) is manufactured by the holes in order in the thickness direction shown in FIGS. 2 and 3 manufactured by the manufacturing apparatus shown in FIG. Using a resin film having a phase with different volume occupancy ratios, a functional layer / functional layer forming coating solution is applied by, for example, gravure coater, dip coater, reverse coater, wire bar coater, die coater, inkjet method, etc. I can do it.

As the functional layer forming coating solution for forming the functional layer shown in FIGS. 1A and 1B, a solvent having a permeability to a resin film of 1 g / (cm ² · min) or more is 5% of the total mass. A coating solution containing 20% by weight to 70% by weight of the total weight of the reactive curable resin is included.

  The permeability indicates a value obtained by conducting the following permeability test.

Penetration test Attach a lid that can be removed with a slide to both ends of the glass tube, fill the inside with a liquid whose permeability is to be measured, measure the mass, remove the upper lid, and attach it to the sample to be measured. Turn the sample and the glass tube over and remove the upper lid at the same time and keep the state for the measurement time. When the time has elapsed, place the lid on the top and turn it over, remove the sample, close the lid, and measure the reduced liquid mass. The cross-sectional area is calculated from the inner diameter of the tube, and the value obtained by converting the reduced mass into the reduced amount per unit area and unit time is used as the value for permeability evaluation.

  Any material can be used for the material of the tube and the lid as long as they are not affected by the liquid, but those having a small volume change due to temperature or the like are preferable.

  Usually, the permeability is measured under the condition that the sample is not deformed or broken. When the permeability test is performed, a solvent in which a resin film is dissolved during the measurement for 1 minute and a hole is formed and an accurate permeability evaluation cannot be performed is described as being impossible to measure. Although the conditions such as the hole size and the time until the occurrence differ depending on the solvent type, all the films having holes in the film after the measurement were disabled.

When the permeability is less than 1 g / (m ² · min), the applied functional layer does not sufficiently adhere to the resin layer, causing interference jima, or when the resin layer and the functional layer are processed during processing into a display. Since it peels off, it is not preferable.

Further, even when the permeability is 1 g / (m ² · min) or more, if the addition amount is 5% or less of the total mass, the applied functional layer does not sufficiently adhere to the resin layer, thereby causing interference jitter. This is not preferable because it occurs or the resin layer and the functional layer are peeled off during processing into a display.

  Even if the solvent has high permeability and the resin layer dissolves and penetrates, there is no problem even if it is used for forming the functional layer as long as the addition amount is 80% or less of the total mass. If the added amount exceeds 80%, the influence of dissolution of the base material becomes large, and it is not preferable because separation of components, reduction in strength of the resin layer, deterioration of surface smoothness, and uniform molding of the functional layer become difficult.

  When the reactive curable resin is less than 20% by mass, it takes a long time to dry, which is not preferable because the formation of a uniform functional layer and the influence on the resin layer are increased. When the reactive curable resin exceeds 80% by mass, it is not preferable because it is difficult to form a uniform functional layer and ensure the smoothness of the surface due to a decrease in fluidity.

  Although there is no limitation in particular as a functional layer shown by Fig.1 (a) and FIG.1 (b), For example, a hard-coat layer and an antireflection layer are mentioned. An explanation will be given below when a hard coat layer is applied. The hard coat layer is usually formed by coating a reactive curable resin. The reactive curable resin is a resin whose main component is a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams.

  The hard coat layer is formed by irradiating actinic rays during or after drying after applying a hard coat layer forming coating solution obtained by dissolving a reactive curable resin in an organic solvent. The coating method for the hard coat layer coating composition is not particularly limited. For example, the coating composition can be coated by a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, or an inkjet method.

  The coating amount is suitably 7 μm to 30 μm as a wet film thickness, and preferably 10 μm to 25 μm. The dry film thickness is 5 μm to 20 μm, preferably 5 μm to 15 μm.

The coating composition for hard coat layer is preferably irradiated with actinic rays as described above after coating, during or after drying. The irradiation time is preferably about 0.1 seconds to 5 minutes, and more preferably 0.1 to 20 seconds from the viewpoint of the curing efficiency or work efficiency of the ultraviolet curable resin. Moreover, it is preferable that the illumination intensity of an ultraviolet irradiation part is 50-150 mW / m < ² >. The hard coat layer coating composition will be described later.

As a light source for curing an ultraviolet curable resin by a photocuring reaction to form a cured film layer, any light source that generates ultraviolet rays can be used without any limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is preferably 5 to 200 mJ / cm ² , and particularly preferably 20 to 100 mJ / cm ² .

  This will be described in the case where an antireflection layer is applied as a functional layer. As a method for forming an antireflection layer (also referred to as a metal oxide layer) by coating, for example, a method in which fine particles of metal oxide are dispersed in a binder resin dissolved in a solvent, followed by coating and drying, a polymer having a crosslinked structure is bound as a binder. Examples of the coating method include a method used as a resin, a method of containing an ethylenically unsaturated monomer and a photopolymerization initiator, and forming a layer by irradiating actinic rays. The coating method can be formed by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, micro gravure coating, extrusion coating, or ink jet method. I can do it.

  The antireflection layer (metal oxide layer) is preferably selected from a high refractive index layer, a medium refractive index layer, and a low refractive index layer as necessary. The refractive index of the high refractive index layer is preferably 1.55 to 2.30, and more preferably 1.57 to 2.20. The refractive index of the middle refractive index layer is preferably 1.55-1.80. The thickness of each layer is preferably 5 nm to 0.5 μm, more preferably 10 nm to 0.3 μm, and most preferably in the range of 30 nm to 0.2 μm.

  The haze of the antireflection layer (metal oxide layer) is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the antireflection layer (metal oxide layer) is preferably 3H or more, and most preferably 4H or more, with a pencil hardness of 1 kg. When the metal oxide layer is formed by coating, it is preferable to include inorganic fine particles and a binder.

The inorganic fine particles used for the antireflection layer (metal oxide layer) preferably have a refractive index of 1.80 to 2.80, more preferably 1.90 to 2.80. The primary particle mass average diameter of the inorganic fine particles is preferably 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm. The mass average diameter of the inorganic fine particles in the layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, still more preferably 10 to 100 nm, and most preferably 10 to 80 nm. . The average particle diameter of the inorganic fine particles is measured by a light scattering method if it is 20-30 nm or more and by an electron micrograph if it is 20-30 nm or less. The specific surface area of the inorganic fine particles, a measured value by the BET method, is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, a 30 to 150 m ² / g Is most preferred.

  FIG. 2 is an enlarged schematic view of the base resin film used in the optical resin film shown in FIG. Fig.2 (a) is an expanded schematic sectional drawing of the resin film of the base material currently used for the optical resin film shown by Fig.1 (a). FIG. 2B is an enlarged schematic view of a portion indicated by L in FIG.

  In the figure, 2 indicates a resin film as a base material. The occupied volume ratio of the pores 201 of the first phase 2a is preferably 5% to 20% in consideration of the structure of the resin film (first phase / second phase). The occupied volume ratio of the voids 201 of the second phase 2b is preferably 0% to 1% in consideration of the function of the resin film, the function maintenance as the second phase, and the like. The occupied volume ratio of the voids 201 is a value obtained by calculating the occupied volume by the following method and calculating from the following formula.

Method for obtaining the occupied volume ratio of pores Method for obtaining the volume of individual pores From the cross-sectional imaging of a resin film photographed with an SEM (magnification 15000 times), the maximum diameter of the pores was measured and the average value was obtained. One half of the maximum diameter was used as the hole radius r. Using the obtained radius r, it was obtained by calculation from the equation (4πr ^3/3 ) for obtaining the volume of the sphere.

Volume of pores in a fixed volume = volume of individual pores × number of holes in a fixed volume Occupied volume ratio (%) = volume of holes in a fixed volume / constant volume of resin film size of the holes 201 In consideration of the uniformity of pore distribution, maintenance of the optical performance of the resin film, etc., the maximum diameter of the pores is 80% or more of the pores and is distributed in the range of 1.0 nm to 1000 nm. preferable.

  The size of the hole 201 refers to the maximum diameter of the hole 201 in the cross-sectional shape. The maximum diameter is a value obtained by measuring the cross section of the resin film by photographing (magnification: 15000 times) using SEM and actually measuring the maximum diameter of the holes from the obtained image.

  The hole 201 has an opening 201 a on the surface of the resin film 2, and is a hole in a sealed state inside the resin film 2. Since the size of the opening 201a differs depending on the position of the hole 201 from the surface of the resin film 2 and the size of the hole 201, it is difficult to uniquely define the size. The cross-sectional shape of the hole 201 is not particularly limited, and examples thereof include a circle and an ellipse.

  FIG. 3 is an enlarged schematic view of the base resin film used in the optical resin film shown in FIG. FIG. 3A is an enlarged schematic cross-sectional view of a base resin film used in the optical resin film shown in FIG. FIG. 3B is an enlarged schematic view of a portion indicated by M in FIG.

  In the figure, 4 indicates a resin film as a base material.

  The occupied volume ratio of the holes 401 of the first phase 4a is preferably 5% to 20% in consideration of the permeation rate of the solvent, physical strength, and the like. The occupied volume ratio of the holes 401 of the second phase 4b is preferably 0% to 1% in consideration of the permeation rate of the solvent, physical strength, and the like. The occupied volume ratio of the holes 401 of the third phase 4c is preferably 5% to 20% in consideration of the permeation rate of the solvent, physical strength, and the like. The occupied volume ratio of the holes 401 indicates a value obtained by the same method as that for the resin film 2 shown in FIG. The size of the holes 401 is distributed in the range of 1.0 nm to 1000 nm with a maximum diameter of 80% or more of the holes in consideration of uniformity of distribution of holes and maintenance of the optical performance of the resin film. It is preferable.

  The size of the hole 401 refers to the maximum diameter of the hole 401 in the cross-sectional shape. The maximum diameter is a value obtained by measuring the cross section of the resin film by photographing (magnification: 15000 times) using SEM and actually measuring the maximum diameter of the holes from the obtained image. Some of the holes are elliptical, and the diameter is measured with the maximum diameter measured from the cross-sectional photograph. In addition, the maximum diameter was also used when calculating the porosity, and the ratio of the number having the maximum diameter exceeding the specified range was calculated at the same time.

  The holes 401 are in a state having an opening 401 a on the surface of the resin film 4 (the surface of the first phase 4 a), and are sealed in the resin film 4. Since the size of the opening 401a differs depending on the position of the hole 401 from the surface of the resin film 4 and the size of the hole 401, it is difficult to uniquely define the size. The cross-sectional shape of the hole 401 is not particularly limited, and examples thereof include a circle and an ellipse. The holes 401 are also in the same state on the back surface of the resin film 4 (the surface of the third phase 4c).

  A method for producing a resin film having at least two phases having different volume occupancy rates due to pores in the thickness direction as shown in FIGS. 2 and 3 will be described with reference to FIG.

  As a function of a resin film having at least two phases having different volume occupancy rates due to pores in the thickness direction as shown in FIGS. 2 and 3, 1) improvement of permeability by pores, 2) surface opening Part anchor effect, 3) solvent drying speed improvement effect and the like.

  When the resin film having the structure shown in FIGS. 2 and 3 is used and a functional layer is applied as shown in FIGS. 1A and 1B, the following effects can be obtained.

  1) The solvent of the coating liquid for forming the functional layer is quickly penetrated into the resin film due to the pores, and the solvent is evaporated from the surface opposite to the coated surface, so that the solvent stays in the coated functional layer. Residence in the resin layer is shortened. The three-phase resin film shown in FIG. 3 is more excellent in promoting the evaporation of the solvent than the two-phase resin film shown in FIG. As a result, the time from the application of the functional layer forming coating solution to the permeation and drying of the solvent to form the functional layer is shortened, and the production efficiency can be improved.

  2) Since the retention of the solvent in the coating liquid for forming the functional layer is shortened, there is no influence on the functional layer and the resin layer, and surface properties, physical strength, and uniformity can be improved.

  3) When a part of the coating liquid for forming the functional layer enters the opening where the coating surface exists, the adhesion of the functional layer is improved by the anchor effect of the opening, and the peeling resistance is improved. As a result, it is not necessary to install an intermediate layer for improving adhesion, and production efficiency can be improved. In addition, cutting to a small size is facilitated, and it is possible to expand applications and speed up response.

  Next, it is comprised from the resin film comprised from two phases from which the volume occupation rate of a void | hole shown by Fig.1 (a) differs, and the three phase from which the volume occupation rate of a void | hole shown by FIG.1 (b) is different. One example of the resin film manufacturing method will be described with reference to FIG. FIG. 4 shows a method for producing the resin film shown in FIGS. 1 (a) and 1 (b) by a solution casting method using an endless belt, but solution casting or melting using an endless drum. It can also be produced by a casting method.

  FIG. 4 is a schematic view of an apparatus for producing a resin film by a solution casting method using an endless belt support. FIG. 4 (a) shows the production of a resin film by a solution casting method using an endless belt support that is preliminarily dried in the first drying step after casting, then transported as a tenter, and then dried in the second drying step. It is the schematic of an apparatus. FIG. 4B is a schematic diagram of an apparatus for producing a resin film by a solution casting method using an endless belt support that is transported by a first tenter and a second tenter after casting and then subjected to main drying in a second drying step. FIG. FIG.4 (c) is the schematic of the manufacturing apparatus of the resin film by the solution casting method using the endless belt support which provided the MD extending process between the 1st tenter and the 2nd tenter.

  A description will be given of the resin film manufacturing apparatus shown in FIG.

  In the drawing, reference numeral 6a denotes a production apparatus for a resin film solution casting method. The manufacturing apparatus 6a includes a casting process 601, a first drying process 602, a stretching process 603, a second drying process 604, and a winding process 605.

  The casting step 601 includes a mirror-like endless belt support 601a, a die 601b for casting a dope 7 in which a resin is dissolved in a solvent, and the heating device 601c. The endless belt support 601a is held by a roll 601a1 and a roll 601a2, and can be rotated (in the direction of the arrow in the figure).

  Reference numeral 8 denotes a web in which the dope 7 is cast on an endless belt support 601a. Reference numeral 9 denotes a peeling roll for peeling the solidified web. The thickness of the web 8 can be set as necessary so that the thickness of the resin film collected in the winding process 605 becomes a set film thickness.

  The heating device 601c is disposed to remove the solvent so that the dope 7 cast on the endless belt support 601a can be peeled from the endless belt support 601a.

  The heating device 601c includes a drying box 601c1, a first heating air supply device 601d disposed in the drying box 601c1, a second heating air supply device 601e, and an exhaust pipe 601f. The first heated air supply device 601d has a heated air supply pipe 601d1 and a header 601d2. The second heated air supply device 601e has a heated air supply pipe 601e1 and a header 601e2.

  The temperature of the web 7 on the endless belt support 601a on the first heating air supply device 601d side and the temperature of the web on the endless belt support 601a on the second heating air supply device 601e side are the conveyance speeds accompanying the evaporation time of the solvent. In consideration of foaming due to solvent evaporation, predetermined pore size, pore density formation, productivity, etc., a range of −5 ° C. to 70 ° C. is preferable, and a range of 0 ° C. to 60 ° C. is particularly preferable. .

  The wind pressure of the heating air supplied from the first heating air supply device 601d and the second heating air supply device 601e takes into consideration the uniformity of solvent evaporation, uneven density of holes in the resin film, the size of the holes, and the like. 50 Pa to 5000 Pa is preferable.

  The temperature of the heating air supplied to the web 7 on the endless belt support 601a by the first heating air supply device 601d may be dried at a constant temperature, or several steps in the moving direction of the endless belt support 601a. It may be supplied separately. Moreover, the supply of the heating air supplied to the web 7 on the endless belt support 601a by the second heating air supply device 601e is the same.

  Although the heating device 601c shown in this figure shows the case where heated air is used, the heating means is not particularly limited. Besides this, for example, a method of heating the web on the endless belt support 601a with an infrared heater, A method of blowing warm air to the back surface of the endless belt support 601a and heating from the back surface side can be mentioned, and can be appropriately selected as necessary.

  After the dope is cast on the endless belt support 601a, the time from the endless belt support 601a to peeling of the web 8 varies depending on the film thickness of the resin film to be produced and the solvent used, but the endless belt support In consideration of peelability from 601a, a range of 0.5 to 5 minutes is preferable.

  The endless belt support 601a to be used is preferably a mirror-finished surface, for example, a metal belt whose surface is plated with a casting is preferably used. The width of the endless belt support 601a is preferably 1700 mm to 2700 mm. The cast width is preferably 80% to 99% with respect to the width of the endless belt support 601a.

  The total residual solvent amount of the web 8 when the web 8 is peeled from the endless belt support 601a is the peelability from the endless belt support, the residual solvent amount at the time of peeling, the transportability after peeling, and the resin that is produced after transporting and drying. Considering the physical properties of the film, etc., 30% by mass to 200% by mass is preferable. In addition, the ratio of the good solvent amount to the total residual solvent amount is determined by the peelability of the web from the endless belt support, the residual solvent amount at the time of peeling, the transportability after peeling, the physical properties of the resin film produced after transporting and drying, etc. Considering 30% to 120% is preferable. More preferably, it is 50% to 95%. The solvent to be used will be described later.

  The amount of residual solvent of the web 8 from the time when it is peeled off from the endless belt support 601a to the start of stretching in the stretching process is preferably 5% by mass to 50% by mass in consideration of curl, wrinkles, etc. of the resin film as a product. .

  The concentration of the resin for forming the resin film of the dope 7 is preferably higher when the concentration of the resin for forming the resin film is too high. Increase in the load, decrease in filtration accuracy, decrease in pore formation, and the like. The concentration for achieving both of these is preferably 10% by mass to 35% by mass, and more preferably 15% by mass to 25% by mass.

  When the web 4 is peeled from the endless belt support 601a, the web 8 is stretched in the MD (Machine Direction) direction due to the peeling tension and the subsequent conveying tension. Therefore, in the present invention, the web is peeled from the endless belt support 601a. In this case, it is preferable that the peeling and conveying tension be 50 N / m to 400 N / m.

  The first drying step 602 includes a drying box 602a having a drying air intake port 602b and a discharge port 602c, an upper conveyance roll 602d that conveys the web 8, and a lower conveyance roll 602e. The upper transport roll 602d and the lower transport roll 602e are a set of upper and lower, and are composed of a plurality of sets. It is possible to adjust the amount of solvent contained in the web 8 before entering the stretching step 603 in the first drying step 602.

  The drying temperature varies depending on the amount of residual solvent in the web 8 when entering the stretching process, but it takes into account condensation on the surface of the web as the solvent evaporates, adjustment of the residual solvent amount, stretching rate, foaming of the web by the solvent, etc. In the range of 20 ° C. to 80 ° C., the amount may be appropriately selected and determined depending on the amount of residual solvent, and may be dried at a constant temperature or may be divided into several stages of temperature.

  In the case of the manufacturing apparatus 6a shown in this figure, the stretch rate in the MD direction of the web 8 is peeled off from the endless belt support 601a and until the start of stretching in the stretching step 603 is the elastic modulus, optical characteristics, etc. of the finished resin film. Considering 1% to 25% is preferable. The stretch rate in the TD (Transverse Direction) direction of the web 8 is preferably -1% to -25% in consideration of the elastic modulus, optical characteristics, etc. of the finished resin film.

  The stretching step 603 includes an outer box 603a having a dry air intake port 603b and a discharge port 603c, and a tenter stretching device 603d placed in the outer box 603a. The tenter used in the tenter stretching apparatus 603d is not particularly limited, and examples thereof include a clip tenter and a pin tenter, which can be selected and used as necessary. The tenter stretching device 603d can stretch the web 4 in the transport direction (MD direction) or in the direction perpendicular to the transport direction (TD direction) as necessary.

  The dry air intake port 603b and the discharge port 603c may be reversed. Although the case where heated air is used is shown as the solvent removing means in the stretching step 603, the solvent removing means is not particularly limited, and other examples include infrared rays.

  The total residual solvent amount of the web at the start of stretching in the stretching step 603 is preferably 10% by mass to 30% by mass in consideration of scratches, shrinkage, deformation, and the like. In addition, the ratio of the good solvent amount to the total residual solvent amount is preferably 5% to 70% in consideration of the physical characteristics of the resin film obtained after transport and drying. Preferably, it is 20% to 65%. More preferably, it is 30% to 60%.

  The second drying step 604 includes a drying box 604a having a drying air intake port 604b and a discharge port 604c, an upper conveyance roll 604d that conveys the web 8, and a lower conveyance roll 604e. The upper conveyance roll 604d and the lower conveyance roll 604e are a set of upper and lower, and are composed of a plurality of sets. The number of transport rolls disposed in the second drying step 604 varies depending on the drying conditions, the method, the length of the optical film to be manufactured, and the like, and is appropriately set. The upper conveyance roll 604d and the lower conveyance roll 604e are free rotation rolls that are not rotationally driven by a drive source. In addition, between the drying process and the winding process, a transport roll that freely rotates is not used. Usually, one to several transport drive rolls (roll driven to rotate by a drive source) are installed. Need. Basically, the purpose of the transport drive roll is to transport the resin film by its drive, so that the transport of the resin film and the rotation of the drive roll are synchronized by nip or suction (air suction). With the mechanism.

  In the 2nd drying process 604, you may use heating air, infrared rays alone, or heating air and infrared drying together. It is preferable to use heated air in terms of simplicity. This figure shows the case where heated air is used. The drying temperature varies depending on the amount of residual solvent in the web when entering the drying process, but is appropriately selected depending on the amount of residual solvent in the range of 30 ° C to 180 ° C in consideration of drying time, shrinkage unevenness, stability of the amount of expansion and contraction, etc. The temperature may be determined, may be dried at a constant temperature, or may be divided into three to four stages of temperature and may be divided into several stages of temperature.

  The residual solvent amount of the resin film after the drying treatment in the second drying step 604 is preferably 0.01% by mass to 15% by mass in consideration of the load of the drying step, the dimensional stability stretch rate during storage, and the like. In the present invention, the web formed in the casting step is gradually removed in the second drying step 604, and the web having the total residual solvent amount of 15% by mass or less is referred to as a resin film.

  The winding and collecting step 605 has a winding device (not shown), and winds the resin film 10 having the residual solvent amount set in the second drying step 604 to a necessary amount to be wound around the winding core. Reference numeral 605a denotes a roll-shaped resin film wound around the winding core. The temperature at the time of winding is preferably cooled to room temperature in order to prevent scratches and loosening due to shrinkage after winding. The winder to be used may be a commonly used winder, and can be wound by a winding method such as a constant tension method, a constant torque method, a taper tension method, or a program tension control method with a constant internal stress.

  The expansion ratio of the resin film 10 collected in the winding and collecting step 605 is 0% to 20% in the MD direction and the expansion ratio in the TD direction in consideration of the physical characteristics of the resin film that is obtained after transportation and drying. Is preferably −3% to 20%.

  A description will be given of the resin film manufacturing apparatus shown in FIG. The difference from the manufacturing apparatus 1a shown in FIG. 4 (a) is that the first drying step 602 in FIG. 1 (a) is different from the roll conveying method, and in FIG. 4 (b), the first drying step by the tenter conveying method is different. It is to have. Everything else is the same as in FIG.

  In the figure, 6b shows a manufacturing apparatus for the solution casting method of an optical film. The manufacturing apparatus 6 b includes a casting process 601, a first drying process 602 ′, a stretching process 603, a second drying process 604, and a winding process 605. The casting process 601, the stretching process 603, the second drying process 604, and the winding process 605 are the same as those in the manufacturing apparatus shown in FIG.

  The first drying step 602 ′ includes an outer box 602′a having a dry air intake port 602′b and a discharge port 602′c, and a tenter transfer device 602′d placed in the outer box 602′a. Have. As the tenter used for the tenter conveying device 602′d, the same tenter as that used in the stretching step 603 can be used. In the tenter transport device 602′d, both ends of the web 8 are transported while being held by the tenter, so that contraction in the MD direction can be controlled. It is possible to adjust the amount of solvent contained in the web 8 before entering the stretching step 603 in the first drying step 602 ′.

  The drying temperature varies depending on the amount of residual solvent of the web when entering the stretching process, but it takes into account condensation on the surface of the web accompanying evaporation of the solvent, adjustment of the residual solvent amount, stretching ratio, foaming of the solvent, etc. What is necessary is just to select and determine suitably with the amount of residual solvents in the range of -80 degreeC, and it may dry at fixed temperature and may be divided and divided into several steps of temperature. Other symbols are the same as those in FIG.

  In the case of the manufacturing apparatus shown in this figure, the total residual solvent amount of the web 8 when the web 8 is peeled from the endless belt support 601a and the ratio of the good solvent amount to the total residual solvent amount are the case of the manufacturing apparatus 6a shown in FIG. Is the same. The expansion / contraction rate in the MD direction of the web 8 is peeled from the endless belt support and is stretched in the stretching step 603 until the start of stretching, and is the same as that in the manufacturing apparatus 6a shown in FIG. The total residual solvent amount of the web and the ratio of the good solvent amount to the total residual solvent amount when the processing in the first drying step 602 ′ is completed and the stretching in the stretching step 603 is started are shown in FIG. Same as the case. The stretch rate in the MD direction and the stretch rate in the TD direction of the web 8 after peeling from the endless belt support and starting stretching in the stretching step 603 are the same as those in the manufacturing apparatus 6a shown in FIG. The expansion / contraction rate of the resin film 10 recovered in the winding recovery step 605 is the same as that in the case of the manufacturing apparatus 6a shown in FIG.

  A description will be given of the resin film manufacturing apparatus shown in FIG. The difference from the manufacturing apparatus 6a shown in FIG. 4 (a) is that the first drying step 602 in FIG. 4 (a) is compared with the roll conveying method, and in the case of FIG. 4 (c), the first drying is performed by the tenter conveying method. Step 602 ′ is included, and an MD stretching step 603 ′ is included between the stretching steps 603. Everything else is the same as in FIG.

  In the figure, reference numeral 6c denotes a production apparatus for a resin film solution casting method. The manufacturing apparatus 6 c includes a casting process 601, a first drying process 602 ′, an MD stretching process 603 ′, a stretching process 603, a second drying process 604, and a winding process 605. The casting process 601, the stretching process 603, the second drying process 604, and the winding process 605 are the same as those in the manufacturing apparatus 6 a shown in FIG. 4A, and the first drying process 602 ′ is illustrated in FIG. Since it is the same as the case of the manufacturing apparatus 6b shown by 4 (b), description is abbreviate | omitted.

  The MD stretching step 603 ′ includes a heating device 603′a, a feed roll 603′g on the first drying step 602 ′ side and a feed roll 603′h on the stretching step 603 side across the heating device 603′a. ing. The MD stretching ratio can be adjusted by the balance of the peripheral speeds of the feed roll 603'b and the feed roll 603'c.

  The heating device 603'a includes a drying box 603'd having a dry air intake 603'b and a discharge port 603'c, an upper transport roll 603'e for transporting the web 8, and a lower transport roll 603'f. And have. The heating device 603'a shown in this figure shows the case where heating air is used, but the heating means is not particularly limited. In addition, there is a method of heating with an infrared heater, which is appropriately selected as necessary. Is possible. The number of conveyance rolls can be set as appropriate depending on the MD stretching rate. In the MD stretching step 603 ′, the amount of solvent contained in the web 3 before entering the stretching step 603 can be adjusted.

  In the heating device 603′a, heating air, infrared rays, etc. alone or heating air and infrared drying may be used in combination. It is preferable to use heated air in terms of simplicity. This figure shows the case where heated air is used.

  The heating temperature varies depending on the amount of residual solvent of the web conveyed from the first drying step 602 ′ or the amount of residual solvent of the web when entering the stretching step, but condensation on the surface of the web accompanying evaporation of the solvent, In consideration of adjustment of the residual solvent amount, expansion / contraction ratio, foaming of the solvent, etc., it is preferable to appropriately select, determine, adjust and heat in the range of 20 ° C. to 80 ° C. depending on the residual solvent amount. Further, it may be dried at a constant temperature or may be dried in several steps.

  In the case of the manufacturing apparatus shown in FIG. 4 (c), the residual solvent amount of the web 8, the width distribution of the residual solvent amount, and the ratio of the good solvent amount to the total residual solvent amount when peeling from the endless belt support 601a are shown. This is the same as the case of 4 (a). The expansion / contraction rate in the MD direction of the web 3 from the endless belt support until the start of stretching in the stretching step 603 is the same as that in FIG. The width distribution of the residual solvent amount of the web when the treatment in the first drying step 602 ′ is completed and the stretching in the stretching step 603 is started, the total residual solvent amount, and the ratio of the good solvent amount to the total residual solvent amount Is the same as in FIG. The stretch rate in the MD direction and the stretch rate in the TD direction of the web 8 from the endless belt support until the start of stretching in the stretching step 603 are the same as those in FIG. The expansion / contraction rate of the resin film 10 collected in the winding process 605 is the same as that in the case of FIG. The dope used in the manufacturing apparatus shown in FIGS. 4A to 4C is the same.

  The film thickness of the resin film produced by the production apparatus shown in FIGS. 4 (a) to 4 (c) is 40 μm in consideration of variation in pore diameter due to tension during conveyance, increase in solvent removal time, and productivity. It is preferably ˜80 μm.

  The structure of the resin film 10 manufactured by the manufacturing apparatus shown in FIGS. 4 (a) to 4 (c) is composed of two phases in which the volume occupancy ratios due to the holes are sequentially different in the thickness direction shown in FIG. It becomes the resin film which has. In addition, a dope is cast on the side of the phase (second phase 2a shown in FIG. 4) in which the volume occupancy by the voids is low, using the resin film 10 being manufactured or manufactured. By drying and stretching, it is possible to produce a resin film having three phases having different volume occupancy ratios due to pores in the thickness direction shown in FIG.

  The amount of residual solvent (mass%) when producing a resin film using the production apparatus by the solution casting method shown in FIG. 4 is such that a web (resin film) of a certain size is 1 hour at 115 ° C. When the mass of the web (resin film) when dried is B and the mass of the web (resin film) before drying is A, ((AB) / B) × 100 = residual solvent amount (mass%) This is the value obtained in.

  The ratio of the good solvent amount to the total residual solvent amount when the resin film is produced using the production apparatus by the solution casting method shown in FIG. Extraction was performed using a co-solvent, and measurement was performed using a gas chromatography 5890 type SERISII and headspace sampler HP7694 manufactured by Hewlett-Packard Co., to which a headspace sampler was connected, and values measured under the following measurement conditions.

Headspace sampler heating conditions: 120 ° C, 20 minutes GC introduction temperature: 150 ° C
Temperature rise: 40 ° C, hold for 5 minutes → 100 ° C (8 ° C / min)
Column: J-W DB-WAX (inner diameter 0.32 mm, length 30 m).

  The expansion / contraction rate in the MD direction in the present invention is a value obtained from the conveyance speed at the start of stretching relative to the conveyance speed during casting or the conveyance speed during winding relative to the conveyance speed during casting.

  The expansion / contraction ratio in the TD direction is a value obtained from the web width at the start of stretching relative to the web width during casting or the resin film width during winding relative to the web width during casting.

  The width of the resin film produced by the method of producing a resin film using the production apparatus by the solution casting method shown in FIG. 4 is such that the optical resin film having a functional layer is applied to a liquid crystal display device like a large TV. In consideration of use, use efficiency of the film at the time of polarizing plate processing, production efficiency, etc., 1000 mm to 2400 mm is preferable. The film thickness is preferably 40 μm to 80 μm in view of thinning of the liquid crystal display device and stabilization of production of the resin film. The film thickness indicates an average film thickness, and 20 to 200 positions in the width direction are measured with a contact-type film thickness meter manufactured by Mitutoyo Corporation, and an average value is shown.

  The dope 7 used in the manufacturing apparatus shown in FIGS. 4A to 4C is manufactured by using a resin material for a resin film as a mixed solvent composed of a good solvent and a poor solvent. In the present invention, what dissolves the resin used alone is called a good solvent, and what swells or does not dissolve alone is called a poor solvent.

  The ratio of the poor solvent in the solvent constituting the dope 7 and the dope 7 ′ is preferably 10% by mass to 100% by mass in consideration of the formation of vacancies and the precipitation of the resin in the dope transporting process. More preferably, it is 20 mass%-60 mass%.

  The ratio of the solute to the total solvent of the dope 7 and the dope 7 ′ is preferably 200% by mass to 1000% by mass in consideration of resin precipitation, casting speed, productivity, and the like in the dope conveying step. More preferably, it is 300 mass%-800 mass%.

  Next, the materials and manufacturing methods used for manufacturing the optical resin film according to the present invention will be described.

(Resin material)
Examples of the resin forming the resin film of the present invention include cellulose ester resins such as cellulose diacetate resin, cellulose triacetate resin, cellulose acetate butyrate resin, and cellulose acetate propionate resin, polyester resins, polycarbonate resins, Polyarylate resin, polysulfone (including polyether sulfone) resin, polyethylene terephthalate resin, polyester resin such as polyethylene naphthalate resin, polyethylene resin, polypropylene resin, cellophane, polyvinylidene chloride resin, polyvinyl alcohol resin, ethylene vinyl alcohol resin , Syndiotactic polystyrene resin, polycarbonate resin, cycloolefin resin, polymethylpentene resin, polyetherke Down resin, polyether ketone imide resin, polyamide resin, fluorine resin, nylon resin, polymethylmethacrylate resin, and acrylic resin. Among these, cellulose ester resins, cycloolefin resins, polycarbonate resins, and polysulfone (including polyethersulfone) resins are preferred. In the present invention, cellulose ester resins are particularly mentioned. Among these, cellulose acetate resins, A cellulose propionate resin, a cellulose butyrate resin, a cellulose acetate butyrate resin, and a cellulose acetate propionate resin are preferable, and among them, a cellulose acetate propionate resin is preferably used.

  Hereinafter, the cellulose ester resin will be described. The cellulose ester resin is a cellulose ester resin having a mixed fatty acid ester of cellulose in which X and Y are in the following ranges, where X is the substitution degree of acetyl group and Y is the substitution degree of propionyl group or butyryl group. Preferably used.

Formula (I) 2.0 ≦ X + Y ≦ 2.6
Formula (II) 0.1 ≦ Y ≦ 1.2
Furthermore, a cellulose acetate propionate (total acyl group substitution degree = X + Y) resin of 2.4 ≦ X + Y ≦ 2.6 and 1.4 ≦ X ≦ 2.3 is preferable. Among them, 2.4 ≦ X + Y ≦ 2.6, 1.7 ≦ X ≦ 2.3, 0.1 ≦ Y ≦ 0.9, cellulose acetate propionate resin, cellulose acetate butyrate (total acyl group substitution degree = X + Y ) Resins are preferred. The portion not substituted with an acyl group usually exists as a hydroxyl group. These cellulose ester resins can be synthesized by a known method. The measuring method of the substitution degree of an acyl group can be measured according to the provisions of ASTM-D817-96.

  As a resin material for the resin film according to the present invention, when a cellulose ester resin is used, cellulose as a raw material for the cellulose ester resin is not particularly limited, but cotton linter, wood pulp (derived from coniferous trees, derived from broadleaf trees), Kenaf and the like can be mentioned. Moreover, the cellulose ester-type resin obtained from them can be mixed and used in arbitrary ratios, respectively. When the acylating agent is an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride), these cellulose ester resins use an organic acid such as acetic acid or an organic solvent such as methylene chloride, It can obtain by making it react with a cellulose raw material using such a protic catalyst.

When the acylating agent is acid chloride (CH ₃ COCl, C ₂ H ₅ COCl, C ₃ H ₇ COCl), the reaction is carried out using a basic compound such as an amine as a catalyst. Specifically, it can be synthesized with reference to the method described in JP-A-10-45804. The cellulose ester resin used in the present invention is obtained by mixing and reacting the above acylating agent amounts in accordance with the degree of substitution. In the cellulose ester resin, these acylating agents react with hydroxyl groups of cellulose molecules. To do. Cellulose molecules are composed of many glucose units linked together, and the glucose unit has three hydroxyl groups. The number of acyl groups derived from these three hydroxyl groups is called the degree of substitution (mol%). For example, cellulose triacetate has acetyl groups bonded to all three hydroxyl groups of the glucose unit (actually 2.6 to 3.0).

  As described above, the cellulose ester-based resin used in the present invention may be propionate group or butyrate in addition to acetyl group such as cellulose acetate propionate resin, cellulose acetate butyrate resin, or cellulose acetate propionate butyrate resin. A mixed fatty acid ester of cellulose to which a group is bonded is particularly preferably used. In addition, the cellulose acetate propionate resin containing a propionate group as a substituent is excellent in water resistance and is useful as a film for a liquid crystal image display device.

  The number average molecular weight of the cellulose ester-based resin is preferably 40000 to 200000, and has a high mechanical strength when molded, and an appropriate dope viscosity in the case of a solution casting method, and more preferably 50000 to 150,000. . The weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably in the range of 1.4 to 4.5.

  The cycloolefin resin according to the present invention will be described. The cycloolefin resin used in the present invention is composed of a polymer resin containing an alicyclic structure. A preferred cycloolefin resin is a resin obtained by polymerizing or copolymerizing a cyclic olefin. Examples of the cyclic olefin include norbornene, dicyclopentadiene, tetracyclododecene, ethyltetracyclododecene, ethylidenetetracyclododecene, tetracyclo [7.4.0.110, 13.02,7] trideca-2,4. Unsaturated hydrocarbons of polycyclic structures such as 6,11-tetraene and derivatives thereof; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclo Examples thereof include monocyclic unsaturated hydrocarbons such as octene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, cycloheptene, cyclopentadiene, cyclohexadiene, and derivatives thereof. These cyclic olefins may have a polar group as a substituent. Examples of the polar group include a hydroxyl group, a carboxyl group, an alkoxyl group, an epoxy group, a glycidyl group, an oxycarbonyl group, a carbonyl group, an amino group, an ester group, and a carboxylic acid anhydride group. Or a carboxylic anhydride group is preferred.

  Preferred cycloolefin resins may be those obtained by addition copolymerization of monomers other than cyclic olefins. Addition copolymerizable monomers include ethylene, propylene, 1-butene, 1-pentene, and other ethylene or α-olefins; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl- Examples include dienes such as 1,4-hexadiene and 1,7-octadiene.

The cyclic olefin is obtained by an addition polymerization reaction or a metathesis ring-opening polymerization reaction. The polymerization is carried out in the presence of a catalyst. Examples of the addition polymerization catalyst include a polymerization catalyst composed of a vanadium compound and an organoaluminum compound. As a catalyst for ring-opening polymerization, a polymerization catalyst comprising a metal halide such as ruthenium, rhodium, palladium, osmium, iridium, platinum, nitrate or acetylacetone compound, and a reducing agent; or titanium, vanadium, zirconium, tungsten, molybdenum And a polymerization catalyst composed of a metal halide such as acetylacetone compound and an organoaluminum compound. The polymerization temperature, pressure and the like are not particularly limited, but the polymerization is usually carried out at a polymerization temperature of -50 ° C to 100 ° C and a polymerization pressure of 0 to 490 N / cm ² .

  The cycloolefin resin according to the present invention is preferably a resin obtained by polymerizing or copolymerizing a cyclic olefin, followed by a hydrogenation reaction to change the unsaturated bond in the molecule to a saturated bond. The hydrogenation reaction is performed by blowing hydrogen in the presence of a known hydrogenation catalyst. Examples of hydrogenation catalysts include cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, transition metal compounds such as titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium / alkyl. Homogeneous catalyst consisting of a combination of metal compounds; heterogeneous metal catalyst such as nickel, palladium, platinum; nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth And a heterogeneous solid-supported catalyst in which a metal catalyst such as palladium / alumina is supported on a carrier.

  Or the following norbornene-type resin is also mentioned as a cycloolefin resin. The norbornene-based resin preferably has a norbornene skeleton as a repeating unit. Specific examples thereof include, for example, JP-A-62-252406, JP-A-62-2252407, and JP-A-2-133413. JP, JP 63-145324, JP 63-264626, JP 1-224017, JP 57-8815, JP 5-2108, JP 5-39403. JP-A-5-43663, JP-A-5-43834, JP-A-5-70655, JP-A-5-279554, JP-A-6-206985, JP-A-7-62028, JP-A-8-176411, JP-A-9-241484, JP-A-2001-277430, JP-A-2003-139 No. 50, JP-A No. 2003-14901, JP-A No. 2003-161832, JP-A No. 2003-195268, JP-A No. 2003-111588, JP-A No. 2003-211589, JP-A No. 2003-268187 Gazette, JP-A-2004-133209, JP-A-2004-309799, JP-A-2005-121183, JP-A-2005-164632, JP-A-2006-72309, JP-A-2006-178191, Although what was described in Unexamined-Japanese-Patent No. 2006-215333, Unexamined-Japanese-Patent No. 2006-268065, Unexamined-Japanese-Patent No. 2006-299199 etc. is mentioned, It is not limited to these. Moreover, these may be used individually by 1 type and may use 2 or more types together. Specifically, ZEONEX, ZEONOR manufactured by Nippon Zeon Co., Ltd., Arton manufactured by JSR Corporation, APPEL manufactured by Mitsui Chemicals, Inc. (APL8008T, APL6509T, APL6013T, APL5014DP, APL6015T) and the like are preferably used.

  The molecular weight of the cycloolefin polymer according to the present invention is appropriately selected depending on the purpose of use, but polyisoprene measured by gel permeation chromatography method of cyclohexane solution (toluene solution when the polymer resin does not dissolve). Alternatively, when the weight average molecular weight in terms of polystyrene is usually in the range of 5,000 to 500,000, preferably 8,000 to 200,000, more preferably 10,000 to 100,000, the mechanical strength and molding processability of the molded body are highly balanced. It is preferable.

  Moreover, when a low-volatile antioxidant is blended at a ratio of 0.01 to 5 parts by mass with respect to 100 parts by mass of the cycloolefin polymer, it can effectively prevent the polymer from being decomposed or colored during the molding process. I can do it.

  The polycarbonate resin according to the present invention will be described. There are various types of polycarbonate resins, and aromatic polycarbonates are preferable from the viewpoint of chemical properties and physical properties, and bisphenol A polycarbonates are particularly preferable. Among them, more preferred is a bisphenol A derivative in which a benzene ring, a cyclohexane ring, or an aliphatic hydrocarbon group is introduced into bisphenol A, and these groups are introduced asymmetrically with respect to the central carbon. A polycarbonate having a structure in which the anisotropy in the unit molecule is reduced, obtained by using the obtained derivative is preferable. For example, one in which two methyl groups on the central carbon of bisphenol A are replaced with a benzene ring, and one hydrogen on each benzene ring in bisphenol A is replaced asymmetrically with respect to the central carbon by a methyl group or a phenyl group The polycarbonate resin obtained is preferable. Specifically, 4,4′-dihydroxydiphenylalkane or a halogen-substituted product thereof can be obtained by a phosgene method or a transesterification method. For example, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenylethane 4,4'-dihydroxydiphenylbutane and the like. In addition, for example, polycarbonate resins described in JP-A-2006-215465, JP-A-2006-91836, JP-A-2005-121813, JP-A-2003-167121 and the like can be mentioned. It is done.

  The resin film made of the polycarbonate resin used in the present invention may be used by mixing with a transparent resin such as a polystyrene resin, a methyl methacrylate resin, or a cellulose acetate resin, or at least one of the cellulose acetate films. A polycarbonate resin may be laminated on the surface.

  The resin film made of a polycarbonate resin used in the present invention has a glass transition point (Tg) of 110 ° C. or higher and a water absorption rate (measured under conditions of 23 ° C. water and 24 hours) of 0.3% or less. It is better to use one. More preferably, Tg is 120 ° C. or higher and water absorption is 0.2% or less.

(Dope)
The dope according to the present invention is manufactured using a mixed solvent composed of a good solvent and a poor solvent. For example, in the case of a cellulose ester resin, the good solvent and the poor solvent change depending on the acyl group substitution degree of the cellulose ester. For example, when acetone is used as the solvent, the cellulose ester acetate ester (acetyl group substitution degree 2.4), cellulose Acetate propionate is a good solvent, and cellulose acetate (acetyl group substitution degree 2.8) is a poor solvent.

  Since the good solvent and the poor solvent differ depending on the resin to be used, a case of a cellulose ester resin will be described as an example. Examples of the good solvent include methylene chloride, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-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, but organic halogen compounds such as methylene chloride, Dioxolane derivatives, methyl acetate, ethyl acetate, acetone and the like are mentioned as preferred organic solvents (that is, good solvents). That.

  Examples of the poor solvent include alcohols having 1 to 8 carbon atoms such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol, methyl ethyl ketone, methyl isobutyl ketone, propyl acetate, and monochloro. Examples thereof include benzene, benzene, cyclohexane, tetrahydrofuran, methyl cellosolve, ethylene glycol monomethyl ether, and the like. These poor solvents can be used alone or in combination of two or more.

  Next, a method for preparing a dope will be described as an example when a cellulose ester resin is used. As a method for dissolving the cellulose ester resin when preparing the dope, a general method can be used. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure. It is preferable to stir and dissolve while heating at a temperature that is equal to or higher than the boiling point of the solvent at normal pressure and that the solvent does not boil under pressure, in order to prevent the formation of massive undissolved materials called gels and mamacos. In addition, a method in which a cellulose ester resin is mixed with a poor solvent and wetted or swollen, and then a good solvent is added and dissolved is also preferably used.

  The pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of 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 with the addition of a solvent is preferably higher from the viewpoint of the solubility of the cellulose ester, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates. A preferable heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and still more preferably 70 ° C to 105 ° C. The pressure is adjusted so that the solvent does not boil at the set temperature. Alternatively, a cooling dissolution method is also preferably used, whereby the cellulose ester resin can be dissolved in a solvent such as methyl acetate.

  Next, this cellulose ester resin solution is filtered using a suitable filter medium such as filter paper. As the filter medium, it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like, but there is a problem that the filter medium is likely to be clogged if the absolute filtration accuracy is too small. For this reason, a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is still more preferable.

  There are no particular restrictions on the material of the filter medium, and ordinary filter media can be used. However, plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel do not drop off fibers. preferable. It is preferable to remove and reduce impurities, particularly bright spot foreign matter, contained in the raw material cellulose ester by filtration.

Bright spot foreign matter is when two polarizing plates are placed in a crossed Nicol state, a cellulose ester film is placed between them, light is applied from the side of one polarizing plate, and observed from the side of the other polarizing plate. It is a point (foreign matter) where light from the opposite side appears to leak, and the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm ² or less. More preferably, it is 100 pieces / cm < ² > or less, More preferably, it is 50 pieces / m < ² > or less, More preferably, it is 0-10 pieces / cm < ² > or less. Further, it is preferable that the number of bright spots of 0.01 mm or less is small.

  The dope can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration. The increase in the difference (referred to as differential pressure) is small and preferable. A preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and still more preferably 45 to 55 ° C.

  A smaller filtration pressure is preferred. The filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.

(Plasticizer)
Although it does not specifically limit as a plasticizer, Phosphate ester plasticizer, phthalate ester plasticizer, trimellitic acid ester plasticizer, pyromellitic acid plasticizer, glycolate plasticizer, citrate plasticizer Polyester plasticizers can be preferably used. Examples of the phosphate ester include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, and the like. Examples of the phthalic acid ester include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, and butyl benzyl phthalate. Examples of trimellitic acid plasticizers include tributyl trimellitate, triphenyl trimellitate, triethyl trimellitate, and the like. Examples of the pyromellitic acid ester plasticizer include tetrabutyl pyromellitate, tetraphenyl pyromellitate, and tetraethyl pyromellitate. Examples of glycolic acid esters include triacetin, tributyrin, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, and butyl phthalyl butyl glycolate. Examples of the citrate plasticizer include triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, and acetyl tri-n- (2-ethylhexyl) citrate. As the polyester plasticizer, a copolymer of a dibasic acid such as an aliphatic dibasic acid, an alicyclic dibasic acid, or an aromatic dibasic acid and a glycol can be used. The aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyl dicarboxylic acid and the like can be used.

  As the glycol, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol and the like can be used. These dibasic acids and glycols may be used alone or in combination of two or more. The molecular weight of the polyester is preferably in the range of 500 to 2000 in terms of weight average molecular weight from the viewpoint of compatibility with the cellulose ester.

  In the present invention, it is particularly preferable to use a plasticizer having a vapor pressure of less than 1333 Pa at 200 ° C., more preferably a compound having a vapor pressure of 666 Pa or less, and more preferably 1 to 133 Pa. The non-volatile plasticizer is not particularly limited, and examples thereof include arylene bis (diaryl phosphate) ester, tricresyl phosphate, trimellitic acid tri (2-ethylhexyl), and the above polyester plasticizer. These plasticizers can be used alone or in combination of two or more.

  In consideration of dimensional stability and processability, the plasticizer can be added in an amount of 1 to 40% by mass, preferably 3 to 20% by mass, based on the cellulose ester resin. More preferably, it is 4 to 15% by mass. If the amount is less than 3% by mass, a smooth cut surface cannot be obtained when slitting or punching, resulting in increased generation of chips.

  It is preferable to add an antioxidant or an ultraviolet absorber to the resin film according to the present invention. As the antioxidant, a hindered phenol compound is preferably used, and 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl). -4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-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-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- ( , 5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate Etc. In particular, 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] is preferred. Further, for example, hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di-t A phosphorus-based processing stabilizer such as -butylphenyl) phosphite may be used in combination. The amount of these compounds added is preferably 1 ppm to 1.0%, more preferably 10 to 1000 ppm in terms of mass ratio with respect to the cellulose ester.

  In addition, heat stabilizers such as inorganic fine particles such as kaolin, talc, diatomaceous earth, quartz, calcium carbonate, barium sulfate, titanium oxide, and alumina, and alkaline earth metal salts such as calcium and magnesium may be added. Good.

  The resin film produced by the production method of the present invention can be used for a polarizing plate or a liquid crystal display member because of its high dimensional stability. In this case, for preventing deterioration of the polarizing plate or the liquid crystal. An ultraviolet absorber is preferably used.

  As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties. Specifically, the transmittance at 380 nm is preferably less than 10%, more preferably less than 5%.

  Specific examples of preferably used ultraviolet absorbers include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, triazine compounds, and the like. For example, the ultraviolet absorbers described in JP-A-10-182621 and JP-A-8-337574 are preferably used. Moreover, the polymeric ultraviolet absorbers described in JP-A-6-148430 and JP-A-12-273437 are also preferably used. Or you may add the ultraviolet absorber described in Unexamined-Japanese-Patent No. 10-152568.

  Among these ultraviolet absorbers, benzotriazole ultraviolet absorbers and benzophenone ultraviolet absorbers are preferable ultraviolet absorbers. Although the specific example of a benzotriazole type ultraviolet absorber is given to the following, this invention is not limited to these.

2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3) '-Tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy -3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3-tetramethyl) Butyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl)- -Chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba Specialty Chemicals), octyl-3- [ 3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5- Chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba Specialty Chemicals)
Specific examples of the benzophenone-based ultraviolet absorber are shown below, but the present invention is not limited thereto. 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenylmethane) It is done.

  The ultraviolet absorber may be added by dissolving the ultraviolet absorber in an organic solvent such as alcohol, methylene chloride, dioxolane and the like, or adding it directly to the dope composition. For an inorganic powder that does not dissolve in an organic solvent, it is preferable to use a dissolver or a sand mill in the organic solvent and the cellulose ester resin to disperse and then add to the dope. The amount of the ultraviolet absorber used is preferably 0.1% by mass to 2.5% by mass in consideration of the effect as an ultraviolet absorber, transparency, and the like. Furthermore, Preferably, it is 0.8 mass%-2.0 mass%.

  In addition, fine particles may be added to the cellulose ester resin film as a matting agent in order to prevent the films from sticking to each other or to impart slipperiness to facilitate handling. The fine particles include inorganic compound fine particles and organic compound fine particles. Inorganic compounds include silicon-containing compounds, silicon dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, etc. More preferred is an inorganic compound containing silicon or zirconium oxide, but silicon dioxide is particularly preferably used since the turbidity of the cellulose ester laminated film can be reduced.

  As fine particles of silicon dioxide, for example, AEROSIL-200, 200V, 300, R972, R972V, R974, R976, R976S, R202, R812, R805, OX50, TT600, RY50, RX50, NY50, NAX50, NA50H manufactured by Aerosil Co., Ltd. NA50Y, NX90, RY200S, RY200, RX200, R8200, RA200H, RA200HS, NA200Y, R816, R104, RY300, RX300, R106, and the like. Among these, AEROSIL-200V and R972V are preferable in terms of controlling dispersibility and particle size.

  As the fine particles of zirconium oxide, commercially available products such as Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) can be used.

  As an organic compound, polymers, such as a silicone resin, a fluororesin, and an acrylic resin, are preferable, for example, Among these, a silicone resin is preferably used.

  Among the above-described silicone resins, those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120 and 240 (above Toshiba Silicone Co., Ltd.) ) Etc. can be used.

  The primary average particle diameter of the fine particles according to the present invention is preferably 20 nm or less, more preferably 5 to 16 nm, and particularly preferably 5 to 12 nm, from the viewpoint of keeping the haze low.

  The apparent specific gravity of the fine particles is preferably 70 g / liter or more, more preferably 90 to 200 g / liter, and particularly preferably 100 to 200 g / liter. Larger apparent specific gravity makes it possible to make a high-concentration dispersion, which improves haze and agglomerates, and is preferable when preparing a dope having a high solid content concentration as in the present invention. Are particularly preferably used.

  Silicon dioxide fine particles having an average primary particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more are, for example, a mixture of vaporized silicon tetrachloride and hydrogen burned in air at 1000 to 1200 ° C. Can be obtained. Further, for example, Aerosil 200V and Aerosil R972V (manufactured by Nippon Aerosil Co., Ltd.) are commercially available, and these can be used.

  The apparent specific gravity was calculated by the following equation by measuring a weight of silicon dioxide fine particles in a graduated cylinder and measuring the weight at that time.

Apparent specific gravity (g / liter) = Mass of silicon dioxide (g) ÷ Volume of silicon dioxide (liter)
Examples of the method for preparing a dispersion of fine particles according to the present invention include the following three types.

<< Preparation Method A >>
After stirring and mixing the solvent and the fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. The fine particle dispersion is added to the dope solution and stirred.

<< Preparation Method B >>
After stirring and mixing the solvent and the fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. Separately, a small amount of cellulose ester is added to the solvent and dissolved by stirring. As the cellulose ester added here, it is particularly preferable to add the solid material of the present invention. The fine particle dispersion is added to this and stirred. This is a fine particle addition solution. The fine particle additive solution is sufficiently mixed with the dope solution using an in-line mixer.

<< Preparation Method C >>
Add a small amount of cellulose ester to the solvent and dissolve with stirring. Fine particles are added to this and dispersed by a disperser. This is a fine particle addition solution. The fine particle additive solution is sufficiently mixed with the dope solution using an in-line mixer.

  Preparation method A is excellent in dispersibility of silicon dioxide fine particles, and preparation method C is excellent in that silicon dioxide fine particles are difficult to re-aggregate. Among them, the preparation method B described above is a preferable preparation method that is excellent in both dispersibility of the silicon dioxide fine particles and that the silicon dioxide fine particles are less likely to reaggregate.

《Distribution method》
The concentration of silicon dioxide when the silicon dioxide fine particles are mixed with a solvent and dispersed is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and most preferably 15 to 20% by mass. A higher dispersion concentration is preferable because liquid turbidity with respect to the added amount tends to be low, and haze and aggregates are improved.

  The solvent used is preferably lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. Although it does not specifically limit as solvents other than a lower alcohol, It is preferable to use the solvent used at the time of film forming of a cellulose ester.

  The amount of silicon dioxide fine particles added to cellulose ester is preferably 0.01 to 0.3 parts by mass, more preferably 0.05 to 0.2 parts by mass, and more preferably 0.0 to 0.2 parts by mass with respect to 100 parts by mass of cellulose ester. Most preferred is 08 to 0.12 parts by mass. The larger the added amount, the better the dynamic friction coefficient, and the smaller the added amount, the lower the haze and the fewer agglomerates.

  As the disperser, a normal disperser can be used. Dispersers can be broadly divided into media dispersers and medialess dispersers. For dispersing silicon dioxide fine particles, a medialess disperser is preferred because of its low haze. Examples of the media disperser 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 dispersion device is a device that creates special conditions such as high shear and high pressure by passing a composition in which fine particles and a solvent are mixed at high speed through a narrow tube. When processing with a high-pressure dispersion apparatus, for example, the maximum pressure condition inside the apparatus is preferably 9.807 MPa or more in a thin tube having a tube diameter of 1 to 2000 μm. More preferably, it is 19.613 MPa or more. Further, at that time, those having a maximum reaching speed of 100 m / second or more and those having a heat transfer speed of 420 kJ / hour or more are preferable.

  The high-pressure dispersing apparatus as described above includes an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation or a nanomizer manufactured by Nanomizer. Examples include UHN-01 manufactured by Wako Co., Ltd.

  These fine particles may be uniformly distributed in the thickness direction of the film, but it is more preferable that they are mainly distributed so as to exist mainly in the vicinity of the surface. It is preferable to add fine particles mainly to the dope arranged on the surface layer side using a dope of a seed or more because a film having high slip properties and low haze can be obtained. It is preferable to add fine particles mainly to two dopes on the surface layer side using three kinds of dopes.

  In addition, an optical film having a preferable impedance can be obtained by adding a conductive substance to the optical resin film according to the present invention. Although it does not specifically limit as an electroconductive substance, The antistatic agent etc. which have compatibility with an ionic electroconductive substance, electroconductive fine particles, or a cellulose ester can be used.

  Here, the ion conductive substance is a substance that shows electric conductivity and contains ions that are carriers for carrying electricity, and examples thereof include ionic polymer compounds.

  Examples of the ionic polymer compound include anionic polymer compounds such as those described in JP-B-49-23828, JP-A-49-23827, and JP-A-47-28937, such as JP-B-55-734, JP-A-50- An ionene type polymer having a dissociating group in the main chain, as shown in Japanese Patent No. 54672, Japanese Patent Publication Nos. 59-14735, 57-18175, 57-18176, 57-56059, etc. No. 13223, No. 57-15376, No. Sho 53-45231, No. 55-145578, No. 55-65950, No. 55-67746, No. 57-11342, No. 57-19735, No. Sho-58- No. 56858, JP-A 61-27853, and 62-9346, a cationic pender having a cationic dissociation group in the side chain It can be mentioned door type polymers, and the like.

Examples of the conductive fine particles include conductive metal oxides. As an example of the metal oxide, ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O ₅ , or a composite oxide thereof is preferable. In particular, ZnO, TiO ₂ and SnO ₂ are preferred. Examples of containing different atoms include, for example, addition of Al, In, etc. to ZnO, addition of Nb, Ta, etc. to TiO ₂ , and addition of Sb, Nb, halogen elements, etc. to SnO ₂ . Addition is effective. The amount of these different atoms added is preferably in the range of 0.01 to 25 mol%, particularly preferably in the range of 0.1 to 15 mol%.

The volume resistivity of these conductive metal oxide powders is 10 ⁷ Ωcm or less, particularly 10 ⁵ Ωcm or less, the primary particle diameter is 10 nm or more and 0.2 μm or less, and the major structure has a major axis of 30 nm. It is preferable that the powder having a specific structure of 6 μm or less is included in at least a part of the film in a volume fraction of 0.01% or more and 20% or less.

  It is particularly preferable to contain an ionene conductive polymer described in JP-A-9-203810 or a quaternary ammonium cation conductive polymer having intermolecular crosslinking.

  The characteristic of the cross-linked cationic conductive polymer is the dispersible granular polymer obtained, and it can have a high concentration and high density of the cationic component in the particles, so it has not only excellent conductivity. No deterioration of conductivity was observed even under low relative humidity, and although the particles were well dispersed in the dispersed state, the adhesion of the particles was good in the film-forming process after coating, so the film strength was also low. It is strong and has excellent adhesion to other substances such as substrates, and has excellent chemical resistance.

  The dispersible granular polymer, which is a crosslinked cationic conductive polymer, generally has a particle size range of about 0.01 μm to 0.3 μm, preferably a particle size of 0.05 μm to 0.15 μm. As used herein, the term “dispersible particulate polymer” is a polymer that appears to be a clear or slightly turbid solution by visual observation but appears as a particulate dispersion under an electron microscope.

  The addition of the antistatic agent or matting agent is preferably included in the surface layer portion (portion of 10 μm from the surface) of the optical film, and the antistatic agent and / or matting agent is added to the surface of the film by a method such as co-casting. It is preferable to contain. Specifically, a dope A containing a conductive material and / or a matting agent and a dope B substantially not containing these are used, and the dope B is cast so that the dope A is present on at least one side of the dope B. It is preferable.

  If necessary, an antistatic agent, a flame retardant, a lubricant, an oil agent, a matting agent, and other additives may be added.

A description will be given below of materials for providing a hard coat layer or an antireflection layer as a functional layer.
(Reactive cured resin layer (hard coat layer))
(Actinic radiation curable resin material)
As the reactive curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and a hard coat layer is formed by curing by irradiation with an active ray such as an ultraviolet ray or an electron beam. Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, and a resin curable by ultraviolet irradiation is preferable.

  As the ultraviolet curable resin, for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, or an ultraviolet curable epoxy resin is preferable. Used.

  UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate) in products obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, those described in JP-A-59-151110 can be used.

  For example, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) is preferably used.

  Examples of UV curable polyester acrylate resins include those that are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyols. JP-A-59-151112 Can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photoreaction initiator added thereto, and reacted to form an oligomer. The thing as described in 105738 can be used.

  Specific examples of UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. I can list them.

  Specific examples of the photoreaction initiator of these ultraviolet curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer. The photoinitiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate photoinitiator, a sensitizer such as n-butylamine, triethylamine, tri-n-butylphosphine can be used. The photoreaction initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the composition.

  Examples of the resin monomer include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond. Monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above-mentioned trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  Examples of commercially available ultraviolet curable resins that can be used in the present invention include ADEKA OPTMER KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (Asahi Denka ( Co., Ltd.); Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS -101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP -10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (manufactured by Dainichi Seika Kogyo Co., Ltd.) KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (manufactured by Daicel UCB); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120 RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.); 340 clear (manufactured by China Paint Co., Ltd.); Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (manufactured by Sanyo Chemical Industries); SP -1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.); RCC-15C (manufactured by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.), etc. Can be selected as appropriate.

  Specific examples of compounds include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, and the like. .

  These ultraviolet curable resin layers can be coated by a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, or an ink jet method.

As a light source for curing an ultraviolet curable resin by a photocuring reaction to form a cured film layer, any light source that generates ultraviolet rays can be used without any limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. The irradiation conditions vary depending on individual lamps, the dose of active ray is preferably a ^{5mJ / cm 2 ~300mJ / cm 2} , particularly preferably from ^{100mJ / cm 2 ~200mJ / cm 2} .

  Examples of the organic solvent for the active ray curable resin layer coating composition include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl). Ketone), esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, propylene glycol monoalkyl ether (1 to 4 carbon atoms of alkyl group) or propylene glycol monoalkyl ether acetate (carbon of alkyl group) The number of atoms can be appropriately selected from 1-4) and other organic solvents, or these can be mixed and used.

  In addition, it is particularly preferable to add a silicone compound to the active ray curable resin layer coating composition. For example, polyether-modified silicone oil is preferably added. The number average molecular weight of the polyether-modified silicone oil is, for example, 1,000 to 100,000, preferably 2,000 to 50,000. When the number average molecular weight is less than 1,000, the coating film is dried. On the contrary, when the number average molecular weight exceeds 100,000, it tends to be difficult to bleed out on the surface of the coating film.

  Commercially available silicone compounds include DKQ8-779 (trade name, manufactured by Dow Corning), SF3771, SF8410, SF8411, SF8419, SF8421, SF8428, SH200, SH510, SH1107, SH3749, SH3771, BX16-034, SH3746, SH3749, SH8400, SH3771M, SH3772M, SH3773M, SH3775M, BY-16-837, BY-16-839, BY-16-869, BY-16-870, BY-16-004, BY-16-891, BY-16 872, BY-16-874, BY22-008M, BY22-012M, FS-1265 (trade name, manufactured by Toray Dow Corning Silicone), KF-101, KF-100T, KF351, KF 52, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, Silicone X-22-945, X22-160AS (above, trade name made by Shin-Etsu Chemical Co., Ltd.), XF3940, XF3949 (above, trade name made by Toshiba Silicone Corporation) ), Disparon LS-009 (manufactured by Enomoto Kasei Co., Ltd.), Granol 410 (manufactured by Kyoeisha Oil Chemical Co., Ltd.), TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicone), BYK-306, BYK- 330, BYK-307, BYK-341, BYK-344, BYK-361 (manufactured by BYK-Japan) L series (for example, L7001, L-7006, L-7604, L-9000) manufactured by Nippon Unicar Co., Ltd. Y Leeds, FZ series (FZ-2203, FZ-2206, FZ-2207) and the like, it is preferably used.

  These components enhance the applicability to the substrate and the lower layer. When added to the outermost surface layer of the laminate, it not only enhances the water repellency, oil repellency and antifouling properties of the coating film, but also exhibits an effect on the surface scratch resistance. These components are preferably added in a range of 0.01 to 3% by mass with respect to the solid component in the coating solution.

  In order to prevent blocking, improve scratch resistance, etc., or adjust the refractive index of the cured resin layer, fine particles of an inorganic compound or an organic compound can be added to the cured resin layer thus obtained.

  For example, the inorganic fine particles used in the actinic ray curable resin layer (hard coat layer) include silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, calcium carbonate, strontium carbonate, talc, clay, calcined kaolin, calcined Mention may be made of calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. In particular, silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used.

  Organic particles include polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicone resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, and melamine resin powder. Polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, or polyfluoroethylene resin powder can be added to the ultraviolet curable resin composition. Particularly preferred are cross-linked polystyrene particles (for example, SX-130H, SX-200H, SX-350H, manufactured by Soken Chemical) and polymethyl methacrylate-based particles (for example, MX150, MX300, manufactured by Soken Chemical).

  The average particle diameter of these fine particle powders is preferably 0.005 to 5 μm, and particularly preferably 0.01 to 1 μm. The shape of these particles is not particularly limited, and spherical, flat and needle-like particles are preferably used. As for the ratio of a ultraviolet curable resin composition and fine particle powder, it is desirable to mix | blend so that it may be 0.1-30 mass parts with respect to 100 mass parts of resin compositions.

  The actinic radiation curable resin layer is a clear hard coat layer having a center line average roughness (Ra) defined by JIS B 0601 of 0.001 to 0.1 μm, or a Ra of about 0.1 to 1 μm. A glare layer is preferred. The center line average roughness (Ra) is preferably measured with an optical interference type surface roughness measuring instrument, and can be measured using, for example, RST / PLUS manufactured by WYKO.

(Antireflection film)
(Inorganic fine particles)
The inorganic fine particles used in the antireflection layer are preferably particles formed from a metal oxide. Examples of metal oxides include titanium dioxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, and the like. Of these, titanium dioxide, tin oxide, and indium oxide are particularly preferable. The inorganic fine particles are mainly composed of oxides of these metals and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.

  The inorganic fine particles are preferably surface-treated. The surface treatment can be performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina, silica, zirconium oxide and iron oxide. Of these, alumina and silica are preferable. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, a silane coupling agent is most preferable. It may be processed by combining two or more types of surface treatments.

  The shape of the inorganic fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a layer shape, a spindle shape, or an indefinite shape. Two or more kinds of inorganic fine particles may be used in combination in the metal oxide layer.

  The proportion of the inorganic fine particles in the metal oxide layer is preferably 5 to 90% by volume. The addition amount is adjusted according to the target refractive index.

(Dispersion solvent)
The inorganic fine particles are supplied to a coating liquid for forming a metal oxide layer in a dispersion state dispersed in a medium. As the dispersion medium for the inorganic fine particles, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate). , Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, Examples include dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), and ether alcohol (eg, 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The inorganic fine particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (eg, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  The metal oxide layer preferably uses a polymer having a crosslinked structure (hereinafter also referred to as “crosslinked polymer”) as a binder polymer. Examples of the crosslinked polymer include polymers having a saturated hydrocarbon chain such as polyolefin (hereinafter collectively referred to as “polyolefin”), crosslinked products such as polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. Among them, a crosslinked product of polyolefin, polyether and polyurethane is preferred, a crosslinked product of polyolefin and polyether is more preferred, and a crosslinked product of polyolefin is most preferred. Further, it is further preferable that the crosslinked polymer has an anionic group. The anionic group has a function of maintaining the dispersion state of the inorganic fine particles, and the crosslinked structure has a function of imparting a film forming ability to the polymer and strengthening the film. The anionic group may be directly bonded to the polymer chain or may be bonded to the polymer chain via a linking group, but is bonded to the main chain as a side chain via the linking group. Is preferred.

  The refractive index of the low refractive index layer used in the antireflective layer of the present invention is preferably 1.46 or less, and particularly preferably 1.3 to 1.45, by silicon alkoxide as a coating composition by a sol-gel method. A low refractive index layer can be formed. Alternatively, a low refractive index layer can be formed using a fluororesin. In particular, it is preferably composed of a cured product of thermosetting or ionizing radiation curable fluorine-containing resin and the cured product and ultrafine particles of silicon oxide.

  The dynamic friction coefficient of the cured product is preferably 0.02 to 0.2, and the pure water contact angle is preferably 90 to 130 °. Examples of the curable fluorine-containing resin include perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane) and fluorine-containing copolymers (crosslinkable groups). Monomer and fluorine-containing monomer as structural units). Specific examples of the fluorine-containing monomer unit include, for example, hexafluoroethylene, hexafluoropropylene, tetrafluoroethylene, and fluoroolefins (for example, vinylidene fluoride perfluoro-2,2-dimethyl-1,3-dioxole, fluoroethylene, etc.) , Fluorinated alkyl ester derivatives of (meth) acrylic acid (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)), fluorinated vinyl ethers, and the like. As a monomer having a crosslinkable group, a (meth) acrylate monomer having a crosslinkable functional group in the molecule in advance such as glycidyl methacrylate, and a (meth) acrylate having a carboxyl group, an amino group, a hydroxyl group, a sulfonic acid group, etc. And monomers (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.). It is described in JP-A-10-25388 and JP-A-10-147739 that a crosslinked structure can be introduced after copolymerization.

  Moreover, not only the polymer which uses the said fluorine-containing monomer as a structural unit but the copolymer with the monomer which does not contain a fluorine atom can be used. There are no particular limitations on the monomer units that can be used in combination, for example, acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate), methacrylate esters (methyl methacrylate, ethyl methacrylate, Butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, α-methylstyrene, vinyltoluene, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, acrylonitrile Derivatives, olefins (ethylene, propylene, isoprene, vinylidene chloride, vinyl chloride, etc.), vinyl ethers (methyl vinyl ether, etc.), vinyl esters (vinyl acetate, propionic acid) Alkenyl, vinyl cinnamate) may be mentioned.

  In order to improve the scratch resistance, it is preferable to add silicon oxide fine particles to the fluorine-containing resin used for forming the low refractive index layer. The addition amount is adjusted in consideration of the refractive index and scratch resistance. As the silicon oxide fine particles, silica sol dispersed in a commercially available organic solvent can be added to the coating composition as it is, or various commercially available silica powders can be dispersed in an organic solvent and used.

  The coating composition for forming a low refractive index layer of the antireflection film of the present invention preferably contains a solvent having a low boiling point mainly. Specifically, the solvent having a boiling point of 100 ° C. or less is preferably 50% by mass or more of the total solvent. As a result, for example, even when applied to a substrate surface having irregularities such as an anti-glare layer, it can be quickly dried, the fine film thickness unevenness due to the flow of the coating liquid is reduced, and the reflectance is increased. It is suppressed. Moreover, when the solvent whose boiling point is 100 degreeC or more is contained, since a drying nonuniformity and white turbidity nonuniformity are suppressed, it is preferable that the solvent whose boiling point is 100 degreeC or more contains 0.1-50 mass%.

  Low boiling point solvents used in the coating composition for the low refractive index layer include ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, ether alcohols such as methyl cellosolve, methanol, ethanol, and isopropanol. Among these alcohols, those having high solubility of the solid content contained in the coating composition are preferably used. Coating solvents having a boiling point exceeding 100 ° C. include ketones such as cyclohexanone, cyclopentanone and methyl-isobutyl ketone, ether alcohols such as diacetone alcohol and propylene glycol monomethyl ether, and alcohols such as 1-butanol and 2-butanol. Etc. are used.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1
A cellulose acetate propionate film having two phases in which the volume occupancy rate of the voids in the thickness direction in the thickness direction shown in FIG. 1-a. A cellulose acetate propionate film having no pores in the thickness direction for comparison was produced. 1-b.

(Preparation of dope)
<Fine particle dispersion>
Fine particles (Aerosil R972V (manufactured by Nippon Aerosil Co., Ltd.)) 11 parts by mass (average primary particle diameter 16 nm, apparent specific gravity 90 g / liter)
89 parts by mass of ethanol or more was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin.

<Fine particle additive solution>
The following cellulose ester resin was added to a dissolution tank containing methylene chloride and heated to completely dissolve, and this was then added to Azumi Filter Paper No. Azumi Filter Paper No. Filtered using 244. While finely stirring the filtered cellulose ester solution, the fine particle dispersion was slowly added thereto. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution.

Methylene chloride 99 parts by weight Cellulose acetate propionate (acetyl group substitution degree 1.5, propionyl group substitution degree 1.0, total acyl group substitution degree 2.5) 4 parts by weight Fine particle dispersion 11 parts by weight Poor for all solvents used A main dope having the following composition was prepared by setting the ratio of the solvent to 50% and the ratio of the total amount of the solvent used to the dissolved mass to 360%. First, methylene chloride as a good solvent and ethanol as a poor solvent were added to the pressure dissolution tank. Cellulose acetate propionate resin was added to a pressure dissolution tank containing a solvent while stirring. This was heated and stirred to completely dissolve, and a plasticizer and an ultraviolet absorber were further added and dissolved. This was designated as Azumi Filter Paper No. The main dope was prepared by filtration using 244.

  The main dope was added so as to be 100 parts by mass and 5 parts by mass of the fine particle additive solution, and sufficiently mixed with an in-line mixer (Toray static in-tube mixer Hi-Mixer, SWJ) to obtain a dope.

<Composition of main dope>
Methylene chloride 500 parts by weight Ethanol 500 parts by weight Cellulose acetate propionate (acetyl group substitution degree 1.5, propionyl group substitution degree 1.0, total acyl group substitution degree 2.5) 100 parts by weight Plasticizer: Aromatic terminal ester Sample No. 4 5 parts by mass Plasticizer: Trimethylolpropane tribenzoate 5.5 parts by mass UV absorber: Tinuvin 109 (manufactured by Ciba Specialty Chemicals)
1 part by mass UV absorber: Tinuvin 171 (manufactured by Ciba Specialty Chemicals)
1 part by mass (production of cellulose acetate propionate film)
Using the manufacturing apparatus shown in FIG. 4 (a), the prepared dope was cast on a stainless steel endless belt having a length of 60 m, a width of 2500 mm, and a mirror-finished surface at a temperature of 20 ° C. and a casting speed of 30 m. / Min., The web is peeled off at the peeling point (1.5 minutes from casting to peeling), the first drying step, the stretching step, the second drying step, the winding step, and the width Two-phase structure as shown in FIG. 2 having a structure of 1500 mm, a thickness of 80 μm, a length of 30000 m, an MD direction stretch rate (stretch rate) of −10%, and a TD direction stretch rate (stretch rate) of −1.5%. A cellulose acetate propionate film having a thickness of 3000 m was produced under the following conditions. The structure of the produced cellulose acetate propionate film is shown below.

  The volume occupancy of the voids due to the pores of the first phase is 14.8%, the volume occupancy of the voids of the voids of the second phase is 0.5%, the maximum diameter of the voids is 838 nm, the thickness of the first phase Was 59% of the total thickness of the resin film, and the thickness of the second phase was 41% of the total thickness of the resin film.

Method for Measuring Volume Occupancy Rate of Void by Holes of First Phase and Second Phase 200 cm of 5 m resin film was taken out from the end of winding, and the volume occupancy rate of voids by holes was determined by the following method.

How to find the volume of individual holes From the cross-sectional image of the resin film taken with SEM (magnification 15000 times), the maximum diameter of 10 holes was measured on a C-type JIS grade 1 steel scale, and the average value was obtained. The half of the maximum diameter obtained was used as the radius r of the hole. Using the obtained radius r, it was obtained by calculation from the equation (4πr ^3/3 ) for obtaining the volume of the sphere.

Volume of vacancies in a constant volume = volume of vacancies × number of vacancies in a constant volume Volume occupancy (%) = volume of vacancies in a constant volume / constant volume of a resin film Method for measuring the ratio of two phases From a cross-sectional image of a resin film taken with an SEM (magnification 15000 times), a line is drawn at a location where the number of holes is 1/10 μm ² to obtain a boundary line between the first and second phases. It was calculated by the following formula. Ratio (%) of first phase (second phase) = (thickness of second phase (first phase) / total thickness of first phase and second phase (thickness of resin film)) × 100
Measuring method of pore size From the cross-sectional image of the resin film taken with SEM (15,000 times magnification), the maximum diameter of 10 pores was measured on a C-type JIS1 grade steel scale, and the average value was measured. The size of the hole. The first drying step was 100 m long, and the second drying step was 1000 m long. The stretching process had a total length of 40 m. As a uniaxial stretching apparatus for the stretching process, a clip tenter was used.

  The thickness of the web is a value obtained by calculating an average value by measuring 10 locations in the width direction and 10 locations in the web casting direction using a laser displacement meter manufactured by Keyence Corporation. Manufacturing conditions are shown below.

Supply conditions of drying air in the casting process In order to dry the web on the stainless endless belt support, dry air having a temperature of 35 ° C. and a wind pressure of 500 Pa (wind speed 29 m / sec) was supplied from the first supply device. Dry air was supplied from the second supply device at a temperature of 35 ° C. and a wind pressure of 500 Pa (wind speed 29 m / sec).

Drying conditions in the first drying step The peel tension from the stainless endless belt support was set at 150 N / m, the drying temperature in the first drying step was 50 ° C., the time was 2 minutes, and the conveyance speed was 30 m / min.

  The total residual solvent amount of the web peeled from the stainless endless belt support was 100% by mass. The value of the residual solvent amount (% by mass) of the web peeled from the stainless endless belt support is B when the web of a certain size is dried at 115 ° C. for 1 hour, and the mass of the web before drying is When A, ((A−B) / B) × 100 = value obtained by the amount of residual solvent (% by mass).

Stretching conditions of stretching process The tenter stretching apparatus uses a clip tenter, and the stretching rate (stretching rate) in the TD direction of the cellulose acetate propionate film collected at the temperature of 120 ° C and the winding process is -1.5%. The film was stretched in the TD direction. The temperature in the stretching process was 120 ° C., the time was 1 minute, and the conveyance speed was 30 m / min. The stretching ratio in the stretching step indicates a value obtained by calculation from the following calculation formula.

Stretch rate (%) = (width from center to end of web after stretching / width from center to end of web before stretching) × 100
For the width from the center of the web to the end, a value obtained by measuring the width with a C-type JIS grade 1 steel scale is used.

Drying conditions of the second drying step The drying temperature of the second drying step was 110 ° C., the time was 30 minutes, and the conveyance speed was 30 m / min.

Winding process The winder was wound at a tension of 200 N / m using a constant tension method.

(Manufacture of cellulose acetate propionate film without pores in the thickness direction)
The ratio of the poor solvent to the total solvent used was 20%, the ratio of the total solvent volume to the dissolved mass was 360%, and all other conditions were made under the same conditions as in the method for producing a cellulose acetate propionate film having pores.

<Solvent composition>
Methylene chloride 800 parts by mass Ethanol 200 parts by mass (formation of functional layer)
A hard coat layer was formed as a functional layer on the surface of the first phase of a cellulose acetate propionate film prepared under the following conditions.

(Preparation of hard coat layer forming coating solution)
After stirring and dissolving the ultraviolet curable resin composition material which is the following reactive curable resin, as shown in Table 2, when preparing the following actinic radiation curable resin composition, the cellulose acetate propionate film shown in Table 1 was prepared. Solvent No. with different permeability Prepare a coating solution for forming a hard coat layer using A to D, changing the content of the solvent whose permeability to the total mass was changed, and changing the amount of the actinic radiation curable resin as shown in Table 2 and Table 3. No. 1-1 to 1-56. An ultraviolet curable resin was used as the actinic radiation curable resin. After dissolution, the solution was filtered through a polypropylene filter having a pore size of 0.4 μm.

(UV curable resin composition)
Pentaerythritol triacrylate 20 parts by mass Pentaerythritol tetraacrylate 60 parts by mass Urethane acrylate (trade name U-4HA manufactured by Shin-Nakamura Chemical Co., Ltd.) 50 parts by mass Irgacure 184 (manufactured by Ciba Specialty Chemicals) 20 parts by mass Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.) 12 parts by weight Polyether-modified silicone oil (KF-351, Shin-Etsu Chemical Co., Ltd.) 0.8 part by weight Polyoxyalkyl ether (Emulgen 1108, Kao Co., Ltd.) 1.0 part by weight Solvent * 110 parts by weight Solvent *: A solvent prepared by using any one of propylene glycol monomethyl ether, methyl acetate, toluene, and ethanol and propanol (0.5 g / m ² · min) and adjusting the total to 110 parts by mass was used.

(Application of coating liquid for forming hard coat layer)
The prepared cellulose acetate propionate film No. 1-a and 1-b, the prepared coating liquid No. 1-1 to 1-56 were applied using a micro gravure coater, dried at 90 ° C. for 1 minute, and then irradiated with an ultraviolet lamp at an irradiation intensity of 100 mW / cm ² and an irradiation dose of 0.2 J / cm ^2. The coating layer was cured to form a hard coat layer with a dry film thickness of 10 μm to produce a hard coat film. 101-170.

Evaluation The produced sample No. Tables 4 and 5 show the results of evaluation on dry pencil hardness and peeling resistance according to the following methods, and evaluation according to the following evaluation ranks.

(Drying)
Samples are taken immediately after curing, 5 pieces of 30 cm × 30 cm are prepared, the drying temperature is 45 ° C., the drying time is changed to 1, 2, 3, 5, 10 hours, and the mass change rate is calculated from the following calculation formula. The drying time that the calculated rate of change was 1% or less was measured and defined as the drying property.

Mass change rate (%) = (mass after drying / mass before drying) × 100
Evaluation method of pencil hardness It is the value measured according to the pencil hardness evaluation method prescribed | regulated by JISK5400 using the test pencil prescribed | regulated by JISS6006. A pencil hardness tester (HA-301 Clemens type scratch hardness tester) was used for the test.

Evaluation method of peel resistance Adhesion was evaluated by a method based on JIS K 5400.

  Eleven cuts were made vertically and horizontally at intervals of 1 mm, 100 mm grids of 1 mm square were created, cellophane tape was applied, and peeled off quickly at an angle of 90 degrees, and adhesion was evaluated in the grid pattern.

Evaluation rank for peeling resistance ◎: No peeling is observed ○: Slight peeling is observed at the edge of the grid pattern △: The edge is peeled, but practical use is possible ×: Peeling

  The effectiveness of the present invention was confirmed.

Example 2
When a cellulose acetate propionate film was produced in Example 1, the ratio of the good solvent and the poor solvent of the main dope used and the ratio of the total amount of solvent used with respect to the dissolved mass were changed as shown in Table 6. In the same manner as in Example 1, a cellulose acetate propionate film having the structure shown in FIG. 2 in which the volume occupancy of the voids due to the pores in the first phase and the volume occupancy of the voids due to the voids in the second phase was changed was manufactured. 2-1 to 2-10.

(Formation of functional layer)
The prepared cellulose acetate propionate film No. On the surface of the first phase of 2-1 to 2-10, the hard coat layer forming coating solution No. 1 prepared in Example 1 was used. The same hard coat layer forming coating solution as 1-32 was applied under the same conditions as in Example 1 to form a hard coat layer to produce a hard coat film. 201-210.

Evaluation The produced sample No. Table 7 shows the results of evaluation on the dryness, pencil hardness, and peeling resistance according to the same method as in Example 1 and evaluation according to the same evaluation rank as in Example 1.

  The effectiveness of the present invention was confirmed.

Example 3
In Example 1, cellulose acetate propionate film no. The same main dope as the main dope used for producing 1-32 was prepared, and as shown in Table 8, the thickness of the first phase and the second phase with respect to the total thickness of the cellulose acetate propionate film was changed. A pionate film was prepared and no. 3-1 to 3-7. The measurement of the volume occupancy ratio of the voids by the pores of the first phase and the second phase, the maximum diameter of the pores, the ratio of the first phase and the second phase shows values measured by the same method as in Example 1.

(Formation of functional layer)
The prepared cellulose acetate propionate film No. On the surface of the first phase of 3-1 to 3-7, the hard coat layer forming coating solution No. 1 prepared in Example 1 was used. The same hard coat layer forming coating solution as 1-32 was applied under the same conditions as in Example 1 to form a hard coat layer to produce a hard coat film. 301 to 307.

Evaluation The produced sample No. Table 9 shows the results of evaluations on dryness, pencil hardness, and peeling resistance according to the same methods as in Example 1 and evaluation according to the same evaluation rank as in Example 1.

  The effectiveness of the present invention was confirmed.

Example 4
In Example 1, cellulose acetate propionate film no. When producing 1-32, the same main dope as the main dope prepared in Example 1 was used, and the temperature and time from the start of casting of the main dope to peeling of the web from the endless belt support were changed. A cellulose acetate propionate film having the structure shown in FIG. 2 was produced in the same manner as in Example 1 except that the maximum pore diameter was changed as shown in FIG. 4-1 to 4-10.

  The thickness of the first phase with respect to the total thickness was 60%, and the thickness of the second phase with respect to the total thickness was 40%. The temperature was adjusted so that the volume occupation ratio of voids in the pores was 17% for the first phase and 0.5% for the second phase.

  The maximum diameter of holes, the ratio of the maximum diameter holes to the total holes, the volume occupancy of the first phase, the volume occupancy of the first phase, the thickness of the first phase relative to the total thickness, the second phase relative to the total thickness The thickness of shows the value measured by the same method as Example 1.

(Formation of functional layer)
The prepared cellulose acetate propionate film No. On the surface of the first phase of 4-1 to 4-10, the hard coat layer forming coating solution No. 1 prepared in Example 1 was used. The same hard coat layer forming coating solution as 1-32 was applied under the same conditions as in Example 1 to form a hard coat layer to produce a hard coat film. 401-410.

Evaluation The produced sample No. Table 11 shows the results of evaluations on dryness, pencil hardness, and peel resistance in the same manner as in Example 1, and according to the same evaluation rank as in Example 1.

  The effectiveness of the present invention was confirmed.

Example 5
In Example 1, cellulose acetate propionate film no. When producing 1-32, the same main dope as the main dope prepared in Example 1 was used, and the drying air temperature was changed so that the casting amount of the main dope and the drying speed were the same. A cellulose acetate propionate film having the structure shown in FIG. 5-1 to 5-12.

  The thickness of the first phase with respect to the total thickness was 40%, and the thickness of the second phase with respect to the total thickness was 60%. The ratio of the maximum pore diameter distribution in the range of 1 nm to 1000 nm is 85%, and the volume occupancy rate of the voids by the pores is the speed and temperature so that the first phase is 17% and the second phase is 0.5%. Adjusted.

  Maximum diameter of holes The ratio of the maximum diameter holes to the total holes, the volume occupancy of the first phase, the volume occupancy of the first phase, the thickness of the first phase relative to the total thickness, the thickness of the second phase Here, the value measured by the same method as in Example 1 is shown.

(Formation of functional layer)
The prepared cellulose acetate propionate film No. On the surface of the first phase of 5-1 to 5-12, the hard coat layer forming coating solution No. 1 prepared in Example 1 was used. The same hard coat layer forming coating solution as 1-32 was applied under the same conditions as in Example 1 to form a hard coat layer to produce a hard coat film. 501-512.

Evaluation The produced sample No. Table 13 shows the results of evaluations on dryness, pencil hardness, and peel resistance in the same manner as in Example 1 and evaluation according to the same evaluation rank as in Example 1.

  The effectiveness of the present invention was confirmed.

Example 6
Using the same main dope as prepared in Example 1, using the same main dope as in Example 1, the total thickness was 40 μm, the thickness of the first phase was 90% of the total thickness, and the thickness of the second phase was the total thickness Cellulose having 10%, 85% of the maximum pore diameter distribution in the range of 1 nm to 1000 nm, 18% volume occupancy of first phase vacancies, 0.7% volume occupancy of second phase vacancies An acetate propionate film was prepared. Thereafter, this cellulose acetate propionate film is used, and the amount of ethanol, which is a poor solvent, is 600 parts by mass on the second phase, and methylene chloride, which is a good solvent, is 400 parts by mass. By casting the main dope and changing the temperature and drying time, a three-phase cellulose acetate propionate film shown in FIG. . 6-1 to 6-7. The first phase thickness was 40% of the total thickness, the second phase thickness was 20% of the total thickness, and the third phase thickness was 40% of the total thickness.

  Total thickness, thickness of the first phase relative to the total thickness, thickness of the second phase relative to the total thickness, maximum hole diameter, ratio of maximum diameter holes to total holes, volume occupation of first phase holes Rate, volume occupancy of the second phase pores, the thickness of the first phase relative to the total thickness, the thickness of the second phase relative to the total thickness, and the thickness of the third phase relative to the total thickness are the same as in Example 1. Indicates the measured value.

(Formation of functional layer)
The prepared cellulose acetate propionate film No. The same coating liquid for forming a hard coat layer as the coating liquid for forming a hard coat layer prepared in Example 1 was applied to the surface of the first phase of 6-1 to 6-7. 1-32 was applied under the same conditions as in Example 1 to form a hard coat layer to produce a hard coat film. 601-607.

Evaluation The produced sample No. Table 15 shows the results of evaluations on dryness, pencil hardness, and peel resistance according to the same evaluation rank as in Example 1, and evaluation according to the same evaluation rank as in Example 1.

  The effectiveness of the present invention was confirmed.

Example 7
Using the same main dope as the main dope prepared in Example 1, a two-phase cellulose acetate propionate film having a total thickness of 48 μm shown in Table 16 was prepared in the same manner as in Example 1. 7-a to 7-g. Thereafter, the cellulose acetate propionate film No. 7-a to 7-g are used, and as shown in Table 17, the same main dope is flowed on the second phase except that the dope component is 600 parts by mass of the poor solvent ethanol and the good solvent Michikuro is 400 parts by mass. A three-phase surface cellulose acetate propionate film having a total thickness of 80 μm shown in FIG. 7-1 to 7-7. The total thickness of the first phase and the second phase with respect to the total thickness was 60%, and the thickness of the third phase with respect to the total thickness was 40%.

(Formation of functional layer)
The prepared cellulose acetate propionate film No. The hard coat layer forming coating solution No. 7-1 prepared in Example 1 was formed on the surface of the first phase of 7-1 to 7-7. The same hard coat layer forming coating solution as 1-32 was applied under the same conditions as in Example 1 to form a hard coat layer to produce a hard coat film. 701-707.

Evaluation The produced sample No. Table 18 shows the results of evaluation on the dryness, antiglare property, transmitted image definition, white turbidity, pencil hardness, and peeling resistance according to the same evaluation rank as in Example 1 and evaluation according to the same evaluation rank as in Example 1. Shown in

  The effectiveness of the present invention was confirmed.

It is a schematic sectional drawing of the optical resin film manufactured with the manufacturing method of this invention. FIG. 2 is an enlarged schematic view of the base resin film used in the optical resin film shown in FIG. It is the expansion schematic of the resin film of the base material currently used for the optical resin film shown by FIG.1 (b). It is the schematic of the manufacturing apparatus of the resin film by the solution casting method using an endless belt support body.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1a, 1b Optical resin film 2, 4 Resin film 2a, 4a 1st phase 2b, 4b 2nd phase 201, 401 Hole 3, 5 Functional layer 4c 3rd phase 6a-6c, 6a'-6c 'Manufacturing apparatus 601 , 601 'casting process 601a endless belt support 601'a endless drum support 602, 602' first drying process 603 stretching process 603 'MD stretching process 604 second drying process 605 winding process

Claims (12)

Using a resin film having at least two phases with different volume occupancy rates due to pores in the thickness direction, 5% of the total mass of a solvent having a permeability of 1 g / (cm ² · min) or more to the resin film Optically characterized in that at least one functional layer is formed by applying a functional layer forming coating solution containing ~ 80% and containing 20% by mass to 70% by mass of a reactive curable resin. A method for producing a resin film. The optical phase according to claim 1, wherein the phase has a first phase and a second phase, and the first phase is on a surface on which the resin layer of the second phase is applied. A method for producing a resin film. 3. The volume occupation ratio of voids due to the first phase holes is 5% to 20%, and the volume occupation ratio of voids due to the second phase holes is 0% to 1%. The manufacturing method of the resin film for optics as described in any one of. The thickness of the first phase is 60% to 99% of the total thickness of the resin film, and the thickness of the second phase is 1% to 40% of the total thickness of the resin film. 4. A method for producing an optical resin film as described in 3. The method for producing an optical resin film according to claim 2, wherein the third phase is provided on a surface opposite to the surface on which the first phase of the second phase is formed. 6. The method for producing an optical resin film according to claim 5, wherein the volume occupancy ratio of the voids due to the holes of the third phase is 5% to 20%. The thickness of the first phase is 40% to 60% of the total thickness of the resin film, the thickness of the second phase is 1% to 20% of the total thickness of the resin film, and the thickness of the third phase is The method for producing an optical resin film according to claim 5 or 6, wherein the thickness is 40% to 60% of the total thickness of the resin film. The method for producing an optical resin film according to claim 1, wherein the resin layer is formed on the first phase. The production of an optical resin film according to any one of claims 1 to 8, wherein a maximum diameter is distributed in a range of 1.0 nm to 1000 nm with 80% or more of the holes. Method. The method for producing an optical resin film according to claim 1, wherein the resin film has a thickness of 40 μm to 80 μm, and the functional layer has a thickness of 4 μm to 16 μm. The method for producing an optical resin film according to claim 1, wherein the resin film is produced by a solution casting method. A hard coat film produced by the method for producing an optical resin film according to claim 1.

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