JP2008038106A - Method and apparatus for producing dope, and cellulose resin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and an apparatus for producing a dope, sufficiently suppressing the formation of undissolved material, and to provide a cellulose resin film produced by using the dope. <P>SOLUTION: The method for producing the dope, including a step for cooling the dope at the outlet of a heat exchanger by the heat exchanger arranged at the vicinity of the output side of a liquid-sending pump is regulated so that the temperature of the dope in a pressurized vessel at the start of the liquid sending may be 10-30°C higher than the boiling point of a solvent, and the dope at the outlet of the heat exchanger may be cooled to the temperature ≥5°C lower than the boiling point of the solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a dope manufacturing method for dissolving a resin in a solvent to obtain a dope, a dope manufacturing apparatus, and a cellulose resin film manufactured using the dope.

  In recent years, liquid crystal display devices are widely used as monitors because they save space and energy compared to conventional CRT display devices. Furthermore, it is also spreading for TV. In such a liquid crystal display device, various optical films such as a polarizing film and a retardation film are used.

  By the way, as for the polarizing film of the polarizing plate used for a liquid crystal display device, the cellulose-ester film is laminated | stacked as a protective film on the single side | surface or both surfaces of the polarizer which consists of a stretched polyvinyl alcohol film. The retardation film is used for the purpose of increasing the viewing angle and improving the contrast, and is provided with retardation by stretching a film of polycarbonate, cyclic polyolefin resin, cellulose ester or the like. Sometimes called an optical compensation film.

  These optical films are required to have no optical defects, uniform retardation, and particularly no phase axis variation. In particular, as the size of monitors and TVs increases and the definition becomes higher, these required qualities are becoming stricter.

  Optical film production methods are roughly classified into a melt casting film forming method and a solution casting film forming method. The former is a method in which a polymer is heated and dissolved and cast on a support, cooled and solidified, and further stretched as necessary to form a film. The latter is a method in which the polymer is dissolved in a solvent to support the solution. It is a method of casting on the body, evaporating the solvent, and further stretching to make a film if necessary.

  In any film forming method, the molten polymer or polymer solution is cooled and solidified on the support. And after peeling from a support body, processes, such as drying and extending | stretching, are made | formed, while a polymer film is conveyed using a some conveyance roll.

  In the solution casting film forming method, a dope in which a resin is dissolved in a solvent is produced, and a film is produced using this dope.If undissolved material is present in the dope, it adversely affects the quality of the film, In particular, a poor expression of retardation occurs after the stretching treatment. Further, in order to sufficiently dissolve the undissolved material, a treatment such as increasing the dissolution time is required, and the productivity is lowered. Furthermore, if the filtration is performed with the undissolved material as it is, the life of the filter medium is shortened, and the work by exchanging the filter medium causes an increase in cost.

  For this reason, an improved method for producing a dope has been proposed in order to increase the solubility of the resin in the dope.

  Patent Document 1 proposes a method and an apparatus for dissolving a dope solution by applying a shearing force with a stirrer.

  In Patent Document 2, cellulose acylate and a solvent are continuously supplied to a first mixing container, retained in the container for 1 minute or longer, mixed and swelled, and then supplied to a second mixing container. A method for improving the solubility has been proposed.

  Patent Document 3 proposes a method in which a polymer and a solvent are roughly dissolved and heated while feeding the dope to promote dissolution.

  In patent document 4, the method of melt | dissolving using a special stirrer is proposed.

  Patent Document 5 proposes a method in which cellulose acylate and a solvent are continuously supplied to a disperser and the cellulose acylate is dispersed in the solvent with a residence time of less than 1 minute. This is because the resin is uniformly dispersed in the solvent at the start of dissolution, so that the subsequent dissolution is performed smoothly.

Patent Document 6 proposes a method for preventing the generation of a gel substance by transferring a dissolved dope while keeping it warm.
JP 2000-273184 A JP 2000-273239 A JP 2003-221449 A JP 2003-221450 A JP-A-2005-97378 JP 2006-70253 A

  However, even with the means described in Patent Documents 1 to 6, there remains a problem that the generation of undissolved substances cannot be sufficiently suppressed.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a dope production method, a dope production apparatus, and a cellulose produced by using the dope, in which generation of undissolved substances is sufficiently suppressed. It is to provide a resin film.

  The above object of the present invention can be achieved by the following means.

1.
Dissolving the resin in the solvent by heating and stirring in a pressure vessel;
A step of feeding the dope dissolved in the step of dissolving from the pressure vessel with a liquid feed pump;
Cooling the dope at the outlet of the heat exchanger by a heat exchanger disposed adjacent to the outlet side of the liquid pump;
In a method for producing a dope including:
The temperature of the dope in the pressure vessel at the start of liquid feeding from the liquid feeding pump is a temperature that is 10 ° C to 30 ° C higher than the boiling point of the solvent,
The method for producing a dope, wherein the temperature of the dope at the outlet of the heat exchanger is cooled to a temperature lower by 5 ° C. or more than the boiling point of the solvent.

2.
2. The method for producing a dope according to 1, wherein the maximum temperature of the dope in the dissolving step is 30 ° C. to 50 ° C. higher than the boiling point of the solvent.

3.
3. The method for producing a dope according to 1 or 2, wherein the heat exchanger is a scraped heat exchanger.

4).
The method for producing a dope according to 1 or 2, wherein the heat exchanger is a static mixed heat exchanger.

5.
3. The dope manufacturing method according to claim 1 or 2, wherein the heat exchanger is a trace type heat exchanger in which a cold water pipe is wound around a dope pipe.

6).
The capacity of the pipe from the outlet of the pressure vessel to the inlet of the heat exchanger is 5 to 50% of the capacity of the dope dissolved in the pressure vessel, and the pipe is in the pressure vessel at the start of liquid feeding. The method for producing a dope according to any one of 1 to 5, wherein the temperature is kept within ± 5 ° C of the temperature of the dope.

7).
A dope manufacturing apparatus using the method for manufacturing a dope according to any one of 1 to 6.

8).
A cellulose resin film formed by a solution casting film forming method using the dope prepared by the method for producing a dope according to any one of 1 to 6.

  According to the present invention, a heat exchanger is provided on the outlet side of the dope feed pump, and by adjusting the temperature of the feed pump inlet and the heat exchanger outlet to an appropriate range, even if the production speed is increased, Generation | occurrence | production of the undissolved substance in dope can be suppressed. Therefore, there are effects of shortening the production time of the dope solution, and accompanyingly improving the productivity in the film production apparatus using the dope production apparatus of the present invention and improving the performance of the produced film.

  Hereinafter, the present invention will be specifically described.

  The method for producing a dope according to the present invention includes a step of dissolving a resin in a solvent by heating and stirring in a pressure vessel, a step of feeding the dope dissolved in the dissolving step from the pressure vessel with a liquid feed pump, Cooling the dope at the outlet of the heat exchanger by a heat exchanger disposed adjacent to the outlet side of the liquid pump, and in the pressure vessel at the start of liquid feeding from the liquid pump The temperature of the dope is higher by 10 ° C. to 30 ° C. than the boiling point of the solvent, and the temperature of the dope at the outlet of the heat exchanger is cooled to a temperature lower than the boiling point of the solvent by 5 ° C. or more. To do.

  FIG. 1 shows a flow sheet of a cellulose resin film production line using the dope production method of the present invention.

  The dope manufacturing apparatus A includes a main dope charging pot 1 as a pressure vessel, a discharge valve 6, a dope feed pump 2, and a heat exchanger 20.

  In the main dope charging pot 1, a cellulose resin is dissolved while mixing a predetermined amount of a cellulose resin and a solvent for dissolving the cellulose resin, a plasticizer, a flame retardant, fine particles, and the like to prepare a dope.

  The dope prepared in the main dope charging pot 1 passes through the main filter 4 and the dope filter 5 as a filtration step through the dope stationary pot 3 by the dope feed pump 2. Next, the dope is used as a film forming process to uniformly cast (cast process) from the casting die 11 onto the stainless steel band support 101, and the cast mixed solution is a part of the solvent on the stainless steel band support 101. Evaporates (casting process), becomes a film, and is peeled off by the peeling roll 102, then passes through the tenter / drying device 104 and the roll transport / drying device 105 (film drying process), and is wound on the film winding device 106. In this way, a cellulose resin film is produced.

  Examples of the cellulose ester according to the present invention include cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, and cellulose acetate propionate. In the case of cellulose triacetate, cellulose triacetate having a polymerization degree of 250 to 400 and a bound acetic acid amount of 54 to 62.5% is particularly preferable, and a base strength having a bound acetic acid amount of 58 to 62.5% is strong and more preferable. As the cellulose triacetate, either cellulose triacetate synthesized from cotton linter or cellulose triacetate synthesized from wood pulp can be used alone or in combination.

  It is preferable to use a large amount of cellulose triacetate synthesized from a cotton linter that has good releasability from a belt or a drum because of high productivity efficiency. Since the ratio of cellulose triacetate synthesized from cotton linter is 60% by mass or more and the effect of releasability becomes remarkable, 60% by mass or more is preferable, more preferably 85% by mass or more, and further, it can be used alone. Most preferred.

  Examples of the solvent for the cellulose resin according to the present invention include lower alcohols such as methanol, ethanol, n-propyl alcohol, iso-propyl alcohol and n-butanol, lower aliphatic hydrocarbon chlorides such as cyclohexanedioxane and methylene chloride. Things can be used. As the solvent ratio, for example, 70 to 95% by mass of methylene chloride and 5 to 30% by mass of other solvents are preferable. The concentration of the cellulose resin is preferably 10 to 50% by mass.

  In order to improve the properties of the film formed, an additive may be added to the dope. Examples of the additive include, but are not limited to, a plasticizer, an ultraviolet absorber, fine particles as a matting agent, a thickener, an oil gelling agent, and a retardation control agent. The additive may be added when the resin is dissolved in a solvent, or may be mixed in-line with the prepared dope. Moreover, when adding an additive, only an additive may be added and the additive solution which dissolved the additive in the solvent may be added.

  The kind of fine particles as a matting agent in the cellulose resin film may be an inorganic compound or an organic compound. Examples of the inorganic compound include fine particles such as silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, and tin oxide. In this, it is preferable that it is a compound containing a silicon atom, and especially a silicon dioxide fine particle is preferable. Examples of the silicon dioxide fine particles include AEROSIL 200, 200V, 300, R972, R972V, R974, R976, R976S, R202, R812, R805, OX50, TT600, RY50, RX50, NY50, NAX50, NA50H, NA50Y manufactured by Aerosil Co., Ltd. , NX90, RY200S, RY200, RX200, R8200, RA200H, RA200HS, NA200Y, R816, R104, RY300, RX300, R106 and the like. AEROSIL 200V and R972V are preferable in terms of controlling dispersibility and particle size.

  The fine particles have different primary particle sizes, particle sizes after being dispersed in a solvent, and particle sizes in the film. Among these, the particle size of the fine particles in the final film affects the cracking failure during storage of the original film, the convex failure due to the generation of foreign matter, and the haze. Therefore, it is important to control the particle size of the fine particles in the film.

  Finally, the average secondary particle size of the fine particles in the film needs to be 100 nm to 500 nm. Preferably, they are 150 nm-400 nm, More preferably, they are 200 nm-350 nm. The average secondary particle size in the film can be confirmed by taking and observing a cross-sectional photograph. If the particle diameter exceeds 500 nm, haze deterioration or the like may be observed, or it may cause a failure in a wound state as a foreign matter. Moreover, when it is smaller than 100 nm, sufficient effect of improving the winding property is not seen, and particularly when the film thickness of the cellulose resin film is 20 to 65 μm, it is remarkable.

  The haze of the film can be measured, for example, according to ASTM-D1003-52. The haze is preferably 0 to 0.6%, more preferably 0 to 0.4%, and still more preferably 0.1 to 0.2%.

  It is preferable to add 0.02 to 0.1% by mass of the fine particles in the film state from the viewpoints of cracking failure during storage of the film raw material, convex failure due to generation of foreign matter, and haze. More preferably, it is 0.04-0.08 mass%.

  The plasticizer is not particularly limited, but in the phosphate ester type, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc., in the phthalate ester type , Diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, etc., in glycolic acid ester system, triacetin, tributyrin, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, methyl It is preferable to use phthalyl ethyl glycolate, butyl phthalyl butyl glycolate or the like alone or in combination.

  If necessary, two or more plasticizers may be used in combination. In this case, the use ratio of the phosphate ester plasticizer is 50% or less, which hardly causes hydrolysis of the cellulose resin film and is durable. It is preferable because of its excellent properties.

  It is more preferable that the ratio of the phosphate ester plasticizer is small, and it is particularly preferable to use only a phthalate ester or glycolate ester plasticizer.

  It is preferable to use an ultraviolet absorber for the cellulose resin film. As the ultraviolet absorber, the wavelength is 400 nm from the viewpoint of excellent absorption of ultraviolet rays having a wavelength of 370 nm or less from the viewpoint of preventing deterioration of the liquid crystal and good liquid crystal display properties. Those that absorb as little visible light as possible are preferably used. In particular, the transmittance at a wavelength of 370 nm needs to be 10% or less, preferably 5% or less, more preferably 2% or less.

  Examples of commonly used compounds include, but are not limited to, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like.

  One or more of these ultraviolet absorbers are preferably used, and may contain two or more different ultraviolet absorbers.

  Preferably used ultraviolet absorbers include benzotriazole ultraviolet absorbers and benzophenone ultraviolet absorbers. An embodiment in which a benzotriazole-based ultraviolet absorber with less unnecessary coloring is added to the cellulose resin film is particularly preferable.

  The ultraviolet absorber may be added to the dope after dissolving the ultraviolet absorber in an organic solvent such as alcohol, methylene chloride, dioxolane, or directly into the dope composition. For an inorganic powder that does not dissolve in an organic solvent, a dissolver or a sand mill is used in the organic solvent and the cellulose resin to be dispersed and then added to the dope.

  The amount of the ultraviolet absorber used in the present invention is 0.1% by mass to 2.5% by mass, preferably 0.5% by mass to 2.0% by mass, and more preferably 0.8% by mass with respect to the cellulose resin. It is mass%-2.0 mass%. When the amount of the ultraviolet absorber used is more than 2.5% by mass, the transparency tends to deteriorate, which is not preferable.

  The process for producing the cellulose resin film in the present invention is not particularly limited, and may be a method generally used in the art. For example, U.S. Pat. Nos. 2,492,978, 2,739,070, 2 739,069, 2,492,977, 2,336,310, 2,367,603, 2,607,704, British Patents 64,071, 735,892 The methods described in JP-B-45-9074, JP-A-49-4554, JP-A-49-5614, JP-A-60-27562, JP-A-61-39890, and JP-A-62-4208 can be referred to.

  In the present invention, as a method for producing the dope, when the dope dissolved in the main dope charging pot 1 is sent to the next step by the liquid feed pump 2, the dope temperature on the inlet side of the liquid feed pump 2 and the liquid feed pump It is important to adjust the temperature on the outlet side, and for this purpose, a heat exchanger for temperature adjustment is installed adjacent to the outlet side of the liquid feed pump. This point will be described in detail below.

  In the preparation of the dope, the type of the pressure vessel is not particularly limited as long as it can withstand a predetermined pressure and can be heated and stirred under pressure.

  In addition to the pressure vessel, other instruments such as a pressure gauge and a thermometer are appropriately disposed. The pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or by increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside. For example, a jacket type is preferable because temperature control is easy.

  After dissolution, it is preferable to take out the main dope charging pot 1 with the liquid feed pump 2 and cool it with the heat exchanger 20, and then pass at least one filtration step from the viewpoint of foreign matter control, and then use this for film formation. .

  At this time, the temperature of the dope in the pressure vessel 1 at the start of liquid feeding from the liquid feeding pump 2 is 10 ° C. to 30 ° C. higher than the boiling point of the solvent, and the temperature of the dope at the outlet of the heat exchanger 20 is the solvent. It is preferable to cool to a temperature 5 ° C. or more lower than the boiling point. By doing in this way, generation | occurrence | production of an undissolved substance can be suppressed even if the dope fully melt | dissolved with the main dope charging pot 1 is rapidly cooled with the heat exchanger 20, and it sends to the next process, and high temperature In this state, since the liquid can be fed from the main dope charging pot 1, the productivity of the film is improved. When the temperature of the dope in the pressure vessel 1 at the start of liquid feeding from the liquid feeding pump 2 is lower than the temperature 10 ° C. higher than the boiling point of the solvent, the solubility of the resin is lowered and undissolved matter is generated. Further, when the temperature exceeds 30 ° C. higher than the boiling point, boiling occurs in the pipe and bubbles are generated, so that the performance of the film is deteriorated. Further, when the temperature of the dope at the outlet of the heat exchanger 20 is not cooled to a temperature lower than the boiling point of the solvent by 5 ° C. or more, the film forming speed cannot be significantly improved, and the productivity cannot be improved.

  Moreover, it is preferable that the maximum temperature when melt | dissolving resin with the main dope charging pot 1 is 30 to 50 degreeC higher than the boiling point of a solvent. If it is less than 30 ° C., it takes a long time to dissolve, or if it exceeds 50 ° C., bubbles are easily generated due to boiling, which is not good.

  The heat exchanger 20 is preferably a scraped heat exchanger, a static mixed heat exchanger, or a trace heat exchanger in which a cold water pipe is wound around a dope pipe.

  Of these, a scraped heat exchanger or a static heat exchanger is preferable. In the scraped heat exchanger or the static heat exchanger, since the dope can be stirred in the pipe at the same time, the generation of undissolved substances can be further suppressed even if the film forming speed is increased.

  As the scraping-type heat exchanger, for example, an onlator manufactured by Sakai Seisakusho can be used. Moreover, as a static mixing heat exchanger, the static mixer made from Takumina, for example can be used. By using such a heat exchanger, the dope temperature can be controlled efficiently.

  Further, the capacity of the pipe from the outlet of the main dope charging pot 1 which is a pressure vessel to the inlet of the heat exchanger 20 is 5 to 50% of the capacity of the dope dissolved in the main dope charging pot 1, and the pipe is fed. It is preferable that the temperature is kept within ± 5 ° C. of the temperature of the dope in the pressure vessel at the start of the liquid. The outlet of the pressure vessel at this time refers to the position where the discharge valve is located.

  Thus, by making piping capacity | capacitance and dope temperature in piping into the said range, generation | occurrence | production of an undissolved substance can be suppressed between a pressure vessel exit to a heat exchanger entrance.

As a capacity | capacitance of a pressure vessel, 2-50 m < ³ > is preferable, More preferably, it is 5-20 m < ³ >. If the capacity is 2 m ³ or less, a large number of pressure vessels are required to obtain a certain amount of dope, and if it is 50 m ³ or more, undissolved substances are generated, which is not preferable.

  In the film forming process of the present invention, the dope after being fed from the liquid feed pump 2 and cooled by the heat exchanger 20 is cast on the support (casting process), and then heated to remove a part of the solvent. (After drying on the support) After peeling from the support, the peeled film is dried (film drying step) to obtain a cellulose resin film. The dope after being cooled by the heat exchanger 20 may be allowed to stand in the dope stationary pot 3, and after being filtered by the filter 4, it may be cast.

  As the support in the casting process, a support in which a belt-like or drum-like stainless steel is mirror-finished is used. The temperature of the support in the casting process can be cast in a general temperature range of 0 ° C. to a temperature lower than the boiling point of the solvent, but the dope is gelled by casting on a support at 5 ° C. to 30 ° C. In order to increase the peeling limit time, it is preferable to cast on a support at 5 to 15 ° C. The peeling limit time is the time during which the cast dope is on the support at the limit of the casting speed at which a transparent and flat film can be continuously obtained. A shorter peeling limit time is preferable because of excellent productivity.

  In the drying step on the support, after the dope is cast and gelled, the time from casting to peeling is defined as 100%, and the dope temperature is 40 ° C. to 70 ° C. within 30% from the casting. By promoting the evaporation of the solvent, it can be peeled off from the support as quickly as possible, and the peel strength is further increased, and it is more preferable that the dope temperature be 55 ° C to 70 ° C within 30%. . This temperature is preferably maintained at 20% or more, more preferably 40% or more.

  Drying on the support is preferably peeled from the support with a residual solvent amount of 60% to 150% because the peel strength from the support is reduced, and more preferably 80 to 120%. The dope temperature at the time of peeling is preferably 0 ° C. to 30 ° C., because the base strength at the time of peeling can be increased and the base breakage at the time of peeling can be prevented, and 5 ° C. to 20 ° C. is more preferable.

  The amount of residual solvent in the film is represented by the following formula.

Residual solvent amount (mass%) = residual volatile matter mass / heat-treated film mass × 100
The residual volatile matter mass is a value obtained by subtracting the film mass after the heat treatment from the film mass before the heat treatment when the film is heat treated at 115 ° C. for 1 hour.

  In the film drying step, the film peeled from the support is further dried, and the residual solvent amount is 3% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less. It is preferable for obtaining a good film. In the film drying process, generally, a roll suspension system, a pin tenter system, or a clip tenter system is used for drying while transporting the film. For the liquid crystal display member, it is preferable to dry while maintaining the width by a tenter method in order to improve the dimensional stability. In particular, maintaining the width where the amount of residual solvent is large immediately after peeling from the support exhibits a greater effect of improving dimensional stability. In particular, in the drying process after peeling from the support, the film tends to shrink in the width direction due to evaporation of the solvent, so that the shrinkage increases as the film is dried at a higher temperature. In order to improve the flatness of the finished film, it is preferable to dry while suppressing the shrinkage as much as possible. From this point, for example, a method of drying the whole drying process or a part of the process as shown in Japanese Patent Application Laid-Open No. 62-46625 while holding the both ends of the web with a width in the width direction (tenter method) ) Is preferred.

  The means for drying the film is not particularly limited, and is generally performed with hot air, infrared rays, a heating roll, microwaves, or the like. It is preferable to carry out with hot air in terms of simplicity. The drying temperature is preferably in the range of 40 ° C. to 150 ° C. and divided into 3 to 5 stages, and it is preferable that the drying temperature is increased stepwise. .

  These steps from casting to post-drying may be performed in an air atmosphere or an inert gas atmosphere such as nitrogen gas.

  It goes without saying that the dry atmosphere is carried out in consideration of the explosion limit concentration of the solvent.

  The winding machine relating to the production of the cellulose resin film of the present invention may be a commonly used winding method such as a constant tension method, a constant torque method, a taper tension method, a program tension control method with a constant internal stress. Can be rolled up.

  The thickness of the cellulose resin film according to the present invention is generally used in a thickness of 20 to 200 μm, but 20 to 65 μm is required in order to reduce the thickness and weight of the polarizing plate used in the liquid crystal display device. More preferably, it is 30-60 micrometers, More preferably, it is 35-50 micrometers. If it is thinner than this, the stiffness of the film will decrease, so it will be easy to cause problems due to wrinkles on the polarizing plate making process, and if it is thicker than this, it will contribute to the thinning of the polarizing plate. Less is.

  In order to stabilize the winding property, a so-called knurling process may be performed in which unevenness is imparted to both ends in the width direction of the cellulose resin film to make the ends bulky.

  When the ratio of the knurling height (a: μm) to the film thickness (d: μm) X (%) = (a / d) × 100, the range of X = 1 to 25% stabilizes the winding property. Good for. Preferably, it is 1 to 15%, more preferably 1 to 10%. From this range, if the knurling height ratio is large, the winding shape is likely to be deformed, and if the ratio is small, the winding property is deteriorated, which is not preferable.

  It is preferable that there are few foreign substances contained in the cellulose resin film according to the present invention. Foreign materials include foreign materials that are recognized in the polarization crossed Nicol state, and foreign materials due to aggregates of fine particles protruding on the film surface.

  The foreign substance recognized in the polarization crossed Nicol state refers to that measured by placing two polarizing plates in a direct (crossed Nicol) state and placing a cellulose resin film between them. In the polarization crossed Nicol state, such a foreign substance is observed by shining only the part of the foreign substance in the dark field, so that the size and number can be easily identified.

(Example 1)
FIG. 1 shows a flow sheet of the cellulose resin film production apparatus used in Example 1.
<Dope composition>
(Dope composition 1)
Cellulose triacetate 100 parts by mass (Mn = 148000, Mw = 310000, Mw / Mn = 2.1)
Triphenyl phosphate 8 parts by weight Ethylphthalyl ethyl glycolate 2 parts by weight Methylene chloride 440 parts by weight Ethanol 40 parts by weight Tinuvin 109 (manufactured by Ciba Specialty Chemicals) 0.5 part by weight Tinuvin 171 (Ciba Specialty Chemicals) 0.5 mass parts Aerosil 972V (manufactured by Nippon Aerosil Co., Ltd.) 0.2 mass parts (dope composition 2)
Cellulose acetate propionate 100 parts by mass (Mn = 70000, Mw = 220,000, Mw / Mn = 3.14)
Triphenyl phosphate 8 parts by mass Ethylphthalyl ethyl glycolate 2 parts by mass Methylene chloride 300 parts by mass Ethanol 60 parts by mass Tinuvin 109 (manufactured by Ciba Specialty Chemicals) 0.5 part by mass Tinuvin 171 (Ciba Specialty Chemicals) 0.5 parts by mass Aerosil 972V (manufactured by Nippon Aerosil Co., Ltd.) 0.2 parts by mass (dope composition 3)
Cellulose acetate propionate 100 parts by mass (Mn = 70000, Mw = 220,000, Mw / Mn = 3.14)
Triphenyl phosphate 8 parts by weight Ethylphthalyl ethyl glycolate 2 parts by weight Methylene chloride 260 parts by weight Ethanol 52 parts by weight Tinuvin 109 (manufactured by Ciba Specialty Chemicals) 0.5 part by weight Tinuvin 171 (Ciba Specialty Chemicals) 0.5 parts by mass Aerosil 972V (manufactured by Nippon Aerosil Co., Ltd.) 0.2 parts by mass <Preparation of dope>
Each of the dope compositions 1 to 3 was put into a pressure vessel, heated, stirred, and completely dissolved and filtered. The pressure vessel is provided with a jacket-type hot water circulation device, and is heated and cooled with 95 ° C. hot water and 15 ° C. cold water. Stirring is performed with a dissolver rotating at high speed and an anchor rotating at low speed. In the state heated up to the dissolution temperature of Table 1, it melt | dissolved by circulating with the disperser of Table 1, respectively. In the comparative example, a disperser is not used. Filtration was carried out after a filter press filtration, and was uniformly cast on a stainless steel band support at a temperature of 35 ° C. and a width of 1800 mm using a belt casting apparatus through a sintered metal filter (captured particle size = 10 microns). With the stainless steel band support, the solvent was evaporated until the amount of residual solvent reached 100%, and then peeled off from the stainless steel band support. The peeled film was stretched with a tenter on the way and dried until the residual solvent amount was 0.1% to obtain a cellulose ester film. The stretch ratio in the tenter was 5% for the dope 1 composition and 25% for the dope compositions 2 and 3.
<Evaluation methods>
1. Number of bright spot foreign matters of 10 μm or more (pieces / cm ² )
A sample is placed between two polarizing plates arranged in an orthogonal state (crossed Nicols), light is applied from the outside of one polarizing plate with a transmission microscope, and the outside of the other polarizing plate is observed at a magnification of 50 times. Then, the number of foreign matters (bright spot foreign matter) that appeared to shine in an area of 25 cm ² was counted and converted per 1 cm ² . The above observation was measured at 10 points per sample, and the average value was obtained.
2. Number of foreign objects (pieces / 100m)
The film being transported was photographed with a plurality of CCD cameras, and deformations having a diameter of 100 μm or more were counted as foreign matters based on the images.
3. Ro (nm), Rt (nm)
For Ro and Rt, the values calculated from the following formulas were measured uniformly at 10 points in the width direction of the film, and used as the average values.

Ro = (Nx−Ny) × d
Rt = ((Nx + Ny) / 2−Nz) × d
However,
Nx: refractive index in the slow axis direction,
Ny: refractive index in the fast axis direction,
Nz: refractive index in the thickness direction,
d: film thickness (nm),
It is.

  Nx, Ny, and Nz were measured using an automatic birefringence meter KOBRA-21ADH (manufactured by Oji Scientific Instruments) at a wavelength of 590 nm under an atmosphere of 23 ° C. and 55% RH.

  The evaluation results are shown in Table 1.

  As is clear from the results of Table 1 above, in Examples 1 to 14 of the present invention, both the number of bright spot foreign materials having a size of 10 μm or more and the number of foreign materials are very small, and from the start of dissolution to the start of liquid feed by the liquid feed pump. It can be seen that the time (minutes) is short. Moreover, when Examples 11-14 and Comparative Examples 2 and 3 are compared, it can be seen that the expression of retardation of the film according to this Example is improved.

  As described above, according to the present invention, it is possible to meet the demands for improving the film productivity and improving the quality.

It is a flow sheet which shows the manufacturing method of the cellulose resin film of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Main dope charging tank 2 Dope liquid feeding pump 20 Heat exchanger 3 Dope stationary pot 4 Main filter 5 Dope filter 6 Discharge valve 11 Casting die 101 Stainless steel band support 102 Peeling roll 103 Film 104 Tenter / drying device 105 Roll conveying / drying device 106 Film winding device

Claims (8)

Dissolving the resin in the solvent by heating and stirring in a pressure vessel;
A step of feeding the dope dissolved in the step of dissolving from the pressure vessel with a liquid feed pump;
Cooling the dope at the outlet of the heat exchanger by a heat exchanger disposed adjacent to the outlet side of the liquid pump;
In a method for producing a dope including:
The temperature of the dope in the pressure vessel at the start of liquid feeding from the liquid feeding pump is a temperature that is 10 ° C to 30 ° C higher than the boiling point of the solvent,
The method for producing a dope, wherein the temperature of the dope at the outlet of the heat exchanger is cooled to a temperature lower by 5 ° C. or more than the boiling point of the solvent. 2. The method for producing a dope according to claim 1, wherein the maximum temperature of the dope in the dissolving step is 30 ° C. to 50 ° C. higher than the boiling point of the solvent. The dope manufacturing method according to claim 1, wherein the heat exchanger is a scraping-type heat exchanger. The dope manufacturing method according to claim 1, wherein the heat exchanger is a static mixed heat exchanger. The dope manufacturing method according to claim 1 or 2, wherein the heat exchanger is a trace type heat exchanger in which a cold water pipe is wound around a dope pipe. The capacity of the pipe from the outlet of the pressure vessel to the inlet of the heat exchanger is 5 to 50% of the capacity of the dope dissolved in the pressure vessel, and the pipe is in the pressure vessel at the start of liquid feeding. The method for producing a dope according to any one of claims 1 to 5, wherein the temperature is kept within ± 5 ° C of the temperature of the dope. An apparatus for producing a dope using the method for producing a dope according to any one of claims 1 to 6. A cellulose resin film formed by a solution casting film forming method using the dope prepared by the method for producing a dope according to any one of claims 1 to 6.

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