JP2005179689A - Method for preparing dope - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prepare a dope by dissolving a polymer into a solvent quickly and completely. <P>SOLUTION: The solvent is delivered from a solvent tank 11 to a solution tank 12. The polymer in an amount of 15-20 wt.% relative to the solvent is sent to the solution tank 12 by a meter 14. A plasticizer in an amount of 5-15 wt.% relative to the polymer is sent to the solution tank 12 from a plasticizer tank 15. The mixture is stirred in the solution tank 12 at 80 rpm for 30 minutes by the stirring blade 18 to obtain a crude solution 19. The crude solution 19 is heated at 85°C by a heater 26 for 10 minutes to dissolve all of the components required for the dope, so that only impurities are filtered out at a filter 28. The filtrate is sent to a dope tank 37 to be used as a dope 38 for the solution film-forming. The film formed from the dope 38 has a retardation of 40 nm, small optical anisotropy and good optical properties. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a dope preparation method for obtaining a dope by dissolving a polymer in a solvent.

  A film formed from cellulose acylate, particularly cellulose triacetate having an average degree of acetylation of 57.5% to 62.5% (hereinafter referred to as TAC film) is a photographic light-sensitive material because of its toughness and flame retardancy. Is used as a support for In addition, since the TAC film is excellent in optical isotropy, the TAC film is suitable for use as a protective film for a polarizing plate of a liquid crystal display device and a color filter whose market is expanding in recent years.

The TAC film is generally produced by a solution casting method. The solution casting method can produce a film having excellent optical properties and physical properties as compared with other production methods such as a melt casting method. In the solution casting method, after a polymer is dissolved in a solvent (mainly an organic solvent) to prepare a dope, the dope is cast on a support such as a band or a drum to form a film (for example, non- (See Patent Document 1).
Japan Society for Invention and Innovation Public Technical Bulletin No. 2001-1745

  However, some cellulose esters (particularly TAC) used for film production by the solution casting method use natural materials as raw materials. Some of them contain a small amount of components that are insoluble or difficult to dissolve in the main organic solvent. In addition, there are impurities contained in the cellulose ester and other raw materials and foreign matters mixed in the raw material transporting step and the dissolving step. These foreign substances are removed by a filter in the liquid feeding process. In order to keep the composition of the polymer solution constant, it is necessary that the polymer is completely dissolved in the organic solvent upstream of the filter for the purpose of removing foreign substances. Usually, these reactions are carried out in a dissolution tank in which raw materials are charged and dissolved and mixed. However, in this dissolution tank, a very large shear force is applied to completely dissolve the polymer in an organic solvent. A large stirrer was required and the time required for the reaction was long.

  The present invention provides a dope preparation method in which a polymer can be rapidly and completely dissolved in a solvent to prepare a dope.

  As a result of diligent research, the present inventors have found that in a dissolution tank into which raw materials (polymer solids, organic solvent) are charged, a crude solution containing gel-like polymer (polymer) undissolved material for shortening the dissolution time. It was found that the dope can be efficiently prepared and the preparation time can be shortened by preparing the dope by promoting the dissolution in the liquid feeding process and completely dissolving it before the filtration filter. Thereby, the speed of the process in dope preparation can be aimed at.

  The dope preparation method of the present invention is a method of preparing a dope by dissolving a polymer in a solvent. The first step of roughly dissolving the polymer in the solvent and the solution roughly dissolved in the first step are fed. A second step of preparing the dope by promoting dissolution, and sending the liquid to at least one of a multi-tube heat exchanger and a static mixing stirrer in the second step. The roughly dissolved liquid means a solution in which a part of the polymer remains undissolved in the solvent.

  It is preferable that the multi-tubular heat exchanger or the static mixing stirrer is made of at least one of stainless steel, titanium, or hastelloy. In the case where the multi-tube heat exchanger is used in the second step, the multi-tube heat exchanger is composed of two flow paths by winding two plates in a spiral shape from the center. A spiral heat exchanger is preferred. Preferably, after the second step, a third step of cooling the dope to a boiling point or less of the main solvent of the dope is included.

  According to the dope preparation method of the present invention, in a method for preparing a dope by dissolving a polymer in a solvent, a first step of roughly dissolving the polymer in a solvent and a solution roughly dissolved in the first step are fed. A second step of preparing the dope by promoting dissolution while feeding the liquid to at least one of a multi-tubular heat exchanger and a static mixing stirrer in the second step, In one step, the dope can be obtained by ending the step in a time sufficient to prepare a crude solution in which the polymer is roughly dissolved, and then promoting dissolution in the second step. In addition, the liquid can be efficiently dissolved in the second step.

[polymer]
Although the polymer used for this invention is not specifically limited, It is preferable to use a cellulose ester. Among the cellulose esters, it is preferable to use cellulose acylate, and it is particularly preferable to use cellulose acetate. Further, among the cellulose acetates, it is most preferable to use cellulose triacetate having an average degree of acetylation of 57.5% to 62.5%. The degree of acetylation means the amount of bound acetic acid per unit weight of cellulose. The degree of acetylation follows the measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like). In the present invention, cellulose acylate particles are used, and 90% by weight or more of the particles used have a particle diameter of 0.1 to 4 mm, preferably 1 to 4 mm. Also, preferably 95% by weight or more, more preferably 97% by weight or more, further preferably 98% by weight or more, and most preferably 99% by weight or more of particles have a particle size of 0.1 to 4 mm. Furthermore, it is preferable that 50% by weight or more of the particles used have a particle diameter of 2 to 3 mm. More preferably 70% by weight or more, still more preferably 80% by weight or more, and most preferably 90% by weight or more of the particles have a particle size of 2 to 3 mm. The particle shape of the cellulose acylate is preferably as close to a sphere as possible.

[solvent]
Examples of the solvent used in the present invention include halogenated hydrocarbons, esters, ketones, and ethers, but are not particularly limited. The solvent is not particularly limited as long as it is commercially available. The solvent may be used alone (100% by weight), or may be a mixture of alcohols having 1 to 6 carbon atoms, ketones, esters and ethers. Examples of solvents that can be used include halogenated hydrocarbons (eg, methylene chloride, etc.), esters (eg, methyl acetate, methyl formate, ethyl acetate, amyl acetate, butyl acetate, etc.), ketones (eg, acetone, Methyl ethyl ketone, cyclohexanone, etc.), ethers (eg, dioxane, dioxolane, tetrahydrofuran, diethyl ether, methyl-t-butyl ether, etc.). In particular, it is preferable to use a halogenated hydrocarbon as a main component as a solvent used in the present invention because the above-mentioned polymer is easily dissolved. Specifically, it is preferable that 70 to 95% by weight in the solvent for preparing the dope is a halogenated hydrocarbon.

[Additive]
Examples of the additive used in the present invention include a plasticizer and an ultraviolet absorber. Examples of the plasticizer include phosphate esters (for example, triphenyl phosphate (hereinafter referred to as TPP), tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate (hereinafter referred to as BDP), trioctyl. Phosphate, tributyl phosphate, etc.), phthalate esters (eg, diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, etc.), glycolate esters (eg, triacetin, tributyrin, butyl phthalyl butyl glycolate, ethyl phthalyl) Ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, etc.) and other plasticizers can be used.

  An ultraviolet absorber may be added to the dope. For example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and other ultraviolet absorbers can be used. Particularly preferred ultraviolet absorbers are benzotriazole compounds and benzophenone compounds.

  Furthermore, various additives such as a mold release agent, a release accelerator, and a fluorosurfactant may be added to the dope at any stage after preparation of the dope before preparation.

[Dope Preparation Method]
FIG. 1 shows a dope preparation line 10 used in the dope preparation method according to the present invention. In the dope preparation method, a necessary amount of solvent is first sent from the solvent tank 11 to the dissolution tank 12. The solvent tank 11 is filled with the above-described solvent (even when a mixed solvent is used, in the following description, it may be simply referred to as a solvent). This solvent is fed while adjusting the liquid feeding amount by a solvent tank opening / closing valve 13 attached between the solvent tank 11 and the dissolution tank 12.

  Next, the polymer charged in the meter 14 is fed into the dissolution tank 12 while being metered. The polymer is preferably charged in an amount of 15.0 to 25.0% by weight with respect to the above-mentioned solvent, and a film having a good film quality obtained by forming a dope thus prepared can be obtained. However, the amount of polymer charged into the solvent in the present invention is not limited to the above range. In addition, although it is preferable to use TAC for a polymer, it is not limited to this.

  Further, the plasticizer is sent from the plasticizer tank 15 to the dissolution tank 12. A plasticizer tank opening / closing valve 16 is attached between the plasticizer tank 15 and the dissolution tank 12, and a necessary amount of plasticizer is fed into the dissolution tank 12. In addition, although it is preferable that a triphenyl phosphate is used for a plasticizer, it is not limited to this. In FIG. 1, the plasticizer is fed into the dissolution tank 12 as a solution in which the plasticizer is dissolved in a solvent, but the present invention is not limited to this method. When the plasticizer is liquid at normal temperature, it can be fed into the dissolution tank 12 in the liquid state. Further, when the plasticizer is solid, it can be fed into the dissolution tank 12 using a measuring instrument. In the present invention, when the amount of the plasticizer fed into the dissolution tank 12 is 5.0 to 15.0% by weight with respect to the polymer, the plasticity of the film formed from the prepared dope is a product. The one with the most favorable flexibility is obtained. However, the amount of plasticizer fed into the dissolution tank in the present invention is not limited to the above-described range.

  In the above description, the order of charging into the dissolution tank 12 is the order of solvent, polymer, and plasticizer, but the present invention is not necessarily limited to this order. For example, after a polymer is weighed and sent to the dissolution tank 12, a preferred amount of solvent can be sent. Further, the plasticizer is not necessarily sent to the dissolution tank 12 in advance, and can be mixed in a later step with a mixture of a polymer and a solvent (hereinafter, the mixture may also be referred to as a dope). It is also possible to feed the aforementioned additives other than the plasticizer into the dissolution tank 12.

  The dissolution tank 12 is provided with a stirring blade 18 that is rotated by a motor 17. By rotating the stirring blade 18, the solvent, polymer, and plasticizer and other additives that have been fed into the dissolution tank 12 are agitated, so that a solute such as a polymer is added to the solvent. Dissolve roughly. The rough dissolution means a state where the solute is not completely dissolved in the solvent. In the following description, this roughly dissolved solution is referred to as a crude solution 19. In the present invention, in order to prepare the crude solution 19, the time for stirring with the stirring blade 18 in the dissolution tank 12 is preferably 30 to 90 minutes, but is not limited to this range. If it is less than 20 minutes, the amount of solutes such as polymers dissolved is too small to be completely dissolved even by dissolution by heating described later, and the dope may not be prepared. In addition, if the dope is prepared with the dissolution tank 12 for more than 120 minutes, the object of the present invention to obtain a good quality dope in a shorter time cannot be obtained.

  From the viewpoint of cost, it is preferable to carry out the continuous batch process in which the crude dissolving liquid 19 is once sent to the storage tank 20, the inside of the dissolving tank 12 is emptied, and the process of forming the crude dissolving liquid 19 is repeated. The storage tank 20 is also provided with an agitating blade 22 that is rotated by a motor 21, and agitation is performed on the fed coarse solution 19 to make it uniform. The crude solution 19 in the storage tank 20 passes through the coarse filter 23 to remove impurities such as dust that are not necessary for the dope preparation. However, the coarse filter 23 is not necessarily attached. The crude solution 19 in the storage tank 20 is sent to the heater 26 through the pipe 25 by the pump 24. In addition, this process is not limited to what was illustrated.

  When the crude solution 19 is sent from the pump 24 to the heater 26, the pipe 25 is preferably kept warm or heated. Since the dissolution of the solute such as the polymer not dissolved in the solvent in the crude solution 19 is progressed by heating the crude solution 19 when it is fed through the pipe 25, the dope is added in a short time. Can be prepared.

  Next, the dope can be prepared by dissolving the solute such as a polymer necessary for film formation by heating the crude solution 19 with the heater 26. The heating time is preferably 5 to 30 minutes and the heating temperature is preferably 60 to 120 ° C., but is not limited to these ranges. If it is less than 5 minutes, the dope may not be completely prepared, and even if it is heated for more than 30 minutes, the necessary solute components are completely dissolved in the solvent, which is a waste of time. At the same time, the prepared dope may be altered. Further, if the heating temperature is less than 50 ° C., the dope may not be completely prepared, and if it exceeds 120 ° C., necessary solute components may be modified.

  The heater 26 includes a multi-tube heat exchanger (shell & tube method) and a static mixing stirrer (also referred to as a static mixer) having a heating means provided with a tube of two or more tubes in order to efficiently prepare the dope. It is preferable to use an in-line mixer such as) in order to shorten the dope preparation time. In particular, it is more preferable to use a spiral heat exchanger from the viewpoint of heat exchange efficiency. The spiral heat exchanger is composed of two flow paths by winding two plates in a spiral shape from the center. This structure is a device that is extremely excellent in heat exchange efficiency because the heat transfer area can be increased with respect to the cross-sectional area of the flow path of the process liquid. Moreover, it is preferable to use a material having high corrosion resistance as the material of the heater 26, and more specifically, it is more preferable to use a material formed from stainless steel, titanium, Hastelloy (trade name) or the like. Thereby, it is possible to increase the speed for mass production of the dope without changing the capacity of the dissolution tank 12.

  It is preferable to send the dope prepared by the heater 26 to the cooler 27 and cool it below the boiling point of the main solvent constituting the dope in order to prepare a dope for forming a film of good quality. . In general, methylene chloride (methylene chloride) is used as the main solvent constituting the dope. In this case, it is preferable to cool the dope to a range of 30 to 38 ° C. However, in the present invention, it is not always necessary to cool the prepared dope by the cooler 27.

  In the present invention, the method for preparing the dope from the crude solution 19 is not necessarily performed by the heater 26 described above. For example, it is possible in some cases to prepare the dope simply by heating the pipe 25 and feeding the crude solution 19. Alternatively, in some cases, it is possible to prepare the dope by rapidly rotating the stirring blade 22 in the storage tank 20. The method for preparing the dope from the crude solution 19 as described above is not necessarily limited to the heating method using the heater 26 described above.

  In the dope preparation method described above, when the polymer contained in the prepared dope is 100% by weight, the above-mentioned crude solution 19 contains a polymer in the range of 50 to 90% by weight in advance. Dissolving is a preferable method for obtaining a good quality dope in a short time. However, the present invention is not limited to this numerical range.

  Impurities unnecessary for film formation are removed from the dope prepared by the above-described method by passing through the filtration filter 28. That is, the components necessary for film formation must be completely dissolved in the dope immediately before passing through the filter 28 for filtering out impurities. At this time, if an insoluble solute component is present in the dope, it is removed by the filtration filter 28, and the component ratio of the solvent sent to the dissolution tank 12 and the solute such as polymer is different. This is because a dope having a composition ratio of Although FIG. 1 illustrates an example in which four filtration filters 28 are attached in parallel, the present invention is not limited to this embodiment. Then, the dope from which impurities have been removed by passing through the filter 28 is sent to the dope tank 37 by the pump 29 and becomes a uniform dope 38.

  Further, the waste liquid after washing the filter 28 is sent to the solvent tank 41 after filter washing through a pipe (not shown). The waste liquid is processed by a solution processing apparatus (not shown) and then sent to the recycle solution tank 43 by the pump 42. This recycled solvent is sent to the dissolution tank 12 for use as a dope preparation solvent. The recycled solution preferably contains 0.1 to 25.0% by weight of polymer with respect to the solvent because a uniform dope is prepared. The recycled solution preferably contains 0.1 to 20.0% by weight of a plasticizer with respect to the polymer in the solution.

  Although not shown in the figure, it is a more preferable operation method for continuous operation on the dope preparation line 10 to flow a dope prepared in advance to a newly used filter before switching the filtration filter 28.

[Solution casting method]
As shown in FIG. 2, the film forming apparatus 50 is divided into a band zone 51 and a drying zone 52. The dope tank 37 in which the dope 38 is charged is connected to the film forming apparatus 50 through a pump 53 and a filter 54. The dope tank 37 is provided with a stirring blade 56 that is rotated by a motor 55 so that the dope 38 is always uniform. Furthermore, a commercially available solvent can be used as a solvent for preparing the dope 38, but a solvent recovered from the film forming apparatus 50 can be mixed and used.

  The band zone 51 is provided with a casting band 59 that is stretched around the support drums 57 and 58, and the casting band 59 is rotated by a driving device (not shown). A casting die 60 is provided on the casting band 59. The dope 38 is fed from the dope tank 37 by the pump 53, and after impurities are removed by the filter 54, the dope 38 is sent to the casting die 60. The casting die 60 casts the dope 38 onto the casting band 59. The dope 38 is gradually dried until it has self-supporting properties while being conveyed by the casting band 59, and is peeled off from the casting band 59 by the peeling roller 61 to form a film 62.

  The film 62 is dried while being conveyed by the tenter 63. At this time, it is preferable that at least one axis is stretched to a predetermined width. In FIG. 2, the dope 38 is cast on the casting band 59 which is an endless support. However, the present invention is not limited to the illustrated form, and is also applied to a solution casting method for casting on a rotating drum. it can.

  The film 62 sent from the tenter 63 to the drying zone 52 is wound around a plurality of rollers 64 and dried in the drying zone 52. The dried film 62 is taken up by a winder 65. The temperature in the drying zone 52 is preferably controlled in the range of 50 to 150 ° C. for uniform drying of the film 62.

  In FIG. 2, a solution film forming method using a single-layer casting die 60 is shown. However, the present invention is also applicable to other solution casting methods. For example, a solution casting method by co-casting with a casting die 70 having a multi-manifold as shown in FIG. 3 can also be applied. The casting die 70 is a multi-manifold provided with a plurality of (three in FIG. 3) manifolds. The manifolds 71, 72, and 73 are doped with the dope for the back layer, the dope for the intermediate layer, and the dope for the surface layer prepared by the above-described dope preparation method, and the respective dopes are merged inside the casting die 70. Then, the casting ribbon 74 is cast on the casting band 75 to form a film. In the present invention, the number of dope layers to be laminated when co-casting is not limited to the three layers shown.

  FIG. 4 shows a part of an outline of an example in which the present invention is applied to a solution casting method for sequential casting (sequential casting). In this method, a casting band 82 is provided around support drums 80 and 81 provided in the band zone, and the casting band 82 is rotated by a driving device (not shown). On the casting band 82, two casting dies 83, 84 are arranged. From each of the casting dies 83 and 84, the dope for the back surface layer and the dope for the surface layer respectively prepared by the above-described dope preparation method are cast to form a film. In the present invention, the film formation by sequential casting is not limited to the embodiment using the two casting dies shown in the drawing, and three or more casting dies may be arranged on the casting band 82. .

  It is preferable that the Rth (retardation) of the film formed by any one of the solution casting methods described above is in the range of 1 to 200 nm in order to use the film in a product described later.

  The film formed by the solution casting method described above can be used as a polarizing plate protective film. A polarizing plate can be formed by pasting this polarizing plate protective film on both surfaces of a polarizing film made of polyvinyl alcohol or the like. Furthermore, it can also be used as an optical functional film such as an optical compensation film having an optical compensation sheet affixed on a film, or an antireflection film having an antiglare layer laminated on the film. It is also possible to constitute a part of the liquid crystal display device from these products.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to this.

  The dope was prepared using the dope preparation line shown in FIG. As a solvent for preparing the dope, a mixed solvent in which methylene chloride, which is a halogenated hydrocarbon, and an alcohol mixture (mixing ratio of methanol: n-butanol = 34: 1) are mixed at 83 wt%: 17 wt% is used. The solution was sent to the dissolution tank 12. With respect to this mixed solvent, 20% by weight of cellulose triacetate (acetylation degree 60%) as a polymer was fed into the dissolution tank 12 by the measuring instrument 14. Further, a mixture of TPP and BDP (weight mixing ratio; TPP: BDP = 2: 1), which is 11.0% by weight of plasticizer with respect to cellulose triacetate, was fed into the dissolution tank 12. These mixtures were stirred by a motor 17 with an output of 45 kW for 30 minutes at a speed of 80 rpm to produce a crude solution 19 and stored in a storage tank 20, then sent to a heater 26 and supplied at 85 ° C. The temperature was raised to in-line and held for 10 minutes. When the obtained solution was visually confirmed, the insoluble matter of the polymer was not confirmed. This solution was passed through a filter 28 to remove impurities contained in the raw material, and a dope 38 was obtained.

  Next, a film 62 was formed from the dope 38 obtained by the above-described method using the film forming apparatus 50 shown in FIG. For film formation, the dope 38 was cast from a casting die 60 onto a casting band 59 at 50 ° C. The casting was performed so that the thickness of the dried film 62 was 80 μm. After drying on the casting band 59 until it had self-supporting property, the film 62 was peeled off by the peeling roller 61 and dried while being transported by the tenter 63 for 10 minutes. Further, the film 62 was dried at 130 ° C. for 30 minutes in the drying zone 52 and wound up by the winder 65. The retardation (Rth) of the obtained film 62 was 40 nm when measured at a wavelength of 632.8 nm using an ellipsometer (an ellipsometer), and a film having excellent optical anisotropy was obtained. I found out.

[Comparative example]
A mixture having the same composition as in the example was dissolved in the dissolution tank 12 shown in FIG. When the stirring blade 18 was rotated at 80 rpm by the motor 17 having an output of 45 kW to stir the mixture, it took 5 hours for the polymer to completely dissolve.

  As described above, when the dope was prepared by the dope preparation method according to the present invention, the preparation time was less than 1 hour. However, when a dope is prepared only by conventional stirring, a time of 5 hours is required.

It is the schematic of the apparatus used in order to implement the dope preparation method concerning this invention. It is the schematic of the apparatus used in order to implement the solution casting method which concerns on this invention. It is a principal part schematic diagram of the other apparatus used in order to implement the solution casting method concerning this invention. It is a principal part schematic diagram of the other apparatus used in order to implement the solution casting method concerning this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Dope preparation line 12 Dissolution tank 17 Motor 18 Stirring blade 19 Coarse solution 25 Pipe 26 Heater 28 Filtration filter 37 Dope tank 38 Dope

Claims (4)

In a method for preparing a dope by dissolving a polymer in a solvent,
A first step of roughly dissolving the polymer in a solvent;
Including the second step of preparing the dope by promoting dissolution while feeding the liquid that was roughly dissolved in the first step,
In the second step, the liquid is fed to at least one of a multi-tube heat exchanger and a static mixing stirrer.   The dope preparation method according to claim 1, wherein the multi-tubular heat exchanger or the static mixing stirrer is formed of at least one of stainless steel, titanium, and hastelloy. In the case of using the multi-tubular heat exchanger in the second step,
3. The multi-tubular heat exchanger is a spiral heat exchanger configured by winding two plates in a spiral shape from a central portion and comprising two flow paths. Dope preparation method. The dope preparation method according to any one of claims 1 to 3, further comprising a third step of cooling the dope to a boiling point or less of a main solvent of the dope after the second step.

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