TWI344019B - Cellulose acylate solution for film products - Google Patents

Description

1344019 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a cellulose halide solution for film production, and more particularly to a cellulose halide solution for film production for a polarizing filter and a liquid crystal display. [Prior Art] Cellulose halide film is used for photographic film, animated film, etc., and has properties such as transparency, proper water penetration and high mechanical strength, and dimensional resistance, regardless of humidity and temperature. And widely used in the field of optics. Recently, as the demand for liquid crystal displays has become large, performance has progressed and liquid crystal displays have become larger. The demand for polarizing filter protective films for liquid crystal displays has apparently increased. Recently, liquid crystal displays require more detailed display of images. Therefore, it is more necessary to increase the smoothness of the cellulose halide film for liquid crystal displays and to reduce foreign materials. ‘ Cellulose telluride films are often produced by solution casting, which produces films with extremely high smoothness. However, the high smoothness causes the different surface portions of the film to adhere when the manufactured film is wound around the reel. When the film is used, it is unwound to peel off the surface portion to which it adheres, thereby exerting an unnecessary force on the surface of the film. Therefore, the film is deformed or deformed by the surface and is deformed, so that the function of the polarizing filter protective film is greatly reduced. In order to prevent adhesion, the surface of the film needs to have an appropriate thickness, so that particles called a matting agent are contained in the film. If the matting agent is properly content, it will prevent damage to the film, such as deformation. 1344019 Matting agents are available in several metal oxides, metal salts, organic materials, polymers, etc., and they always contain agglomerated clusters (coarse particles). When the mixed particles and the cluster become a material other than the film, the material is additionally damaged by the film. Further, when filtration is performed to remove clusters from a polymer solution (hereinafter referred to as a dope), the clusters are immediately absorbed by the pores, and thus it is not possible to stably carry out series production. Therefore, it is difficult to use a matting agent for a coating liquid without any method of dispersing the particles by any means. Each of the microparticles has some warp groups on its surface and thus has hydrophilic properties. This fine particles are easily aggregated in a coating liquid using a hydrophobic solvent, and a representative example thereof is SiO 2 particles. In order to reduce agglomeration, Japanese Patent Laid-Open Publication No. 7_11〇55 (page 2_4, Fig. 2) suggests that each particle surface may have a methyl group to provide hydrophobic properties to the particles. In this case, surface methylation is performed. In addition, it is proposed that the surface of each particle may have an alkyl group, and the number of carbon atoms of each alkyl group on the surface may be at least 2 and at most 20 to provide hydrophobic properties to the particles. In this case, surface alkylation is carried out. Incidentally, in the solution casting method, the coating liquid of the cellulose halide solution is prepared from cellulose halide and several additives. The coating liquid is cast on the substrate using a mold. When the coating liquid on the substrate forms a polymer film, the polymer film is peeled off from the substrate and dried in a drying process. As for the substrate, a continuously rotatable cylinder or a movable belt can be used. Coatings prepared by dissolving cellulose halides and additives in a solvent typically contain a number of insoluble materials, such as impurities and gel-like materials. When the film is produced by casting the coating liquid, the insoluble foreign material remains in the film to damage the surface condition of the film. Therefore, the quality of the product film is low, 1 1344019 and the film cannot be used. Therefore, at least one filtration is performed before casting. In the filtration, several filters are used depending on the characteristics of the coating liquid and the desired properties. As for the filter material, there is a filter cloth 'filter paper, metal mesh, metal fiber, non-woven fabric, and the like. Further, in the case where the coating liquid of the cellulose halide solution is used for the production of a film, the basis of the low content of the insoluble foreign material is extremely strict. Therefore, a plurality of filtering devices are connected in series so that the coating liquid can be filtered several times to improve the properties of the coating liquid. The filter for filtration has a filter orifice which is a very narrow coating liquid passage. When the coating liquid flows through the filter holes to perform filtration, the material having a larger diameter than the filter holes is removed from the coating liquid. In addition, in some filters, the diameter of the filter holes is not uniform, and the filter channels are complicated to bend and branch. Thus, particles having a diameter smaller than the filter holes are also captured or captured in the branched or curved portion. The filtered solution is thus cleaned by filtration to remove foreign materials. However, in the surface hydrophobizing of the SiO 2 particles, it is difficult to prevent the continuous presence or generation of the aggregate, and the produced film is not suitable for use in a liquid crystal display which displays extremely fine images. In addition, the particles are transported through the filter along the flow path of the coating liquid. On the upstream side of the filter, the flow path is thickened at the filter, so that the distance between the particles becomes smaller and aggregates are generated more. This phenomenon cannot be prevented by hydrophobization as described above because the surface of the fine particles cannot be completely hydrophobized, or the inside of the particles apparently forms an interface with the solvent when the particles are dispersed. As described above, in the continuous filtration, a part of the agglomerated clusters are trapped by the filter material, and the ratio of the absorption filter becomes high and the filtration pressure becomes large. As the filtration pressure becomes higher, some of the capture particles are extruded from the filter and 1344019 is mixed in the filtered solution flowing downstream of the filter. Thus, the particles extruded from the filter are contained in the produced film, and the quality of the product becomes low. : / [Summary of the Invention] OBJECT OF THE INVENTION An object of the present invention is to provide a cellulose oxime solution for film production in which a foreign material mixture is prevented from being caused by an increase in filtration pressure. To provide a cellulose halide solution for film production in which agglomeration of solid materials is prevented. In order to achieve this and other objects, the cellulosic halide solution of the present invention contains particles which are positively charged on the surface. Further, the particles are preferably an antimony compound including ceria. Particularly preferably, the cellulose halide solution is obtained by the step of initially adding charged particles and then filtering by retaining the particles. Further, the cellulose halide solution is cast to form a cellulose halide film. The cellulose halide solution according to the present invention prevents the filtration pressure applied to the filtered cellulose halide solution from increasing in the procedure for producing the cellulose halide Φ film to mix the impurities with the filtered solution. Thus the cellulosic halide solution of the present invention effectively reduces the solid material agglomeration through the filter. [Embodiment] In Fig. 1, a film manufacturing apparatus 11 is fed from a raw material tank 12, a pump 13 'filtering device 14 , a storage tank 17 , a solution casting device 18 , and a solution which is serially connected thereto. Path composition. Further, the solution casting device 18 is substantially 1344019 from a mold 2 1 , a belt 2 2 ' as a substrate, a plurality of rollers 23 for transporting the cellulose vapor film 3 1 b, a drying device 26, and a winding device 27 Composition. It should be noted in this particular embodiment that the strip 22 is used as the substrate' which is continuously moved by rotating the support roller 28. However, a cylinder is also used as the substrate in the present invention. Further, the present invention is not limited to the above film manufacturing apparatus. The raw material tank 12 contains a cellulose halide solution 31a (or coating liquid) prepared from cellulose halide 30a, solvent 30b and particles 30c. The pump 13 is driven to feed the cellulose halide solution 3 1 a from the raw material tank 12 to the storage tank 17 via the filtration device 14 for storage. The cellulose halide solution 3 1 is then fed from the storage tank 17 and cast on the belt 22 by a casting die 2 1 . The cellulose halide solution 31 on the belt 22 then has a self-supporting property to form a cellulose vapor film 3 1 b ' which is stripped from the belt 2 2 . The stripped cellulose vapor film 3 1 b is transported to the drying unit 26 by a roller 2 3 . In the drying device 26, the cellulose halide film 31b is sufficiently dried by the transport of the roller 23. The cellulose vaporized film 31b is then wound by a winding device 27. In the drying device 26, a tenter device (not shown) is sometimes provided to adjust the width of the cellulose vapor film 31b or to stretch the cellulose vapor film 31b with drying. It should be noted that the cellulose halide solution 3 1 a of the present invention includes the dispersion in which the insoluble material is dispersed and the main content of the solid material before dissolution is cellulose halide. In the cellulose halide solution 3 1 a, cellulose halide, a plurality of additives, and the like are dissolved or dispersed in a solvent. This additive contains a matting material and uses particles as a matting material. It should be noted that matting agents are often referred to as anti-blocking agents or anti-fracturing agents. Preferably, the surface of the particles of the cellulose halide solution 3 1 a is positively charged 1344019. There are many known methods for positively charging a surface. For example, there is a method of bonding a cationic monomer to a molecule on the surface of a particle. Further, in the case where the surface band / i is positively charged, there are cationic functional groups on the surface of the particles, for example, an amine group, an ammonium group, a scaly group, a pyridyl group and the like. Thus in the present invention the surface is positively charged. When the cellulose halide solution 3 1 a is prepared or flows through the filtration device, the "particle agglomeration is prevented, and the properties and characteristics of the cellulose halide solution 3 1 a and the cellulose halide film 3 1 are improved. The positively charged particles on the surface are organic and inorganic compounds. Preferred inorganic compounds of the particles are cerium-containing compounds (cerium oxide, etc.), titanium dioxide, zinc oxide φ, aluminum oxide, cerium oxide, chromium oxide, cerium oxide, cerium oxide, tin oxide, antimony tin oxide, calcium carbonate, talc, Calcined kaolin 'calcined calcium citrate, calcium citrate hydrate 'aluminum citrate, magnesium citrate, calcium phosphate, and the like. Particularly preferred are chromium oxide and inorganic compounds containing ruthenium. Particularly preferred is an anthracene derivative such as ruthenium dioxide or the like because the turbidity of the cellulose ruthenium film is lowered. Further, preferred organic compounds of the positively charged particles are polymers such as 'polyoxyxylene resins, fluorocarbon resins, acrylate resins and the like. It is particularly preferred to be a polyoxyl resin and is particularly preferably a polyoxyl resin having a three-dimensional network structure. • The method of adding particles to the cellulose halide solution in the present invention is not limited. For example, the particles are added after mixing the cellulose halide with the solvent or after preparing a mixture of the cellulose brewing compound and the solvent. In addition, the particles can be added just before the flow of the cellulose halide solution. The particles may be added directly or the particles may be first dissolved in a solvent' and it is preferred to use a cellulose halide as a binder. Further, there is a case where the particles are dispersed to prepare a stable dispersion or solution. More specifically, three methods are described below. First, the particles and solvent

I -10- 1344019 The mixture was stirred and then dispersed in a solvent in a dispersing device to prepare a dispersion. The dispersion is then stirred into the cellulose halide. Second, the particles and the solvent are stirred and mixed' and then the particles are dispersed in a solvent in a dispersing device to prepare a dispersion. The cellulose halide is added to the solvent, and the mixture is stirred to dissolve the cellulose halide in the solvent. This dispersion is then added to the cellulose mash solution and stirred to obtain a granulated cellulose mash solution, which is then used to make a mixture of granules and solution in a tank and in-line mixer. Third, a small amount of cellulose halide is stirred into a solvent to prepare a solution, and particles are added thereto. The dispersion of the particles is produced by a dispersing device to obtain a liquid containing particles. This liquid and the cellulose halide solution are thoroughly mixed using a tank and an in-line mixer. In terms of keeping the haze of the film produced low, the average diameter of the particles is preferably from 0.001 to 20 μm, particularly from 0.001 to 10 μm, particularly from 0.001 to 1 μm, and most particularly from 0.005 to 0.5 μm. Initially, the average diameter of the particles was measured by a penetrating electron microscope to obtain an average diameter. The apparent specific gravity of the particles is preferably at least 30 g/liter, particularly 50 g/liter to 200 g/liter, and particularly 50 g/liter to 1 g/l. The particle concentration at the time of dispersing the mixture of the particles and the solvent can be appropriately set. When cerium oxide is used as the particulate material, the concentration is preferably at most 30% by mass, preferably at most 20% by mass, and especially 1% by mass to! 〇 Quality %. The solvent material used for the dispersion is a lower alcohol, preferably methanol, ethanol 'propanol, isopropanol, butanol or the like. Other solvent materials other than the lower alcohols are not particularly limited. However, it is preferred that the solvent material (other than the alcohol) used for the preparation of the dispersion is the same as that used for the production of the film. Dispersion for dispersing particles in a solvent or cellulose halide solution -11 - 1344019 The device is of a medium type and a medium type. The medium type has a ball mill 'sand mill' refiner and the like. There are no medium type, ultrasonic type, centrifugal type, high pressure type, etc. In the high-pressure type dispersion device, a capillary having a diameter of from 1 μm to 2000 μm is used and that the maximum pressure in the dispersion device is preferably at least 9.8 MPa. It is therefore preferred that the maximum speed is at least 1 mil / sec and the heat transfer rate is at least 420 仟 jo / hr. It should be noted that the high pressure type dispersion device has an excess pressure homogenizer (

Micro FluidizerTM manufactured by Microfluidics Corporation or a micronizer (manufactured by Nanomazaa KK). In addition, other types of high pressure types are mantongouline type, for example, including IzumiFoodMachineryCo-

The homogenizer manufactured by Ltd., UHN-01 manufactured by Sanwa Machine Co. Ltd., etc. In order to prepare the cellulose halide solution 31a, the solute is usually dissolved or dispersed at room temperature. However, the coating liquid can be prepared by a cold solution method and a hot solution method. In the cold solution method, cellulose oxime and additives (e.g., granules, etc.) are simultaneously added at a temperature close to room temperature of -10 ° C to 40 ° C, or gradually added by stirring with a stirrer. Alternatively, a solution or dispersion containing the individual ingredients may be prepared, followed by mixing and then cooling the mixture, in which case an ice bath may be used, for example, in a dry ice/methanol bath (-75 ° C) or a diethylene glycol solution. Bath (-30 ° C to -20 ° C). During cooling of the mixture, the mixture is solidified, and then the mixture is heated to a temperature of about 〇 ° C to 20 ° to obtain a coating liquid in which each component flows in a solvent. Note that the mixture can be allowed to stand at room temperature or in a hot water bath to make the temperature higher. In the hot melt method, the polymer and the additive are gradually added to the solvent at the same time as the temperature range of -10 ° C to 4 ° C to the room temperature while stirring with a stirrer. The mixed -12-1344019 compound is heated to a temperature in the range of 70 ° C to 240 ° C under a pressure of 0.2 MPa to 30 MPa. Preferably, the temperature is 8 〇. (: to 2 2 0. The heating solution or dispersion is cooled to a temperature lower than the lowest boiling point of the solvent used, and the temperature at which the solution or dispersion is cooled is usually -10 ° C to 50 t. Preferably, The mixture is cooled by a cooling device in which a cooling medium (cooling water or the like) is used. In the above method, the prepared cellulose halide solution 31a can have a high concentration even if it is not condensed, and the cellulite solution has excellent stability. However, in order to dissolve the cellulose halide more easily, condensation can be carried out using a condensation device. The condensation method is not particularly limited, for example, in a condensation method, a low concentration solution is fed to the cylindrical member and disposed on the cylindrical member. The rotatable vanes can be rotated. The temperature of the cylindrical member is then controlled such that there is a temperature difference between the cylindrical member and the feed solution. Solvent evaporation is thus performed and a high concentration solution can be obtained. In another condensation method, it will be low. The concentration solution is heated and sprayed from the nozzle into the tank so that it evaporates rapidly before the spray solution reaches the tank wall. The solvent vapor is then condensed and then removed from the tank, and The tank obtains a high concentration solution. This method is known to be applicable to the present invention. Further, in the present invention, the filtration of the cellulose halide solution is carried out after its preparation, so that the resulting film can have better properties and optical functions. The filter has a filter cloth 'filter paper, metal mesh, metal fiber, non-woven fabric, etc. In addition, when the basis of the content of the insoluble foreign material in the cellulose halide solution is extremely strict, the filtration device is connected in series to perform multiple filtration to improve Solution properties. In the present invention, it is preferred that the 'filter system is carried out in the case where the solution contains particles. Part of the particles are the main objects to be removed by filtration. Therefore, when the particles are added to the particles-13-1344019, the filtration effect becomes low. In the present invention, the absolute filtration accuracy of the filter in the filter device for filtering the cellulose hydrazine solution 3 1 a is 〇·1 - 1 0 0 μm. The absolute filter correctness is preferably 0 · 5 - 2 5 μm. The thickness of the filter is preferably 〇.] - 1 〇 mm, especially 0.2·2 mm. The drip, pressure is preferably at most 2.0 MPa, especially at most 1.5 MPa, and special The maximum concentration is 1. 〇 MPa. When filtering, the viscosity of the cellulose solution 3 1 a is preferably at most 1 〇〇〇 Pa-s', especially at a maximum of 500 Pa, s, especially at most 1 〇〇 pa.s, and Most especially the maximum of 50 Pa.s. As for the main material of the filter, it is preferably known materials such as glass fiber, cellulose fiber, filter paper, fluorocarbon resin (including polytetrafluoroethylene), and especially ceramic, metal. Etc. The shape of the filter may be surface type or depth type. However, the depth type is preferred because it is difficult to close the filter. In the present invention, the cellulose halide solution 3 1 a can be cast to form a single layer. Or forming a plurality of layers. When designed to form a plurality of layers, the cellulose halide solution may be sequentially cast by a casting die in which the belts 22 are arranged in a moving direction, or the cellulose halide solution may be simultaneously flowed from a plurality of solution outlets of a casting die. Extend for co-casting. The present invention is not limited to these casting methods, and other methods can be applied. The plurality of cellulose halide solutions may be the same or different in forming the multilayer casting. Further, when it is designed to form at least three layers in the casting, the particles can be effectively contained at least in the outermost layer, and thus the particles are added to form the outermost cellulose-containing telluride solution. In this case it should be noted that other layers than the outermost layer may contain particles, and all layers may also be included. In addition, it is often necessary to provide a multi-layered cellulose halide layer with different functions when forming multiple layers. In this case, 1344019 is prepared to form a multi-layered cellulose halide solution which is cast from the solution outlet. Further, in the present invention, not only the cellulosic brewing solution but also different solutions of other functional layers, such as an adhesive layer, a dye layer, an electrostatic layer, a U V absorbing layer, a polarizing layer and the like, are sequentially formed or simultaneously cast. In the present invention, the preferred solvent material of the cellulose halide solution 3 1 a is preferably an organic solvent material selected from the group consisting of ester 'ketones, ethers (each having 3 to 2 carbons), and halogenated hydrocarbons (each The molecule is 1-7 carbons). The esters, ketones and ethers may have a ring structure. Further, 'a compound having at least two ester, ketone and ether functional groups (ie, -〇_, -CO-, and -COO-) is used as a main solvent, and may have at least two other functional groups such as an alcoholic hydroxyl group. . In this case, the number of carbon atoms in a molecule is determined based on the range of the corresponding functional groups above. Further, the ester of '3-12 carbon atoms is, for example, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, and valeric acid acetate as the main solvent of 3 - 12 carbon atoms. The ketone is, for example, an ether of 3 to 12 carbon atoms in which acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone' and methylcyclohexanone oxime are used as a main solvent, for example, Diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, methoxybenzene, and phenylethyl ether. It should be noted that the organic solvent material having at least two functional groups is, for example, 2-ethoxyethyl acetate, 2-methoxyethanol, and 2-butoxyethanol. Further, the halogenated hydrocarbon is, for example, methylene chloride, dichloromethylene or the like. Further, in the present invention, the solvent may contain an alcohol. Preferred alcohols are monoalcohols or glycols wherein each molecule has at least one and up to 8 carbon atoms, and 1344019 and particularly preferred alcohols are, for example, 'methanol, ethanol, 1-propanol, 2-propane. Alcohol, butanol, 2-butanol, tert-butanol '1-pentanol, 2-methyl-2-butanol, cyclohexanol, and the like. Only one of the main solvent' may be mixed and a mixture of at least two thereof may be added to the main solvent. The weight percentage of the above alcohol to the total solvent material is preferably from 2% by weight to 40% by weight, particularly preferably from 3% by weight to 30% by weight, and especially from 5% by weight to 20% by weight, based on the fibers of the present invention. The bismuth telluride film 31b can be stretched using a rack device. The stretching of the cellulose oxime film 3 1 b is carried out so that the enthalpy of the film on the surface of the film becomes high. The stretching is carried out at room temperature or by heating the cellulose brewing film 3 1 b. Further, 'uniaxial stretching or biaxial stretching is performed. The heating temperature for stretching is preferably lower than the glass transition temperature of the cellulose halide. The cellulose halide film 3 1 b can be stretched in the drying process and the stretching effect is particularly large when the solvent remains in the cellulose halide film 3 1 b. For example, when the rotational speed of the light 2 3 is adjusted so that the winding speed of the cellulose vaporized film 31b is higher than the peeling speed, the cellulose vaporized film 3 1 b is stretched. Further, the side portion of the cellulose vapor film 3 1 b can be held by the rack type device, so that the film is stretched so that the width thereof becomes gradually larger. Alternatively, after the cellulose vapor film 31b is dried, it is stretched using a stretching machine such as a long stretching machine or the like. The thickness of the cellulose halide film 31b of the present invention varies depending on the purpose of use, and thus is not limited. The thickness is adjusted by adjusting the solid material content in the cellulose halide solution, the distance between the lips of the casting die 21, the pressure of the solution from the casting die 2, the moving speed of the belt 22, and the output fiber of the self-casting die 21. The flow rate of the bismuth telluride solution is adjusted. [Experiment] -16-1344019 The experiment of the present invention was carried out. The explanation is made below, and the present invention is not limited by the following. The dispersion was prepared from the following contents. It was mixed and the dispersion was precisely controlled by a honing machine so that the average diameter in the volume was 〇 5 μm. Thus, a dispersion containing fine particles was obtained. The average diameter in the volume was measured by a laser diffraction particle size analyzer LA920 (manufactured by H〇riba Ltd.). It should be noted that the surface of the cerium oxide particles described below is positively charged. The cerium oxide particles are 2.00% by weight (Aerosil RA200HS manufactured by Nippon Aerosil) 2.0 0% by weight 0.1 6% by weight 0.0 8% by weight 8 8.10% by weight 7.6 6wt%

Cellulose triacetate (61.0% degree of acetylation) Triphenyl phosphate (TPP) Biphenyl diphenyl phosphate Dichloromethane Methanol

A solvent mixture of dichloromethane and methanol was prepared so that the weight ratio thereof was 92:8. The mixture solvent is then added to the following solid material. This mixture was stirred to dissolve, and a 18.5% by weight cellulose halide solution was obtained as a base material. More than 6.5 wt% of the dispersion was added to 100% by weight of the base material. Then, the cellulose oxime solution 3 1 a was obtained by stirring, and it was passed through a 'filter paper (#63 manufactured by Toyo Roshi Kaisha Ltd.). Cellulose triacetate 8 9.3 wt% (degree of acetylation is 6 1 0%) i -17- 1344019 triphenyl phosphate (Τ PP ) 7 ·] weight ° / bisphosphonium biphenyl diphenyl ester 3.6 weight % The cellulose mash solution 3 1 a obtained by the above method was stored in the raw material tank 12 and then filtered by a filtering device 14. As for the material of the filtration device 14, a metal filter (No. 6 N manufactured by Nippon Seisen Co., Ltd., a nominal pore diameter of 1 μm) was used. The flow rate of the pump 13 is controlled so that the filtration pressure can be 0.3x1 O6 Pa at the start of feeding the cellulose halide solution. The cellulose oxime solution 3 1 a was cast on the belt 2 2 and dried to be peeled off from the belt 22 to form a cellulose oxime film 3 1 b. The cellulose halide film 3 1 b was then dried in a drying process to give a thickness of 80 μm. Then, a 0.1 m square of cellulose phthalate film 3 1 b was sampled and placed on a platform. The amount of foreign material was counted by visual observation. In this sample, there were no foreign materials observed and areas where foreign materials were observed. The areas of a foreign material are each cut into pieces, and elemental analysis of each area is performed using an elemental analyzer (XMA). Considering the result of the elemental analysis, the quantity A containing the foreign material exceeding the area in which the foreign material is not observed, and the quantity B containing the foreign material having the same or less than the area are counted separately. The results are shown in Table 1. In Table I, 'solution X is the cellulose oxime solution 31a sampled when the filtration pressure is increased to O.hlO6 Pa, and the solution γ is the cellulose oxime sampled when the filtration pressure is increased to .Ox] 06 Pa. Compound solution 3 ! a . Sample X is a film made from solution X, and sample γ is a film made from solution γ. [Comparative] The silica sand particles are Aerosil R97 2 (manufactured by Nippon Aerosll) 1344019. Other conditions are the same as the examples.

The cellulose halide solution 31a was manufactured in the same manner as the comparative example A & B. Therefore, when the filtration pressure is low, the amount of the material is almost the same as that detected by the sample X'. However, when the filtration pressure is increased to UdO6 Pa, the quantity A in the comparison is much larger than the example 'and the number is almost the same as the number B of the comparison. Therefore, when the coating liquid contains a positively charged surface, the amount of material other than the sample Y having a higher filtration pressure becomes smaller.

Since the different elements between the samples X and Y are only the filtration pressure, the film formed by the coating liquid containing the positively charged particles is much better than the coating liquid containing the particles having no positive electrodes on the surface. Based on the results of this experiment, the following estimates can be made. When the positively charged particles are used, no agglomeration occurs in the filter, so the experimental result may be that the filtered solution does not contain clusters (or aggregated particles) even if the pressure is high. Various changes and modifications are possible in the present invention, and it should be understood that they are included in the present invention. BRIEF DESCRIPTION OF THE DRAWINGS The above objects and advantages of the present invention will be readily understood by those skilled in the art in the light of the <RTIgt; Figure. -19- 1344019 [Explanation of main component symbols] 1 1...Film manufacturing equipment 12...Material tank 1 3...Pump 14...Filter unit 17...Storage tank 18...Solution casting device 21...Casting die

22... belt 23...roll 2 6...drying device 27...winding device 28...support roller

3 0a···Cellulose Telluride 3 0b...Soluble IJ 3 0 c...granules

3 1 a... Cellulose Telluride Solution 3 lb... Cellulose Telluride Film -20- 1344019 X. Patent Application Range: 1. A cellulose halide solution containing positively charged particles on the surface. 2. The cellulosic halide solution of claim 1, wherein the particle is a barium compound comprising cerium oxide. 3. A cellulose halide solution according to claim 2, wherein the cellulose halide solution is obtained by initially adding the charged particles and then filtering by retaining the particles. 4. A cellulosic halide solution according to claim 3, wherein the cellulose halide solution is cast to form a cellulose vapor film. -twenty one -

Claims (1)

1344019 'Day correction replacement page XI, schema: 〇H