TWI451960B - Anti-glare film, and manufacturing method thereof - Google Patents

Description

Anti-glare film, and method of manufacturing same

The present invention relates to an anti-glare film and a method of producing the same.

In order to prevent external light from being reflected on the surface of the image display device, display performance with less sparkle is obtained, and fine unevenness is provided on the surface to impart anti-glare property to dissipate the reflected light. Further, an antireflection layer is further provided above the uneven surface.

The anti-glare layer has a visibility that reduces the reflection image by blurring the contour of the surface reflection image, and is used for an image display device such as a liquid crystal display, an organic EL display, or a plasma display without reflection of a reflection image. Further, the light from the light source side is appropriately blurred, and the effect of suppressing the sparkle of the display pixel is also obtained. Moreover, there are many opportunities for the surface of the display to be touched by the hand, and it is also required to be free from damage and fingerprints.

An anti-glare film which is used as a front panel of such an image display device is formed by coating a surface of a transparent film substrate or by embossing or the like. Further, an antireflection layer is formed on the antiglare film by coating or chemical or physical vapor deposition.

In recent years, in order to increase the size of the display device, the width of the anti-glare film is required to be wide. In particular, in the large screen, an anti-glare film having excellent planarity is required, but the conventional anti-glare film is not excellent in planarity particularly in a wide width, and the scratch resistance is also not obtained in a wide-area film. Fully satisfied.

Conventionally, on the anti-glare film, it is known that a plurality of inorganic or organic particles of a single type or different particle diameters are coated on the film, and a method of providing irregularities on the surface is known, but there is a problem of glittering due to larger particles. And the problem of impurity barriers during manufacturing.

On the other hand, a method in which a special anti-glare layer is not provided, an unevenness is provided on the substrate itself, and a hard coat layer and an anti-reflection layer are provided thereon to obtain an anti-glare film having an anti-glare effect have been known from the past. Regarding such a patent document which imparts irregularities to the substrate itself and causes an anti-glare effect, the following documents have been conventionally used.

Patent Document 1 discloses a polarizing plate in which a protective substrate mainly composed of a cellulose-based plastic is adhered, and a surface of the protective substrate is embossed to form a fine uneven surface, and the uneven surface is partially dissolved in an organic solvent. A technology that provides a non-reflective polarizer.

Further, in Patent Document 2, it is disclosed that in the production of a triacetone cellulose film, an uneven surface is provided on a support of a mixed liquid flow, and unevenness is imparted to the film surface at the same time as film formation, and an anti-glare triethylene fiber is produced. Membrane technology.

Further, Patent Document 3 discloses a method of performing embossing of a regular shape on a film containing a residual solvent state.

Further, in Patent Document 4, after the antireflection layer or the hard coat layer is provided on the support, the layer is pre-cured by irradiation of an active energy ray, and then embossed, and then the active energy ray is irradiated again to obtain A method of preventing an anti-glare film.

Patent Document 1: Special Fair No. 4-59605

Patent Document 2: Japanese Patent Publication No. Hei 10-119067

Patent Document 3: JP-A-2005-258055

Patent Document 4: JP-A-2005-195726

However, in the method of Patent Document 1, since the organic solvent is dissolved by the uneven surface, the substrate itself is deteriorated in planarity due to the solvent, and the solvent is turbid due to the solvent, which is not preferable. In the method of Patent Document 2, it is necessary to form a special flow support in the flow device, and to form an uneven surface in a state containing a high residual solvent. Therefore, it is difficult to control the formation of the uneven surface, and it is difficult to peel off and peeling easily occurs. Obstacles, the problem of poor flatness of the film. Moreover, it costs a lot of money for cleaning and maintenance of the rogue support, and the productivity is poor.

In the method of Patent Document 3, the solvent content at the start of the embossing process is processed in a state of 2.0 to 4.0 times higher than the solid content of the film, so that the coil (film) is soft, and the counter-processed surface which must be flat also occurs. Deformation, when the coil (film) enters the embossing processing roll, has the disadvantage that lifting and wrinkling are liable to occur. Further, when the amount of the residual solvent of the coil (film) is large, the shrinkage of the film in the wide axial direction or the conveying direction is large due to the drying of the film during processing, and the uneven shape of the casting roll for embossing is difficult due to shrinkage. Precision transfer, in particular, has a problem of fine damage in the direction of the wide axis due to shrinkage in the direction of the wide axis of the film.

Further, in the method of Patent Document 4, the release property of the coating liquid and the embossing processing roll is inferior according to the pre-hardening condition, the coating film is peeled off, the surface unevenness is likely to be uneven, the surface is cracked, the antireflection layer or The hard coating peels off and is susceptible to humidity fluctuations.

Therefore, in recent years, in order to realize an anti-glare film which can produce a wide and/or thin film anti-glare film at a low cost and which is difficult to cause sparking of the film surface and impaired impurities, and having excellent planarity.

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the prior art described above, and to provide an anti-glare film which is excellent in planarity, reduces surface sparking, and impairs impurities, and a method for producing the same.

In view of the above-mentioned results, the inventors of the present invention have found that the resin is dissolved in a solvent mixture (resin solution) according to the solution flow film forming method, and flows on a rotary drive support having a smooth surface to volatilize the solvent. When the web is formed by peeling off from the support and forming a roll (a film containing a residual solvent after flowing the blend on the support is referred to as a roll), the roll containing the residual solvent peeled off by the support is excellent in workability. The coil material is easy to perform full embossing processing. On the other hand, since the coil material is soft, the precision of the mold processing roller and the support roller during embossing processing is apt to wrinkle, and it is assumed that even The accuracy is sufficient, and the film thickness distribution of the meandering and/or skewing and the wide-axis direction of the coil during the conveyance of the coil is fluctuating, and wrinkles are likely to occur, upstream of the coil conveying direction of the mold processing roll. In the side or the downstream side, by adjusting the conveying tension of the coil to the left and right end portions of the coil to be different from each other, it is possible to prevent the left and right unevenness of the coil conveyance from being reduced, and to prevent the film from being lifted. Wrinkles, and reached completion of the present invention.

In order to achieve the above object, the invention of claim 1 is a resin solution in which a resin is dissolved in a solvent, which flows on a rotary drive support having a smooth surface, and volatilizes the solvent until it can be peeled off from the support to form a coil ( After the film containing the residual solvent after the flow of the support liquid is referred to as a coil material, the mold processing roller is pressed against the surface of the film on the surface of the film after the step of drying the web from which the support is peeled off. A method for producing an anti-glare film which is formed by a solution flow film forming method, which is characterized in that a tension of a web in an upstream side or a downstream side of a roll conveying direction of a mold processing roll is applied to the left and right ends of the coil. The departments are adjusted to be different from each other.

The invention of claim 2 is the method for producing an anti-glare film according to the first aspect of the invention, characterized in that the coil is conveyed on the upstream side or the downstream side of the coil processing direction of the mold processing roll. The tension is adjusted to a coil conveyance tension adjusting mechanism different from each other at the left and right end portions of the coil, and means for independently measuring the tension of the web conveyance is provided on the same side, and the coils of the left and right ends of the coil are measured according to the measuring means. The measurement value difference of the conveyance tension is 1 to 5%, and the coil conveyance tension adjustment mechanism is finely adjusted.

The invention of claim 3 is the method for producing an anti-glare film according to the first or second aspect of the invention, wherein the amount of residual solvent in the coil when the mold forming roll is formed into irregularities is 10 to 70% by mass.

The invention of claim 4 is the method for producing an anti-glare film according to any one of claims 1 to 3, characterized in that, when the forming rolls are formed into irregularities, the coil is cast. The contact time of the type processing roll is 2.5 × 10 ^-3 to 1.0 second.

The invention of claim 5 is the method for producing an anti-glare film according to any one of claims 1 to 4, characterized in that the pressure of the casting processing roll for the coil is 200 to 50000 N. /m.

The invention of claim 6 is the method for producing an anti-glare film according to the second aspect of the invention, characterized in that the coil conveying tension adjusting mechanism transports the coils at the left and right ends of the coil according to the measuring means. The difference between the measured values of the tension is adjusted to 2 to 4.5%.

The invention of the anti-glare film of claim 7 is characterized in that it is produced by the method described in any one of claims 1 to 6.

The invention of claim 1 is a blending solution (resin solution) in which a thermoplastic resin is dissolved in a solvent, which flows on a rotary drive support having a smooth surface, and volatilizes the solvent until it can be peeled off on the support to form a coil. After the step of drying the web to which the support is peeled off, the mold processing roll is pressed against the surface of the coil, and a method for producing an anti-glare film by forming a film on the surface of the film is formed. The web conveying tension in the upstream side or the downstream side of the coil conveying direction of the processing roll is adjusted to be different from each other at the left and right end portions of the coil, and the invention according to the first aspect of the patent application does not occur. Lifting, wrinkles, and minor damage to the surface, and achieving an effect of producing an anti-glare film excellent in planarity, reducing surface sparking, and impurity barriers under high productivity.

The invention of claim 2 is the method for producing an anti-glare film according to the first aspect of the invention, characterized in that the coil is formed on the upstream side or the downstream side of the coil processing direction of the mold processing roll. The conveying tension is adjusted to a coil conveying tension adjusting mechanism different from each other at the left and right end portions of the coil, and means for independently measuring the web conveying tension on the same side is provided on the same side, and the left and right ends of the coil are measured according to the measuring means. If the measured value difference of the material conveying tension is 1 to 5%, the fine adjustment of the coil conveying tension adjusting mechanism may not cause lifting, wrinkles, and minor damage on the surface according to the invention of the second application of the patent application. Moreover, the effect of producing an anti-glare film which is excellent in planarity, reduces surface sparking, and impaired impurities can be obtained under high productivity.

The invention of the third aspect of the invention is the method for producing an anti-glare film according to the first or second aspect of the invention, wherein the amount of residual solvent in the coil when the forming roll is formed by the forming roll is 10 to 70 If the quality is %, according to the invention of the third paragraph of the patent application, the lifting, the wrinkles and the minor damage of the surface are not caused, and the anti-glare film which is excellent in flatness, reduces surface sparking, and impairs impurities is not obtained. Effect.

The invention of claim 4 is the method for producing an anti-glare film according to any one of claims 1 to 3, wherein when the forming rolls are formed into irregularities, the coil is processed for the mold. If the contact time of the roller is 2.5 × 10 ^-3 to 1.0 second, according to the invention of the fourth aspect of the patent application, the lifting, the wrinkles and the minor damage of the surface do not occur, and the high productivity can be achieved. The effect of producing an anti-glare film which is excellent in planarity and reduces surface sparking and impurity barriers.

The invention of claim 5 is the method for producing an anti-glare film according to any one of claims 1 to 4, according to the anti-glare film according to item 5 of the patent application. According to the invention, the flatness is excellent, the surface glittering, and the impurity barrier are reduced.

Next, an embodiment of the present invention will be described with reference to the drawings, but the present invention is not limited thereto.

In this specification, the front, back, and left and right are based on FIG. 1, and the former means the right side of FIG. 1, that is, the conveying direction of the web or the film, and the term "back" means the same as the left side, and the left and right means the front side.

The method for producing an anti-glare film of the present invention is a blending solution (resin solution) in which a resin is dissolved in a solvent, flowing on a rotary drive support having a smooth surface, and volatilizing the solvent until it can be peeled off from the support to form a roll. After the material is scraped, the mold processing roll is brought into contact with the surface of the coil to form a solution flowing and forming a film on the surface of the film.

Then, the method for producing the anti-glare film of the present invention is such that the web conveyance tension in the upstream side or the downstream side of the coil processing direction of the mold processing roll is adjusted to be different from each other at the left and right end portions of the coil.

Generally, the coil material containing the amount of residual solvent is soft in the surface of the coil and excellent in surface workability. However, when the coil is pressed to the casting roll, the coil is liable to be hoisted and wrinkled. The lifting and wrinkling of the coiled material is a non-uniformity in the width direction of the film thickness by the conveyance of the coil material, a slight left-right deviation of the conveying device such as a roller row, or a left-right wind speed difference of the drying wind during drying. And the temperature difference occurs. The left and right deviation of the equipment is reduced as much as possible even during the installation of the production equipment, and the change in temperature due to the repeated temperature changes at the beginning and end of the production causes a change in time, which is extremely difficult to maintain for a long period of time without lifting and wrinkling. Folded state.

Then, in the present invention, it is found that the occurrence of lifting and wrinkles can be suppressed by the difference in the conveying tension between the left and right end portions of the coil in the upstream side or the downstream side of the web conveying direction of the casting processing roll. In the upstream side of the coil, the tension between the left and right end portions of the coil is different, and it is difficult to cause lifting and wrinkling by the tension applied to the width direction of the coil. Further, it is considered that when the conveying tension between the left and right end portions of the coil is different on the downstream side of the coil, the tension applied to the width direction of the coil acts to resist the lifting and wrinkles that have occurred.

In this embodiment, in the upstream side or the downstream side of the roll processing direction of the roll processing roll, the web conveyance tension adjustment in which the conveyance tension of the web is adjusted to be different from each other in the left and right end portions of the web is provided. The mechanism is provided on the same side as the means for independently measuring the tension of the coil conveyance. Then, the difference in the measured value of the web conveying tension between the left and right end portions of the coil of the measuring means is 2 to 4.5%, and the coil conveying tension adjusting mechanism is finely adjusted.

Here, according to the measurement values of the web conveyance tension of the left and right ends of the coil of the measuring means, if the control is adjusted in the same manner, it is likely to be affected by the disorder of the arrangement of the apparatus, the variation of the thickness of the processed coil, and the like. It is easy to cause unevenness in the width direction and the conveying direction of the web, which is not preferable. Further, the web material has a different film thickness variation in the width direction depending on the conveyance direction, and the web conveyance tension at the left and right end portions fluctuates from time to time. However, if the fluctuation is adjusted and controlled to be zero, the roll is rolled. The material is slightly lifted in the conveying direction, and unevenness occurs due to the lifting, which is not preferable. Further, if the difference in the measured value of the web conveying tension between the left and right end portions of the coil of the measuring means is too large, the coil is likely to be hoisted and wrinkled when it enters the casting processing roll. For such reasons, the difference in conveying tension between the left and right ends of the coil is preferably from 1 to 5%, and more preferably from 2 to 4.5%.

In the method of the present invention, the amount of residual solvent in the web when the mold forming rolls are formed into irregularities is preferably 10 to 70% by mass.

Here, when the surface of the coil containing the residual solvent amount is processed, the coil is dried to shrink the coil in the wide axis direction and the conveying direction, and has a relative speed to the surface of the casting roll, and the casting roll The unevenness of the surface causes minute damage in the width direction and the conveying direction of the surface of the coil. This damage can be suppressed by the residual solvent amount of the coil material being 70 mass% or less. However, when the amount of the residual solvent of the coil is less than 10% by mass, it is necessary to apply a large pressing force to the uneven processing of the mold roll, and wrinkles of the film are more likely to occur.

Further, in the present invention, when the unevenness is formed by the mold processing roll, the contact time of the film with the mold processing roll is preferably 2.5 × 10 ^-3 to 1.0 second.

That is, when the coating angle and the packaging time of the film and the mold roll are large, hoisting and damage are liable to occur, and in the case of the film, the workability is deteriorated, and the appropriate coating angle and packaging time are present.

If the method according to the invention is used, no lifting will occur. Wrinkles and minor damage to the surface make it possible to produce an anti-glare film with excellent planarity and reduced surface sparkling and impurity barriers under high productivity.

The method for producing the antiglare film of the present invention is a film forming method according to a solution flow, and will be described below in order.

(polymer)

The resin preferably used in the method for producing an anti-glare film of the present invention may, for example, be a cellulose acetate, cellulose acetate propionate or cellulose acetate butyrate having a thiol substitution degree of 1.8 to 2.80. a cellulose ester resin, a cellulose ether resin having a degree of alkyl substitution of from 2.0 to 2.80, such as cellulose methyl ether, cellulose ether or cellulose propyl ether, a cycloolefin resin, a norbornene resin, or a polycarbonate resin. Or a polyamine resin of a polymer of an alkyl dicarboxylic acid and a diamine, a polymer of an alkyl dicarboxylic acid and a diol, a polymer of an alkyl diol and a dicarboxylic acid, and a cyclohexane. a polymer of a dicarboxylic acid and a diol, a polymer of a cyclohexanediol and a dicarboxylic acid, a polyester resin of an aromatic dicarboxylic acid and a diol, or a polyvinyl acetate or a vinyl acetate copolymer a vinyl acetate resin, or a polyvinyl acetal such as polyvinyl acetal or polyvinyl butyral, an epoxy resin, a ketone resin, an alkyl diisocyanate and an alkyl diol. a polyurethane resin or the like, and the like, and at least one selected therein Better.

Among them, cellulose ester resins such as cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate, a cycloolefin resin, a norbornene resin, and a polycarbonate resin are particularly preferred. Further, a blend of two or more kinds of compatible polymers may be dissolved in a blend described later, but the present invention is not limited thereto.

Other resins preferably used in the present invention include monomers or copolymers having ethylenically unsaturated monomer units. More preferably, polymethyl acrylate, polyethyl acrylate, poly propyl acrylate, polycyclohexyl acrylate, alkyl acrylate copolymer, polymethyl methacrylate, polyethyl methacrylate, polymethacrylic acid A monomer or copolymer of acrylic acid or methacrylate such as a cyclohexyl ester or an alkyl methacrylate copolymer. Further, since the ester of acrylic acid or methacrylic acid is excellent in transparency and compatibility, it is a monomer or copolymer having an acrylate or methacrylate unit, particularly, having an acrylic acid or methyl methacrylate unit. A monomer or copolymer is preferred. Specifically, polymethyl methacrylate is preferred. The alicyclic alkyl ester of acrylic acid or methacrylic acid like polyacrylic acid or polycyclomethacrylate is preferably one having the advantages of high heat resistance, low hygroscopicity, and low birefringence.

(cellulose ester)

The cellulose of the cellulose ester raw material used in the present invention is not particularly limited, and examples thereof include cotton cotton linters, wood pulp, and kenaf. The cellulose esters obtained therefrom are used singly or in any ratio.

In the present invention, in the case where the cellulose ester is a anhydride (acetic anhydride, propionic anhydride, butyric anhydride), an organic solvent such as an organic acid such as acetic acid or dichloromethane is used, and sulfuric acid is used. The protonic catalyst reacts as usual.

In the case where the oxime agent is decyl chloride (CH ₃ COCl, C ₂ H ₅ COCl, C ₃ H ₇ COCl), an amine-like basic compound can be used as a catalyst for the reaction. Specifically, it can be synthesized by the method described in JP-A-10-45804.

The cellulose ester reacts with a hydroxyl group of a cellulose molecule with a mercapto group. Cellulose molecules are composed of a plurality of glucose units linked to each other having three hydroxyl groups per glucose unit. The number of fluorenyl groups derived from the three hydroxyl groups is referred to as the degree of substitution. For example, cellulose triacetate in which all three hydroxyl groups of the glucose unit are combined with an ethyl hydrazide group.

The cellulose ester film can be used as a cellulose ester, and the total thiol substitution degree is preferably 2.4 to 2.8.

The molecular weight of the cellulose ester used in the present invention may be a number average molecular weight (Mn) of 50,000 to 200,000. It is preferably 60,000 to 200,000, and is particularly good at 80,000 to 200,000.

The cellulose ester used in the present invention has a mass average molecular weight (Mw) to a number average molecular weight (Mn), and Mw/Mn is preferably from 1.4 to 3.0, more preferably from 1.7 to 2.2.

The average molecular weight and molecular weight distribution of the cellulose ester can be measured by a known method using high speed liquid chromatography. The number average molecular weight and the mass average molecular weight were calculated using this, and the ratio (Mw/Mn) was calculated. The measurement conditions were as follows.

Solvent: dichloromethane

Column: Shodex-K806, K805, K803G (3 columns of Showa Denko Co., Ltd.)

Column temperature: 25 ° C

Sample concentration: 0.1% by mass

Detector: RI Model 504 (made by GL Science)

Pump: L6000 (made by Hitachi, Ltd.)

Flow rate: 1.0ml/min

Calibration curve: A calibration curve of 13 samples using standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 1000000 to 500. It is preferred that 13 samples are used at approximately equal intervals.

The cellulose ester used in the present invention is a carboxylate having a carbon number of from 2 to 22, particularly preferably a lower fatty acid ester of cellulose.

The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. For example, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate 酞 can be used. Mixed fatty acids such as cellulose acetate acrylate, cellulose acetate butyrate, etc., as described in U.S. Patent No. 2,319,052, and the like. ester. The aromatic carboxylic acid, cellulose ester, and cellulose oxime described in JP-A-2002-265639, JP-A-2002-265639, and JP-A-2002-265638 are also preferably used.

Among the above, the lower fatty acid ester of cellulose which is particularly preferably used is cellulose triacetate and cellulose acetate acrylic acid. These cellulose esters can also be used in combination.

A preferred cellulose ester other than cellulose triacetate has a fluorenyl group having 2 to 4 carbon atoms as a substituent, and the degree of substitution of the ethyl thiol group is regarded as X, and the degree of substitution of the propyl fluorenyl group or the butyl fluorenyl group is regarded as In the case of Y, the cellulose esters of the following formulas (a) and (b) are simultaneously satisfied.

Formula (a) 2.4≦X+Y≦2.8

Equation (b)0≦X≦2.5

The moiety that has not been replaced by a thiol group is usually present in a hydroxyl form. It can be synthesized by a known method.

These thiol substitutions can be determined according to the method specified in ASTM-D817-96.

In the case of acetaminophen, if the vinegarization rate is to be increased, the time of the acetification reaction must be prolonged. However, if the reaction time is too long, the decomposition proceeds at the same time, causing the cutting of the polymer chain and the decomposition of the acetyl group, which also causes a poor effect. Therefore, it is necessary to set the reaction time to a certain range by increasing the degree of acetification and suppressing the decomposition to some extent. The reaction conditions specified by the reaction time are various, and the other conditions of the reaction apparatus and equipment are greatly changed, so that it is not suitable. As the polymer is decomposed and the molecular weight distribution is broadened, in the case of the cellulose ester, the degree of decomposition can also be defined by the value of the mass average molecular weight (Mw) / number average molecular weight (Mn) which is usually used. That is, in the vinegarization process of cellulose triacetate, the mass average molecular weight (Mw) / number average molecular weight of an index which is not excessively long and decomposed and which is subjected to a sufficient time for vinegarization reaction on vinegar is used. (Mn) value.

When an example of the method for producing a cellulose ester is shown below, 100 parts by mass of cottoned cotton linters as a cellulose raw material is pulverized, 40 parts by mass of acetic acid is added, and pretreatment is carried out at 36 ° C for 20 minutes. Thereafter, 8 parts by mass of sulfuric acid, 260 parts by mass of acetic anhydride, and 350 parts by mass of acetic acid were added, and esterification was carried out at 36 ° C for 120 minutes. After neutralizing with 11 parts by mass of a 24 mass% magnesium acetate aqueous solution, it was alkalized and aged at 63 ° C for 35 minutes to obtain acetaminophen cellulose. This was stirred for 160 minutes at room temperature using a 10-fold aqueous acetic acid solution (acetic acid: water = 1:1 (mass ratio)), and then filtered and dried to obtain purified acetonitrile cellulose having a degree of substitution of 2.75. This acetamidine cellulose had an Mn of 92,000, a Mw of 156,000, and a Mw/Mn of 1.7. Similarly, the cellulose ester having different degree of substitution and Mw/Mn ratio can be synthesized by adjusting the esterification conditions (temperature, time, stirring) and hydrolysis conditions of the cellulose ester.

Further, it is preferred that the cellulose ester to be synthesized is subjected to purification to remove low molecular weight components and to remove unacetified components by filtration.

Further, in the case of the acidified cellulose ester, it can be obtained by the method described in JP-A-10-45804. The method for determining the degree of substitution of the thiol group can be determined in accordance with ASTM-817-96.

Further, the cellulose ester is also affected by a trace amount of metal components in the cellulose ester. It is considered that it is related to the water used in the production step, and it is preferable that the component having an insoluble core is small, and the metal ion such as iron, calcium or magnesium forms a salt with a polymer decomposition product or the like which may have an organic acid group. Insoluble matter can be formed, so it is preferable to use less. The iron (Fe) component is preferably 1 ppm or less. The calcium (Ca) component is contained in a lot of groundwater, river water, etc., and if it is a lot of water, it becomes hard water, and it is not suitable as drinking water, and acidic components, such as a carboxylic acid, and a sulfonic acid, and many ligands are formed easily. The coordination compound, ie, the complex, forms a residue (insoluble precipitate, turbidity) from many insoluble calcium.

The calcium (Ca) component is 60 ppm or less, preferably 0 to 30 ppm. When the magnesium (Mg) component is too large, an insoluble component is produced. Therefore, it is preferably 0 to 70 ppm, particularly preferably 0 to 20 ppm. The metal component such as the content of iron (Fe), the content of calcium (Ca), and the content of magnesium (Mg) is such that the dried cellulose ester is subjected to a micro-dip wet decomposition apparatus (sulfuric acid decomposition) and alkali fusion. After the pretreatment, analysis can be carried out by using ICP-AES (Induction Combined Plasma Luminescence Spectroscopic Analyzer).

(Organic solvents)

Useful organic solvents for dissolving the cellulose ester to form a blending solution (solution) are a chlorine-based organic solvent and a non-chlorine-based organic solvent. The chlorine-based organic solvent is exemplified by dichloromethane and is suitable for dissolution of a cellulose ester.

The use of non-chlorinated organic solvents was reviewed by recent environmental issues. Examples of the non-chlorine organic solvent include methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, and 1,3-two. Alkane, 1,4-two Alkane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1, 1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3 , 3-pentafluoro-1-propanol, nitroethane, and the like.

When these organic solvents are used in the case of using a cellulose ester, it is also possible to use a dissolution method at normal temperature, and it is possible to reduce insoluble matter by a dissolution method using a high-temperature dissolution method, a cooling dissolution method, a high-pressure dissolution method, or the like. It is better. For the cellulose ester other than cellulose triacetate, dichloromethane can be used, but methyl acetate, ethyl acetate or acetone is preferably used. In particular, methyl acetate is preferred. In the present invention, an organic solvent having good solubility to the above cellulose ester is referred to as a good solvent.

In the present invention, it is preferred that the blend liquid contains 1 to 40% by mass of an alcohol having 1 to 4 carbon atoms in addition to the above organic solvent. After the mixture is flowed on the support, the solvent is evaporated, and if the ratio of the alcohol is increased, the blended film (coil) is gelatinized, and the coil becomes firm, and is used as a glue which can be easily peeled off from the metal support. The solvent is also used, and when it is less in proportion, it also has a function of promoting dissolution of the cellulose ester of the non-chlorine-based organic solvent.

Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, and third butanol. Among them, ethanol is preferred from the viewpoints of excellent stability of the blending liquid, low boiling point, and good drying property. These organic solvents alone have no solubility for cellulose esters and are therefore referred to as poor solvents.

The concentration of the cellulose ester in the blending liquid is 15 to 30% by mass, and the viscosity of the blending liquid is such that the measured value of the B-type viscometer is adjusted to a range of 10 to 100 Pa·s, which is preferable in obtaining a good film surface quality.

The additives added to the blending solution are plasticizers, ultraviolet absorbers, antioxidants, dyes, and fine particles. In the present invention, these additives may be added at the time of preparing a cellulose ester solution, and may also be added at the time of preparation of a fine particle dispersion such as a matting agent.

It is preferable to add a plasticizer, an antioxidant, an ultraviolet absorber, etc. which impart heat resistance and moisture resistance to the polarizing plate used for the liquid crystal image display device. The following description pertains to the additive.

(plasticizer)

In the present invention, in the cellulose ester solution or the blending liquid, a so-called plasticizer is added for the purpose of improving mechanical properties, imparting flexibility, imparting water absorption resistance, reducing water vapor permeability, adjusting retention, and the like. It is preferred to know the compound, for example, a phosphate ester and a carboxylate are preferably used.

Examples of the phosphate ester include triphenyl phosphate, tricresyl phosphate, and phenyl diphenyl phosphate.

The carboxylic acid esters are phthalic acid esters and citrate esters, and examples of the phthalic acid esters include dimethyl phthalate, diethyl phosphate, dioctyl phthalate and diethyl hexyl citrate. Ethyl triethyl citrate and tributyl citrate. Further, examples thereof include butyl oleate, methyl decyl ricinolate, dibutyl sebacate, and triacetin. Alkyl mercaptoalkyl glycolate is also preferably used for this purpose. The alkyl group of the alkyl mercaptoalkyl glycolate is an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl mercapto alkyl glycolate include methyl mercapto methyl glycolate, ethyl mercapto ethyl glycolate, propyl mercapto glycol glycolate, and butyl mercapto butyl glycolate. , octyl decyl octyl glycolate, methyl decyl ethyl glycolate, ethyl decyl methyl glycolate, ethyl decyl propyl glycolate, propyl decyl ethyl glycolate , methylmercaptopropyl glycolate, methyl decyl butyl glycolate, ethyl decyl butyl glycolate, butyl decyl methyl glycolate, butyl decyl ethyl glycolate , propyl decyl butyl glycolate, butyl decyl propyl glycolate, methyl decyl octyl glycolate, ethyl decyl octyl glycolate, octyl decyl methyl glycolate , octyl decyl ethyl glycolate, etc., and methyl decyl methyl glycolate, ethyl decyl ethyl glycolate, propyl decyl propyl glycolate, butyl decyl butyl Glycolate, octyldecyl octyl glycolate is preferably used. Further, these alkyl mercapto alkyl glycol esters may be used in combination of two or more kinds.

Further, a polyvalent alcohol ester is also preferably used.

The polyvalent alcohol used in the present invention is represented by the following general formula.

R ¹ -(OH)n

However, in the formula, R ¹ is an organic group representing n valence, n is a positive integer indicating 2 or more, and OH group is an alcoholic and/or phenolic hydroxyl group.

The polyvalent alcohol ester-based plasticizer is a plasticizer composed of an ester of a divalent or higher aliphatic polyvalent alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. An aliphatic polyvalent alcohol ester having a valence of 2 to 20 is preferred.

Examples of preferred polyvalent alcohols include, for example, the following, but the present invention is not limited thereto. Examples thereof include ribitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2- Butylene glycol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexyl Alkanediol, hexanetriol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, o-di-tertiol, sorbitol, trimethylolpropane, trihydroxyl Methyl ethane, xylitol, and the like. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferred.

The monocarboxylic acid used for the polyvalent alcohol ester is not particularly limited, and a known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid or the like can be used. When an alicyclic monocarboxylic acid or an aromatic monocarboxylic acid is used, it is preferable in terms of improving moisture permeability and retention.

The preferred examples of the monocarboxylic acid include the following, but the present invention is not limited thereto.

As the aliphatic monocarboxylic acid, a fatty acid having a linear or side chain having 1 to 32 carbon atoms is preferably used. The number of carbon atoms is preferably from 1 to 20, and particularly preferably from 1 to 10. If acetic acid is contained, the compatibility with the cellulose ester is increased, so that it is preferable to use acetic acid in combination with other monocarboxylic acids.

Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, 2-ethyl-hexanoic acid, undecanoic acid, lauric acid, Tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, tetracosanoic acid, dihexadecanoic acid, Saturated fatty acids such as heptacosanoic acid, montanic acid, melamine acid, lacquer acid, etc., unsaturated fatty acids such as undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, etc. .

Examples of preferred alicyclic monocarboxylic acids include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, or a derivative thereof.

Examples of the preferred aromatic monocarboxylic acid include those in which a benzene ring of benzoic acid such as benzoic acid or toluic acid is introduced into an alkyl group, and two or more benzene rings such as a biphenylcarboxylic acid, a naphthalenecarboxylic acid or a tetrahydronaphthalenecarboxylic acid. An aromatic monocarboxylic acid, or a derivative thereof. Especially benzoic acid is preferred.

The molecular weight of the polyvalent alcohol ester is not particularly limited, and is preferably from 300 to 1,500, more preferably from 350 to 750. It is preferable that the molecular weight is large, and it is preferable that it is small in terms of moisture permeability and compatibility with cellulose ester.

The carboxylic acid used for the polyvalent alcohol ester may be one type or a mixture of two or more types. Further, the OH group in the polyvalent alcohol may be all esterified, and a part of the OH group may remain as it is.

These compounds are preferably contained in an amount of from 1 to 30% by mass, preferably from 1 to 20% by mass, based on the cellulose ester. Further, in order to suppress bleeding during stretching and drying, a compound having a vapor pressure at 200 ° C of 1400 Pa or less is preferred.

These compounds can be added together with the cellulose ester and the solvent when preparing the cellulose ester solution, and can also be added after solution preparation and preparation.

Furthermore, in the present invention, an aromatic terminal ester-based plasticizer represented by the following general formula (2) is preferably used.

General formula (2) B-(G-A)n-G-B

(wherein B represents a benzene monocarboxylic acid residue, G represents an alkyl diol residue having 2 to 12 carbon atoms or an aryl diol residue having 6 to 12 carbon atoms, or a carbon number of 4 ～12 Oxyalkylene glycol residue, A is an alkyl dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and n is 1 or more The integer).

In the general formula (2), the benzene monocarboxylic acid residue represented by B and the alkyl diol residue or the oxygen alkyl diol residue or the aryl diol residue represented by G, The alkylene dicarboxylic acid residue or the aryl dicarboxylic acid residue represented by A can be obtained by the same reaction as a usual polyester plasticizer.

The benzene monocarboxylic acid component of the aromatic terminal ester-based plasticizer used in the present invention is, for example, benzoic acid, p-tert-butylbenzoic acid, o-toluic acid, meta-toluic acid, p-toluic acid, dimethylbenzoic acid, ethyl Benzoic acid, n-propyl benzoic acid, amino benzoic acid, ethoxy benzoic acid, and the like may be used alone or in combination of two or more.

The aromatic terminal ester-based plasticizer used in the present invention has an alkylene glycol component having 2 to 12 carbon atoms, which is ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, and 1,2-butanediol. 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (new Pentanediol), 2,2-diethyl-1,3-propanediol (3,3-dihydroxymethylpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3, 3-dimethylol heptane), 3-methyl-1,5-pentanediol 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-nonanediol, 1,12-octadecane As the diol or the like, one type or a mixture of two or more types may be used as the diol.

Further, the oxygen-terminated alkyl diol component having 4 to 12 carbon atoms of the aromatic terminal ester is, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol or tripropylene glycol, and the like. One type or a mixture of two or more types may be used.

Further, the aryl diol component having 6 to 12 carbon atoms of the aromatic terminal ester is, for example, hydroquinone, resorcin, bisphenol A, bisphenol F or bisphenol, and one type of these diols can be used. Or a mixture of two or more.

The alkylene dicarboxylic acid component having 4 to 12 carbon atoms of the aromatic terminal ester is, for example, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, sebacic acid or sebacic acid. And dodecanedicarboxylic acid, etc., which can use 1 type or a mixture of 2 or more types, respectively. The aryldicarboxylic acid component having 6 to 12 carbon atoms is citric acid, p-citric acid, 1,5-naphthalene dicarboxylic acid, 1,4-naphthalenedicarboxylic acid or the like.

The aromatic terminal ester-based plasticizer preferably has a number average molecular weight of from 300 to 2,000, more preferably from 500 to 1,500. Further, the acid value is 0.5 mgKOH/g or less, the hydroxyl value is 25 mgKOH/g or less, more preferably the acid value is 0.3 mgKOH/g or less, and the hydroxyl value is 15 mgKOH/g or less.

In addition, the acid value of the aromatic terminal ester means the number of milligrams of potassium hydroxide required for neutralizing the acid (carboxy group present at the molecular terminal) contained in 1 gram of the sample. The acid value and the hydroxyl value can be measured in accordance with JIS K 0070 (1992).

The content of the aromatic terminal ester-based plasticizer used in the present invention is preferably from 1 to 20% by mass, particularly preferably from 3 to 11% by mass, based on the cellulose ester film.

(UV absorber)

In the present invention, the cellulose ester film may contain an ultraviolet absorber.

Examples of the ultraviolet absorber that can be used include a hydroxybenzophenone-based compound, a benzotriazole-based compound, a salicylate-based compound, a benzophenone-based compound, a cyanoacrylate-based compound, and a nickel-salted salt-based compound. ,three A compound or the like is preferably a benzotriazole-based compound having less coloration. Further, the ultraviolet absorbers described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The polymer ultraviolet absorber described in Japanese Laid-Open Patent Publication No. Hei. No. 2002-113317, and JP-A-2003-113317 is also preferably used. The ultraviolet absorber is excellent in ultraviolet absorption energy at a wavelength of 370 nm or less from the viewpoint of preventing deterioration of a polarizer and a liquid crystal, and is preferably a light absorption having a wavelength of 400 nm or more from the viewpoint of liquid crystal display properties.

Specific examples of the ultraviolet absorber usable in the present invention include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy-3',5'-di- Tributylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3' , 5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-(3",4",5",6"-tetrahydroindole醯iminomethyl)-5'-methylphenyl)benzotriazole, 2,2-methylenebis(4-(1,1,3,3-tetramethylbutyl)-6-( 2H-benzotriazol-2-yl)phenol), 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl)-6-(linear and side chain dodecyl)-4-methylphenol, octyl-3-[3-tert-butyl-4-hydroxy- 5-(Chloro-2H-benzotriazol-2-yl)phenyl]propionate with 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro A mixture of benzyl-2H-benzotriazol-2-yl)phenyl]propionate, etc., but is not limited thereto. Further, commercially available products ITNUVIN 109, TINUVIN 171, and TINUVIN 326 (all manufactured by Ciba Specialty Chemicals Co., Ltd.) are preferably used. Examples of the polymer ultraviolet absorber include a reactive ultraviolet absorber RUVA-93 manufactured by Otsuka Chemical Co., Ltd.

Specific examples of the benzophenone-based compound include 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, and 2-hydroxy-4-methoxy-5-sulfonate. But benzophenone, bis(2-methoxy-4-hydroxy-5-benzylidene phenylmethane), and the like, but is not limited thereto.

The above-mentioned ultraviolet absorber which is preferably used in the present invention is preferably a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber having high transparency and excellent effect of preventing deterioration of a polarizing plate and a liquid crystal element, and is not necessarily colored. Fewer benzotriazole-based UV absorbers are particularly preferred.

The method for adding the ultraviolet absorber to the blending solution is not limited if the ultraviolet absorber is dissolved in the blending solution. In the present invention, the ultraviolet absorber is dissolved in dichloromethane, methyl acetate, and the like. a mixed organic solvent which is a good solvent for a cellulose ester, or a poor solvent of a good solvent and a lower aliphatic alcohol (methanol, ethanol, propanol, butanol, etc.) and a cellulose ester in the form of a UV absorber solution. It may be added to the solution or added directly to the composition of the blend. If it is insoluble in an organic solvent like an inorganic powder, it can be added to the blending solution by using a dissolving rod and sanding in an organic solvent and a polymer, and dispersing.

The content of the ultraviolet absorber is 0.01 to 5% by mass, particularly 0.5 to 3% by mass.

In the present invention, the ultraviolet absorbers may be used singly or in combination of two or more kinds.

(Antioxidants)

The antioxidant is preferably a hindered phenol-based compound, for example, 2,6-di-t-butyl-p-cresol, pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4) -hydroxyphenyl)propionate], triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol - bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3 ,5-di-t-butylanilino)-1,3,5-three , 2,2-thio-di-extended ethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5 -di-t-butyl-4-hydroxyphenyl)propionate, N,N'-extended bis(3,5-di-t-butyl-4-hydroxy-hydroaminocyanide), 1,3 ,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-t-butyl-4- Hydroxybenzyl)-isocyanurate and the like. Especially 2,6-di-t-butyl-p-cresol, pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], triethylene Alcohol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] is preferred. Further, for example, a metal inert agent such as N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propene]fluorene or the like may be used in combination. A phosphorus-based processing stabilizer such as (2,4-di-t-butylphenyl) phosphite. The amount of such a compound to be added is preferably from 1 ppm to 1.0% by mass based on the cellulose ester, and more preferably from 10 to 1,000 ppm.

Hereinafter, examples of the fine particles used in the present invention are listed, but are not limited thereto.

Examples of the fine particles include inorganic compound particles or organic compound particles.

Examples of the inorganic compound particles include metal oxides such as cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, kaolin, talc, clay, calcined calcium citrate, calcium citrate hydrate, aluminum silicate, magnesium citrate, and calcium phosphate. A substance, a hydroxide, a citrate, a phosphate, a carbonate, a calcium citrate, a potassium titanate, an aluminum borate, a basic magnesium sulfate, a glass fiber or the like.

Examples of the organic compound particles include fine particles of a polyfluorene oxide resin, a fluororesin, and an acrylic resin, and a polyoxyxylene resin is preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, the same 105, the same 108, the same 120, the same 145, the same 3120, and the same 240 (manufactured by Toshiba Silicone Co., Ltd.) can be mentioned.

Further, it is also possible to use two or more different types (compositions) and shape particles.

Examples of the cerium oxide microparticles include Aerosil (AEROSIL) 200, 200V, 300, R972, R972V, R974, R202, R812, R805, OX50, TT600, etc., manufactured by Aerosil Co., Ltd., preferably Aerosil 200V, R972, R972V, R974, R202, R812. These fine particles may be used in combination of two or more kinds. When two or more types are used in combination, they may be used in any ratio.

(surfactant)

The blending liquid or the fine particle dispersion liquid used in the present invention preferably contains a surfactant, and is not particularly limited to a phosphate system, a sulfonic acid system, a carboxylic acid system, a nonionic system, or a cationic system. For example, it is described in JP-A-61-243837. The amount of the surfactant added is preferably 0.002 to 2% by mass based on the cellulose halide, and more preferably 0.01 to 1% by mass. When the amount of addition is less than 0.001% by mass, the effect of addition cannot be sufficiently exhibited. When the amount is more than 2% by mass, precipitation or insoluble matter occurs.

The nonionic surfactant is a surfactant of a polyoxyethylene, polyoxypropylene, polyoxybutylene, polyglycidyl group, and sorbitan as a nonionic hydrophilic group, and specific examples thereof include polyoxyethylene. Alkane ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene-polyoxypropylene glycol, polyvalent alcohol fatty acid partial ester, polyoxyethylene polyvalent alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, fatty acid Diethanolamine, triethanolamine fatty acid partial ester.

The anionic surfactant is a carboxylate, a sulfate, a sulfonate or a phosphate salt, and is represented by a fatty acid salt, an alkylbenzenesulfonate, an alkylnaphthalenesulfonate, an alkylsulfonate or an alpha-olefin. Sulfonate, dialkyl sulfosuccinate, α-sulfonated fatty acid salt, N-methyl-N-oleyl taurine, petroleum sulfonate, alkyl sulfate, sulfated fat, polyoxyethylene An alkyl ether sulfate, a polyoxyethylene alkyl phenyl ether sulfate, a polyoxyethylene styrene phenyl ether sulfate, an alkyl phosphate, a polyoxyethylene vinyl ether phosphate, a naphthalene sulfonate formaldehyde condensate, and the like.

Examples of the cationic surfactant include an amine salt, a quaternary ammonium salt, and a pyridinium salt, and examples thereof include a first to third aliphatic amine salt and a quaternary ammonium salt (tetraalkylammonium salt, trialkylbenzylammonium salt, and Alkyl pyridinium salt, alkyl imidazolium salt, etc.). The amphoteric surfactants are carboxybetaine, sulfobetaine, etc., N-trialkyl-N-carboxymethylammonium betaine, N-trialkyl-N-sulfoalkylammonium betaine, and the like.

Further, the fluorine-based surfactant is a surfactant having a fluorocarbon chain as a water-repellent group.

(peeling accelerator)

Further, a peeling accelerator for reducing the load at the time of peeling may be added to the blending liquid. It is effective for the surfactant, and is a phosphate type, a sulfonic acid type, a carboxylic acid type, a nonionic type, a cationic type, etc., but it is not limited to this. Such a peeling accelerator is described, for example, in JP-A-61-243837. A polyethoxylated phosphate ester is disclosed as a release accelerator in JP-A-57-500833. It is disclosed in JP-A-61-69845 that a non-esterified hydroxyl group is a mono- or di-phosphate of a free acid form, and can be quickly peeled off by adding it to a cellulose ester. Further, JP-A-1-299847 discloses that a phosphate compound containing a non-esterified hydroxyl group and a propylene oxide chain and inorganic particles are added, whereby the peeling load can be reduced.

(other additives)

Further, thermal stabilizers such as inorganic fine particles such as kaolin, talc, diatomaceous earth, quartz, barium sulfate, titanium oxide, and aluminum oxide, and alkaline earth metal salts such as calcium and magnesium may be added. Further, antistatic agents, flame retardants, slip agents, oil agents, and the like are sometimes added.

The method for producing an anti-glare film of the present invention comprises a step of preparing a blending liquid (dissolution step), a flowing step, a drying step, and a winding step.

[Solution step]

In the method for producing an anti-glare film of the present invention, in the case where the polymer film is a cellulose ester film, first, the dissolution of the cellulose ester is a stirring and dissolving method generally used in a dissolving pan, a heating and dissolving method, A method of heating, stirring, and dissolving at a temperature above the boiling point of a solvent at a normal pressure of a solvent and at a temperature at which the solvent does not boil under pressure, because the so-called gel and dough are prevented from being blocked. It is better because the undissolved matter occurs. Further, a method of cooling and dissolving as described in JP-A-H09-95538, or a method of dissolving under high pressure as described in JP-A-11-21379 can be used.

A method in which a cellulose ester is mixed with a poor solvent to wet or swell, and then dissolved in a good solvent is preferably used. At this time, means for mixing or swelling the cellulose ester with the poor solvent and a device for mixing and dissolving with the good solvent may be separately provided.

The type of the pressurized container used for dissolving the cellulose ester is not particularly limited, and if it can withstand the specified pressure, it can be heated and stirred under pressure. In the pressurized container, a gauge such as a pressure gauge or a thermometer may be appropriately disposed. The pressurization may be carried out by a method of pressurizing an inert gas such as nitrogen gas or by increasing the vapor pressure of the solvent by heating. It is preferable that the heating is performed from the outside, and for example, the sleeve type is easy to control the temperature and is preferable.

The heating temperature of the solvent to be added is not less than the boiling point of the solvent to be used, and in the case of a mixed solvent of two or more kinds, it is preferably heated at a temperature higher than the boiling point of the solvent having a lower boiling point and at a temperature in which the solvent is not boiling. If the heating temperature is too high, the necessary pressure becomes large and the productivity is deteriorated. The preferred heating temperature ranges from 20 to 120 ° C, more preferably from 30 to 100 ° C, and even more preferably from 40 to 80 ° C. Also, the pressure is adjusted at the set temperature until the solvent does not boil.

In addition to the cellulose ester and the solvent, an additive such as a plasticizer or an ultraviolet absorber as needed is a solvent which is previously mixed with a solvent, dissolved or dispersed, and then put into a solvent before dissolution of the cellulose ester, or a mixture of the cellulose ester dissolved therein. can.

After the cellulose ester is dissolved, it is taken out from the container while being cooled, or pumped out from the container by a pump or the like, and cooled by a heat exchanger or the like, and the mixed solution of the obtained polymer is supplied to the film, and the cooling temperature at this time is also It can be cooled to room temperature.

The particle diameter d of the cellulose ester as a raw material is composed of a ratio of particles of 0.1 mm ≦d ≦ 20 mm to 60% by mass or more, since agglomerates of cellulose ester do not occur and good solubility can be obtained. It is better.

The mixture of the raw material cellulose ester and the solvent is dissolved in a dissolving pot having a stirrer. In this case, the peripheral speed of the stirring blade is at least 0.5 m/sec or more, and it is preferred to stir and dissolve for 30 minutes or more.

In the process of the present invention, the cellulose ester blend dissolved in the pot is dissolved, pumped to a filter, and filtered in a filter. This filtration can be carried out according to the usual method, but the method of heating and filtering under the pressure of the solvent at a temperature above the boiling point of the normal pressure and under the boiling range of the solvent, so that the differential pressure before and after the filter material (hereinafter, referred to as the filtration pressure) ) The rise is small, which is better.

In the method of the present invention, the cellulose ester blending liquid must be impurities which are different from the image recognition by filtering to remove impurities, particularly in a liquid crystal image display device. The quality of the protective film for a polarizing plate can also be determined by this filtration.

The filter medium used for the filtration is preferably one having a small absolute filtration accuracy. However, if the absolute filtration accuracy is too small, the pores of the filter material are liable to clog, and frequent replacement of the filter material may cause a problem of lowering productivity.

Therefore, in the method of the present invention, the filter medium used in the cellulose ester blending solution is preferably an absolute filtration accuracy of 0.020 mm or less. The filter paper may, for example, be No. 244 and 277 of Ampson Filter Co., Ltd., which is a commercial product, and is preferably used.

The material of the filter material is not particularly limited, and a normal filter medium can be used, and a filter material made of a plastic fiber such as polypropylene or Teflon (registered trademark) and a metal filter material such as stainless steel fiber are not detached from the fiber, and are preferably used. .

The preferred temperature range for the blending solution is 45 to 120 ° C, more preferably 45 to 70 ° C, and more preferably 45 to 55 ° C.

The filtration pressure is preferably 3,500 kPa or less, more preferably 3,000 kPa or less, and more preferably 2,500 kPa or less. In addition, the filtration pressure can be controlled by appropriately selecting the filtration flow rate and the filtration area. The blend liquid obtained in this manner is stored in a storage tank and defoamed, and is used in a flowing stream.

Thus, in the dissolution pot, the functional zone material and the cellulose ester and the solvent are mixed in advance to prepare the blending liquid, and usually, it is not necessary to add the functional zone forming material to the pipeline. However, all or a portion of the functional zone forming material may be mixed in the pipeline as needed.

For example, the fine particle dispersion mixed or dispersed in a suitable solvent in a dissolving pot is pumped to a filter and filtered in a filter. The obtained blend liquid was stored in the second storage tank and defoamed.

a cellulose ester solution (or a mixture solution) transferred from a first storage tank by means of a pump in a conduit, and a functional zone material solution (microparticle dispersion) transferred from a second storage tank by means of a pump in a conduit ), confluence with a confluence tube.

In front of the merging pipe, a filter is disposed, for example, the block and large impurities generated by the path accompanying the exchange of the filter material can be removed from the fine particle dispersion or the dope solution in the liquid supply. Here, a metal filter having solvent resistance is preferably used.

The filter material is preferably metal, particularly stainless steel, from the viewpoint of durability. From the viewpoint of clogging of the pores, the porosity is preferably from 60 to 80%. It is preferable to filter the metal filter material having an absolute filtration accuracy of 30 to 60 μm and a porosity of 60 to 80%, so that it is possible to remove coarse impurities for a long period of time. Examples of the metal filter material having an absolute filtration accuracy of 30 to 60 μm and a porosity of 60 to 80% include, for example, NF-10 of the Fine Pore NF series manufactured by Nippon Seisakusho Co., Ltd., NF-12, and NF-13.

Since the two liquids merged as described above are transferred in a layered manner in the catheter, it is difficult to mix them as they are. Then, after the two liquids are combined, they are transferred to the next step while being thoroughly mixed by a mixer (19) like a line mixer.

A line mixer which can be used in the present invention, for example, a Static Mixer SWJ (manufactured by Toray Static In-Tube Mixer, Hi-Mixer, manufactured by Toray Engineering) is preferred.

[rogue step]

Fig. 1 is a schematic flow chart of an apparatus for producing an antiglare film comprising a concave-convex surface forming apparatus using a casting roll for carrying out the method of the present invention. Fig. 1a is a schematic overall side view, and Fig. 1b is a plan view of the same main part.

Referring to FIG. 1a, the blending liquid prepared by dissolving the pot is fed to the rogue mold (1) via a conduit, and is in a flowing position on the support body (2) which is infinitely transferred, for example, a rotary drive stainless steel endless belt. The step of mixing the flowing stream by the flowing mold (1).

In the present invention, the flowing mold (1) is preferably a press mold which can adjust the slit shape of the nozzle portion and which is easy to make the film thickness uniform.

The flowing mold (1) preferably has an angle of 40 to 90° with respect to the surface of the inner slit and the surface of the support (2), and particularly preferably 60 to 75°. It is preferable that the gap between the die lip of the flowing mold (1) and the surface of the support (2) is spaced apart by a gap of 0.2 to 10 mm, and more preferably a gap of 0.5 to 5 mm. The slit of the slit of the flowing mold (1) is preferably 0.05 to 1.5 mm, and more preferably 0.15 to 1.0 mm.

Next, the surface roughness Ra of the flow raft support (2) is 0.0001 to 1 μm, more preferably 0.0003 to 0.1 μm, and further preferably 0.0005 to 0.05 μm.

In the film forming apparatus including the rotary drive endless belt as the support (2), the belt support (2) is disposed between the pair of drums and the middle thereof, and the upper portion of the endless belt support (2) is moved and The lower transition portions are respectively constituted by a plurality of support rollers (not shown) supported on the back side.

Further, one of the both ends of the endless belt support (2), or both drums, is provided with a driving device for applying tension to the belt support (2), and thereby the belt support (2) is It is used in a state of being pulled apart by tension.

In the case where the endless belt is used as the support (2), the belt temperature at the time of film formation is from 0 ° C in the normal temperature range to less than the boiling point of the solvent, and is in the range of 5 ° C to the boiling point of the solvent - 5 ° C. good. At this time, the ambient atmosphere humidity must be controlled above the dew point.

In addition, the conveying speed of the support (2) is 10 m/min or more, and the flow of the flowing film which is formed in the lip of the rogue mold (1) is suppressed to be mixed with air, and the stripe is formed in the width direction of the film. The flowing tape is sticky, and a decompression chamber is provided on the upstream side of the flowing mold (1), and the pressure is preferably 10 to 600 Pa, more preferably 10 to 200 Pa.

When the gap between the lower end surface of the decompression chamber and the surface of the support (2) is 0.5 to 5 mm, the suction air volume is not excessively large, so that it is preferable to suppress the dry film of the blending liquid at the lip end portion of the flowing mold (1). .

Further, in order to increase the film forming speed, two or more pressurized weir molds (1) may be provided on the flow support member (2), and the amount of the mixed liquid may be divided and superposed to form a film.

When the blend liquid flows on the support (2), it is controlled so as not to reach the boiling point of the solvent used for dissolving the base polymer, and the mixed solvent is preferably controlled to a boiling temperature of the solvent which does not reach the lowest boiling point.

In the method of using the endless belt as the support (2), on the support (2), the coil (the film containing the residual solvent after the flow of the blend on the support is referred to as a coil) (10) is dried and cured to be The film strength which can be peeled off by the peeling roll (3) in the support (2) is preferably such that the amount of residual solvent in the coil (10) is preferably 150% by mass or less, and more preferably 80 to 120%. Further, it is preferable that the temperature of the coil when the coil (10) is peeled off from the support (2) is 0 to 30 °C. Further, immediately after the coil (10) is peeled off from the support (2), the temperature is temporarily lowered rapidly due to evaporation of the solvent from the side of the support surface of the support (2), and the vapority and solvent vapor in the atmosphere are volatile. Since the component is easily concentrated, it is more preferable that the coil temperature at the time of peeling is 5 to 30 °C.

Here, the amount of residual solvent is represented by the following formula.

Residual solvent amount (% by mass) = {(M - N) / N) × 100

In the formula, M is the mass of the coil at any time, and N is the mass of the mass M material dried at 110 ° C for 3 hours. [Solvent evaporation step]

The blended film (coil) formed from the blended liquid flowing on the endless support (2) is heated on the support (2), and the solvent is evaporated to the peelable roll (3) by the support (2) The step of peeling off the coil.

The solvent is evaporated, and there is a method of blowing air from the side of the coil, and/or a method of transferring heat from the inside of the support (2) by liquid, a method of transferring heat from the surface by radiant heat, or the like.

[Peeling step]

In the method of using the endless belt in the support (2), the peeling tension when the support (2) and the coil (10) are peeled off by the peeling roll (3) is usually peeled off at 20 to 25 kg/m, but more than before. The filmed cellulose ester film produced by the present invention is preferably not peeled off at the time of peeling (10), and is preferably peeled off at a minimum tension of -17 kg/m, and preferably at a minimum. Peeling was carried out at a tension of ~14 kg/m.

[Forming the bump step]

Next, referring to Fig. 1a and Fig. 1b, the method for producing an anti-glare film of the present invention is a blending solution (resin solution) in which a thermoplastic resin is dissolved in a solvent, flowing from a flowing mold (1) to a rotary-driven stainless steel having a smooth surface. The web (support) (2) is formed into a web (10), and is cast in the step of drying the web (10) which is peeled off by the peeling roller (3) by the support (2). The type processing roll (7) presses the surface of the web (10) and forms an uneven surface on the surface of the film via the opposite back roll (8).

Thereafter, the web (10) is dried by a drying device (13) to form a film, which is taken up by a take-up roll (15), which will be described later.

The concave-convex processed surface of the coil (10) can be appropriately selected from the air side (A surface) when flowing to the support (2), or the surface (B surface) connected to the support (2), but it is easy to process. In terms of properties and uniformity, it is better to process the B side.

In the method of the present invention, the amount of residual solvent in the coil (10) when the mold forming rolls (7) are formed into irregularities is preferably from 10 to 70% by mass, more preferably from 15 to 50% by mass.

Here, when the surface of the coil (10) containing the residual solvent amount is processed, the coil (10) is dried by shrinking the coil (10) in the width direction and the conveying direction, and the casting roll is applied to the casting roll. (7) The surface has a relative speed, and the unevenness of the surface of the casting roll (7) causes minute damage in the wide axis direction and the conveying direction of the surface of the coil. This damage can be suppressed by the amount of residual solvent of the coil (10) being 70% by mass or less. Moreover, when the amount of residual solvent of the coil (10) at the time of the uneven processing is too large, the coil (10) is soft and easy to process, but it is easy to cause hoisting, wrinkles, and, depending on the case, the web to be conveyed (10) )fracture. However, if the amount of residual solvent of the coil (10) is less than 10% by mass, it must be subjected to a large pressing force on the uneven processing of the casting roll (7), and it is still prone to occur by bending deformation of the back roll (8). Lifting ‧ wrinkles

The film has a width of from 1000 mm to 3000 mm and a thickness of from 20 to 200 μm.

The casting roll (7) / back roll (8) may also have a temperature adjustment mechanism as needed. The concave and convex shape can be controlled at an appropriate temperature. Further, when the amount of the residual solvent of the coil (10) at the time of processing is 30% by mass or more, the casting roll (7)/back roll (8) is heated to prevent the solvent and other substances volatilized from the coil (10). The additive was concentrated on a casting roll (7) / back roll (8). The appropriate temperature of the casting roll (7)/back roll (8) varies depending on the amount of residual solvent of the coil (10), but is preferably 10 to 100 °C. When a high temperature roll is used when the amount of residual solvent is large, planarity is deteriorated.

The temperature of the casting roll (7)/back roll (8) is such that the temperature-controlled heat medium in the roll circulates and a metal heater is placed inside the roll to control it.

In the present invention, the mold processing roll (7) for forming the uneven surface can be appropriately selected from those having a fine shape and a thick shape, and a concave or convex portion formed by a part of a spherical surface can be used as a bottom plate shape or a lenticular lens shape. The molds forming the prismatic irregularities are regularly aligned or randomly arranged.

For example, a concave portion or a convex portion having a convex portion or a concave portion having a diameter of 5 to 100 μm and a height of 0.1 to 2 μm may be used, and large irregularities and small irregularities may be combined.

When the concavo-convex processing is performed in a state in which the amount of residual solvent is present in the film, the film shrinkage in the conveyance direction/wide axis direction/thickness direction is assumed to be caused by drying of the film after the processing, and is selected to become a desired film concavity after drying and winding. The shape of the shape of the casting roll (7). When the width is stretched by the tenter before or after the unevenness is processed, and when the conveyance direction is stretched, the surface shape of the mold roll (7) must be selected in order to form a suitable film uneven shape after the drawing.

In the case where the film stretching after the uneven processing is greatly different in the width direction and the conveying direction, the thickness and the pitch of the casting roll (7) may be different in the wiring direction and the axial direction. Further, in the case where the hard coat layer and the antireflection layer are applied after the unevenness is formed, the surface of the mold roll (7) which reduces the uneven shape of the uneven hole by coating is selected.

The surface unevenness of the film to be completed is preferably an average thickness (Ra) of 0.1 to 1.5 μm as defined in JIS B 0601, and a pitch (Sm) of 5 to 100 μm.

The material of the casting roll (7) and the back roll (8) can be made of metal, stainless steel, carbon steel, aluminum alloy, titanium alloy, ceramic, glass, hard rubber, plastic or the like, but by strength and processing. In terms of easiness, the casting roll (7) is preferably metal. In particular, the ease of washing and durability are also important, and it is preferable to use a casting roll (7) made of stainless steel or hard chrome. Moreover, the surface may also be water repellent or water repellent.

The method for forming the desired uneven surface on the mold roll (7) may be a sandblasting method, a pulsed laser method, a mechanical processing method of electrical discharge machining, a chemical method such as an etching method, or even a reactive material. A method in which a mechanical method and a chemical method are simultaneously blown with an abrasive may be combined. Further, after the surface of the roll is applied, the fine particles are blown onto the undried binder, and the binder is dried and fixed to the fine particles, and the material containing the fine particles and the binder is blown to the roll, and a metal mold may be used.

The back roll (8) is preferably made of a hard rubber, a hard plastic or metal roll, or a metal elastic roll.

The casting roll (7) or the back roll (8) may be formed as a free roll or driven by either one. As in the case of the present invention, when the film containing the residual solvent is processed, since the conveying direction of the film is contracted, it is preferable to control the driving speed by the tension.

Further, the eccentricity of the mold roll (7) and the back roll (8) is preferably 50 μm or less, more preferably 20 μm or less, and particularly preferably 0 to 5 μm.

The diameter of the casting roll (7) is preferably 5 to 200 cm, more preferably 10 to 100 cm, and particularly preferably 10 to 50 cm.

The roll pressure at the time of forming the unevenness is 200 to 50,000 N/m, more preferably 500 to 30,000 N/m, and is appropriately determined in consideration of the type of the thermoplastic resin, the shape of the unevenness formed, the temperature, and the like.

Next, the method for producing the anti-glare film of the present invention is such that the web (10) in the upstream side of the coil processing direction of the mold processing roll (7) conveys the tension and is adjusted at the left and right ends of the coil (10). Different from each other.

Generally, the coil (10) containing the amount of residual solvent is soft on the surface of the coil and excellent in surface workability. However, when the coil (10) is pressed against the casting roll (7), the coil (10) is liable to hang. Wrinkles and wrinkles. The lifting and wrinkling of the coil (10) is a non-uniformity in the width direction of the coil material in the conveyance, and a slight left-right deviation of the conveying device such as a roller row or a dry wind at the time of drying. Wind speed difference and temperature difference occur. The left and right deviation of the equipment is reduced as much as possible even during the installation of the production equipment, and the change in temperature due to the repeated temperature changes at the beginning and end of the production causes a change in time, which is extremely difficult to maintain for a long period of time without lifting and wrinkling. Folded state.

Then, in the present embodiment, the conveyance tension of the coil (10) is independently measured in the upstream side of the coil processing direction of the mold processing roll (7), and as a result, the coil conveyance tension adjusting mechanism is operated. When the difference between the measured values of the web conveyance tension at the right and left end portions of the coil is reduced to the allowable range, the occurrence of lifting and wrinkles can be suppressed.

Specifically, the web (10) peeled off from the support (2) by the peeling roll (3) is conveyed to the mold processing roll (7) via the guide roll (4), and the mold processing roll (7) In the upstream side of the web conveying direction, a web conveying tension adjusting mechanism that adjusts the conveying tension of the web to the left and right end portions of the web to be different from each other is provided, and the left and right independent measuring coil conveying tension is provided on the same side. In the tensiometer (9A) (9B) of the means, the difference in the measured value of the web transport tension between the left and right end portions of the tension meter (9A) (9B) is 1 to 5%, preferably 2 to 4.5%. In general, the coil adjustment tension adjustment mechanism is finely adjusted.

That is, the right and left tensions before the uneven processing of the coil (10) are independently measured left and right by the tensiometer (9A) (9B) shown in Figs. 1a and 1b, and the film guiding device (11) on the upstream side is passed. (12) When the roller moves to the left or right, the value of the tensiometer (9A) (9B) can be adjusted to a desired value or less.

In Fig. 1a and Fig. 1b, the right end portion (5a) (6a) of the two transport tension adjusting rollers (5) (6) arranged at a plurality of intervals in the front and rear is used as a base point, so that the same left end portion (5b) 6b) Shake back and forth separately to adjust.

Next, for example, on the rear side of Fig. 1a and Fig. 1b, if the right end portion (5a) of the lower roller (5) is used as a base point, the left end portion (5b) of the same roller is rocked in front, and the left end portion (5b) of the same roller is The pressure is applied to the left end portion of the conveyance coil (10), so that the film conveyance tension is increased in this portion. On the other hand, on the front side of Fig. 1a and Fig. 1b, if the right end portion (6a) of the upper roller (6) serves as a base point and the left end portion (6b) of the same roller is rocked in the front, the left end portion (6b) of the same roller When the pressure is applied to the left end portion of the conveyance coil, the film conveyance tension is increased in this portion, so that the conveyance tension of the left end portion of the conveyance coil (10) and the conveyance tension of the same right end portion can be opposite to each other. Different changes.

Further, in the method of the present invention, when the unevenness is formed by the mold processing roll (7), the contact time of the film with the mold processing roll (7) is preferably 2.5 × 10 ^-3 to 1.0 second.

That is, when the coating angle and the packaging time of the film and the casting roll (7) are large, hoisting and damage are liable to occur, and in the case of the film, the workability is deteriorated, and the appropriate coating angle and packaging time are present.

If the method according to the invention is used, no lifting will occur. Wrinkles and minor damage to the surface make it possible to produce an anti-glare film with excellent planarity and reduced surface sparkling and impurity barriers under high productivity.

Fig. 2 is a side elevational view showing the principal part of a second embodiment of the apparatus for forming a concave-convex surface using a film tension adjusting mechanism and a casting roll (7) for carrying out the method of the present invention, and using two for one back roll (8). Casting roll (7A) (7B).

The number of the embossing rolls (7) may be one. However, when a plurality of casting rolls (7) are used, the uniformity of the unevenness is increased, and a complicated uneven shape can be easily obtained. Further, when a plurality of mold rolls (7A) (7B) are used, the mold roll (7A) (7B) having different surface irregularities can be used to easily control the anti-glare property and the image sharpness, and the film can be made thin. The white blur and sparkle of the surface are reduced.

Thus, when two casting rolls (7A) (7B) are used for one back roll (8), the position of the casting rolls (7A) (7B) is set at 180° with respect to the center of the back roll (8). At the position, it is not easy to cause unevenness of the unevenness due to the bending of the back roll (8), so that it is preferable.

Fig. 3 is a side elevational view showing a principal part of a third embodiment of the apparatus for forming a concave-convex surface using a film tension adjusting mechanism and a casting roll (7) for carrying out the method of the present invention, using four castings for one back roll (8). Roller (7A) 7B) (7C) (7D). When four casting rolls (7A) (7B) (7) are used for one back roll (8), if the position of the casting rolls (7A) (7B) (7C) (7D) is relative to the back roll (8) When the center of the center is placed at the front and rear sides, it is not easy to cause unevenness of the unevenness due to the bending of the back roll (8), so that it is preferable.

Fig. 4 is a view showing a fourth embodiment of the apparatus for forming a concave-convex surface using a film tension adjusting mechanism and a casting roll (7) for carrying out the method of the present invention. In this embodiment, when the forming roll (7) is formed into irregularities, The coil (10) is directed to the entire circumference by about 1/3 of the circumference of the casting processing roll (7) so that the contact time of the film (web) (10) with respect to the casting processing roll (7) is increased.

In other words, when the coating angle and the packaging time of the film (coil) (10) and the mold roll (7) are appropriate, it is possible to prevent lifting and damage from occurring, and the workability is excellent.

Fig. 5 is a view showing a fifth embodiment of the apparatus for forming a concave-convex surface using a film tension adjusting mechanism and a casting roll (7) for carrying out the method of the present invention. In the method of the present invention, a plurality of molds may be disposed at one place. A combination of a roller (7) and a back roller (8).

As shown in the figure, two sets of one mold roll (7) and one back roll (8) were used.

Thus, if a plurality of mold rolls (7) are used, the unevenness of the mold roll (7) can be more uniformly or randomly formed, and a complicated uneven shape can be easily formed.

Fig. 6 is a schematic flow chart showing another apparatus for manufacturing an anti-glare film according to a sixth embodiment of the casting roll (7) for carrying out the method of the present invention, and Fig. 6a is a schematic overall side view, Fig. 6b For the same main floor plan. In the sixth embodiment, the tension meter (9A) (9B) and the film guiding roller (11) (12) are provided on the downstream side of the mold processing roller (7) and the back roller (8) in the web conveying direction.

Further, in the second embodiment to the sixth embodiment of the present invention in the above-described Figs. 2 to 6 , in the present invention, the coil is independently measured on the upstream side in the coil conveying direction of the casting processing roll (7). (10) The conveyance tension (10), and according to the result, the coil conveyance tension adjustment mechanism is operated, and the difference in the measured value of the web conveyance tension at the left and right end portions of the coil is as small as the allowable range, and the lifting and the lifting can be suppressed. The occurrence of wrinkles is the same as in the case of the first embodiment described above.

Specifically, in the second embodiment to the sixth embodiment of the present invention shown in FIGS. 2 to 6 , the coil (10) is provided on the upstream side of the coil processing direction of the mold processing roll (7). The tensioning mechanism (9A) (9B) (9A) (9B) is used to adjust the tension of the web to the left and right sides of the coil (10). The measurement value difference of the coil conveyance tension of the left and right ends of the coil of the tension meter (9A) (9B) is 1 to 5%, preferably 2 to 4.5%, and the jog adjustment coil conveying tension adjusting mechanism .

In other words, the left and right tensions before the uneven processing of the coil (10) are independently measured by the tension meter (9A) (9B), and the rollers of the film guiding device (11) (12) located on the upstream side thereof move left and right. The value of the tensiometer (9A) (9B) can be adjusted to below the desired value.

The right end portion (5a) (6a) of the two transport tension adjusting rollers (5) and (6) arranged at a plurality of intervals in the front and rear is used as a base point, and the left end portions (5b) (6b) are respectively rocked back and forth to adjust .

Next, if the right end portion (5a) of the roller (5) in the lower side of the rear side is used as a base point, and the left end portion (5b) of the same roller is rocked in the front, the left end portion (5b) of the same roller is pressed to the conveying coil. At the left end of (10), the film transport tension is increased in this portion. On the other hand, if the right end portion (6a) of the roller (6) in the preceding stage is used as the base point and the left end portion (6b) of the same roller is rocked in the front, the left end portion (6b) of the same roller is pressed to the transporting roller. In the left end portion of the material, the film conveyance tension is increased in this portion. Thus, the conveyance tension of the left end portion of the conveyance coil (10) and the conveyance tension of the right end portion can be changed to be different from each other.

[Drums of the drums]

Fig. 7 is a schematic flow chart showing still another apparatus for producing an anti-glare film according to the method of the present invention, using a drum as a support (22), Fig. 7a is a schematic overall side view, and Fig. 7b is a plan view of a main portion.

As described above, the uneven surface forming apparatus used in the present invention can be applied not only to the apparatus using the flow band, but also to the apparatus using the flow drum (22). In this case, a casting roll (7) for forming an uneven surface and a back roll (8) opposed thereto are also disposed.

In the same figure, in the same manner as above, a blending solution (resin solution) in which a thermoplastic resin is dissolved in a solvent is prepared, and the blending liquid is passed through a pressurized type quantitative gear pump and sent to a flowing mold (1) in a flowing position. The blending liquid flows from the flowing mold (1) to the hard chrome-plated drum support (22) to obtain the coil (10), and the coil (10) is moved about 3 by the rotation of the drum support (22). /4 weeks, peeled off with a peeling roll (3).

In the case where the drum is used as the support (22), the drum support (22) is dried and solidified until the film strength of the web (10) can be peeled off by the support (22), so the temperature of the drum support (22) is cooled. It is preferably at most 10 ° C, and more preferably cooled to below 0 ° C, and more preferably cooled to below -10 ° C. The blending liquid on the surface of the drum increases the strength (film strength) of the gel film by cooling gelation, and increases the strength (film strength) of the gel film by promoting drying between stripping.

Next, the amount of the residual solvent to be supported in the coil (10) is preferably from 10 to 250% by mass, and more preferably from 20 to 220% by mass. When the amount of the residual solvent is more than 250% by mass, peeling of the thermoplastic resin occurs on the support (22). Moreover, it is preferable that the peeling tension at the time of peeling of the drum support body (22) and the coil material (10) is 0.1-6 kg/m.

In the embodiment of FIG. 7, the conveyance tension of the coil (10) is independently measured on the downstream side of the roll processing direction of the mold processing roll (7), and according to the result, the web is conveyed by the tension. When the adjustment mechanism operates to reduce the difference in the measured value of the web transport tension between the left and right ends of the coil to the allowable range, the occurrence of lifting and wrinkles can be suppressed as in the case of the first embodiment described above. In the drawing, the same symbol is attached to the same part.

[Treading machine stretching step]

Next, although not shown in the drawings, the web (10) is subjected to a stretching process in the widthwise direction or the web conveyance direction as needed before or after the formation of the unevenness of the web (10).

In the image display member film, a tenter method in which both side edges of the web (or film) (10) are fixedly stretched by a clip or the like is known, and it is preferable because the flatness and dimensional stability can be improved.

In particular, in the drying step after the support (2) is peeled off, the web (or film) is shrunk in the broad axis direction by evaporation of the solvent. The more dry at high temperatures, the greater the shrinkage. By suppressing this shrinkage as much as possible and drying it, the planarity of the finished film is good and preferable.

From this point of view, the method of using a tenter is preferably a method/later method in which both steps of drying or a part of the steps of drying the both ends of the width of the web with the clip in the wide-axis direction and drying is performed.

When the residual solvent amount is from 10 to 100% by mass, at 80 to 130 ° C, and/or the residual solvent amount is from 5 to 10% by mass, when held at 90 to 150 ° C, the width is maintained by a tenter or the film width is 1 The stretching of about -20% is particularly advantageous for improving the planarity of the high cellulose ester film.

Further, it is preferable that the difference in the tension of the web (10) before and after the tenter in the transport direction is 8 N/mm ² or less.

In addition, a preheating step of preheating the coil (10) is provided. After the preheating step, the step of stretching the web (10) by using a tenter dryer, and the step of stretching, The coil (10) is only subjected to a relaxation step which is less than the amount of stretching of the stretching step, and the temperature T1 in the preheating step and the stretching step is (the glass transition temperature of the film Tg-60 ° C) The above, and the temperature T2 in the relaxation step is preferably (T1 ° C - 10 ° C) or less.

In particular, the ratio of the elongation of the web (10) of the above-mentioned stretching step is 0 to 30% with respect to the width of the web before entering the stretching step. On the other hand, the web of the easing step is desired. The elongation rate of (10) is -10 to 10%.

In the stretching step of the tenter apparatus, for example, the elongation ratio at the time of producing the cellulose ester film is 1.01 to 3 times, preferably 1.5 to 3 times, with respect to the film forming direction or the broad axis direction. When extending in the biaxial direction, the stretching side at a high magnification is 1.01 to 3 times, preferably 1.5 to 3 times, and the stretching ratio in the other direction is 0.8 to 1.5 times, preferably 0.9 to 1.2 times. Pull.

It is preferable that the width maintaining or the lateral stretching of the manufacturing step is performed by a tenter device, and it may be a tenter tenter or a pinch tenter.

In addition, in the stretching step of the tenter device, the warm air (24) is blown in from the front portion of the bottom portion of the tenter device, and the wind (24) is discharged from the rear portion of the tenter of the tenter device to make the coil (10) At the same time, it is stretched and dried.

[Drying step]

After the stretching step of the tenter device (not shown), for example, as shown in Figs. 1, 6, and 7, it is preferable to provide a drying device (13). In the drying device (13), the web (10) is meandered by a plurality of conveying rollers (14) arranged in a staggered configuration on the side, during which the web (10) is dried. Further, the film transporting tension of the drying device (13) is preferably 30 to 250 N/m, depending on the physical properties of the blending liquid, the amount of residual solvent during peeling and the film transporting step, and the temperature of the drying device (13). More preferably 60 to 150 N/m. 80 to 120 N/m is the best.

Further, the means for drying the coil (or film) (10) is not particularly limited, and is generally carried out by hot air, infrared rays, heating rolls, microwaves or the like. It is preferable to dry by hot air from the viewpoint of simplicity, for example, by blowing the warm air discharged from the rear portion of the bottom portion of the drying device (13) to the rear portion of the drying device (13). The drying temperature is preferably from 40 to 160 ° C, and is preferably from 50 to 160 ° C in planarity and good dimensional stability.

The steps from flowing to drying are carried out under an air atmosphere, and may also be carried out under an inert gas atmosphere such as nitrogen. At this time, of course, the dry atmosphere is carried out in consideration of the critical concentration of the explosion of the solvent.

The web conveying tension at the time of drying is 30 to 300 N/width m, and more preferably 40 to 270 N/width m.

After the drying is completed, the cutter is cut off before the winding, and it is preferable to obtain a good roll posture.

[embossing step]

Next, it is preferable that the polymer film which has been subjected to the transport drying step is subjected to embossing of the film via the embossing device before the introduction of the winding step.

Here, the height h (μm) of the embossing is set to be in the range of 0.05 to 0.3 times the film thickness T, and the width W is set to be in the range of 0.005 to 0.02 times the film width L. For example, when the film thickness is 40 μm and the film width is 100 cm, the thickness of the embossing 31 is 2 to 12 μm, and the embossing width is set to 5 to 30 mm.

Embossing can also be formed on both sides of the film. At this time, the height h1+h2 (μm) of the embossing is set to be in the range of 0.05 to 0.3 times the film thickness T of the film, and the width W is in the range of 0.005 to 0.02 times the film width L. For example, when the film thickness is 40 μm, the height h1+h2 (μm) of the embossing is set to 2 to 12 μm. The embossing width is preferably set to 5 to 30 mm.

[rolling step]

The dried film (20) is taken up by a winding device (15) to obtain a basic roll of the anti-glare film. When the amount of the residual solvent of the film (20) which has been dried is 0.5% by mass or less, preferably 0.1% by mass or less, a good film having dimensional stability can be obtained.

If the film winding method is a general winding machine, a method of controlling the tension such as a constant torque method, a constant tension method, a tapered tension method, or a program tension control method with a constant internal stress can be used. Just use it.

The joining of the film to the take-up core (core) can be carried out on either side or on one side.

The film thickness of the anti-glare film of the present invention varies depending on the purpose of use. However, from the viewpoint of reducing the thickness of the liquid crystal display device, the film is preferably in the range of 10 to 150 μm, and more preferably in the range of 20 to 100 μm. It is particularly preferably in the range of 25 to 80 μm.

When the film thickness of the film is too small, for example, the strength required as a protective film for a polarizing plate may not be obtained. If the film thickness of the film is too thick, the superiority of the film formation of the previous cellulose ester film becomes insufficient.

In the adjustment of the film thickness, it is preferred to control the concentration of the blending solution, the amount of the liquid to be pumped, the slit gap of the nozzle of the flowing mold, the pressing pressure of the flowing mold, and the speed of the support at a desired thickness. Further, the means for making the film thickness uniform is preferably a film thickness detecting means for feeding back the programmed feedback information to the respective devices.

In the step from the flow of the solution flowing film forming method to the drying, the atmosphere in the drying device may be air, or may be carried out under an inert gas atmosphere such as nitrogen or carbon dioxide gas. However, it is of course necessary to always consider the critical danger of explosion of the evaporating solvent in the dry atmosphere.

The antiglare film of the present invention is used for a member for liquid crystal display in terms of good moisture permeability, dimensional stability, and the like, and is particularly preferably used for a protective film for a polarizing plate. In particular, in the protective film for a polarizing plate which has strict requirements for moisture permeability and dimensional stability, the antiglare film of the present invention is preferably used.

In general, when a cellulose ester film is used as a protective film for a polarizing plate, alkali alkalining treatment is performed in order to obtain a good adhesion to a polarizer. The film and the polarizer after the alkalization treatment of the alkali are adhered by using the aqueous solution of polyvinyl alcohol as a binder, so if the contact angle of the alkali of the cellulose ester film with water is high, the polyethylene cannot be used. The adhesion of the alcohol is a problem as a protective film for a polarizing plate.

When the cellulose ester film produced by the method of the present invention is used as a member for LCD, in order to reduce light leakage of the film, high planarity is required, and the center line average roughness (Ra) of the anti-glare film is defined by JIS B 0601. The measurement method may, for example, be a stylus method or an optical method.

In the present invention, the cellulose ester film preferably has a center line average roughness (Ra) of 20 nm or less, more preferably 10 nm or less, and particularly preferably 4 nm or less.

The polarizing plate is, for example, a protective film for a polarizing plate comprising an antiglare film produced by the method of the present invention on at least one side.

The liquid crystal display device has the above-described polarizing plate on at least one side of the liquid crystal element.

Next, a description will be given of such a polarizing plate and a liquid crystal display device using the polarizing plate.

The polarizing plate can be produced by a general method. The cellulose ester film of the present invention which is alkalized by alkali is a method in which a polyvinyl alcohol-based film is immersed in at least one surface of a polarizer produced by stretching in an iodine solution, and is adhered to a fully alkalized polyvinyl alcohol aqueous solution. good. The cellulose ester film of the present invention can also be used on the other side, and other protective films for polarizing plates can also be used.

For the antiglare film of the present invention, a commercially available cellulose ester film can be used as the protective film for the polarizing plate used for the other side. For example, a commercially available cellulose ester film is preferably KC8UX2M, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC8UY-HA, KC8UX-RHA, KC8UX-RHA-N (above, Konica-Minoltaopto Co., Ltd.) or the like. Alternatively, a film of a cyclic olefin resin, an acrylic resin, a polyester, or a polycarbonate other than the cellulose ester film may be used as the protective film for a polarizing plate on the other surface.

At this time, since the saponification is low in suitability, it is preferably processed through a suitable subsequent layer to the polarizing plate.

In the polarizing plate, the antiglare film of the present invention is used as a protective film for a polarizing plate on at least one side of a polarizer. At this time, the retardation axis of the anti-glare film is preferably arranged in a substantially parallel or perpendicular to the absorption axis of the polarizer.

This polarizing plate is preferably used as a polarizing plate in which a liquid crystal element of a horizontal electric field switching type is sandwiched, and the cellulose ester film of the present invention is disposed on the liquid crystal display element side.

The polarizer which is preferably used for the polarizing plate is a polyvinyl alcohol-based polarizing film which is used for dyeing iodine in a polyvinyl alcohol-based film and dyeing with a dichroic dye. As the polyvinyl alcohol-based film, a modified polyvinyl alcohol-based film modified with ethylene is preferably used. The polarizer is a film formed by using a polyvinyl alcohol aqueous solution, and is subjected to uniaxial stretching dyeing, or after uniaxial stretching after dyeing, preferably subjected to durability treatment with a boron compound.

The film thickness of the polarizer is 5 to 40 μm, preferably 5 to 30 μm, and particularly preferably 5 to 20 μm. On the surface of the polarizer, the anti-glare film of the present invention is bonded to one side to form a polarizing plate. It is preferred to bond them with a water-based adhesive containing, as a main component, a fully alkalized polyvinyl alcohol. Further, in the case of a resin film other than the cellulose ester film, it is processed through a suitable adhesive layer to a polarizing plate.

Since the polarizer is stretched in the uniaxial direction (usually in the long axis direction), if the polarizing plate is placed in a high temperature and high humidity environment, the stretching direction (usually the long axis direction) shrinks, relative to the stretching. Extends in the vertical direction (usually the broad axis direction). When the film thickness of the protective film for a polarizing plate is thinner, the expansion ratio of the polarizing plate is increased, and the amount of shrinkage in the stretching direction of the polarizer is large. In general, the direction in which the polarizer is stretched is bonded to the flow direction (MD direction) of the protective film for a polarizing plate. Therefore, when the protective film for a polarizing plate is formed into a thin film, it is particularly important to suppress the expansion ratio in the flow direction. Since the antiglare film of the present invention is excellent in dimensional stability, it is suitably used as a protective film for such a polarizing plate.

The polarizing plate is formed by attaching a protective film to the other surface of the polarizing plate and bonding the insulating film to the reverse side. The protective film and the release film are used for the purpose of protecting the polarizing plate when the polarizing plate is shipped or during product inspection.

The liquid crystal display device using the anti-glare film produced by the method of the present invention has excellent quality such as no unevenness on the screen.

Since the polarizer is stretched in the uniaxial direction (usually in the long axis direction), if the polarizing plate is placed in a high temperature and high humidity environment, the stretching direction (usually the long axis direction) shrinks, relative to the stretching. Extends in the vertical direction (usually the broad axis direction). When the film thickness of the protective film for a polarizing plate is thinner, the expansion ratio of the polarizing plate is increased, and the amount of shrinkage in the stretching direction of the polarizer is large. In general, the direction in which the polarizer is stretched is bonded to the flow direction (MD direction) of the protective film for a polarizing plate. Therefore, when the protective film for a polarizing plate is formed into a thin film, it is particularly important to suppress the expansion ratio in the flow direction. Since the antiglare film of the present invention is excellent in dimensional stability, it is suitably used as a protective film for such a polarizing plate.

The polarizing plate is formed by attaching a protective film to the other surface of the polarizing plate and bonding the insulating film to the reverse side. The protective film and the release film are used for the purpose of protecting the polarizing plate when the polarizing plate is shipped or during product inspection.

(liquid crystal display device)

By assembling a polarizing plate using the anti-glare film of the present invention to a liquid crystal display device, it is possible to produce a liquid crystal display device having excellent visibility.

The anti-glare film of the present invention preferably uses various types of driving such as reflective, transmissive, semi-transmissive LCD or TN type, STN type, OCB type, HAN type, VA type (PvA type, MVA type), IPS type, and the like. The way the LCD. In particular, in a display device with a screen size of 30 吋 or more, especially for a large screen of 30 吋 to 54 ,, there is no whitening in the peripheral portion of the screen, and this effect can be maintained for a long period of time, and a remarkable effect is observed in the MVA type liquid crystal display device. . In particular, there are few spots, sparkles, and wavy spots, and even if it is used for a long time, it has the effect that the eye nitrile does not fatigue.

As described above, the liquid crystal display device having the polarizing plate using the anti-glare film of the present invention on at least one side of the liquid crystal element is excellent in display quality.

Example

Hereinafter, the embodiments of the present invention will be described, but the present invention is not limited thereto.

Examples 1-9 (Cellulose ester film 1) (Production of cerium oxide dispersion A)

Aerosil 972V (manufactured by Nippon Aerosil Co., Ltd.) 12 parts by mass

(The average particle size of the primary particles is 16 nm, and the apparent specific gravity is 90 g/L)

Ethanol 88 parts by mass

The above materials were stirred and mixed with a dissolution bar for 30 minutes, and then dispersed by a homogenizer to prepare a ceria dispersion A.

Next, in the cerium oxide dispersion A, 88 parts by mass of dichloromethane was introduced while stirring, and the mixture was stirred and mixed for 30 minutes with a dissolving rod to prepare a cerium oxide dispersion diluent A.

(Production of pipeline addition liquid A)

TINUVIN 109 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 11 parts by mass

TINUVIN 171 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 5 parts by mass

Methylene chloride 100 parts by mass

The above-mentioned material was placed in a sealed container, and while stirring, it was stirred, completely dissolved, and filtered. In the above, 36 parts by mass of the above-mentioned cerium oxide dispersion diluent A was added while stirring, and after stirring for further 30 minutes, the cellulose acetate acrylate (acetate substitution degree 1.9, propyl ketone substitution degree 0.8) 6 mass The mixture was added while stirring, and after stirring for another 60 minutes, it was filtered with Advantech Toyo Co., Ltd. polypropylene Wind Catridge Filter TCW-PPS-1N to prepare a line addition liquid A.

(Modulation of Blend A)

Cellulose triacetate 100 parts by mass

(Synthesized from cottonseed cotton, Mn=95000, Mw=323000, Mw/Mn=3.4, acetonitrile substitution degree 2.9)

Trimethylolpropane tribenzoate 5.0 parts by mass

(aliphatic polyvalent alcohol ester)

Ethyl decyl ethyl glycolate 5.5 parts by mass

Methylene chloride 440 parts by mass

40 parts by weight of ethanol

The above-mentioned material was placed in a sealed container, and the mixture was stirred while being heated, and completely dissolved. The mixture was filtered using Angki Paper Co., Ltd., manufactured by Anime Paper Co., Ltd., to prepare a blend A.

Next, to 100 parts by mass of the filtered blend A, a filtered portion of the added liquid A2 was added, and thoroughly mixed with a line mixer (Hi-Mixer, SWJ, Donglei static in-line mixer).

Next, the belt flowing device shown in Fig. 1 was used, and the flowing mold (1) was uniformly flowed on the stainless steel belt support (2) at a temperature of 35 ° C and 1800 mm width. On the stainless steel belt support (2), the solvent was evaporated until the residual solvent amount was 100%, and the stainless steel belt support (2) was peeled off by a peeling roll (3).

Next, while the solvent (10) of the exfoliated cellulose triacetate was evaporated at 40 ° C, the casting roll (center line average surface roughness Ra; 1.5 μm, uneven pitch Sm; 20 μm) (7) In the embossing device comprising the back roll (the surface of the stainless steel roll is wound with a thickness of 10 mm, MC nylon (registered trademark)) (8), the coil (10) containing the solvent is sandwiched, and the roll is placed on the roll. (10) The B side (the side connected to the side of the stainless steel belt support is regarded as the B side, the reverse side is regarded as the A side), the side touch molding roll (7), and the back side roll (8) is disposed on the side A side. Concavities and convexities are formed on the side of the B surface by passing between the two rolls. The pressing pressure of the casting roll (7) with respect to the back roll (8) was 5000 (N/m), and a static eliminating electric wire was provided in the vicinity of the uneven portion to suppress charging of the film.

Examples 1 to 9 were carried out by adjusting the difference in the amount of residual solvent of the coil (10) and the difference in left and right tension on the side of the coil (10).

The difference in conveyance tension between the left and right end portions of the coil (10) is adjusted to a desired value by a film guiding device (the angle of the changing roller with respect to the film conveying direction) provided on the upstream side of the casting roll (7).

Here, in Examples 1 to 4, the difference in conveyance tension between the left and right end portions of the coil (10) was 2.4%, and in Examples 5 to 8, the difference in conveyance tension between the left and right end portions of the coil (10) was 4.0%. In Example 9, the difference in conveyance tension between the left and right end portions of the coil (10) was 0.8%.

In addition, in the examples 1 to 9, the amount of residual solvent in the coil (10) when the mold processing roll (7) was formed into irregularities was variously changed in the range of 10 to 70% by mass.

Furthermore, the contact time between the casting roll (7) and the coil (10) is the position of the casting roll (7) and the back roll (8) when the specified pressing pressure is measured by a micrometer, and each of the measured rolls The outer diameter of the roll is calculated geometrically. In Examples 1 to 9, the contact time of the casting rolls (7) with the coil (10) was 2.5 × 10 ^-3 seconds.

In this way, after the surface of the coil (10) is formed with irregularities, it is conveyed by a plurality of transfer rolls (14) at a heating zone (13) of 110 ° C and 120 ° C, and the drying is finished, and the thickness is cut into 1400 mm width, and the film is cut into two. The end was subjected to knurling processing of a width of 15 mm and an average height of 10 μm, and was taken up by a take-up roll (15) to obtain a cellulose triacetate film (20). The volume of residual solvent of the wound cellulose triacetate film (20) was 0.1%, the average film thickness was 70 μm, and the number of rolls was 3000 m.

Then, the surface irregularities of the antiglare films of Examples 1 to 9 thus produced were measured by the method of JIS B0651 2001 using Zygo Corporation Newview 6200, and the surface roughness (Ra) of the film was measured, and the unevenness was calculated according to the following formula. Transfer rate.

Transfer rate = (film Ra) / (cast roll Ra) × 100 (%)

The value of the obtained transfer rate was classified into the following four-stage grade, and it was regarded as the evaluation of transferability.

Transferability evaluation

◎: Transfer rate is 70% or more

○: Transfer rate 50 to 70%

△: Transfer rate 30 to 50%

×: The transfer rate is not 30%

In addition, the transfer rate was measured at five points in the width direction of the anti-glare film, and the deviation in the width direction of the transfer rate was calculated, and it was considered as unevenness of unevenness.

Evaluation of unevenness

○: Within 5% of the deviation of the transfer rate

△: The deviation of the transfer rate is within 10%

×: The deviation of the transfer rate is 10% or more

Further, regarding the obtained antiglare films of Examples 1 to 9, the occurrence of wrinkles was visually evaluated.

Wrinkle evaluation

○: no wrinkles occurred

△: A weak wrinkle occurs. Although it can be transported, the product remains wrinkled.

×: Wrinkles were caused by the processing rolls. Unable to transfer.

In the following Table 1, the conveyance tension (tension 1) of the right end (base end side) of the coil (10) and the same left end portion (shaking) are shown in the upstream side of the coil conveyance direction of the mold processing roll. The conveyance tension (tension 2) of the end side), the left and right difference (%), and the amount of residual solvent (% by mass) of the coil (10) on the upstream side of the coil conveyance direction of the mold processing roll, and the mold type When the processing roll forms irregularities, the contact time (seconds) of the coil to the mold processing roll, the result of the press-fitting pressure (N/m) of the mold processing roll, and the transferability evaluation of the unevenness, and the presence or absence of wrinkles Evaluation results.

Examples 10-21

Although it is carried out in the same manner as in the above-described first to ninth embodiments, the difference from the above-described first to ninth embodiments is the residual solvent of the coil in the case where the mold processing rolls (7) are formed into irregularities in the examples 10 to 17. The amount is less than 10% by mass, or more than 70% by mass, and in the examples 18 to 21, the conveying tension of the coil is adjusted to the coil on the upstream side in the coil conveying direction of the casting processing roll. The web transport tension adjusting mechanism is different between the left and right end portions, and the means for independently measuring the web transport tension is provided on the same side, so that the difference in the measured value of the web transport tension between the left and right end portions of the coil of the measuring means is smaller than 1%, or greater than 5%.

With respect to the obtained antiglare films of Examples 10 to 21, the transfer rate, irregularities, and wrinkles were evaluated in the same manner, and the results obtained are shown in Table 1 below.

As a result of the results shown in Table 1, the antiglare films of Examples 1 to 21 all achieved good results, and the antiglare films of Examples 1 to 8 were particularly excellent in transferability and were not observed in wrinkles. fold.

Examples 22-27

Using the apparatus shown in Figs. 2 and 5, the contact time of the mold roll (7) and the film was changed and an experiment was conducted. In the apparatus of Fig. 2, the number of casting rolls (7) was two and the contact time was twice. Further, in the apparatus of Fig. 5, the film is wrapped with a casting roll (7) to control the contact time.

Next, the completed 1400 mm wide anti-glare film was taken to have a length of 1000 mm, and the state of the film surface was examined by visual inspection to evaluate the presence or absence of minute defects.

Whether there is a slight flaw

◎: There is no length of 30 μm or more.

○: There is no length of 50 μm or more.

△: 5 or less in length of 50 μm or more

×: 6 or more in length of 50 μm or more

The results obtained are combined and shown in Table 2 below. In the following Table 2, in the same manner as in the above-described Examples 1 to 21, the right end portion (base end side) of the coil (10) is shown in the upstream side of the coil conveying direction of the mold processing roll. The transport tension (tension 1) and the transport tension (tension 2) at the same left end (shaking end side), and the left and right difference (%), and the upstream side of the coil conveyance direction of the mold processing roll, the coil ( 10) The amount of residual solvent (% by mass), the contact time (seconds) of the coil with respect to the mold processing roll, and the result of the evaluation of the transfer property of the unevenness, and the presence or absence of wrinkles when the unevenness is formed by the mold processing roll. Evaluation results.

As described in the results of Table 2, if the contact time of the coil with respect to the mold processing roll is long, the enthalpy is increased, and the contact time is 1 or less, and an anti-glare film having less wrinkles and less defects is obtained.

Further, in the above-described embodiment, the film transport tension on the upstream side in the film transport direction of the mold roll (7) is independently adjusted, but the film is independently adjusted on the downstream side in the film transport direction of the mold roll (7). The same result was achieved when the tension was transferred.

1. . . Flow mold

2. . . Slewing drive stainless steel endless belt (support)

3. . . Stripping roller

4. . . Guide roller

5. . . Front side conveying tension adjustment roller

5a. . . Right end

5b. . . Left end

6a. . . Right end

6b. . . Left end

6. . . Rear side tension adjusting roller

7. . . Mold processing roll

7A~7D. . . Mold processing roll

8. . . Reverse roller

8A, 8B. . . Reverse roller

9A. . . Tensiometer (measuring method for coil conveying tension)

9B. . . Tensiometer (measuring method for coil conveying tension)

10. . . Coil

11. . . Guide roller

12. . . Guide roller

13. . . Drying device

14. . . Transfer roller

15. . . Take-up roll

20. . . film

twenty two. . . Slewing drive stainless steel drum (support)

Fig. 1 is a schematic flow chart of an apparatus for producing an anti-glare film according to a first embodiment of a casting roll for carrying out the method of the present invention. Fig. 1a is a schematic overall side view, and Fig. 1b is a plan view of a main portion.

Fig. 2 is a side elevational view of the essential part showing a second embodiment of the apparatus for forming a concave-convex surface using a film tension adjusting mechanism and a casting roll for carrying out the method of the present invention.

Fig. 3 is a side elevational view showing the essential part of the third embodiment.

Fig. 4 is a side elevational view showing the essential part of the fourth embodiment.

Fig. 5 is a side elevational view showing the essential part of the fifth embodiment.

Fig. 6 is a schematic flow chart showing another apparatus for producing an anti-glare film using the apparatus for forming a concave-convex surface of a casting roll according to the method of the present invention. Fig. 6a is a schematic overall side view, and Fig. 6b is a plan view of a main portion.

Fig. 7 is a schematic flow chart showing still another apparatus for producing an anti-glare film using the apparatus for forming a concave-convex surface of a casting roll according to the method of the present invention. Fig. 7a is a schematic overall side view, and Fig. 7b is a plan view of a main portion.

1. . . Flow mold

2. . . Slewing drive stainless steel endless belt (support)

3. . . Stripping roller

4. . . Guide roller

5. . . Front side conveying tension adjustment roller

5a. . . Right end

5b. . . Left end

6. . . Rear side tension adjusting roller

6a. . . Right end

6b. . . Left end

7. . . Mold processing roll

8. . . Reverse roller

9A. . . Tensiometer (measuring method for coil conveying tension)

9B. . . Tensiometer (measuring method for coil conveying tension)

10. . . Coil

11. . . Guide roller

12. . . Guide roller

13. . . Drying device

14. . . Transfer roller

15. . . Take-up roll

20. . . film

Claims (6)

A method for producing an anti-glare film, which is a resin solution in which a resin is dissolved in a solvent, which flows on a rotary drive support having a smooth surface, and volatilizes the solvent until it can be peeled off from the support, and after forming a coil, it will support A method for producing an anti-glare film in which a mold processing roll is pressed against a surface of a coil, and a surface of the film is pressed against the surface of the film to form a film on the surface of the film by a solution flowing film forming method, which is characterized in that the mold is processed. The web conveying tension in the upstream side or the downstream side of the roll conveying direction is adjusted to be different from each other at the left and right end portions of the coil. The method for producing an anti-glare film according to the first aspect of the invention, wherein the coil conveying tension is adjusted to the left and right end portions of the coil in the upstream or downstream side of the coil conveying direction of the casting processing roll The coils are transported by the tension adjusting mechanism, and the means for independently measuring the tension of the web is independently provided on the same side, and the difference in the measured value of the web transport tension between the left and right ends of the web obtained by the measuring means is 1 to 5%. In general, the coil adjustment tension adjustment mechanism is finely adjusted. The method for producing an anti-glare film according to the first or second aspect of the invention, wherein the amount of the residual solvent in the coil when the unevenness is formed by the mold processing roll is 10 to 70% by mass. The method for producing an anti-glare film according to the first or second aspect of the patent application, wherein the contact time of the coil to the mold processing roll is 2.5×10 ^-3 to 1.0 second when the unevenness is formed by the mold processing roll . The method for manufacturing an anti-glare film according to claim 1 or 2, wherein the mold processing roll has a pressure of 200~ for the coil. 50000N/m. The method for producing an anti-glare film according to the second aspect of the invention, wherein the coil conveying tension adjusting mechanism adjusts the measured value difference of the web conveying tension of the left and right end portions of the coil obtained by the measuring means to 2 ~4.5%.