JP2005156801A - Glare-proof antireflection film, polarizing plate and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glare-proof antireflection film which has excellent planarity and reduces glare and uneven unevenness of reflected light and to provide a polarizing plate and a display device having excellent visibility by using the same. <P>SOLUTION: In the glare-proof antireflection film, a highly refractive index active ray-curable resin layer and a low refractive index layer containing inorganic fine particles are formed on the uneven surface of a base film comprising thermoplastic resin. Therein, the inorganic fine particles included in the low refractive index layer are porous particles, composite particles having covering layer formed on the surface of the porous particles and hollow particles in which solvent, gas or porous material is filled. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an antiglare antireflection film, a polarizing plate and a display device. More specifically, the present invention relates to an antiglare antireflection film having excellent flatness, glare and reduced reflected light unevenness, and a polarizing plate and visibility using the antiglare antireflection film. The present invention relates to an excellent display device.

  In recent years, high-performance optical films provided with an antireflection function, an antistatic function and the like have been demanded with full-color display of notebook personal computers, mobile phones and the like or with high definition of displays. For example, a computer provided with an anti-glare layer for improving visibility, or with an anti-glare layer that prevents reflections and scatters reflected light with an uneven surface to obtain display performance with less glare And liquid crystal image display devices (also referred to as liquid crystal displays) such as word processors are demanded.

  The antireflection layer and antiglare layer are improved in various types and performances depending on the application, and various films having these functions are placed on the front of the liquid crystal display to reflect on the display for improved visibility. A method for imparting a prevention function or an antiglare function is used. These optical films used as the front plate are provided with an antireflection layer or an antiglare layer formed by coating or sputtering.

  The antiglare layer blurs the outline of the image reflected on the surface so that reflection of the reflected image does not matter when using an image display device such as a liquid crystal display, an organic EL display, or a plasma display.

  In recent years, there has been a demand for thinner and thinner film for display devices, or a wider screen for anti-glare antireflection films for larger screens. Yes. In particular, an anti-glare antireflection film excellent in flatness is required for a large screen, but it has been difficult to obtain a wide anti-glare antireflection film and a thin film excellent in flatness.

  Conventionally, in order to obtain an antiglare film, a method of adding relatively large inorganic or organic particles and fine particles to an antiglare layer and providing irregularities on the surface is known, but there is a problem of glare due to relatively large particles. It was.

  On the other hand, a method for obtaining an antiglare film having an antiglare effect by providing irregularities on the substrate itself and providing a hard coat layer or an antireflection layer thereon without providing a special antiglare layer is disclosed. A polarizing plate made by adhering a protective substrate mainly composed of cellulosic plastic, embossed on the surface of the protective substrate to form a fine uneven surface, and the uneven surface is partially dissolved with an organic solvent to provide non-reflective polarized light. Techniques for providing plates are disclosed. (For example, refer to Patent Document 1.) Also, an uneven surface is provided on the support on which the dope is cast during the production of the triacetyl cellulose film, and an uneven surface is provided on the film surface simultaneously with the film formation to produce an antiglare triacetyl cellulose film. Techniques to do this are disclosed. (For example, refer to Patent Document 2.) However, since the method of Patent Document 1 involves dissolution of the uneven surface by an organic solvent, the reproducibility of forming the uneven surface and the flatness deterioration due to the solvent of the substrate itself are not preferable. In the method of Patent Document 2, a special casting support is required for the casting apparatus, and since the uneven surface is formed in a state containing a higher residual solvent, it is difficult to control the formation of the uneven surface and it is difficult to peel off. Therefore, there is a problem that failure at the time of peeling tends to occur and the flatness of the finished film is inferior. In addition, the cleaning and maintenance of the casting support is expensive and the productivity is poor.

  Furthermore, a method for obtaining an antiglare antireflection film by embossing after an antireflection layer is provided on a support is disclosed. (For example, refer to Patent Document 3.) However, in this method, the deterioration of the polarizing plate after the antiglare and antireflection film is bonded to the polarizer, and the hard coat layer and the antireflection layer have minute cracks and humidity. In particular, when an optical compensation film is provided on the back surface of the polarizing plate, the retardation value tends to fluctuate and the viewing angle characteristics fluctuate.

Therefore, a wide or thin anti-glare film can be stably produced at low cost, and the appearance of an anti-glare film excellent in flatness is awaited.
Japanese Examined Patent Publication No. 4-59605 Japanese Patent Laid-Open No. 10-119067 JP 2003-207602 A

  Accordingly, an object of the present invention is to provide an antiglare antireflection film having excellent flatness, glare and reduced reflected light unevenness, a polarizing plate using the same, and a display device having excellent visibility.

The above object of the present invention is achieved by the following configurations.
(Claim 1)
It has a high refractive index active ray curable resin layer and a low refractive index layer containing inorganic fine particles on the uneven surface of a substrate film containing a thermoplastic resin, and the inorganic fine particles contained in the low refractive index layer are porous particles. And a composite particle having a coating layer provided on the surface of the porous particle, and a hollow particle filled with a solvent, a gas, or a porous substance inside, and an antiglare antireflection film.
(Claim 2)
The antiglare antireflection film according to claim 1, wherein the unevenness of the base film has a center line average roughness (Ra) of 0.03 μm or more.
(Claim 3)
The anti-glare antireflection film according to claim 1, wherein the base film contains fine particles.
(Claim 4)
The anti-glare antireflection film according to any one of claims 1 to 3, wherein the base film has a thermoplastic resin layer containing fine particles in a surface layer.
(Claim 5)
The antiglare antireflection film according to any one of claims 1 to 4, further comprising a surface layer having a glass transition temperature lower than that of the base layer on the surface of the base film.
(Claim 6)
The anti-glare antireflection film according to claim 1, wherein the base film is formed by co-casting or sequential casting.
(Claim 7)
The base film is composed of an ultraviolet absorber and a plasticizer, a total acyl group substitution degree of 2.6 to 2.9, a number average molecular weight (Mn) of 80,000 to 200,000, a weight average molecular weight (Mw) / number average molecular weight ( The antiglare reflection according to any one of claims 1 to 6, which is a stretched cellulose ester film containing a cellulose ester having a value of Mn) of 1.4 to 3.0. Prevention film.
(Claim 8)
A polarizing plate comprising the antiglare antireflection film according to any one of claims 1 to 7 on one surface and an optical compensation film on the other surface.
(Claim 9)
A display device comprising the antiglare antireflection film according to claim 1 provided on a surface thereof.
(Claim 10)
A display device comprising the polarizing plate according to claim 8.

  According to the present invention, it is possible to provide an antiglare antireflection film excellent in flatness, glaring, reflected light unevenness and foreign matter failure, a polarizing plate using the same, and a display device having excellent visibility.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

  The antiglare antireflection film of the present invention contains a high refractive index active ray curable resin layer (hereinafter also simply referred to as an actinic ray curable resin layer) and inorganic fine particles on the uneven surface of a base film containing a thermoplastic resin. A composite particle having a low refractive index layer, the inorganic fine particle having a porous particle and a coating layer provided on the surface of the porous particle, and a hollow particle filled with a solvent, gas, or porous substance inside It is characterized by being.

  The unevenness of the substrate surface on which the actinic radiation curable resin layer is provided preferably has a centerline average roughness Ra (JIS B0601) of 0.03 μm or more, more preferably 0.03 to 5 μm, and more preferably 0.05-1 μm. Especially preferably, it is 0.05-0.3 micrometer. Further, the average interval Sm between the surface irregularities is preferably 100 μm or less, and particularly preferably 5 to 50 μm.

  The method for forming irregularities on the surface of the substrate film containing the thermoplastic resin is not particularly limited. For example, a method of providing a layer having fine particles and a thermoplastic resin, a method for dissolving or swelling the substrate to the surface by coating or the like. It may be formed by a method of containing 0.1 to 100% by mass of a solvent and pressing it onto a roll having a mold to form irregularities, and particularly preferably co-casting a surface layer having fine particles and a thermoplastic resin. You may form by a method.

  In any case, the surface on the side where the actinic radiation curable resin layer is provided has a thermoplastic resin, and it is preferable that the glass transition temperature of the surface is lower than the glass transition temperature inside the film by the above method. In this way, an antiglare antireflection film having better flatness can be obtained. The glass transition temperature is preferably 5 ° C. or more lower than the inside of the film, and is preferably 5 to 100 ° C. lower. Examples of the method for lowering the glass transition temperature on the surface on which the actinic radiation curable resin layer is provided to be lower than the glass transition temperature inside the film include changing the kind of plasticizer, the addition ratio, and the addition amount. Preferably, the plasticizer content is increased, and the content is preferably 1.1 to 3 times the content of the inside. Although resin used for a surface layer is not specifically limited, Acrylic resin, a cellulose ester, polyester, etc. are mentioned. Another method is to provide a thermoplastic resin layer having a low glass transition temperature on the surface layer. In the case of a cellulose ester film, it is preferable to use a film having a number average molecular weight smaller than that of the base layer or a film having a low total acyl group substitution degree. In particular, it is preferable that the surface layer has a mixed carboxylic acid ester of cellulose or diacetyl cellulose, and the base layer has triacetyl cellulose having a total acyl group substitution degree of 2.7 or more.

  The present inventor coated a high refractive index active ray curable resin layer and a low refractive index layer containing specific inorganic fine particles on the uneven surface of the base film containing the thermoplastic resin obtained as described above. It has been found that the object of the present invention can be achieved by the antiglare and antireflection film, and the present invention has been achieved.

  Furthermore, the antiglare antireflection film according to the present invention preferably takes the following aspects.

  (1) The anti-glare antireflection film, wherein the cellulose ester film used has a width in the range of 1.4 m to 4 m.

  (2) The antiglare antireflection film, wherein the cellulose ester film has a thickness of 10 to 70 μm and the high refractive index active ray curable resin layer has a thickness of 1 to 10 μm.

  Hereinafter, the present invention will be described in detail.

  The antiglare antireflection film of the present invention is characterized in that a base film containing a thermoplastic resin has an uneven surface on the surface.

  Examples of the method for forming an uneven surface according to the present invention include the following methods, but are not limited thereto.

  1) A method in which a negative shape having a desired shape is formed on a roll or master, and the shape is given by embossing.

  2) A method in which a negative mold having a desired shape is formed on a roll or a master, a thermosetting resin is filled into the negative mold, and the film is peeled off from the negative mold after heat curing.

  3) A negative shape having a desired shape is formed on a roll or a master, and after applying ultraviolet rays or an electron beam curable resin and filling the concave portions, the ultraviolet rays are applied while the transparent base film is coated on the intaglio via a resin liquid. Alternatively, a method in which the cured resin and the base film to which the resin is adhered are peeled from the negative mold by irradiation with an electron beam.

  4) A solvent casting method in which a negative shape having a desired shape is formed on a casting belt, and the desired shape is imparted during casting.

  5) A method in which a resin that is cured by light or heating is printed on a transparent substrate, and is cured by light or heating to form irregularities.

  6) A method of cutting the surface with a machine tool or the like.

  7) A method in which particles of various shapes such as spheres and polygons are pressed and integrated so as to be partially buried in the surface of the base material to make the base material surface uneven.

  8) A method in which particles of various shapes such as spheres and polygons are dispersed in a small amount of a binder and applied to the surface of the substrate to make the surface of the substrate uneven.

  9) A method in which a binder is applied to the surface of a substrate, and particles of various shapes such as spheres and polygons are dispersed thereon to make the surface of the substrate uneven.

  10) A method of providing a thermoplastic resin layer containing fine particles of various shapes such as spheres and polygons.

  11) A method of providing a layer containing fine particles of various shapes such as spheres and polygons on the surface layer by a co-casting method or a sequential casting method.

  12) A method for imparting irregularities using the inkjet method described in paragraph Nos. [0037] to [0241] of Japanese Patent Application No. 2002-319665.

  Among them, a method of providing a layer having fine particles and a thermoplastic resin is preferable, and a method of forming a surface layer having fine particles and a thermoplastic resin by a co-casting method is particularly preferable.

  The base film containing the thermoplastic resin according to the present invention (hereinafter also referred to as a thermoplastic resin film) will be described.

The thermoplastic resin according to the present invention is not particularly limited, but various polymers can be used. For example, polyester, polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose acetate butyrate, cellulose acetate phthalate, cellulose triacetate, cellulose Nitrate, cellulose esters such as cellulose acetate propionate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, cycloolefin polymer, polyether ketone , Polyethersulfone, polysulfone, polyetherketoneimide, polyamide, fluororesin, nylon, polyester Methyl methacrylate, acrylic resin or polyarylate resin. These resins may be mixed and used, or different resins may be used for the base layer and the surface layer of the thermoplastic resin film. Among these, cellulose esters, polycarbonates, acrylic resins, cycloolefin polymers, polyesters and the like can be mentioned as preferred examples, but the invention is not limited thereto. It is chosen appropriately. For example, protective films for polarizing plates used in liquid crystal display devices, etc., cellulose ester films (TAC films), cellulose ester films such as cellulose acetate propionate, polycarbonate (hereinafter sometimes abbreviated as PC) films, syndiotactic Polystyrene film, polyarylate film, norbornene resin film such as Arton (manufactured by JSR Corporation), Zeonex, Zeonore (manufactured by Nippon Zeon Co., Ltd.) and polysulfone film are transparent, mechanical properties, optical It is preferably used because it has no anisotropy. In particular, a film containing cellulose ester as a main component is preferable. Hereinafter, cellulose ester will be described as a representative example of a preferred thermoplastic resin.

  The ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the cellulose ester in the present invention is preferably 1.4 to 3.0. In the present invention, the cellulose ester film may contain, as a material, a cellulose ester having a Mw / Mn value of 1.4 to 3.0, but the cellulose ester contained in the film (preferably cellulose triacetate). Or the value of Mw / Mn of cellulose acetate propionate) is more preferably in the range of 1.4 to 3.0. In the synthesis process of cellulose ester, it is difficult to make it less than 1.4, and cellulose ester having a uniform molecular weight can be obtained by fractionation by gel filtration or the like. However, this method is very expensive. On the other hand, if it exceeds 3.0, the flatness maintaining effect is lowered, which is not preferable. In addition, More preferably, it is 1.7-2.2.

  Moreover, it is preferable that the number average molecular weights (Mn) of a cellulose ester are 80000-200000.

  When the molecular weight of the cellulose ester is large and the molecular weight distribution is small, it is presumed that the applied plasticizer and ultraviolet absorber are difficult to elute when the actinic radiation curable resin layer is applied. This effect is presumed to be more remarkable when the cellulose ester molecules are oriented in the in-plane direction by stretching. It is also preferable that the total acyl group substitution degree of the cellulose ester is in the range of 2.6 to 2.9, and that an unsubstituted hydroxyl group remains in the cellulose main chain at an appropriate ratio. It is considered that the elution of the absorbent is prevented and the flatness is maintained. The plasticizer to be used is not particularly limited, but preferably contains at least two plasticizers. In that case, it is preferable that the phosphate ester type plasticizer generally used conventionally is not contained substantially. “Substantially not contained” means that the content of the phosphate plasticizer is less than 1% by mass with respect to the total solid content in the cellulose ester film, preferably 0.1% by mass. % And particularly preferably 0% by mass (below the detection limit).

  Particularly preferably, at least one of the plasticizers is a polyhydric alcohol ester plasticizer, which is considered to prevent the elution of other plasticizers, and is more effective than when used alone.

<Cellulose ester>
The molecular weight of the cellulose ester used in the present invention is preferably a number average molecular weight (Mn) of 80,000 to 200,000. More preferred are 100,000 to 200,000, particularly preferably 150,000 to 200,000.

  The cellulose ester used in the present invention has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio, Mw / Mn of 1.4 to 3.0 as described above, but preferably 1.7. It is the range of -2.2.

  The average molecular weight and molecular weight distribution of the cellulose ester can be measured by a known method using high performance liquid chromatography. Using this, the number average molecular weight and the weight average molecular weight can be calculated, and the ratio (Mw / Mn) can be calculated.

The measurement conditions are as follows.
Solvent: Methylene chloride column: Shodex K806, K805, K803G (used by connecting 3 products manufactured by Showa Denko KK)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 100000-500 calibration curves with 13 samples were used. It is preferable to obtain 13 samples at approximately equal intervals.

  The cellulose ester used in the present invention is preferably an aliphatic carboxylic acid ester having about 2 to 22 carbon atoms, an aromatic carboxylic acid ester, or a mixed ester of an aliphatic carboxylic acid ester and an aromatic carboxylic acid ester. A lower fatty acid ester is preferred. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. Specifically, it is described in cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate phthalate and the like, JP-A-10-45804, 8-2311761, U.S. Pat. No. 2,319,052, and the like. Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate can be used. Among the above descriptions, the lower fatty acid esters of cellulose particularly preferably used are cellulose triacetate and cellulose acetate propionate. These cellulose esters can be used as a mixture.

  In the case of cellulose ester, those having a total acyl group substitution degree (acetyl group substitution degree) of 2.6 to 2.9 are preferably used.

  Preferred cellulose esters other than cellulose triacetate have an acyl group having 2 to 22 carbon atoms as a substituent, the substitution degree of the acetyl group is X, and the substitution degree of the acyl group of 3 to 22 carbon atoms is Y. Sometimes, it is a cellulose ester that simultaneously satisfies the following formulas (I) and (II).

Formula (I) 2.6 ≦ X + Y ≦ 2.9
Formula (II) 0 ≦ X ≦ 2.5
Among them, cellulose acetate propionate (total acyl group substitution degree = X + Y) satisfying 1.9 ≦ X ≦ 2.5 and 0.1 ≦ Y ≦ 1.0 is preferable. The portion not substituted with an acyl group usually exists as a hydroxyl group. These can be synthesized by known methods.

  These acyl group substitution degrees can be measured according to the method prescribed in ASTM-D817-96.

  As the cellulose ester, cellulose ester synthesized from cotton linter, wood pulp, kenaf or the like as a raw material can be used alone or in combination. In particular, it is preferable to use a cotton linter (hereinafter sometimes simply referred to as a linter) or a cellulose ester synthesized from wood pulp alone or in combination.

  Moreover, the cellulose ester obtained from these can be mixed and used in arbitrary ratios, respectively. These cellulose esters are prepared by using an organic acid such as acetic acid or an organic solvent such as methylene chloride when sulfuric acid is used as the acylating agent (acetic anhydride, propionic anhydride, butyric anhydride). It can obtain by making it react by a conventional method using a protic catalyst like.

  In the case of acetylcellulose, it is necessary to extend the time for the acetylation reaction in order to increase the acetylation rate. However, if the reaction time is too long, the decomposition proceeds at the same time, and the polymer chain is broken and the acetyl group is decomposed, resulting in undesirable results. Therefore, it is necessary to set the reaction time within a certain range in order to increase the degree of acetylation and suppress decomposition to some extent. It is not appropriate to define the reaction time because the reaction conditions are various and greatly change depending on the reaction apparatus, equipment and other conditions. As the decomposition of the polymer progresses, the molecular weight distribution becomes wider. Therefore, in the case of cellulose ester, the degree of decomposition can be defined by the value of weight average molecular weight (Mw) / number average molecular weight (Mn) that is usually used. That is, in the process of acetylation of cellulose triacetate, the weight average molecular weight is used as one index of the reaction degree for allowing the acetylation reaction to be carried out for a sufficient time for acetylation without being too long and being decomposed too much. The value of (Mw) / number average molecular weight (Mn) can be used.

  An example of a method for producing a cellulose ester is shown below: 100 parts by mass of a flocculent linter was crushed as a cellulose raw material, 40 parts by mass of acetic acid was added, and pretreatment activation was performed 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 performed at 36 ° C. for 120 minutes. After neutralization with 11 parts by mass of a 24% magnesium acetate aqueous solution, saponification aging was carried out at 63 ° C. for 35 minutes to obtain acetylcellulose. This was stirred for 160 minutes at room temperature using a 10-fold acetic acid aqueous solution (acetic acid: water = 1: 1 (mass ratio)), then filtered and dried to obtain purified acetylcellulose having an acetyl substitution degree of 2.75. . This acetylcellulose had Mn of 92000, Mw of 156000, and Mw / Mn of 1.7. Similarly, cellulose esters having different degrees of substitution and Mw / Mn ratios can be synthesized by adjusting the esterification conditions (temperature, time, stirring) and hydrolysis conditions of the cellulose ester.

  The synthesized cellulose ester is preferably purified to remove low molecular weight components or to remove unacetylated or low acetylated components by filtration.

  In the case of mixed acid cellulose ester, it can be obtained by the method described in JP-A-10-45804. The measuring method of the substitution degree of an acyl group can be measured according to the provisions of ASTM-D817-96.

  Cellulose esters are also affected by trace metal components in cellulose esters. These are considered to be related to water used in the production process, but it is preferable that there are few components that can become insoluble nuclei, and metal ions such as iron, calcium, and magnesium contain organic acidic groups. Insoluble matter may be formed by salt formation with a polymer degradation product or the like that may be present, and it is preferable that the amount is small. The iron (Fe) component is preferably 1 ppm or less. About calcium (Ca) component, it is contained in a lot of ground water and river water, etc., and it becomes hard water, and it is unsuitable as drinking water. Coordination compounds with ligands, that is, complexes are easily formed, and scum (insoluble starch, turbidity) derived from many insoluble calcium is formed.

  The calcium (Ca) component is 60 ppm or less, preferably 0 to 30 ppm. The magnesium (Mg) component is preferably in the range of 0 to 70 ppm, particularly preferably 0 to 20 ppm, since too much will cause insoluble matter. Metal components such as iron (Fe) content, calcium (Ca) content, magnesium (Mg) content, etc. are pre-processed by completely digesting cellulose ester with micro digest wet cracking equipment (sulfuric acid decomposition) and alkali melting. After performing, it can obtain | require by performing an analysis using ICP-AES (inductively coupled plasma emission spectroscopy analyzer).

  The cellulose ester film used in the present invention preferably has a refractive index of 1.45 to 1.60 at 550 nm. As a method for measuring the refractive index of the film, an Abbe refractometer is used, and measurement is performed based on Japanese Industrial Standard JIS K 7105. Further, the refractive index of each layer of the antireflection layer described later is calculated from the reflection spectrum of 5 ° regular reflection of the thin film applied to each layer.

<Plasticizer>
In the present invention, in the case of a cellulose ester film having a multilayer structure to be described later, a base layer in which the glass transition temperature of the surface layer on the side on which the active ray curable resin layer is provided is contained in the surface layer side of the base film, and the glass transition temperature of the surface layer is provided inside the film. It is preferable to make it lower than the glass transition temperature.

  The cellulose ester film used in the present invention preferably contains at least two kinds of plasticizers. Moreover, it is preferable not to contain phosphate ester plasticizers, such as a triphenyl phosphate, substantially. “Substantially not containing” means that the content of the phosphoric ester plasticizer is less than 1% by mass, preferably 0.1% by mass, particularly preferably not added.

  By including two or more plasticizers, elution of the plasticizer can be reduced. The reason is not clear, but it seems that elution is suppressed by the ability to reduce the amount added per type and the interaction between the two plasticizers and the cellulose ester.

  The two kinds of plasticizers are not particularly limited, but are preferably selected from polyhydric alcohol ester plasticizers, phthalic acid esters, citric acid esters, fatty acid esters, glycolate plasticizers, polycarboxylic acid esters, and the like. Of these, at least one is preferably a polyhydric alcohol ester plasticizer.

  The polyhydric alcohol ester plasticizer is a plasticizer comprising an ester of a dihydric or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. Preferably it is a 2-20 valent aliphatic polyhydric alcohol ester.

  The polyhydric alcohol used in the present invention is represented by the following general formula (1).

Formula (1) R _1- (OH) _n
However, R ₁ represents an n-valent organic group, n represents a positive integer of 2 or more, and the OH group represents an alcoholic and / or phenolic hydroxyl group.

  Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these. Adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol, mannitol, 3-methylpentane- Examples include 1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, and xylitol. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable.

  There is no restriction | limiting in particular as monocarboxylic acid used for the polyhydric alcohol ester of this invention, Well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention.

  Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto.

  As the aliphatic monocarboxylic acid, a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. The number of carbon atoms is more preferably 1-20, and particularly preferably 1-10. When acetic acid is contained, the compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid.

  Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanoic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.

  Examples of preferable alicyclic monocarboxylic acids include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof.

  Examples of preferred aromatic monocarboxylic acids include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenylcarboxylic acid, naphthalenecarboxylic acid, and tetralincarboxylic acid. The aromatic monocarboxylic acid which has, or those derivatives can be mentioned. Benzoic acid is particularly preferable.

  The molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably 300 to 1500, and more preferably 350 to 750. A higher molecular weight is preferred because it is less likely to volatilize, and a smaller one is preferred in terms of moisture permeability and compatibility with cellulose ester.

  The carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.

  Below, the specific compound of a polyhydric alcohol ester is illustrated.

  The glycolate plasticizer is not particularly limited, but alkylphthalylalkyl glycolates can be preferably used. Examples of alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl Glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycol Butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl glycolate, octyl phthalyl methyl glycolate, octyl phthalate Ethyl glycolate, and the like.

  Examples of the phthalate ester plasticizer include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.

  Examples of the citrate plasticizer include acetyl trimethyl citrate, acetyl triethyl citrate, and acetyl tributyl citrate.

  Examples of fatty acid ester plasticizers include butyl oleate, methylacetyl ricinoleate, and dibutyl sebacate.

  Polycarboxylic acid ester plasticizers can also be preferably used. Specifically, it is preferable to add the polyvalent carboxylic acid ester described in paragraphs [0015] to [0020] of JP-A No. 2002-265639 as one of the plasticizers.

  Examples of the phosphate ester plasticizer include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate and the like.

  The total content of the plasticizer in the cellulose ester film is preferably 5 to 30% by mass with respect to the total solid content. Furthermore, 5-20 mass% is preferable, 6-16 mass% is more preferable, Especially preferably, it is 8-13 mass%. The contents of the two kinds of plasticizers are each at least 1% by mass, preferably 2% by mass or more.

  The polyhydric alcohol ester plasticizer is preferably contained in an amount of 1 to 12% by mass, particularly preferably 3 to 11% by mass. If the amount is too small, deterioration of the flatness is recognized, and if too much, bleeding out tends to occur. The mass ratio between the polyhydric alcohol ester plasticizer and the other plasticizer is preferably in the range of 1: 4 to 4: 1, more preferably 1: 3 to 3: 1. If the amount of the plasticizer added is too large or too small, the film is liable to be deformed, which is not preferable.

<Ultraviolet absorber>
The cellulose ester film according to the present invention preferably contains an ultraviolet absorber. The ultraviolet absorber is intended to improve durability by absorbing ultraviolet rays of 400 nm or less, and is particularly preferably added so that the transmittance at a wavelength of 370 nm is 10% or less. Is 5% or less, more preferably 2% or less.

  Although the ultraviolet absorber used in the present invention is not particularly limited, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, inorganic powders Examples include the body.

  For example, 5-chloro-2- (3,5-di-sec-butyl-2-hydroxylphenyl) -2H-benzotriazole, (2-2H-benzotriazol-2-yl) -6- (linear and side Chain dodecyl) -4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxybenzophenone, etc., and tinuvin 109, tinuvin 171, tinuvin 234, tinuvin 326, tinuvin 327, tinuvin 328, etc. These are commercially available products manufactured by Ciba Specialty Chemicals and can be preferably used.

  For example, as the benzotriazole ultraviolet absorber, a compound represented by the following general formula (A) can be used.

In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different, and are a hydrogen atom, halogen atom, nitro group, hydroxyl group, alkyl group, alkenyl group, aryl group, alkoxyl group, acyloxy Represents a group, aryloxy group, alkylthio group, arylthio group, mono- or dialkylamino group, acylamino group or 5- to 6-membered heterocyclic group, and R ₄ and R ₅ are closed to form a 5- to 6-membered carbocyclic ring May be.

  Moreover, these groups described above may have an arbitrary substituent.

  Although the specific example of the ultraviolet absorber which concerns on this invention is given to the following, this invention is not limited to these.

UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole UV-3 : 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-Chlorobenzotriazole UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole UV-8: 2- (2H-benzotriazol-2-yl) -6 (Linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba)
UV-9: Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- 4-Hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba)
Furthermore, the ultraviolet absorber preferably used in the present invention is a benzophenone ultraviolet absorber or a triazine ultraviolet absorber, and particularly preferably a triazine ultraviolet absorber.

  As the benzophenone-based ultraviolet absorber, a compound represented by the following general formula (B) is preferably used.

In the formula, Y represents a hydrogen atom, a halogen atom or an alkyl group, an alkenyl group, an alkoxyl group, and a phenyl group, and these alkyl group, alkenyl group, and phenyl group may have a substituent. A represents a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a cycloalkyl group, an alkylcarbonyl group, an alkylsulfonyl group or a —CO (NH) _{n -1-} D group, and D represents an alkyl group, an alkenyl group or a substituent. Represents a phenyl group which may have m and n represent 1 or 2.

  In the above, the alkyl group represents, for example, a linear or branched aliphatic group having up to 24 carbon atoms, the alkoxyl group represents, for example, an alkoxyl group having up to 18 carbon atoms, and the alkenyl group has, for example, carbon number An alkenyl group up to 16 represents an allyl group, a 2-butenyl group, or the like. In addition, as substituents to alkyl groups, alkenyl groups, and phenyl groups, halogen atoms such as chlorine atoms, bromine atoms, fluorine atoms, etc., hydroxyl groups, phenyl groups (this phenyl group is substituted with alkyl groups or halogen atoms, etc.) May be used).

  Specific examples of the benzophenone compound represented by the general formula (B) are shown below, but the present invention is not limited thereto.

UV-10: 2,4-dihydroxybenzophenone UV-11: 2,2'-dihydroxy-4-methoxybenzophenone UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-13: Bis (2-methoxy -4-hydroxy-5-benzoylphenylmethane)
Moreover, the compound which has a 1,3,5-triazine ring can be used preferably as a ultraviolet absorber of the optical film of this invention.

  Among them, the compound having a 1,3,5-triazine ring is preferably a compound represented by the following general formula (I).

In the general formula (I), X ¹ is a single bond, —NR ₄ —, —O— or —S—; X ² is a single bond, —NR ₅ —, —O— or —S—; X ³ is a single bond, —NR ₆ —, —O— or —S—; R ¹ , R ² and R ³ are an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; and R ₄ , R ₅ and R ₆ are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. The compound represented by the general formula (I) is particularly preferably a melamine compound.

In the melamine compound, in the general formula (I), X ¹ , X ² and X ³ are —NR ₄ —, —NR ₅ — and —NR ₆ —, respectively, or X ¹ , X ² and X 3 ³ is a single bond, and R ¹ , R ² and R ³ are heterocyclic groups having a free valence on the nitrogen atom. ^{-X 1 -R 1, -X 2 -R} 2 and -X ³ -R ³ are preferably the same substituents. R ¹ , R ² and R ³ are particularly preferably aryl groups. R ₄ , R ₅ and R ₆ are particularly preferably a hydrogen atom.

  The alkyl group is preferably a chain alkyl group rather than a cyclic alkyl group. A linear alkyl group is preferred to a branched alkyl group.

  The number of carbon atoms of the alkyl group is preferably 1-30, more preferably 1-20, still more preferably 1-10, still more preferably 1-8, 6 is most preferred. The alkyl group may have a substituent.

  Specific examples of the substituent include a halogen atom, an alkoxy group (for example, each group such as methoxy, ethoxy, and epoxyethyloxy) and an acyloxy group (for example, acryloyloxy, methacryloyloxy). The alkenyl group is preferably a chain alkenyl group rather than a cyclic alkenyl group. A linear alkenyl group is preferable to a branched chain alkenyl group. The number of carbon atoms in the alkenyl group is preferably 2 to 30, more preferably 2 to 20, still more preferably 2 to 10, still more preferably 2 to 8, 6 is most preferred. The alkenyl group may have a substituent.

  Specific examples of the substituent include a halogen atom, an alkoxy group (for example, each group such as methoxy, ethoxy, and epoxyethyloxy) or an acyloxy group (for example, each group such as acryloyloxy and methacryloyloxy).

  The aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have a substituent.

  Specific examples of the substituent include, for example, a halogen atom, hydroxyl, cyano, nitro, carboxyl, alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, alkoxycarbonyl group, alkenyloxy Carbonyl group, aryloxycarbonyl group, sulfamoyl, alkyl-substituted sulfamoyl group, alkenyl-substituted sulfamoyl group, aryl-substituted sulfamoyl group, sulfonamido group, carbamoyl, alkyl-substituted carmoyl group, alkenyl-substituted carbamoyl group, aryl-substituted carbamoyl group, amide group, alkylthio Groups, alkenylthio groups, arylthio groups and acyl groups are included. The said alkyl group is synonymous with the alkyl group mentioned above.

  The alkyl group of the alkoxy group, acyloxy group, alkoxycarbonyl group, alkyl-substituted sulfamoyl group, sulfonamido group, alkyl-substituted carbamoyl group, amide group, alkylthio group and acyl group is also synonymous with the alkyl group described above.

  The said alkenyl group is synonymous with the alkenyl group mentioned above.

  The alkenyl part of the alkenyloxy group, acyloxy group, alkenyloxycarbonyl group, alkenyl-substituted sulfamoyl group, sulfonamide group, alkenyl-substituted carbamoyl group, amide group, alkenylthio group and acyl group is also synonymous with the alkenyl group described above.

  Specific examples of the aryl group include phenyl, α-naphthyl, β-naphthyl, 4-methoxyphenyl, 3,4-diethoxyphenyl, 4-octyloxyphenyl, and 4-dodecyloxyphenyl. Can be mentioned.

  Examples of the aryloxy group, acyloxy group, aryloxycarbonyl group, aryl-substituted sulfamoyl group, sulfonamido group, aryl-substituted carbamoyl group, amide group, arylthio group, and acyl group are the same as the above aryl group.

When X ¹ , X ² or X ³ is —NR—, —O— or —S—, the heterocyclic group preferably has aromaticity.

  The heterocyclic ring in the heterocyclic group having aromaticity is generally an unsaturated heterocyclic ring, preferably a heterocyclic ring having the largest number of double bonds. The heterocyclic ring is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and most preferably a 6-membered ring.

  The hetero atom in the heterocyclic ring is preferably each atom such as N, S or O, and particularly preferably an N atom.

  As the heterocyclic ring having aromaticity, a pyridine ring (as the heterocyclic group, for example, each group such as 2-pyridyl or 4-pyridyl) is particularly preferable. The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as the examples of the substituent of the aryl moiety.

When X ¹ , X ² or X ³ is a single bond, the heterocyclic group is preferably a heterocyclic group having a free valence on the nitrogen atom. The heterocyclic group having a free valence on the nitrogen atom is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and a 5-membered ring. Is most preferred. The heterocyclic group may have a plurality of nitrogen atoms.

  Moreover, the hetero atom in a heterocyclic group may have hetero atoms other than a nitrogen atom (for example, O atom, S atom). The heterocyclic group may have a substituent. Specific examples of the substituent of the heterocyclic group are the same as the specific examples of the substituent of the aryl moiety.

  Specific examples of the heterocyclic group having a free valence on the nitrogen atom are shown below.

  The molecular weight of the compound having a 1,3,5-triazine ring is preferably 300 to 2,000. The boiling point of the compound is preferably 260 ° C. or higher. The boiling point can be measured using a commercially available measuring device (for example, TG / DTA100, manufactured by Seiko Electronics Industry Co., Ltd.).

  Specific examples of the compound having a 1,3,5-triazine ring are shown below.

  In addition, several R shown below represents the same group.

(1) Butyl (2) 2-Methoxy-2-ethoxyethyl (3) 5-Undecenyl (4) Phenyl (5) 4-Ethoxycarbonylphenyl (6) 4-Butoxyphenyl (7) p-Biphenylyl (8) 4 -Pyridyl (9) 2-naphthyl (10) 2-methylphenyl (11) 3,4-dimethoxyphenyl (12) 2-furyl

(14) phenyl (15) 3-ethoxycarbonylphenyl (16) 3-butoxyphenyl (17) m-biphenylyl (18) 3-phenylthiophenyl (19) 3-chlorophenyl (20) 3-benzoylphenyl (21) 3 -Acetoxyphenyl (22) 3-benzoyloxyphenyl (23) 3-phenoxycarbonylphenyl (24) 3-methoxyphenyl (25) 3-anilinophenyl (26) 3-isobutyrylaminophenyl (27) 3-phenoxy Carbonylaminophenyl (28) 3- (3-ethylureido) phenyl (29) 3- (3,3-diethylureido) phenyl (30) 3-methylphenyl (31) 3-phenoxyphenyl (32) 3-hydroxyphenyl (33) 4-Ethoxycarbonylphenyl (34) 4-butoxyphenyl (35) p-biphenylyl (36) 4-phenylthiophenyl (37) 4-chlorophenyl (38) 4-benzoylphenyl (39) 4-acetoxyphenyl (40) 4-benzoyloxyphenyl ( 41) 4-phenoxycarbonylphenyl (42) 4-methoxyphenyl (43) 4-anilinophenyl (44) 4-isobutyrylaminophenyl (45) 4-phenoxycarbonylaminophenyl (46) 4- (3-ethyl (Ureido) phenyl (47) 4- (3,3-diethylureido) phenyl (48) 4-methylphenyl (49) 4-phenoxyphenyl (50) 4-hydroxyphenyl (51) 3,4-diethoxycarbonylphenyl ( 52) 3,4-dibutoxyphenyl (53) 3 -Diphenylphenyl (54) 3,4-diphenylthiophenyl (55) 3,4-dichlorophenyl (56) 3,4-dibenzoylphenyl (57) 3,4-diacetoxyphenyl (58) 3,4-dibenzoyl Oxyphenyl (59) 3,4-diphenoxycarbonylphenyl (60) 3,4-dimethoxyphenyl (61) 3,4-dianilinophenyl (62) 3,4-dimethylphenyl (63) 3,4-diphenoxy Phenyl (64) 3,4-dihydroxyphenyl (65) 2-naphthyl (66) 3,4,5-triethoxycarbonylphenyl (67) 3,4,5-tributoxyphenyl (68) 3,4,5- Triphenylphenyl (69) 3,4,5-triphenylthiophenyl (70) 3,4,5-trichlorophenyl (71) 3,4,5-tribenzoylphenyl (72) 3,4,5-triacetoxyphenyl (73) 3,4,5-tribenzoyloxyphenyl (74) 3,4,5-triphenoxycarbonylphenyl (75) 3,4,5-trimethoxyphenyl (76) 3,4,5-trianilinophenyl (77) 3,4,5-trimethylphenyl (78) 3,4,5-triphenoxyphenyl (79 ) 3,4,5-trihydroxyphenyl

(80) phenyl (81) 3-ethoxycarbonylphenyl (82) 3-butoxyphenyl (83) m-biphenylyl (84) 3-phenylthiophenyl (85) 3-chlorophenyl (86) 3-benzoylphenyl (87) 3 -Acetoxyphenyl (88) 3-benzoyloxyphenyl (89) 3-phenoxycarbonylphenyl (90) 3-methoxyphenyl (91) 3-anilinophenyl (92) 3-isobutyrylaminophenyl (93) 3-phenoxy Carbonylaminophenyl (94) 3- (3-ethylureido) phenyl (95) 3- (3,3-diethylureido) phenyl (96) 3-methylphenyl (97) 3-phenoxyphenyl (98) 3-hydroxyphenyl (99) 4-Ethoxycarbonylphenyl (100) 4-butoxyphenyl (101) p-biphenylyl (102) 4-phenylthiophenyl (103) 4-chlorophenyl (104) 4-benzoylphenyl (105) 4-acetoxyphenyl (106) 4-benzoyloxyphenyl ( 107) 4-phenoxycarbonylphenyl (108) 4-methoxyphenyl (109) 4-anilinophenyl (110) 4-isobutyrylaminophenyl (111) 4-phenoxycarbonylaminophenyl (112) 4- (3-ethyl (Ureido) phenyl (113) 4- (3,3-diethylureido) phenyl (114) 4-methylphenyl (115) 4-phenoxyphenyl (116) 4-hydroxyphenyl (117) 3,4-diethoxycarbonylphenyl ( 118) 3 , 4-dibutoxyphenyl (119) 3,4-diphenylphenyl (120) 3,4-diphenylthiophenyl (121) 3,4-dichlorophenyl (122) 3,4-dibenzoylphenyl (123) 3,4- Diacetoxyphenyl (124) 3,4-dibenzoyloxyphenyl (125) 3,4-diphenoxycarbonylphenyl (126) 3,4-dimethoxyphenyl (127) 3,4-dianilinophenyl (128) 3,4 -Dimethylphenyl (129) 3,4-diphenoxyphenyl (130) 3,4-dihydroxyphenyl (131) 2-naphthyl (132) 3,4,5-triethoxycarbonylphenyl (133) 3,4,5- Tributoxyphenyl (134) 3,4,5-triphenylphenyl (135) 3 4,5-triphenylthiophenyl (136) 3,4,5-trichlorophenyl (137) 3,4,5-tribenzoylphenyl (138) 3,4,5-triacetoxyphenyl (139) 3,4 5-tribenzoyloxyphenyl (140) 3,4,5-triphenoxycarbonylphenyl (141) 3,4,5-trimethoxyphenyl (142) 3,4,5-trianilinophenyl (143) 3,4 , 5-trimethylphenyl (144) 3,4,5-triphenoxyphenyl (145) 3,4,5-trihydroxyphenyl

(146) phenyl (147) 4-ethoxycarbonylphenyl (148) 4-butoxyphenyl (149) p-biphenylyl (150) 4-phenylthiophenyl (151) 4-chlorophenyl (152) 4-benzoylphenyl (153) 4 -Acetoxyphenyl (154) 4-benzoyloxyphenyl (155) 4-phenoxycarbonylphenyl (156) 4-methoxyphenyl (157) 4-anilinophenyl (158) 4-isobutyrylaminophenyl (159) 4-phenoxy Carbonylaminophenyl (160) 4- (3-ethylureido) phenyl (161) 4- (3,3-diethylureido) phenyl (162) 4-methylphenyl (163) 4-phenoxyphenyl (164) 4-hydroxyphenyl

(165) phenyl (166) 4-ethoxycarbonylphenyl (167) 4-butoxyphenyl (168) p-biphenylyl (169) 4-phenylthiophenyl (170) 4-chlorophenyl (171) 4-benzoylphenyl (172) 4 -Acetoxyphenyl (173) 4-benzoyloxyphenyl (174) 4-phenoxycarbonylphenyl (175) 4-methoxyphenyl (176) 4-anilinophenyl (177) 4-isobutyrylaminophenyl (178) 4-phenoxy Carbonylaminophenyl (179) 4- (3-ethylureido) phenyl (180) 4- (3,3-diethylureido) phenyl (181) 4-methylphenyl (182) 4-phenoxyphenyl (183) 4-hydroxyphenyl

(184) phenyl (185) 4-ethoxycarbonylphenyl (186) 4-butoxyphenyl (187) p-biphenylyl (188) 4-phenylthiophenyl (189) 4-chlorophenyl (190) 4-benzoylphenyl (191) 4 -Acetoxyphenyl (192) 4-benzoyloxyphenyl (193) 4-phenoxycarbonylphenyl (194) 4-methoxyphenyl (195) 4-anilinophenyl (196) 4-isobutyrylaminophenyl (197) 4-phenoxy Carbonylaminophenyl (198) 4- (3-ethylureido) phenyl (199) 4- (3,3-diethylureido) phenyl (200) 4-methylphenyl (201) 4-phenoxyphenyl (202) 4-hydroxyphenyl

(203) phenyl (204) 4-ethoxycarbonylphenyl (205) 4-butoxyphenyl (206) p-biphenylyl (207) 4-phenylthiophenyl (208) 4-chlorophenyl (209) 4-benzoylphenyl (210) 4 -Acetoxyphenyl (211) 4-benzoyloxyphenyl (212) 4-phenoxycarbonylphenyl (213) 4-methoxyphenyl (214) 4-anilinophenyl (215) 4-isobutyrylaminophenyl (216) 4-phenoxy Carbonylaminophenyl (217) 4- (3-ethylureido) phenyl (218) 4- (3,3-diethylureido) phenyl (219) 4-methylphenyl (220) 4-phenoxyphenyl (221) 4-hydroxyphenyl

(222) phenyl (223) 4-butylphenyl (224) 4- (2-methoxy-2-ethoxyethyl) phenyl (225) 4- (5-nonenyl) phenyl (226) p-biphenylyl (227) 4-ethoxy Carbonylphenyl (228) 4-butoxyphenyl (229) 4-methylphenyl (230) 4-chlorophenyl (231) 4-phenylthiophenyl (232) 4-benzoylphenyl (233) 4-acetoxyphenyl (234) 4-benzoyl Oxyphenyl (235) 4-phenoxycarbonylphenyl (236) 4-methoxyphenyl (237) 4-anilinophenyl (238) 4-isobutyrylaminophenyl (239) 4-phenoxycarbonylaminophenyl (240) 4- ( 3-ethylureido Phenyl (241) 4- (3,3-diethylureido) phenyl (242) 4-phenoxyphenyl (243) 4-hydroxyphenyl (244) 3-butylphenyl (245) 3- (2-methoxy-2-ethoxyethyl) ) Phenyl (246) 3- (5-nonenyl) phenyl (247) m-biphenylyl (248) 3-ethoxycarbonylphenyl (249) 3-butoxyphenyl (250) 3-methylphenyl (251) 3-chlorophenyl (252) 3-phenylthiophenyl (253) 3-benzoylphenyl (254) 3-acetoxyphenyl (255) 3-benzoyloxyphenyl (256) 3-phenoxycarbonylphenyl (257) 3-methoxyphenyl (258) 3-anilinophenyl (259) 3-I Butyrylaminophenyl (260) 3-phenoxycarbonylaminophenyl (261) 3- (3-ethylureido) phenyl (262) 3- (3,3-diethylureido) phenyl (263) 3-phenoxyphenyl (264) 3 -Hydroxyphenyl (265) 2-butylphenyl (266) 2- (2-methoxy-2-ethoxyethyl) phenyl (267) 2- (5-nonenyl) phenyl (268) o-biphenylyl (269) 2-ethoxycarbonyl Phenyl (270) 2-Butoxyphenyl (271) 2-Methylphenyl (272) 2-Chlorophenyl (273) 2-Phenylthiophenyl (274) 2-Benzoylphenyl (275) 2-Acetoxyphenyl (276) 2-Benzoyloxy Phenyl (277) 2 Phenoxycarbonylphenyl (278) 2-methoxyphenyl (279) 2-anilinophenyl (280) 2-isobutyrylaminophenyl (281) 2-phenoxycarbonylaminophenyl (282) 2- (3-ethylureido) phenyl ( 283) 2- (3,3-diethylureido) phenyl (284) 2-phenoxyphenyl (285) 2-hydroxyphenyl (286) 3,4-dibutylphenyl (287) 3,4-di (2-methoxy-2) -Ethoxyethyl) phenyl (288) 3,4-diphenylphenyl (289) 3,4-diethoxycarbonylphenyl (290) 3,4-didodecyloxyphenyl (291) 3,4-dimethylphenyl (292) 3, 4-dichlorophenyl (293) 3,4-dibenzoyl Enyl (294) 3,4-diacetoxyphenyl (295) 3,4-dimethoxyphenyl (296) 3,4-di-N-methylaminophenyl (297) 3,4-diisobutyrylaminophenyl (298) 3 , 4-diphenoxyphenyl (299) 3,4-dihydroxyphenyl (300) 3,5-dibutylphenyl (301) 3,5-di (2-methoxy-2-ethoxyethyl) phenyl (302) 3,5- Diphenylphenyl (303) 3,5-diethoxycarbonylphenyl (304) 3,5-didodecyloxyphenyl (305) 3,5-dimethylphenyl (306) 3,5-dichlorophenyl (307) 3,5-dibenzoyl Phenyl (308) 3,5-diacetoxyphenyl (309) 3,5-dimethoxyphenyl (3 0) 3,5-di-N-methylaminophenyl (311) 3,5-diisobutyrylaminophenyl (312) 3,5-diphenoxyphenyl (313) 3,5-dihydroxyphenyl (314) 2,4 -Dibutylphenyl (315) 2,4-di (2-methoxy-2-ethoxyethyl) phenyl (316) 2,4-diphenylphenyl (317) 2,4-diethoxycarbonylphenyl (318) 2,4-di Dodecyloxyphenyl (319) 2,4-dimethylphenyl (320) 2,4-dichlorophenyl (321) 2,4-dibenzoylphenyl (322) 2,4-diacetoxyphenyl (323) 2,4-dimethoxyphenyl ( 324) 2,4-di-N-methylaminophenyl (325) 2,4-diisobutyrylaminopheny (326) 2,4-diphenoxyphenyl (327) 2,4-dihydroxyphenyl (328) 2,3-dibutylphenyl (329) 2,3-di (2-methoxy-2-ethoxyethyl) phenyl (330) 2,3-diphenylphenyl (331) 2,3-diethoxycarbonylphenyl (332) 2,3-didodecyloxyphenyl (333) 2,3-dimethylphenyl (334) 2,3-dichlorophenyl (335) 2, 3-dibenzoylphenyl (336) 2,3-diacetoxyphenyl (337) 2,3-dimethoxyphenyl (338) 2,3-di-N-methylaminophenyl (339) 2,3-diisobutyrylaminophenyl (340) 2,3-diphenoxyphenyl (341) 2,3-dihydroxyphenyl (342 ) 2,6-dibutylphenyl (343) 2,6-di (2-methoxy-2-ethoxyethyl) phenyl (344) 2,6-diphenylphenyl (345) 2,6-diethoxycarbonylphenyl (346) 2 , 6-didodecyloxyphenyl (347) 2,6-dimethylphenyl (348) 2,6-dichlorophenyl (349) 2,6-dibenzoylphenyl (350) 2,6-diacetoxyphenyl (351) 2,6 -Dimethoxyphenyl (352) 2,6-di-N-methylaminophenyl (353) 2,6-diisobutyrylaminophenyl (354) 2,6-diphenoxyphenyl (355) 2,6-dihydroxyphenyl (356 ) 3,4,5-tributylphenyl (357) 3,4,5-tri (2-methoxy-2-ethoxy) Til) phenyl (358) 3,4,5-triphenylphenyl (359) 3,4,5-triethoxycarbonylphenyl (360) 3,4,5-tridodecyloxyphenyl (361) 3,4,5- Trimethylphenyl (362) 3,4,5-trichlorophenyl (363) 3,4,5-tribenzoylphenyl (364) 3,4,5-triacetoxyphenyl (365) 3,4,5-trimethoxyphenyl ( 366) 3,4,5-tri-N-methylaminophenyl (367) 3,4,5-triisobutyrylaminophenyl (368) 3,4,5-triphenoxyphenyl (369) 3,4,5 -Trihydroxyphenyl (370) 2,4,6-tributylphenyl (371) 2,4,6-tri (2-methoxy-2-ethoxyethyl) B) phenyl (372) 2,4,6-triphenylphenyl (373) 2,4,6-triethoxycarbonylphenyl (374) 2,4,6-tridodecyloxyphenyl (375) 2,4,6- Trimethylphenyl (376) 2,4,6-trichlorophenyl (377) 2,4,6-tribenzoylphenyl (378) 2,4,6-triacetoxyphenyl (379) 2,4,6-trimethoxyphenyl ( 380) 2,4,6-tri-N-methylaminophenyl (381) 2,4,6-triisobutyrylaminophenyl (382) 2,4,6-triphenoxyphenyl (383) 2,4,6 -Trihydroxyphenyl (384) Pentafluorophenyl (385) Pentachlorophenyl (386) Pentamethoxyphenyl (38 7) 6-N-methylsulfamoyl-8-methoxy-2-naphthyl (388) 5-N-methylsulfamoyl-2-naphthyl (389) 6-N-phenylsulfamoyl-2-naphthyl (390) ) 5-Ethoxy-7-N-methylsulfamoyl-2-naphthyl (391) 3-methoxy-2-naphthyl (392) 1-ethoxy-2-naphthyl (393) 6-N-phenylsulfamoyl-8 -Methoxy-2-naphthyl (394) 5-methoxy-7-N-phenylsulfamoyl-2-naphthyl (395) 1- (4-methylphenyl) -2-naphthyl (396) 6,8-di-N -Methylsulfamoyl-2-naphthyl (397) 6-N-2-acetoxyethylsulfamoyl-8-methoxy-2-naphthyl (398) 5-acetoxy-7 N-phenylsulfamoyl-2-naphthyl (399) 3-benzoyloxy-2-naphthyl (400) 5-acetylamino-1-naphthyl (401) 2-methoxy-1-naphthyl (402) 4-phenoxy-1 -Naphtyl (403) 5-N-methylsulfamoyl-1-naphthyl (404) 3-N-methylcarbamoyl-4-hydroxy-1-naphthyl (405) 5-methoxy-6-N-ethylsulfamoyl- 1-naphthyl (406) 7-tetradecyloxy-1-naphthyl (407) 4- (4-methylphenoxy) -1-naphthyl (408) 6-N-methylsulfamoyl-1-naphthyl (409) 3- N, N-dimethylcarbamoyl-4-methoxy-1-naphthyl (410) 5-methoxy-6-N-benzylsulfamoyl -1-naphthyl (411) 3,6-di-N-phenylsulfamoyl-1-naphthyl (412) methyl (413) ethyl (414) butyl (415) octyl (416) dodecyl (417) 2-butoxy- 2-Ethoxyethyl (418) benzyl (419) 4-methoxybenzyl

(424) Methyl (425) Phenyl (426) Butyl

(430) methyl (431) ethyl (432) butyl (433) octyl (434) dodecyl (435) 2-butoxy-2-ethoxyethyl (436) benzyl (437) 4-methoxybenzyl

  In the present invention, a melamine polymer may be used as the compound having a 1,3,5-triazine ring. The melamine polymer is preferably synthesized by a polymerization reaction between a melamine compound represented by the following general formula (II) and a carbonyl compound.

In the above synthetic reaction scheme, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

  The alkyl group, alkenyl group, aryl group, heterocyclic group, and substituents thereof have the same meanings as the groups and substituents described in the general formula (I).

  The polymerization reaction between the melamine compound and the carbonyl compound is the same as the method for synthesizing a normal melamine resin (for example, melamine formaldehyde resin). Moreover, you may use a commercially available melamine polymer (melamine resin).

  The molecular weight of the melamine polymer is preferably 2,000 to 400,000. Specific examples of the repeating unit of the melamine polymer are shown below.

MP-1: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OH
^{MP-2: R 13, R} 14, R 15, R 16: CH 2 OCH 3
^{MP-3: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-4: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-5: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
^{MP-6: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-7: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
^{MP-8: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
^{MP-9: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
^{MP-10: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
^{MP-11: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
^{MP-12: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
^{MP-13: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
^{MP-14: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
^{MP-15: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
^{MP-16: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-17: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
^{MP-18: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-19: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
^{MP-20: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
MP-21: R ¹³ , R ¹⁴ , R ¹⁵ : CH ₂ OH; R ¹⁶ : CH _{2 On} -C ₄ H ₉
^{MP-22: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-23: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-24: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
^{MP-25: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2O -n-C 4 H 9
^{MP-26: R 13, R} 14, R 16: CH 2 O-n-C 4 H 9; R 15: CH 2 OH
^{MP-27: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-28: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-29: R 13, R} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-30: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-31: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-32: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-33: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-34: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-35: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-36: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-37: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-38: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
^{MP-39: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-40: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-41: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-42: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-43: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-44: R 13: CH} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
^{MP-45: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-46: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-47: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-48: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-49: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-50: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2

^{MP-51: R 13, R} 14, R 15, R 16: CH 2 OH
^{MP-52: R 13, R} 14, R 15, R 16: CH 2 OCH 3
^{MP-53: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-54: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-55: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
^{MP-56: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-57: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
^{MP-58: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
^{MP-59: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
^{MP-60: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
^{MP-61: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
^{MP-62: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
^{MP-63: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
^{MP-64: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
^{MP-65: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
^{MP-66: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-67: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
^{MP-68: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-69: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
^{MP-70: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-71: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-72: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-73: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-74: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
^{MP-75: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-76: R 13, R} 14, R 16: CH 2 O-n-C 4 H 9; R 15: CH 2 OH
^{MP-77: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-78: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-79: R 13, R} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-80: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-81: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-82: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-83: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-84: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-85: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-86: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-87: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-88: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
^{MP-89: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-90: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-91: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-92: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-93: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-94: R 13: CH} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
^{MP-95: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-96: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-97: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-98: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-99: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-100: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2

^{MP-101: R 13, R} 14, R 15, R 16: CH 2 OH
^{MP-102: R 13, R} 14, R 15, R 16: CH 2 OCH 3
^{MP-103: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-104: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-105: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
^{MP-106: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-107: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
^{MP-108: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
^{MP-109: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
^{MP-110: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
^{MP-111: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
^{MP-112: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
^{MP-113: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
^{MP-114: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
^{MP-115: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
^{MP-116: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-117: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
^{MP-118: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-119: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
^{MP-120: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-121: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-122: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-123: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-124: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
^{MP-125: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-126: R 13, R} 14, R 16: CH 2 O-n-C 4 H 9; R 15: CH 2 OH
^{MP-127: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-128: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-129: R 13, R} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-130: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-131: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-132: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-133: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-134: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-135: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-136: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-137: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-138: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
^{MP-139: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-140: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-141: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-142: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-143: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-144: R 13: CH} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
^{MP-145: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-146: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-147: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-148: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-149: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-150: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2

^{MP-151: R 13, R} 14, R 15, R 16: CH 2 OH
^{MP-152: R 13, R} 14, R 15, R 16: CH 2 OCH 3
^{MP-153: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-154: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-155: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
^{MP-156: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-157: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
^{MP-158: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
^{MP-159: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
^{MP-160: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
^{MP-161: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
^{MP-162: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
^{MP-163: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
^{MP-164: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
^{MP-165: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
^{MP-166: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-167: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
^{MP-168: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-169: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
^{MP-170: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-171: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-172: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-173: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-174: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
^{MP-175: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
MP-176: R ¹³ , R ¹⁴ , R ¹⁶ : CH _{2 On} -C ₄ H ₉ ; R ¹⁵ : CH ₂ OH
^{MP-177: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-178: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-179: R 13, R} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-180: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-181: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-182: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-183: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-184: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-185: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2O -n-C 4 H 9
^{MP-186: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-187: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-188: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
^{MP-189: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-190: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-191: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-192: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-193: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-194: R 13: CH} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
^{MP-195: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-196: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-197: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-198: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-199: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-200: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
In the present invention, a copolymer obtained by combining two or more of the above repeating units may be used. Two or more homopolymers or copolymers may be used in combination.

  Moreover, you may use together the compound which has a 2 or more types of 1,3,5- triazine ring. Two or more kinds of discotic compounds (for example, a compound having a 1,3,5-triazine ring and a compound having a porphyrin skeleton) may be used in combination.

  These additives are preferably contained in an amount of 0.2 to 30% by mass, particularly preferably 1 to 20% by mass with respect to the cellulose ester film.

  Moreover, the triazine type compound shown by the general formula (I) of Unexamined-Japanese-Patent No. 2001-235621 is also preferably used for the cellulose ester film which concerns on this invention.

  The cellulose ester film according to the present invention preferably contains two or more ultraviolet absorbers.

  As the UV absorber, a polymer UV absorber can be preferably used, and in particular, a polymer type UV absorber described in JP-A-6-148430 is preferably used.

  The method of adding the UV absorber may be added to the dope after the UV absorber is dissolved in an alcohol such as methanol, ethanol or butanol, an organic solvent such as methylene chloride, methyl acetate, acetone or dioxolane, or a mixed solvent thereof. Or you may add directly in dope composition. For an inorganic powder that does not dissolve in an organic solvent, a dissolver or a sand mill is used in the organic solvent and cellulose ester to disperse and then added to the dope.

  The amount of the UV absorber used is not uniform depending on the type of UV absorber, the operating conditions, etc., but when the dry film thickness of the cellulose ester film is 30 to 200 μm, it is 0.5 to 10 with respect to the cellulose ester film. % By mass is preferred, 0.5-4% by mass is more preferred, and 0.6-2% by mass is particularly preferred.

<Fine particles>
The cellulose ester film used in the present invention preferably contains fine particles in order to form an uneven surface on the substrate film surface or to have an internal scattering effect.

  Examples of inorganic particles that can be used in the present invention include silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, antimony oxide, magnesium oxide, calcium carbonate, calcium carbonate, talc, Examples thereof include clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, and composite oxides thereof.

  The average primary particle diameter of the fine particles is preferably 5 nm to 5 μm, and more preferably 5 nm to 1 μm. These mainly contain secondary aggregates having a particle size of 0.05 to 1 μm, preferably 0.05 to 0.3 μm. The content of these fine particles in the cellulose ester film is preferably 0.05 to 10% by mass, particularly preferably 0.1 to 1% by mass. In the case of a cellulose ester film having a multilayer structure by a co-casting method, it is preferable that these fine particles are contained in the surface layer at this content.

  As organic particles, polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder, Polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, or polyfluoroethylene resin powder can be added to the cellulose ester film.

  Specific examples of commercially available organic particles include crosslinked acrylic monodisperse particles (MX-150, MX-180, MX-300, MX-500, MX-1000), crosslinked acrylic particles (MR-2HG, MR-7HG, MR). -10HG, MR-3GSN, MR-5GSN, MR-2G, MR-7G, MR-10G), acrylic monodisperse particles (MP-1451, MP-2200, MP-1000, MP-2701, MP-5000, MP) -5500, MP-1600, MP-1400), cross-linked styrene particles (SX-130H, SX-200H, SX-350H, SH-130H, SH-350H), polymethyl methacrylate particles (MX150, MX300, above, Soken) Chemical Co., Ltd.).

  Among these, in order to achieve the antiglare property which is the object of the present invention, silicon oxide particles such as silica, crosslinked acrylic particles, crosslinked styrene particles, or tin oxide, ITO, antimony oxide, zinc oxide, and indium oxide are used. Conductive fine particles having a main component are particularly preferably used. As the silicon oxide particles preferably used here, ultrafine hydrated silicic acid produced by a wet method is preferred among synthetic amorphous silicas because of its great effect of reducing the glossiness. The wet method is a method in which sodium silicate, mineral acid and salts are reacted in an aqueous solution. For example, Silicia (310, 350, 430, 431, 435, 540, 450, 702, 704, 770) manufactured by Fuji Silysia Chemical Ltd. Etc.) and Nippon Sil E manufactured by Nippon Silica Co., Ltd.

<dye>
A dye may be added to the cellulose ester film used in the present invention to adjust the color. For example, a blue dye may be added to suppress the yellowness of the film. Preferred examples of the dye include anthraquinone dyes.

  The anthraquinone dye may have an arbitrary substituent at an arbitrary position from the 1st position to the 8th position of the anthraquinone. Preferred substituents include an anilino group, hydroxyl group, amino group, nitro group, or hydrogen atom. In particular, it is preferable to contain a blue dye described in paragraphs [0034] to [0037] of JP-A No. 2001-154017, particularly an anthraquinone dye. Further, it preferably contains an infrared absorbing dye, and in particular, any one of thiopyrylium squarylium dye, thiopyrylium croconium dye, pyrylium squarylium dye, and pyrylium croconium dye disclosed in JP-A-2001-154017. It is preferable that Specifically, an infrared absorbing dye represented by the general formula (1) or the general formula (2) of the publication can be preferably added.

  Various additives may be batch-added to a dope that is a cellulose ester-containing solution before film formation, or an additive solution may be separately prepared and added in-line. In particular, it is preferable to add a part or all of the fine particles in-line in order to reduce the load on the filter medium.

  When the additive solution is added in-line, it is preferable to dissolve a small amount of cellulose ester in order to improve mixing with the dope. The amount of the cellulose ester is preferably 1 to 10 parts by mass, more preferably 3 to 5 parts by mass with respect to 100 parts by mass of the solvent.

  In order to perform in-line addition and mixing in the present invention, for example, an in-line mixer such as a static mixer (manufactured by Toray Engineering), SWJ (Toray static type in-tube mixer Hi-Mixer) or the like is preferably used.

<Method for producing cellulose ester film>
Next, the manufacturing method of the cellulose ester film used for this invention is demonstrated.

  The cellulose ester film used in the present invention was produced by dissolving a cellulose ester and an additive in a solvent to prepare a dope, casting a dope on a belt-shaped or drum-shaped metal support, and casting. It is carried out by a step of drying the dope as a web, a step of peeling from the metal support, a step of stretching or maintaining the width, a step of further drying, and a step of winding up the finished film. In the present invention, as described above, it is preferable to form a concavo-convex surface by pressing the mold in any of the step of peeling from the metal support, the step of stretching or maintaining the width, and the step of drying.

  The process for preparing the dope will be described. The concentration of cellulose ester in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration of cellulose ester is too high, the load during filtration increases and the filtration accuracy increases. Becomes worse. As a density | concentration which makes these compatible, 10-35 mass% is preferable, More preferably, it is 15-25 mass%.

  The solvent used in the dope of the present invention may be used alone or in combination of two or more. However, it is preferable from the viewpoint of production efficiency that a good solvent and a poor solvent of cellulose ester are mixed and used. The more solvent is preferable from the viewpoint of solubility of the cellulose ester. The preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent. With a good solvent and a poor solvent, what dissolve | melts the cellulose ester to be used independently is defined as a good solvent, and what poorly swells or does not melt | dissolve is defined as a poor solvent. Therefore, depending on the acyl group substitution degree of the cellulose ester, the good solvent and the poor solvent change. For example, when acetone is used as the solvent, the cellulose ester acetate ester (acetyl group substitution degree 2.4) and the cellulose acetate propionate are good. As a solvent, cellulose acetate (acetyl group substitution degree 2.8) is a poor solvent.

  Although the good solvent used for this invention is not specifically limited, Organic halogen compounds, such as a methylene chloride, dioxolanes, acetone, methyl acetate, methyl acetoacetate, etc. are mentioned. Particularly preferred is methylene chloride or methyl acetate.

  Moreover, although the poor solvent used for this invention is not specifically limited, For example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone, etc. are used preferably. Moreover, it is preferable that 0.01-2 mass% of water contains in dope.

  A general method can be used as a method of dissolving the cellulose ester when preparing the dope described above. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure. It is preferable to stir and dissolve while heating at a temperature that is equal to or higher than the boiling point of the solvent at normal pressure and that the solvent does not boil under pressure, in order to prevent the generation of massive undissolved materials called gels and mamaco. Moreover, after mixing a cellulose ester with a poor solvent and making it wet or swell, the method of adding a good solvent and melt | dissolving is also used preferably.

  The pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside. For example, a jacket type is preferable because temperature control is easy.

  The heating temperature with the addition of a solvent is preferably higher from the viewpoint of the solubility of the cellulose ester, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates. A preferable heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and still more preferably 70 ° C to 105 ° C. The pressure is adjusted so that the solvent does not boil at the set temperature.

  Alternatively, a cooling dissolution method is also preferably used, whereby the cellulose ester can be dissolved in a solvent such as methyl acetate.

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

  The material of the filter medium is not particularly limited, and a normal filter medium can be used. However, a plastic filter medium such as polypropylene and Teflon (R) and a metal filter medium such as stainless steel are preferable because there is no loss of fibers. . It is preferable to remove and reduce impurities, particularly bright spot foreign matter, contained in the raw material cellulose ester by filtration.

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

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

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

  Here, the dope casting will be described.

  The metal support in the casting (casting) step preferably has a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support. The cast width can be 1 to 4 m. The surface temperature of the metal support in the casting step is set to −50 ° C. to a temperature at which the solvent boils and does not foam. A higher temperature is preferable because the web can be dried faster, but if it is too high, the web may foam or flatness may deteriorate. The preferable support temperature is appropriately determined at 0 to 100 ° C, and more preferably 5 to 30 ° C. Alternatively, it is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent. The method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short. When using warm air, considering the temperature drop of the web due to the latent heat of vaporization of the solvent, while using warm air above the boiling point of the solvent, there may be cases where wind at a temperature higher than the target temperature is used while preventing foaming. . In particular, it is preferable to perform drying efficiently by changing the temperature of the support and the temperature of the drying air during the period from casting to peeling.

  In order for the cellulose ester film to exhibit good flatness, the residual solvent amount when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. Especially preferably, it is 20-30 mass% or 70-120 mass%.

  In the present invention, the amount of residual solvent is defined by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
M is the mass of a sample collected during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.

  In the film drying process, generally, a roll drying method (a method in which a plurality of rolls arranged on the upper and lower sides are alternately passed through and dried) or a method of drying while transporting the web by a tenter method is adopted.

  In order to produce the cellulose ester film for the antiglare and antireflection film of the present invention, the web is stretched in the conveying direction where the residual solvent amount of the web immediately after peeling from the metal support is large, and both ends of the web are clipped. It is preferable to perform stretching in the width direction by a tenter method gripped by. The preferred draw ratio in both the machine direction and the transverse direction is 1.05 to 1.3 times, and more preferably 1.05 to 1.15 times. It is preferable that the area is 1.12 times to 1.44 times, and preferably 1.15 times to 1.32 times due to longitudinal and lateral stretching. This can be determined by the draw ratio in the longitudinal direction × the draw ratio in the transverse direction.

  In order to stretch in the machine direction immediately after peeling, it is preferable to stretch by peeling tension and subsequent transport tension. For example, it is preferable to peel at a peeling tension of 210 N / m or more, and particularly preferably 220 to 300 N / m.

  By stretching in the longitudinal direction and the lateral direction in the film forming step, the fine particles added to the surface layer are easily exposed, and as a result, there is an effect of forming favorable irregularities.

  The means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roll, microwave, or the like, but it is preferably performed with hot air in terms of simplicity.

  The drying temperature in the web drying step is preferably increased stepwise from 30 to 160 ° C., and more preferably from 50 to 140 ° C. in order to improve the dimensional stability.

  Although the film thickness of a cellulose-ester film is not specifically limited, 10-200 micrometers is used preferably. In particular, it was difficult to obtain an antiglare antireflection film excellent in flatness and hardness with a thin film of 10 to 70 μm, but according to the present invention, the antiglare reflection of a thin film excellent in flatness and hardness was achieved. Since the prevention film is obtained and the productivity is also excellent, the film thickness of the cellulose ester film is particularly preferably 10 to 70 μm. More preferably, it is 20-70 micrometers. Most preferably, it is 35-70 micrometers. Moreover, the cellulose-ester film made into the multilayer structure by the co-casting method mentioned later can also be used preferably. Even when the cellulose ester has a multilayer structure, it has a layer containing an ultraviolet absorber and a plasticizer, and it may be a base layer, a surface layer, or both.

  The variation of the film thickness of the cellulose ester film is preferably within ± 3% in both the width direction and the longitudinal direction, more preferably within ± 2%, and particularly preferably within ± 0.5%.

  The antiglare antireflection film of the present invention preferably has a width of 1 to 4 m.

<Physical properties>
The moisture permeability of the cellulose ester film used in the present invention, 40 ° C., or less 850g / m ² · 24h at 90% RH, preferably ^{20~800g / m 2 · 24h, 20~750g} / m 2 · 24 h is particularly preferable. The moisture permeability can be measured according to the method described in JIS Z 0208.

  The cellulose ester film used in the present invention has a breaking elongation measured by the following measurement of preferably 10 to 80%, more preferably 20 to 50%.

(Measurement of elongation at break)
A film containing an arbitrary residual solvent is cut into a sample width of 10 mm and a length of 130 mm, and stored for 24 hours at 23 ° C. and 55% RH, and a tensile test is performed at a pulling speed of 100 mm / min with a chuck distance of 100 mm. I can do it.

  The visible light transmittance of the cellulose ester film used in the present invention as measured by the following measurement is preferably 90% or more, and more preferably 93% or more.

(Measurement of transmittance)
Transmittance T is 380, 400, 500 nm from spectral transmittance τ (λ) obtained every 10 nm in a wavelength region of 350-700 nm using a spectral altimeter U-3400 (Hitachi, Ltd.). Transmittance can be calculated.

  As for the haze by the following measurement of the cellulose-ester film used for this invention, 1-25% is preferable, More preferably, it is 2-15%, Most preferably, it is 2-10%. The visible light transmittance is preferably 90% or more, more preferably 92% or more, and further preferably 94% or more.

(Measurement of haze value)
According to JIS K-6714, it can be measured using a haze meter (1001DP type, manufactured by Nippon Denshoku Industries Co., Ltd.) and can be used as an index of transparency.

  The in-plane retardation value (Ro) of the cellulose ester film used in the present invention is preferably 0 to 70 nm or less. More preferably, it is 0-30 nm or less, More preferably, it is 0-10 nm or less. The retardation value (Rt) in the film thickness direction is preferably 0 to 400 nm, preferably 10 to 200 nm, and more preferably 30 to 150 nm.

  The retardation value (Ro) (Rt) can be obtained by the following equation.

Ro = (nx−ny) × d
Rt = ((nx + ny) / 2−nz) × d
Here, d is the thickness (nm) of the film, the refractive index nx (also referred to as the maximum refractive index in the plane of the film, the refractive index in the slow axis direction), ny (in the direction perpendicular to the slow axis in the film plane). ) (Refractive index of film in the thickness direction).

  The retardation values (Ro) and (Rt) and the slow axis angle can be measured using an automatic birefringence meter. For example, the wavelength can be obtained at 590 nm in an environment of 23 ° C. and 55% RH using KOBRA-21ADH (Oji Scientific Instruments).

  The slow axis is preferably in the width direction ± 1 ° of the film or in the longitudinal direction ± 1 °.

  In the present invention, the base film is composed of a plurality of layers (base layer and surface layer) by co-casting or sequential casting or coating, and the surface layer contains fine particles to form an uneven surface, on which an active ray curable resin layer is formed. When forming the surface layer, the surface layer is preferably a layer having a glass transition temperature lower than that of the base layer.

  Since the thermoplastic resin has irregularities, fine cracks due to bending are prevented. If the glass transition temperature is low, the effect is excellent, and it is more effective when it contains fine particles.

  As described above, the method for lowering the glass transition temperature of the surface layer to be lower than the glass transition temperature of the base layer includes changing the type, addition ratio, and addition amount of the plasticizer. Preferably, the plasticizer content is increased, and the content is preferably 1.1 to 3 times the content of the inside. As another method, a thermoplastic resin layer having a low glass transition temperature is provided on the surface layer. In the case of a cellulose ester film, it is preferable to use a film having a number average molecular weight smaller than that of the base layer or a film having a low total acyl group substitution degree.

  In the present invention, in the case of a multilayer structure, the layer containing the cellulose ester described above is preferably used as the base layer, and the layer described below is preferably used as the surface layer. It does not specifically limit as resin used for a surface layer, An acrylic resin, polyester, a cellulose ester etc. are mentioned as a preferable example.

[Surface]
The surface layer having the cellulose ester according to the present invention will be described.

  The cellulose ester film according to the present invention preferably has a surface layer having a thickness of 0.1 to 15 μm and lower than the average of the total acyl group substitution degree of the cellulose ester film. Although there is no restriction | limiting in the total acyl group substitution degree of a surface layer, It is preferable to provide at least one surface layer which has a cellulose ester whose total acyl group substitution degree is 2.7 or less especially on a base layer, and to make a cellulose-ester film of a multilayer structure. .

  The present inventor has found that the formation of an uneven surface is easier by using a cellulose ester having a total acyl group substitution degree of 2.7 or less as a surface layer.

  In this invention, it is preferable that the total acyl group substitution degree of the cellulose ester used for surface layer is 2.7 or less, More preferably, it is the range of 1.9-2.7. As the cellulose ester having a total acyl group substitution degree in this range, those similar to the cellulose ester used in the base layer are used, and cellulose diacetate or cellulose acetate propionate is preferable. The total acyl group substitution degree can be adjusted by adjusting the esterification conditions (temperature, time, stirring) and hydrolysis conditions of the cellulose ester as described above.

  The layer configuration may be two or more, and a plurality of layers may be included in the surface layer or the base layer. Preferably, three layers are preferred, two surface layers and one base layer, and three layers are preferred because the effect can be sufficiently improved to produce an excellent antiglare antireflection film of the present invention.

  The film thickness per surface layer is in the range of 0.1 to 15 μm, and in order to obtain the effects of the present invention, it is preferably in the range of 0.5 to 15 μm, and more preferably in the range of 1 to 10 μm. It is especially preferable that it is 5-10 micrometers. When the surface layer is a plurality of layers, the thicknesses of the layers may be the same or different.

  The surface layer preferably contains the aforementioned fine particles. In particular, it is preferable to increase the content of fine particles contained in the surface layer rather than the average fine particle content of the entire film in order to enhance the effect of the present invention. The fine particles are preferably used as the fine particles.

  The surface layer according to the present invention preferably contains a plasticizer. As the plasticizer, a plasticizer used for the base layer can be used. The plasticizer content is preferably greater than the average plasticizer content in the multilayered cellulose ester film.

  In particular, the surface layer on the uneven surface is preferably a composition having a low glass transition temperature, and a resin having a high plasticizer content or a low glass transition temperature is preferably used.

The glass transition temperature (Tg) of the cellulose ester of the present invention is measured by melting 10 mg of a film or pellet (or a fragment obtained by scraping off the corresponding layer) at 300 ° C. in a nitrogen stream of 300 cm ^{3 /} min. Quench in liquid nitrogen. The rapidly cooled sample is set in a differential scanning calorimeter (manufactured by Rigaku Denki Co., Ltd., DSC8230 type), heated in a nitrogen stream of 100 cc per minute at a heating rate of 10 ° C., and Tg and Tm are detected. Tg is the average value of the temperature at which the baseline begins to deviate and the temperature at which the baseline returns to the baseline, and Tm is the peak temperature of the endothermic peak. Note that the measurement start temperature is 50 ° C. or more lower than the measured Tg.

  In order to make the surface layer have a composition having a low glass transition temperature, in the case of a cellulose ester, it is preferable that the substitution degree of the total acyl group is low, and it is desirable to use a cellulose ester having a total acyl group substitution degree of 0.1 or more lower for the surface layer. . For example, when the base layer is cellulose triacetate, cellulose diacetate is preferably used for the surface layer. Alternatively, cellulose mixed carboxylic acid ester is also preferably used because of its low glass transition temperature. For example, when the base layer is cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate or the like is preferably used for the surface layer. In addition, a thermoplastic resin having a low glass transition temperature other than cellulose ester, such as an acrylic resin, can be used for the surface layer.

  Further, the surface layer may contain additives such as the ultraviolet absorber, dye, and organic solvent.

[Multilayer cellulose ester film]
The cellulose ester film having a multilayer structure according to the present invention is formed by a co-casting method or a sequential casting method with different compositions of the surface layer dope and the base layer dope (type of resin, composition of additive, added amount, etc.). It is preferable that it is obtained. The co-casting method has excellent quality uniformity, and the sequential casting has a high film forming speed and excellent productivity. In the present invention, since accuracy is required particularly for the flatness of the base film in relation to the accuracy and flatness of the uneven surface, it is preferably formed by a co-casting method.

[Manufacture of cellulose ester film of multilayer structure]
The layer structure of the cellulose ester film having a multilayer structure useful for the actinic radiation curable resin film of the present invention is a film having a multilayer structure having a base layer and at least one surface layer as described above, and the multilayer structure has three or more layers. However, a three-layer structure having one surface layer on each side of the base layer is more preferable.

  Hereinafter, the manufacturing method of the cellulose-ester film of a multilayer structure is demonstrated.

  FIG. 1 schematically shows a cross section of a film having a three-layer structure, in which 1 and 3 are surface layers, and 2 is a base layer.

[Co-casting and sequential casting]
The multilayered cellulose ester film in the present invention is preferably obtained by laminating a dope in multiple layers by co-casting or sequential casting in a solution casting film forming process.

  FIG. 2 is a diagram showing a co-casting die and cast to form a multi-layered web (the web may also be referred to as a dope film immediately after casting). As shown in FIG. 2, the co-casting has a plurality of slits (three in FIG. 2, surface slits 13 and 15, and base layer slit 14) in the die portion 11 of the co-casting die 10. A web 20 having a multilayer structure of surface layer 21 / base layer 22 / surface layer 23 is formed on the metal support 16 by casting the surface layer dope 17, the base layer dope 18, and the surface layer dope 19 simultaneously from the respective slits. To do.

  FIG. 3 is a view showing a sequential casting die and a web having a multilayer structure. As shown in FIG. 3, the sequential casting is performed by placing a plurality of (three in FIG. 26) surface layer casting dies 30, base layer dies 31 and surface layer casting dies 32 above the metal support 16 at different locations. First, a surface layer dope 33 which is one surface layer is cast from the surface layer die 30 to form a surface layer doped film 36 on the metal support 16, and then the base layer dope 34 is formed on the base layer die. A base layer dope film 37 is formed on the surface layer dope film 36 from the surface layer 31, and a surface layer dope 35 is cast from the next surface layer die 32 to form a surface layer dope film 38, whereby the surface layer / base layer / surface layer A multilayer construction web 39 is formed.

  FIG. 4 is a view showing a cross section of another type of co-casting die. In the co-casting die 50 in which three layers are joined in the main body, the base layer dope 56 and the surface layer dopes 55 and 57 are introduced into the base layer slit 52 and the surface layer slits 51 and 53, respectively. Are merged at the merging slit 58, pass through the slit 54 in a laminar flow, and are cast in three layers on the metal support 16.

  It is preferred to cast the multi-layer web as shown in FIGS. 2, 3 and 4 so that the surface layer is wider than the base layer and the base web is wrapped by the surface web.

[Solution casting film forming method]
The cellulose ester film of the present invention is preferably formed by a solution casting film forming method. Here, the solution casting film forming method according to the present invention will be described with reference to the drawings.

  FIG. 5 is a view schematically showing a dope preparation process of the solution casting film forming apparatus according to the present invention.

  FIG. 6 is a diagram schematically showing from the casting process to the drying process of the solution casting film forming apparatus according to the present invention.

  The following processes will be described with reference to the three-layer co-casting as an example.

(1) Cellulose ester solution preparation process:
The dope preparation step on the upper side of the paper in FIG. 5 is for the base layer, and the dope preparation step on the lower side of the paper is for the surface layer.

  Cellulose ester is dissolved in an organic solvent mainly composed of a good solvent for cellulose ester while stirring the cellulose ester and additives such as a crushed piece of a film to be reused as part of the raw material and a plasticizer in stirring vessel 101. In this step, the solution 100 is formed. For dissolution, a method performed at normal pressure, a method performed below the boiling point of the main solvent, a high-temperature dissolution method performed by pressurization above the boiling point of the main solvent, a cooling dissolution method performed by cooling and a high-pressure dissolution method performed at a considerably high pressure However, in the present invention, the high temperature dissolution method is preferably used. After dissolution, the cellulose ester solution 100 is filtered by a liquid feed pump 102 through a filter 103 (filter press type), left standing in a stock tank 104 and defoamed, and a liquid feed pump 105 (pressure type metering gear pump) for casting. Etc. are often used), and are transferred by a conduit 108 for mixing in a merge tube 120 that merges with an in-line additive solution 110 containing an ultraviolet absorber via a filter 106. When the dope used for the base layer is a cellulose ester solution 100 containing a plasticizer and an ultraviolet absorber, the dope may be sent directly to the casting die after passing through the filter 106.

  When using the in-line additive liquid 110 containing additives (other than a matting agent) such as an ultraviolet absorber, the liquid is prepared and fed through lines indicated by 111 to 117. The in-line additive solution obtained by dissolving the additive and cellulose ester in the organic solvent in the dissolution vessel 111 may be sent by the pump 112, filtered by the filter 113, and returned to the dissolution vessel 111 through the switching valve 119 and circulated as necessary. Alternatively, it may be stored in the stock tank 114 as it is. The liquid is fed through the conduit 117 via the pump 115 and the filter 116.

  Here, filtration will be described. The cellulose ester solution is filtered using an appropriate filter medium such as filter paper for filter press. As the filter medium in the present invention, it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters, etc., but if the absolute filtration accuracy is too small, there is a problem that the filter medium is likely to be clogged. Filter media with an accuracy of 8 μm or less are preferred, filter media in the range of 1-8 μm are more preferred, and filter media in the range of 3-6 μm are even more preferred. Examples of filter paper include No. of Azumi Filter Paper Co., Ltd., a commercially available product. 244 and 277 can be mentioned and are preferably used. Further, the material of the filter medium for filtration is not particularly limited, and a normal filter medium can be used. However, a plastic filter medium such as polypropylene or Teflon (R) or a metal filter medium such as stainless steel may cause the fibers to fall off. Less preferred. Filtration can be performed by a normal method, but the method of filtering while heating or keeping the temperature at a temperature in a range not lower than the boiling point of the organic solvent used under normal pressure and in a range where the organic solvent does not boil is a filter medium. The increase in differential pressure before and after (hereinafter sometimes referred to as filtration pressure) is small and preferable. The preferred temperature range depends on the organic solvent used, but is 45 to 120 ° C, more preferably 45 to 70 ° C, and still more preferably 45 to 55 ° C. The filtration pressure is preferably as small as possible, preferably 0.3 to 1.6 MPa, more preferably 0.3 to 1.2 MPa, and still more preferably 0.3 to 1.0 MPa. In addition, you may add an ultraviolet absorber to a cellulose-ester solution in the dissolution pot 101 previously.

(2) Preparation Step of Inline Additive Solution Containing Fine Particles Here, the inline additive solution containing the fine particle dispersion used for the surface layer dope will be described. The preparation method of the fine particle dispersion containing the organic solvent such as lower alcohol used for the cellulose ester solution, the resin described later and the matting agent fine particle described later is particularly suitable if it can be sufficiently uniformly dispersed in the liquid. Although there is no limitation, the following method is preferable.

  In FIG. 5 (bottom of the paper surface of FIG. 5), the in-line additive liquid 110A containing fine particles is a cellulose ester solution obtained by stirring and dissolving a cellulose ester in an organic solvent in a dissolution / dispersion vessel 111A. Separately, a fine particle dispersion dispersed with a disperser (not shown) such as Menton Goleen or Sand Mill is added. Here, the in-line additive solution 110A containing fine particles is obtained by sufficiently stirring and stabilizing the dispersion. This in-line additive liquid 110A is circulated through a filter 113A with a liquid feed pump 112A, and if necessary, through a switching valve 119A and sent to the dissolution / dispersion kettle 110A to repeatedly remove the same operation several times. You may let them. Thereafter, the switching valve 119A is switched, the in-line additive liquid 110A is temporarily transferred to the stock tank 114A, and after stationary deaeration, transferred by a liquid feed pump 115A (for example, a pressurized metering gear pump), filtered by a filter 116A, and a conduit. Transfer via 117A. Further, the liquid may be fed through the liquid feed pump 115A, the filter 116A, and the conduit 117A without being left in the stock tank 114A. When the surface layer has different compositions on the front side and the back side, a liquid preparation step similar to that shown for 150A can be provided separately.

  In addition, the process of preparing the cellulose ester solution 100A for surface layer of FIG. 5 is the same as the 101-108 line of the above-mentioned cellulose ester solution 100 in the 101A-108A line. 101A to 108A correspond to 101 to 108. The cellulose ester solution 100A and the fine particle in-line additive solution 110A are merged at the merge point 120A.

  Note that the cellulose ester 100 can be used for the base layer and the surface layer by using the 101-108 line and the 101A-108A line in common.

  Examples of the method for preparing the fine particle dispersion according to the present invention include the following three types.

(Preparation method A)
After stirring and mixing the organic solvent and the fine particles, dispersion is performed with a disperser. This is a fine particle dispersion.

(Preparation method B)
After stirring and mixing the organic solvent and the fine particles, dispersion is performed with a disperser to obtain a fine particle dispersion. Separately, add a small amount of resin (resin with good dispersibility to fine particles and moderate viscosity to the liquid, and compatible with cellulose ester or cellulose ester) to an organic solvent, and stir and dissolve the resin solution. prepare. The fine particle dispersion is added to this, stirred and sufficiently dispersed to obtain a fine particle dispersion.

(Preparation method C)
A small amount of resin (a resin having good dispersibility with respect to fine particles and compatible with cellulose ester or cellulose ester) is added to an organic solvent, and dissolved by stirring. Fine particles are added to this and sufficiently dispersed with a disperser to obtain a fine particle dispersion.

  Preparation method A is excellent in dispersibility of silicon dioxide fine particles, and preparation method C is excellent in that the silicon dioxide fine particles are difficult to reaggregate. The preparation method B is a preferable preparation method that is excellent in both dispersibility of the silicon dioxide fine particles and difficulty in reaggregation of the silicon dioxide fine particles.

  The in-line additive solution containing the fine particle dispersion prepared by the preparation methods A to C is added to the cellulose ester solution and stirred to form a dope, but the in-line additive solution 110A and the cellulose ester solution 100A are joined by the in-line mixer 121A. It is preferable to mix well to obtain a dope containing fine particles. The dope containing the fine particles may contain an ultraviolet absorber, and in this case, it is preferably added to the cellulose ester solution.

  In the above preparation method, the concentration of silicon dioxide when the silicon dioxide fine particles are mixed with an organic solvent and dispersed is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and still more preferably 15 to 20% by mass. The higher the dispersion concentration, the lower the liquid turbidity with respect to the amount added, and the lower the haze of the film obtained, and there is no aggregate, which is preferable.

  The organic solvent used is preferably the organic solvent used for the dope, but is not particularly limited. Examples of lower alcohols used for the dope include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like, and ethanol is particularly preferable.

  As a resin that helps dispersibility of fine particles, improves dispersibility, and is compatible with cellulose ester, cellulose ester used for dope may be used. However, the resin described in JP-A-2003-12859 is used for dispersion filtration. At this time, it can be preferably used because it is not easily clogged. For example, Actflow series resins commercially available from Soken Chemical Co., Ltd. can be preferably used.

(Distributor)
As the disperser for dispersing the fine particles, a normal disperser can be used. Dispersers can be broadly divided into media dispersers and medialess dispersers. For dispersion of silicon dioxide fine particles, a medialess disperser is preferred because of low haze. Examples of the media disperser include a ball mill, a sand mill, and a dyno mill. Examples of the medialess disperser include an ultrasonic type, a centrifugal type, and a high pressure type. In the present invention, a high pressure disperser is preferable. A high-pressure dispersion device is a device that creates special conditions such as high shear and high pressure by passing a composition in which fine particles and a solvent are mixed at high speed through a narrow tube.

  When processing with a high-pressure dispersion apparatus, for example, the maximum pressure condition inside the apparatus is preferably 10 MPa or more in a thin tube having a tube diameter of 1 to 2000 μm. More preferably, it is 20 MPa or more. Further, at that time, those having a maximum reaching speed of 100 m / second or more and those having a heat transfer speed of 420 kJ / hour or more are preferable. The high-pressure dispersing apparatus as described above includes an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation or a nanomizer manufactured by Nanomizer, and other manton gorin type high-pressure dispersing apparatuses such as a homogenizer manufactured by Izumi Food Machinery Co., Ltd. Examples include UHN-01 manufactured by Wakki Co., Ltd.

  The in-line additive liquid 110A eliminates the stagnation in the stock tank 114A, and if possible, does not use the liquid feed pump 115A, and is transferred by the pipe 117A immediately after filtration by the final filter 116A. This is desirable because generation of new aggregates can be suppressed.

  The filter for the in-line additive liquid containing fine particles is preferably placed immediately before the in-line mixer.For example, large aggregates generated from the path due to filter medium exchange or the like can be filtered once from the fine particle dispersion in the liquid feed. It is preferable to use a filter made of metal having an organic solvent resistance that can be used for a long period of time and has the absolute filtration accuracy as a filter medium for reliably removing relatively large foreign substances. The filter medium is preferably a metal, particularly stainless steel, from the viewpoint of durability. From the viewpoint of clogging, it is preferable to have a porosity of 60 to 80%. Therefore, it is most preferable to filter with a metal filter medium having an absolute filtration accuracy of 30 to 60 μm and a porosity of 60 to 80%, thereby reliably removing coarse foreign substances over a long period of time. Is preferable. Examples of metal filter media having an absolute filtration accuracy of 30 to 60 μm and a porosity of 60 to 80% include NF-10, NF-12, and NF-13 of Fine pore NF series manufactured by Nippon Seisen Co., Ltd. Any of these is preferably used.

(3) Dope preparation process:
The dope preparation steps 150 and 150A referred to here are steps in which the cellulose ester solution and the in-line additive solution are sufficiently mixed with mixers 121 and 121A such as an in-line mixer to form a dope.

  150 is a step for preparing a base layer and 150A is a dope for a surface layer containing fine particles.

  The cellulose ester solution 100 or 100A and the in-line additive solution 110 or 110A are combined with each other by a merging tube 120 or 120A, and sufficiently mixed by a mixer 121 or 121A such as an in-line mixer to be used for a base layer or a surface layer. Dope. Also. As an in-line mixer that can be preferably used in the present invention, for example, a static mixer SWJ (Toray static type in-pipe mixer Hi-Mixer, manufactured by Toray Engineering) can be exemplified and preferably used.

  In the later-described co-casting die, the dope prepared by changing the components according to the respective purposes is supplied to each slit. The viscosity of the dope used for the base layer is preferably 50 to 10,000 Pa · s (at 35 ° C.), particularly preferably 50 to 1,000 Pa · s. The viscosity of the dope used for the surface layer is preferably 0.1 to 5,000 Pa · s, more preferably 5 to 1,000 Pa · s, still more preferably 10 to 500 Pa · s, and particularly preferably 10 ~ 50 Pa · s. In the present invention, the viscosity of the surface layer dope is preferably lower than that of the base layer.

  Hereinafter, an example of production of the cellulose ester film according to the present invention will be described with reference to FIG.

(4) Co-casting process:
The base layer dope is introduced into the dope supply port 202 of the co-casting die 200, and the surface layer dope containing fine particles is introduced into the surface layer supply port 201 and / or 203 and co-cast.

  FIG. 6 shows, for example, three layers of dope from a co-casting die 200 at a casting position on an endless metal support 204 that moves indefinitely, such as a stainless steel belt or a rotating metal drum 204. It is a process of co-casting. The surface of the metal support 204 is preferably a mirror surface. A co-casting die 200 (for example, a pressure-type co-casting die) is preferable because it can prepare three slit shapes in the die portion and easily make the film thickness uniform. As the co-casting die, those shown in FIG. 2 or FIG. 4 are preferably used, but are not limited thereto. The co-casting die 200 includes a coat hanger die and a T die, and any of them is preferably used.

  In the case of sequential casting, two or more single-layer dies are shifted on the metal support 204 and two or more types of dope amounts are supplied to form a multilayer doped film.

(5) Solvent evaporation step:
For example, a web 206 having a three-layer structure (referred to as a dope film after casting a dope on a metal support) is heated or cooled on the metal support 204 so that the web 206 is transferred from the metal support 204 to the web 206. This is a step of evaporating the solvent until it can be peeled off. In order to evaporate the solvent, there are a method of applying air to the web 206 and / or a method of transferring heat from the back surface of the metal support 204 by liquid or gas, a method of transferring heat from the front and back by radiant heat, and the like. This method is preferable because of good drying efficiency. A method of combining them is also preferable. In the case of backside liquid heat transfer, it is preferable to heat the web temperature on the metal support below the boiling point of the main solvent of the organic solvent used in the dope or the organic solvent having the lowest boiling point. The surface temperature of the metal support for casting is 10 to 55 ° C., the temperature of the solution is 25 to 60 ° C., and the temperature of the solution is preferably equal to or higher than the temperature of the support. More preferably, the temperature is set to a temperature of The higher the solution temperature and the support temperature, the faster the solvent can be dried. However, if the temperature is too high, foaming or flatness may be deteriorated. Although the more preferable range of the temperature of a support body is dependent on the organic solvent to be used, it is 20-55 degreeC, and the more preferable range of solution temperature is 35-45 degreeC.

(6) Peeling process:
In this step, the web 206 having the solvent evaporated on the metal support 204 is peeled off at the peeling position 205. The peeled web 206 is sent to the next (7) drying step (described later). If the amount of residual solvent (explained later) of the web 206 at the time of peeling is too large, it will be difficult to peel off, or conversely if it is dried too much on the metal support 204, it will be difficult to peel off, Part of 206 is peeled off. In the present invention, when the thin web is peeled from the metal support, it is preferable to peel the thin web with a force within 300 N / m from the minimum tension that can be peeled off.

  There is a gel casting method (gel casting) as a method for increasing the film-forming speed (the film-forming speed can be increased because peeling occurs while the amount of residual solvent is as large as possible). For example, a poor solvent for the cellulose ester is added to the dope, and the dope is cast and then gelled, and the temperature of the metal support is lowered to gel. By gelling on the metal support 204 and increasing the strength of the film at the time of peeling, peeling can be accelerated and the film forming speed can be increased. It is preferable to peel in the range of 5 to 150% by mass depending on the setting of the drying conditions of the web 206 on the metal support 204, the length of the metal support 204, etc. If the web 206 is too soft, the flatness at the time of peeling is impaired, or slippage or vertical streaks due to peeling tension are likely to occur, and the amount of residual solvent to be peeled can be determined based on the balance between economic speed and quality. Accordingly, in the present invention, the temperature at the peeling position on the metal support 204 is preferably 0 to 40 ° C, more preferably 10 to 30 ° C.

  In order to maintain good flatness of the cellulose ester film during production, the amount of residual solvent when peeling from the metal support is preferably 10 to 150% by mass, more preferably 80 to 150% by mass. More preferably, it is 100-130 mass%. The ratio of the good solvent contained in the residual organic solvent of the web at the time of peeling is preferably 30 to 90%, more preferably 50 to 85%, and particularly preferably 60 to 80%.

  In the present invention, the drying time on the metal support of the web from dope casting to peeling is preferably a peelable time and within 120 seconds, more preferably 30 to 120 seconds, and further 30 -90 seconds are preferred. The surface property of the web peeled in this range is good. When the metal compound thin film described below is applied to the cellulose ester film after drying, it has excellent flatness and no cracks when repeatedly exposed to high temperature and high humidity conditions. An excellent optical film can be obtained.

(7) Drying process:
After peeling, generally, the web 206 is used by using a roll drying device 208 that alternately conveys the web 206 through vertically arranged rolls 209 and / or a tenter device 207 that grips and conveys both ends of the web 206 with a clip or the like. To dry. In FIG. 29, a roll drying device 208 is disposed after the tenter device 207. As a drying means, hot air is generally blown on both sides of the web, but there is also a means for heating by applying a microwave instead of the wind. Too rapid drying tends to impair the flatness of the finished film. Throughout, the drying temperature is usually in the range of 40 to 250 ° C., preferably 110 to 160 ° C. The drying temperature, the amount of drying air, and the drying time differ depending on the solvent used, and the drying conditions may be appropriately selected according to the type and combination of the solvents used. 210 is winding of the completed cellulose ester film. In the step of drying the cellulose ester film, the amount of residual solvent is preferably 1% by mass or less, and more preferably 0.1% by mass or less.

  In order to produce the cellulose ester film for an antiglare film of the present invention, the web is stretched in the conveying direction immediately after peeling from the metal support where the residual solvent amount is large, and both ends of the web are gripped with clips or the like. It is particularly preferable to perform stretching in the width direction by a tenter method. The preferred draw ratio is as described above.

<Actinic radiation curable resin layer>
The actinic radiation curable resin layer according to the present invention is a high refractive index actinic radiation curable resin layer containing an actinic radiation curable resin and fine particles. Thereby, it is possible to produce an antiglare antireflection film which exhibits a sufficient antiglare effect and exhibits excellent transmission clarity.

  In general, if fine particles having a particle size larger than the average film thickness of the actinic radiation curable resin layer are contained, uneven coating tends to occur when the actinic radiation curable resin layer is provided, and the relationship between the refractive indexes of the large particles is difficult. Prone to occur. In particular, when the width of the cellulose ester film is 1.4 m or more, or the film thickness is a thin film of 10 to 70 μm, the problem of applicability becomes remarkable.

  Moreover, since the anti-glare antireflection film of the present invention has irregularities in the thermoplastic resin portion on the surface of the substrate, the coating solvent is the base when a high refractive index active ray curable resin layer is applied thereon. Since it penetrates into the thermoplastic resin side, the coating film is difficult to flow, and it is preferable that a high refractive index active ray-curable resin layer having irregularities along the irregularities of the base film can be formed.

  Examples of the fine particles used in the actinic radiation curable resin layer include inorganic particles and organic particles.

  Examples of inorganic fine particles that can be used in the present invention include silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, antimony oxide, magnesium oxide, calcium carbonate, calcium carbonate, talc, and clay. , Calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate, or a composite oxide thereof.

  Among these, silicon oxide, titanium oxide, tin oxide, indium oxide, ITO, zirconium oxide, antimony oxide, or complex oxides thereof are preferably used for antiglare property and high refractive index.

  Organic fine particles include poly (meth) acrylate resins, silicon resins, polystyrene resins, polycarbonate resins, acrylic styrene resins, benzoguanamine resins, melamine resins, polyolefin resins, polyester resins, polyamide resins. Polyimide resin, polyfluorinated ethylene resin, etc. can be used. It is particularly preferable to contain conductive fine particles.

  Fine particles having a particle diameter of 5 nm to 10 μm are used, and particles of 5 nm to 5 μm are particularly preferable. In particular, particles having a diameter larger than the average film thickness of the actinic radiation curable resin layer may increase glare, and it is preferable that the amount added is reduced or not contained at all. Particularly preferably, it contains particles of 5 nm to 1 μm. A combination of fine particles having different compositions, particle sizes, and refractive indexes can also be used. For example, silicon oxide and zirconium oxide or silicon oxide and ITO fine particles can be used in combination.

  The actinic radiation curable resin refers to a resin that cures through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams. For example, a component containing a monomer having an ethylenically unsaturated double bond is preferably used and cured by irradiating an active ray such as an ultraviolet ray or an electron beam to form an active ray curable resin layer. Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, and a resin curable by ultraviolet irradiation is preferable.

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

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

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

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

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

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

  Specific examples of the photoreaction initiator of these ultraviolet curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer. The photoinitiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate photoinitiator, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. For example, commercially available products such as Irgacure 184 and Irgacure 907 (manufactured by Ciba Specialty Chemicals) are preferably used. The photoreaction initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the composition.

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

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

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

  In addition, for adjusting the refractive index, hard coat coating solutions containing zirconium oxide ultrafine particle dispersions Desolite Z-7041 and Desolite Z-7042 (manufactured by JSR Co., Ltd.) can be used alone or in other ultraviolet curable resins. It can be added and mixed.

  The actinic radiation curable resin used in the present invention can be cured by irradiation with actinic rays such as electron beams or ultraviolet rays. For example, in the case of electron beam curing, 50 to 1000 KeV emitted from various electron beam accelerators such as a Cockloft Walton type, a bandegraph type, a resonant transformation type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type, Preferably, an electron beam or the like having an energy of 100 to 300 KeV is used. In the case of ultraviolet curing, ultraviolet rays emitted from light beams such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used. .

  The proportion of the actinic radiation curable resin composition and the fine particles is desirably blended so as to be 0.1 to 40 parts by mass with respect to 100 parts by mass of the resin composition.

(Refractive index of actinic radiation curable resin layer)
The refractive index of the actinic radiation curable resin layer according to the present invention is 1.5 to 2.0, preferably 1.55 to 2.0, and more preferably 1.6 to 1.8. The refractive index of the cellulose ester film used as the transparent support is about 1.5. When the refractive index of the actinic radiation curable resin layer is too small, the antireflection property is lowered. Furthermore, when this is too large, the color of the reflected light of the antiglare antireflection film becomes strong, which is not preferable. The refractive index of the actinic radiation curable resin layer according to the present invention is particularly preferably in the range of 1.60 to 1.70 from the viewpoint of optical design for obtaining a low reflective film. The refractive index of the actinic radiation curable resin layer can be adjusted by the refractive index and content of the fine particles to be added.

(Film thickness of actinic radiation curable resin layer)
The film thickness of the actinic radiation curable resin layer according to the present invention is the average of 10 film thicknesses of the resin portion of the actinic radiation curable resin layer when observed with a tomographic electron micrograph, and the film thickness of the present invention is sufficient. From the viewpoint of imparting durability and impact resistance, the thickness of the actinic radiation curable resin layer is preferably in the range of 0.5 μm to 10.0 μm, and more preferably 1.0 μm to 5.0 μm. The actinic radiation curable resin layer may be composed of two or more layers.

(Fine irregularities on the actinic radiation curable resin layer)
The fine irregularities on the surface of the actinic radiation curable resin layer according to the present invention include the irregular surface of the thermoplastic resin film having an irregular surface on the surface according to the present invention, and the addition amount, particle size, film thickness, etc. of the fine particles described above. By adjusting, an active ray curable resin layer having more preferable unevenness can be obtained. Further, the fine irregularities on the surface of the actinic radiation curable resin layer according to the present invention include a convex portion having a height of 0.1 μm to 2 μm or a concave portion having a depth of 0.1 to 2 μm based on the average level of the surface. It is preferably formed as a fine structure having 1 to 100 per 100 μm ² .

Fine irregularities on the surface of the actinic radiation curable resin layer can be measured by a commercially available stylus type surface roughness measuring machine or a commercially available optical interference type surface roughness measuring machine. For example, the unevenness is measured in the range of about 4000 μm ² (55 μm × 75 μm) by an optical interference type surface roughness measuring device, and the unevenness is color-coded like contour lines from the bottom side and displayed two-dimensionally.

Here, the number of convex portions or concave portions having a height of 0.1 μm to 2 μm based on the average level of the surface can be counted and represented by the number per 100 μm ² area. The measurement is obtained as an average value by measuring 10 arbitrary points per 1 m ² of the antiglare low reflection film.

(Average crest and valley spacing of fine irregularities on the surface of the active ray curable resin layer)
The active ray curable resin layer according to the present invention preferably has an average crest / valley spacing of 1 μm to 80 μm, more preferably 10 μm to 40 μm.

  Here, the shape of the fine concavo-convex structure can be measured by a stylus type surface roughness measuring machine or the like. For example, the fine concavo-convex structure is formed via a measuring needle having a diameter of 1 mm with a tip portion made of diamond having a conical shape with an apex angle of 55 degrees. It is possible to obtain knowledge as a surface roughness curve obtained by scanning the surface with a length of 3 mm in a certain direction and measuring the movement change in the vertical direction of the measuring needle in that case. Alternatively, it can be measured by an optical interference type surface roughness measuring machine as described above.

  Here, the average peak-and-valley interval is assumed to be a reference line on which the unevenness change of the surface roughness curve can be evaluated as a protrusion based on a portion where the unevenness change in the surface roughness curve is minute (portion close to flat), Based on the intersection of the surface roughness curve passing from the bottom to the top (or from the top to the bottom) of the surface roughness curve with the average height of the convex part from the reference line as the center line, the distance between the intersections Can be defined as average.

(Haze of actinic radiation curable resin layer)
The haze value of the actinic radiation curable resin layer is preferably 1 to 30%, and particularly preferably 3 to 15%. If the haze is small, the effect of preventing reflection is insufficient, and if the haze value is large, scattering on the surface and inside is too strong, which causes problems such as a decrease in image sharpness and whitening, which is not preferable.

  Here, the haze can be measured according to ASTM-D1003-52.

  As means for adjusting the haze value of the actinic radiation curable resin layer according to the present invention to a preferable range, the above-described particles, fine particles, or solvent-soluble resins (for example, cellulose diacetate, cellulose acetate propionate, cellulose) Acetate butyrate, an acrylic resin, etc. are mentioned as a preferable example.) The method of making these contain 1 to 10%, for example is mentioned.

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

As a light source for curing an ultraviolet curable resin by a photocuring reaction to form a cured film layer, any light source that generates ultraviolet rays can be used without any limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. The irradiation conditions vary depending on individual lamps, the dose of active ray is a 0.5 J / cm ² or less, preferably 0.1 J / cm ² or less.

  The anti-glare antireflection film of the present invention can be cured at a lower dose than in the past, and an anti-glare antireflection film having excellent flatness can be obtained. In the case of an antiglare antireflection film that does not require much hardness, the amount of irradiation can be further reduced, and thus an antiglare antireflection film is produced at a speed far exceeding the coating speed limited by the ability of the ultraviolet irradiation section. And productivity is significantly improved.

The irradiation time for obtaining the irradiation amount of active rays is preferably about 0.1 second to 1 minute, and more preferably 0.1 to 10 seconds from the viewpoint of curing efficiency or work efficiency of the curable resin. Moreover, it is preferable that the illuminance of these active ray irradiation parts is 50-150 mW / m < ² >.

  Moreover, when irradiating actinic radiation, it is preferable to carry out while applying tension | tensile_strength in the conveyance direction of a film, More preferably, it is performing applying tension | tensile_strength also in the width direction. The tension to be applied is preferably 30 to 300 N / m. The method for applying the tension is not particularly limited, and the tension may be applied in the conveying direction on the back roll, or the tension may be applied in the width direction or the biaxial direction by a tenter. This makes it possible to obtain a film having further excellent flatness.

  Examples of the organic solvent of the coating solution for the actinic radiation curable resin layer include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl). Ketone), esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, other organic solvents, or a mixture thereof. Propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate ester (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5 to 80%. It is preferable to use the organic solvent containing at least mass%.

  Further, it is particularly preferable to add a silicon compound to the coating solution for the actinic radiation curable resin layer. For example, polyether-modified silicone oil is preferably added. The number average molecular weight of the polyether-modified silicone oil is, for example, 1000 to 100000, preferably 2000 to 50000. If the number average molecular weight is less than 1000, the drying property of the coating film decreases, and conversely, the number average When the molecular weight exceeds 100,000, it tends to be difficult to bleed out to the coating surface.

  Commercially available silicon compounds include DKQ8-779 (trade name, manufactured by Dow Corning), SF3771, SF8410, SF8411, SF8419, SF8421, SF8428, SH200, SH510, SH1107, SH3749, SH3771, BX16-034, SH3746, SH3749, SH8400, SH3771M, SH3772M, SH3773M, SH3775M, BY-16-837, BY-16-839, BY-16-869, BY-16-870, BY-16-004, BY-16-891, BY-16 872, BY-16-874, BY22-008M, BY22-012M, FS-1265 (above, product names manufactured by Toray Dow Corning Silicone), KF-101, KF-100T, KF351, KF3 2, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, Silicone X-22-945, X22-160AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), XF3940, XF3949 (trade name, manufactured by Toshiba Silicone Co., Ltd.) ), Disparon LS-009 (manufactured by Enomoto Kasei Co., Ltd.), Granol 410 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicone), BYK-306, BYK- 330, BYK-307, BYK-341, BYK-344, BYK-361 (manufactured by BYK-Japan) L series (for example, L7001, L-7006, L-7604, L-9000) manufactured by Nippon Unicar Co., Ltd. Y Over's, FZ series (FZ-2203, FZ-2206, FZ-2207) and the like, are preferably used.

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

  As a method for applying the coating solution for the actinic radiation curable resin layer, the above-described methods can be used. The coating amount is suitably 0.1 to 30 μm, preferably 0.5 to 15 μm, as the wet film thickness.

<Back coat layer>
It is preferable to provide a back coat layer on the surface opposite to the side on which the active ray curable resin layer of the antiglare antireflection film of the present invention is provided. The back coat layer is provided to correct curling caused by forming an uneven surface, providing an actinic radiation curable resin layer, and other layers. That is, the degree of curling can be balanced by imparting the property of being rounded with the surface on which the backcoat layer is provided facing inward. Alternatively, the back coat layer is coated as an anti-blocking layer, and in that case, it is preferable that fine particles are added to the back coat layer coating composition in order to provide an anti-blocking function.

  As fine particles added to the back coat layer, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, tin oxide, and oxidation. Mention may be made of indium, zinc oxide, ITO, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. Fine particles containing silicon are preferable in terms of low haze, and silicon dioxide is particularly preferable.

  These fine particles are commercially available under the trade names of, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, and TT600 (manufactured by Nippon Aerosil Co., Ltd.). . Zirconium oxide fine particles are commercially available under the trade names of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used. Examples of the polymer include silicone resin, fluorine resin, and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) It is marketed by name and can be used.

  Among these, Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large anti-blocking effect while keeping haze low. In the antiglare antireflection film used in the present invention, the dynamic friction coefficient on the back side of the actinic radiation curable resin layer is preferably 0.9 or less, particularly preferably 0.1 to 0.9.

  The fine particles contained in the backcoat layer are preferably contained in an amount of 0.1 to 50% by mass, more preferably 0.1 to 10% by mass with respect to the binder. When the back coat layer is provided, the increase in haze is preferably 1% or less, more preferably 0.5% or less, and particularly preferably 0.0 to 0.1%.

  Specifically, the back coat layer is formed by applying a composition containing a solvent for dissolving or swelling a cellulose ester film. The solvent used may include a solvent to be dissolved and / or a solvent to be swollen in addition to a solvent to be swelled, a composition in which these are mixed at an appropriate ratio depending on the degree of curling of the transparent resin film and the type of resin, and This is done using the coating amount.

  In order to enhance the curl prevention function, it is effective to increase the mixing ratio of the solvent for dissolving the solvent composition to be used and / or the solvent for swelling, and to decrease the ratio of the solvent not to be dissolved. This mixing ratio is preferably (solvent to be dissolved and / or solvent to be swollen) :( solvent to be dissolved) = 10: 0 to 1: 9. Examples of the solvent for dissolving or swelling the transparent resin film contained in such a mixed composition include dioxane, acetone, methyl ethyl ketone, N, N-dimethylformamide, methyl acetate, ethyl acetate, trichloroethylene, methylene chloride, and ethylene chloride. , Tetrachloroethane, trichloroethane, chloroform and the like. Examples of the solvent that does not dissolve include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butanol, cyclohexanol, and hydrocarbons (toluene, xylene).

  These coating compositions are preferably applied to the surface of the transparent resin film with a wet film thickness of 1 to 100 μm using a gravure coater, dip coater, reverse coater, wire bar coater, die coater, spray coating, ink jet coating or the like. Is particularly preferably 5 to 30 μm. Examples of the resin used as the binder of the backcoat layer include vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, vinyl acetate-vinyl alcohol copolymer, partially hydrolyzed vinyl chloride-vinyl acetate copolymer. Polymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, etc. Vinyl polymer or copolymer, nitrocellulose, cellulose acetate propionate (preferably acetyl group substitution degree 1.8-2.3, propionyl group substitution degree 0.1-1.0), diacetyl cellulose, cellulose Cellulose derivatives such as acetate butyrate resin, maleic acid and / or Or acrylic acid copolymer, acrylic ester copolymer, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin Rubber resins such as polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene-butadiene resin, butadiene-acrylonitrile resin, Examples thereof include, but are not limited to, silicone resins and fluorine resins. For example, as an acrylic resin, Acrypet MD, VH, MF, V (manufactured by Mitsubishi Rayon Co., Ltd.), Hyperl M-4003, M-4005, M-4006, M-4202, M-5000, M-5001, M-4501 (manufactured by Negami Kogyo Co., Ltd.), Dialnal BR-50, BR-52, BR-53, BR-60, BR-64, BR-73, BR-75, BR-77, BR-79, BR -80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-90, BR-93, BR-95, BR-100, BR-101, BR-102, BR-105 BR-106, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118, etc. (Mitsubishi Rayon Co., Ltd.) acrylic and The methacrylic monomers such as various homopolymers and copolymers were prepared as raw materials are commercially available, can also be selected preferred mono from this appropriate.

  Particularly preferred are cellulose resin layers such as diacetylcellulose and cellulose acetate propionate.

  The order of applying the backcoat layer may be before or after applying the actinic radiation curable resin layer of the cellulose ester film. However, when the backcoat layer also serves as an antiblocking layer, it is preferably applied first. Alternatively, the backcoat layer can be applied in two or more steps.

(Antireflection layer)
The antiglare antireflection film according to the present invention has a low refractive index layer containing at least a fluorine-containing resin or inorganic fine particles on an active ray curable resin layer, and the inorganic fine particles are porous particles and the surface of the porous particles. It is preferable to be a composite particle having a coating layer provided on or a hollow particle filled with a solvent, gas, or porous substance.

  In the present invention, the method for providing the antireflection layer is not particularly limited, and examples thereof include sputtering, atmospheric pressure plasma treatment, coating, and the like.

  As a method of forming the antireflection layer by coating, a method of dispersing metal oxide powder in a binder resin dissolved in a solvent, coating and drying, a method of using a polymer having a crosslinked structure as a binder resin, ethylenic unsaturated Examples of the method include a method of forming a layer by containing a monomer and a photopolymerization initiator and irradiating with actinic radiation.

  In the present invention, an antireflection layer is provided on a cellulose ester film provided with an actinic radiation curable resin layer, and at least one of the antireflection layers is a low refractive index layer.

  Although the structure of a preferable anti-glare antireflection film is shown below, it is not limited to these.

  Here, the hard coat layer means the actinic radiation curable resin layer described above.

Cellulose ester film / hard coat layer / low refractive index layer Cellulose ester film / hard coat layer / high refractive index layer / low refractive index layer Cellulose ester film / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index Layer Cellulose ester film / thermoplastic resin layer / hard coat layer / low refractive index layer Cellulose ester film / thermoplastic resin layer / hard coat layer / high refractive index layer / low refractive index layer Cellulose ester film / thermoplastic resin layer / hard Coat layer / Medium refractive index layer / High refractive index layer / Low refractive index layer In any case, the back coat layer described above is preferably provided on the side opposite to the side on which the hard coat layer of the cellulose ester film is applied.

  Further, the middle refractive index layer or the high refractive index layer may also serve as the antistatic layer.

  In the antiglare antireflection film, a low refractive index layer is formed as the uppermost layer, a metal oxide layer of a high refractive index layer is formed between the active ray curable resin layer, and an active ray curable resin layer. Providing an intermediate refractive index layer (metal oxide content or ratio with resin binder, metal oxide layer with the refractive index adjusted by changing the type of metal) between the high refractive index layer and the reflectance It is preferable for the reduction of. The refractive index of the high refractive index layer is preferably 1.55 to 2.30, and more preferably 1.57 to 2.20. The refractive index of the medium refractive index layer is adjusted so as to be an intermediate value between the refractive index (about 1.5) of the cellulose ester film as the substrate and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55-1.80. The refractive index of the low refractive index layer is preferably 1.3 to 1.44, more preferably 1.35 to 1.41. The thickness of each layer is preferably 5 nm to 0.5 μm, more preferably 10 nm to 0.3 μm, and most preferably 30 nm to 0.2 μm. The haze of the metal oxide layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the metal oxide layer is preferably 3H or more, and most preferably 4H or more, with a pencil hardness of 1 kg. When the metal oxide layer is formed by coating, it is preferable to include inorganic fine particles and a binder polymer.

  Composite particles having porous particles and a coating layer provided on the surface of the porous particles, preferably contained in the low refractive index layer of the present invention, or hollow particles filled with a solvent, gas, or porous substance inside Will be described.

  The inorganic fine particle is (I) a composite particle comprising a porous particle and a coating layer provided on the surface of the porous particle, or (II) a cavity inside, and the content is a solvent, a gas or a porous substance It is a hollow particle filled with. The low refractive index layer may contain either (I) composite particles or (II) hollow particles, or may contain both.

  The hollow particles are particles having cavities inside, and the cavities are surrounded by particle walls. The cavity is filled with a content such as a solvent, a gas, or a porous material used at the time of preparation. It is desirable that the average particle diameter of such inorganic fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm. The average particle diameter of the inorganic fine particles used is appropriately selected according to the thickness of the transparent film to be formed, and is in the range of 2/3 to 1/10 of the film thickness of the transparent film such as the low refractive index layer to be formed. It is desirable to be in These inorganic fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), and ketone alcohol (for example, diacetone alcohol) are preferable.

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is desirably in the range of 1 to 20 nm, preferably 2 to 15 nm. In the case of composite particles, if the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and silicate monomers and oligomers with a low degree of polymerization, which are coating liquid components described later, are easy. In some cases, the inside of the composite particle enters the inside and the porosity of the inside is reduced, so that the effect of the low refractive index cannot be sufficiently obtained. When the thickness of the coating layer exceeds 20 nm, the silicic acid monomer and oligomer do not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of low refractive index is sufficiently obtained. It may not be possible. In the case of hollow particles, if the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the effect of low refractive index may not be sufficiently exhibited. is there.

The coating layer of the composite particles or the particle wall of the hollow particles is preferably composed mainly of silica. The coating layer of the composite particle or the particle wall of the hollow particle may contain a component other than silica, specifically, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO _2. and _{CeO 2, P 2 O 3,} Sb 2 O 3, MoO 3, ZnO 2, WO 3 and the like. Examples of the porous particles constituting the composite particles include those made of silica, those made of silica and an inorganic compound other than silica, and those made of CaF ₂ , NaF, NaAlF ₆ , MgF, and the like. Of these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly suitable. Examples of inorganic compounds other than silica include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like. 1 type or 2 types or more can be mentioned. In such porous particles, the molar ratio MOX / SiO ₂ when the silica is represented by SiO ₂ and the inorganic compound other than silica is represented by oxide (MOX) is 0.0001 to 1.0, preferably It is desirable to be in the range of 0.001 to 0.3. It is difficult to obtain porous particles having a molar ratio MOX / SiO ₂ of less than 0.0001, and even if obtained, those having a lower refractive index are not obtained. On the other hand, if the molar ratio MOX / SiO _{2 of} the porous particles exceeds 1.0, the silica ratio decreases, so that particles having a small pore volume and a low refractive index may not be obtained.

  The pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g. If the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained. If the pore volume exceeds 1.5 ml / g, the strength of the fine particles is lowered, and the strength of the resulting coating may be lowered. is there.

  Incidentally, the pore volume of such porous particles can be obtained by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous material used at the time of preparing the particles. The solvent may contain an unreacted particle precursor used in preparing the hollow particles, the catalyst used, and the like. Moreover, what consists of the compound illustrated by the said porous particle as a porous substance is mentioned. These contents may be composed of a single component or may be a mixture of a plurality of components.

  As a method for producing such inorganic fine particles, for example, the method for preparing composite oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is suitably employed. Specifically, when the composite particles are composed of silica and an inorganic compound other than silica, the inorganic compound particles are produced from the following first to third steps.

First Step: Preparation of Porous Particle Precursor In the first step, an alkali aqueous solution of a silica raw material and an inorganic compound raw material other than silica is separately prepared in advance, or a silica raw material and an inorganic compound raw material other than silica are prepared in advance. A mixed aqueous solution is prepared, and this aqueous solution is gradually added to an aqueous alkaline solution having a pH of 10 or more while stirring according to the composite ratio of the target composite oxide to prepare a porous particle precursor.

  As the silica raw material, alkali metal, ammonium or organic base silicate is used. Sodium silicate (water glass) or potassium silicate is used as the alkali metal silicate. Examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, and amines such as monoethanolamine, diethanolamine, and triethanolamine. The ammonium silicate or the organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound or the like to a silicic acid solution.

  In addition, alkali-soluble inorganic compounds are used as raw materials for inorganic compounds other than silica. Specifically, an oxo acid of an element selected from Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, W, etc., an alkali metal salt or alkaline earth metal salt of the oxo acid, ammonium Salts and quaternary ammonium salts. More specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, and sodium phosphate are suitable.

Although the pH value of the mixed aqueous solution changes simultaneously with the addition of these aqueous solutions, an operation for controlling the pH value within a predetermined range is not particularly required. The aqueous solution finally has a pH value determined by the type of inorganic oxide and the mixing ratio thereof. There is no restriction | limiting in particular in the addition rate of the aqueous solution at this time. Further, in the production of composite oxide particles, a dispersion of seed particles can be used as a starting material. The seed particles are not particularly limited, but inorganic oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or fine particles of these composite oxides are used. Usually, these sols are used. I can do it. Furthermore, the porous particle precursor dispersion obtained by the above production method may be used as a seed particle dispersion. When the seed particle dispersion is used, the pH of the seed particle dispersion is adjusted to 10 or more, and then the aqueous solution of the compound is added to the above-described alkaline aqueous solution while stirring. Also in this case, it is not always necessary to control the pH of the dispersion. In this way, when seed particles are used, it is easy to control the particle size of the porous particles to be prepared, and particles having a uniform particle size can be obtained.

  The silica raw material and the inorganic compound raw material described above have high solubility on the alkali side. However, when both are mixed in this highly soluble pH region, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into fine particles, or seed particles. It grows on the top and particle growth occurs. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of fine particles.

The composite ratio of silica and inorganic compound other than silica in the first step is that the inorganic compound relative to silica is converted to oxide (MOx), and the molar ratio of MOx / SiO ₂ is 0.05 to 2.0, preferably It is desirable to be within the range of 0.2 to 2.0. Within this range, the pore volume of the porous particles increases as the proportion of silica decreases. However, even when the molar ratio exceeds 2.0, the pore volume of the porous particles hardly increases. On the other hand, when the molar ratio is less than 0.05, the pore volume becomes small. When preparing hollow particles, the molar ratio of MOx / SiO ₂ is preferably in the range of 0.25 to 2.0.

Second step: Removal of inorganic compound other than silica from porous particles In the second step, inorganic compounds other than silica (elements other than silicon and oxygen) are obtained from the porous particle precursor obtained in the first step. At least a portion is selectively removed. As a specific removal method, the inorganic compound in the porous particle precursor is dissolved and removed using a mineral acid or an organic acid, or is contacted with a cation exchange resin for ion exchange removal.

  The porous particle precursor obtained in the first step is a particle having a network structure in which silicon and an inorganic compound constituent element are bonded via oxygen. By removing the inorganic compound (elements other than silicon and oxygen) from the porous particle precursor in this way, porous particles having a larger porosity and a larger pore volume can be obtained. Further, if the amount of removing the inorganic oxide (elements other than silicon and oxygen) from the porous particle precursor is increased, the hollow particles can be prepared.

  In addition, prior to removing inorganic compounds other than silica from the porous particle precursor, a silicic acid solution obtained by removing the alkali metal salt of silica from the porous particle precursor dispersion obtained in the first step. Alternatively, it is preferable to form a silica protective film by adding a hydrolyzable organosilicon compound. The thickness of the silica protective film may be 0.5 to 15 nm. Even if the silica protective film is formed, the protective film in this step is porous and thin, so that it is possible to remove inorganic compounds other than silica described above from the porous particle precursor.

  By forming such a silica protective film, inorganic compounds other than the silica described above can be removed from the porous particle precursor while maintaining the particle shape. Further, when forming the silica coating layer described later, the pores of the porous particles are not blocked by the coating layer, and therefore the silica coating layer described later is formed without reducing the pore volume. I can do it. Note that when the amount of the inorganic compound to be removed is small, the particles are not broken, and thus it is not always necessary to form a protective film.

  When preparing hollow particles, it is desirable to form this silica protective film. When preparing the hollow particles, the inorganic compound is removed to obtain a hollow particle precursor composed of a silica protective film, a solvent in the silica protective film, and an undissolved porous solid content. When a coating layer to be described later is formed on the precursor, the formed coating layer becomes a particle wall to form hollow particles.

  The amount of the silica source added for forming the silica protective film is preferably small as long as the particle shape can be maintained. If the amount of the silica source is too large, the silica protective film becomes too thick, and it may be difficult to remove inorganic compounds other than silica from the porous particle precursor. The hydrolyzable organosilicon compound used for forming the silica protective film includes a general formula RnSi (OR ′) 4-n [R, R ′: hydrocarbon such as alkyl group, aryl group, vinyl group, acrylic group, etc. An alkoxysilane represented by the group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is added to the dispersion of the porous particles, and the alkoxysilane is hydrolyzed. The produced silicic acid polymer is deposited on the surface of the inorganic oxide particles. At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of the porous particle precursor is water alone or when the ratio of water to the organic solvent is high, a silica protective film can be formed using a silicic acid solution. When a silicic acid solution is used, a predetermined amount of the silicic acid solution is added to the dispersion, and at the same time an alkali is added to deposit the silicic acid solution on the surface of the porous particles. In addition, you may produce a silica protective film together using a silicic acid liquid and the said alkoxysilane.

Third Step: Formation of Silica Coating Layer In the third step, a hydrolyzable organosilicon compound or silicic acid solution is added to the porous particle dispersion prepared in the second step (in the case of hollow particles, a hollow particle precursor dispersion). Etc. is added to coat the surface of the particles with a polymer such as a hydrolyzable organosilicon compound or silicic acid solution to form a silica coating layer.

  Examples of the hydrolyzable organosilicon compound used for forming the silica coating layer include the general formula RnSi (OR ′) 4-n [R, R ′: alkyl group, aryl group, vinyl group, acrylic group as described above. Etc., and alkoxysilanes represented by n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is used as a dispersion of the porous particles (in the case of hollow particles, a hollow particle precursor). In addition, the silicic acid polymer produced by hydrolyzing alkoxysilane is deposited on the surface of the porous particles (in the case of hollow particles, hollow particle precursors). At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of porous particles (in the case of hollow particles, the hollow particle precursor) is water alone or a mixed solvent with an organic solvent and the mixed solvent has a high ratio of water to the organic solvent, a silicate solution You may form a coating layer using. The silicic acid solution is an aqueous solution of a low silicic acid polymer obtained by dealkalizing an aqueous solution of an alkali metal silicate such as water glass by ion exchange treatment.

  The silicic acid solution is added to the dispersion of porous particles (in the case of hollow particles, hollow particle precursors), and at the same time, alkali is added to make the low-silicic acid polymer into porous particles (in the case of hollow particles, hollow particle precursors). ) Deposit on the surface. A silicic acid solution may be used in combination with the alkoxysilane for forming a coating layer. The addition amount of the organosilicon compound or silicic acid solution used for forming the coating layer only needs to be sufficient to cover the surface of the colloidal particles, and the finally obtained silica coating layer has a thickness of 1 to 20 nm. In such an amount, it is added in a dispersion of porous particles (in the case of hollow particles, hollow particle precursor) in a dispersion. When the silica protective film is formed, the organosilicon compound or the silicate solution is added in such an amount that the total thickness of the silica protective film and the silica coating layer is in the range of 1 to 20 nm.

  Next, the dispersion liquid of the particles on which the coating layer is formed is heat-treated. By the heat treatment, in the case of porous particles, the silica coating layer covering the surface of the porous particles is densified, and a dispersion of composite particles in which the porous particles are coated with the silica coating layer is obtained. In the case of a hollow particle precursor, the formed coating layer is densified to form hollow particle walls, and a dispersion of hollow particles having cavities filled with a solvent, gas, or porous solid content is obtained.

  The heat treatment temperature at this time is not particularly limited as long as it can close the fine pores of the silica coating layer, and is preferably in the range of 80 to 300 ° C. When the heat treatment temperature is less than 80 ° C., the fine pores of the silica coating layer may not be completely closed and densified, and the treatment time may take a long time. Further, when the heat treatment temperature exceeds 300 ° C. for a long time, fine particles may be formed, and the effect of low refractive index may not be obtained.

  The refractive index of the inorganic fine particles thus obtained is as low as less than 1.44. Such inorganic fine particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow.

  As the binder matrix of the low refractive index layer, a fluorine-containing resin that is crosslinked by heat or ionizing radiation (hereinafter, also referred to as “fluorine-containing resin before crosslinking”) is preferably used.

  Preferred examples of the fluorine-containing resin before crosslinking include a fluorine-containing copolymer formed from a fluorine-containing vinyl monomer and a monomer for imparting a crosslinkable group. Specific examples of the fluorine-containing vinyl monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3 -Dioxoles, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (produced by Osaka Organic Chemicals) or M-2020 (produced by Daikin)), fully or partially fluorinated vinyl ethers, etc. Is mentioned. As monomers for imparting a crosslinkable group, glycidyl methacrylate, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyl glycidyl ether, and other vinyl monomers having a crosslinkable functional group in advance in the molecule. , Vinyl monomers having a carboxyl group, hydroxyl group, amino group, sulfonic acid group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyalkyl vinyl ether, hydroxyalkyl allyl) Ether, etc.). The latter can introduce a crosslinked structure after copolymerization by adding a compound that reacts with a functional group in the polymer and one or more reactive groups. No. 147739. Examples of the crosslinkable group include acryloyl, methacryloyl, isocyanate, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, and active methylene group. When the fluorine-containing copolymer is crosslinked by heating with a crosslinking group that reacts by heating, or a combination of an ethylenically unsaturated group and a thermal radical generator or an epoxy group and a thermal acid generator, it is a thermosetting type. In the case of crosslinking by irradiation with light (preferably ultraviolet rays, electron beams, etc.) by a combination of an ethylenically unsaturated group and a photo radical generator, or an epoxy group and a photo acid generator, the ionizing radiation curable type is used.

  In addition to the above monomers, a fluorine-containing copolymer formed by using a monomer other than the fluorine-containing vinyl monomer and the monomer for imparting a crosslinkable group may be used as the fluorine-containing resin before crosslinking. The monomer that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-acrylic acid 2- Ethyl hexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl vinyl ether) Etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, Ronitoriru derivatives and the like can be mentioned. In addition, it is also preferable to introduce a polyorganosiloxane skeleton or a perfluoropolyether skeleton into the fluorinated copolymer in order to impart slipperiness and antifouling properties. For example, polyorganosiloxane or perfluoropolyether having an acrylic group, methacrylic group, vinyl ether group, styryl group or the like at the terminal is polymerized with the above monomer, and polyorganosiloxane or perfluoropolyester having a radical generating group at the terminal. It can be obtained by polymerization of the above monomers with ether, reaction of a polyorganosiloxane or perfluoropolyether having a functional group with a fluorine-containing copolymer, or the like.

  The proportion of each of the above monomers used to form the fluorinated copolymer before crosslinking is preferably 20 to 70 mol%, more preferably 40 to 70 mol%, more preferably 40 to 70 mol% of the fluorinated vinyl monomer. The amount of the monomer is preferably 1 to 20 mol%, more preferably 5 to 20 mol%, and the other monomer used in combination is preferably 10 to 70 mol%, more preferably 10 to 50 mol%.

  The fluorine-containing copolymer can be obtained by polymerizing these monomers in the presence of a radical polymerization initiator by means such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization.

  The fluorine-containing resin before crosslinking is commercially available and can be used. Examples of commercially available fluorine-containing resins before cross-linking include Cytop (Asahi Glass), Teflon (R) AF (DuPont), polyvinylidene fluoride, Lumiflon (Asahi Glass), Opstar (JSR) and the like. It is done.

  The low refractive index layer containing a cross-linked fluororesin as a constituent component preferably has a dynamic friction coefficient in the range of 0.03 to 0.15 and a contact angle with water in the range of 90 to 120 degrees.

  The low refractive index layer containing a cross-linked fluorine-containing resin as a constituent component contains the aforementioned inorganic particles.

  Various sol-gel materials can also be used as a binder matrix for other low refractive index layers. As such a sol-gel material, metal alcoholates (alcohols such as silane, titanium, aluminum, and zirconium), organoalkoxy metal compounds, and hydrolysates thereof can be used. In particular, alkoxysilane, organoalkoxysilane and its hydrolyzate are preferable. Examples of these include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilane (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), aryltrialkoxysilane (phenyltrimethoxysilane, etc.), dialkyl. Examples thereof include dialkoxysilane and diaryl dialkoxysilane. In addition, organoalkoxysilanes having various functional groups (vinyl trialkoxysilane, methylvinyl dialkoxysilane, γ-glycidyloxypropyltrialkoxysilane, γ-glycidyloxypropylmethyl dialkoxysilane, β- (3,4-epoxy) Dicyclohexyl) ethyltrialkoxysilane, γ-methacryloyloxypropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, γ-chloropropyltrialkoxysilane, etc.), perfluoroalkyl group-containing silane compounds ( For example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc.), containing fluoroalkyl ether group It is also preferable to use a run-compound. In particular, the use of a fluorine-containing silane compound is preferable in terms of lowering the refractive index of the layer and imparting water and oil repellency.

  The low refractive index layer preferably contains the polymer in an amount of 5 to 50% by mass. The polymer has a function of adhering fine particles and maintaining the structure of a low refractive index layer including voids. The amount of the polymer used is adjusted so that the strength of the low refractive index layer can be maintained without filling the voids. The amount of the polymer is preferably 10 to 30% by mass of the total amount of the low refractive index layer. In order to adhere the fine particles with the polymer, (1) the polymer is bonded to the surface treatment agent of the fine particles, (2) the fine particles are used as a core, and a polymer shell is formed around the fine particles. It is preferable to use a polymer as the binder. The polymer to be bonded to the surface treatment agent (1) is preferably the shell polymer (2) or the binder polymer (3). The polymer (2) is preferably formed around the fine particles by a polymerization reaction before preparing the coating solution for the low refractive index layer. The polymer (3) is preferably formed by adding a monomer to the coating solution for the low refractive index layer and performing a polymerization reaction simultaneously with or after the coating of the low refractive index layer. It is preferable to carry out in combination of two or all of the above (1) to (3), and to carry out in combination of (1) and (3) or (1) to (3) all combinations. Particularly preferred. (1) Surface treatment, (2) shell, and (3) binder will be described sequentially.

(1) Surface treatment It is preferable that the fine particles (particularly inorganic fine particles) are subjected to a surface treatment to improve the affinity with the polymer. The surface treatment can be classified into physical surface treatment such as plasma discharge treatment and corona discharge treatment, and chemical surface treatment using a coupling agent. It is preferable to carry out only chemical surface treatment or a combination of physical surface treatment and chemical surface treatment. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Particles when made of SiO _2, surface treatment with a silane coupling agent can be particularly effectively conducted. As a specific example of the silane coupling agent, a silane coupling agent described later is preferably used.

  The surface treatment with the coupling agent can be carried out by adding the coupling agent to the fine particle dispersion and allowing the dispersion to stand at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

(2) Shell The polymer forming the shell is preferably a polymer having a saturated hydrocarbon as the main chain. A polymer containing a fluorine atom in the main chain or side chain is preferred, and a polymer containing a fluorine atom in the side chain is more preferred. Polyacrylic acid esters or polymethacrylic acid esters are preferred, and esters of fluorine-substituted alcohols with polyacrylic acid or polymethacrylic acid are most preferred. The refractive index of the shell polymer decreases as the content of fluorine atoms in the polymer increases. In order to lower the refractive index of the low refractive index layer, the shell polymer preferably contains 35 to 80% by mass of fluorine atoms, and more preferably contains 45 to 75% by mass of fluorine atoms. The polymer containing a fluorine atom is preferably synthesized by a polymerization reaction of an ethylenically unsaturated monomer containing a fluorine atom. Examples of ethylenically unsaturated monomers containing fluorine atoms include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole), Mention may be made of esters of fluorinated vinyl ethers and fluorine-substituted alcohols with acrylic acid or methacrylic acid.

  The polymer forming the shell may be a copolymer composed of a repeating unit containing a fluorine atom and a repeating unit not containing a fluorine atom. The repeating unit containing no fluorine atom is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer containing no fluorine atom. Examples of ethylenically unsaturated monomers that do not contain fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylic acid esters (eg, methyl acrylate, ethyl acrylate, acrylic acid 2- Ethyl hexyl), methacrylic acid esters (for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate), styrene and its derivatives (for example, styrene, divinylbenzene, vinyltoluene, α-methylstyrene), vinyl ether ( For example, methyl vinyl ether), vinyl esters (for example, vinyl acetate, vinyl propionate, vinyl cinnamate), acrylamide (for example, N-tertbutylacrylamide, N-cyclohexylacrylic) Amides), methacrylamide and acrylonitrile.

  When the binder polymer (3) described later is used in combination, a crosslinkable functional group may be introduced into the shell polymer to chemically bond the shell polymer and the binder polymer by crosslinking. The shell polymer may have crystallinity. When the glass transition temperature (Tg) of the shell polymer is higher than the temperature at the time of forming the low refractive index layer, it is easy to maintain microvoids in the low refractive index layer. However, if Tg is higher than the temperature at which the low refractive index layer is formed, the fine particles are not fused, and the low refractive index layer may not be formed as a continuous layer (resulting in a decrease in strength). In that case, it is desirable to use a binder polymer (3) described later in combination, and form the low refractive index layer as a continuous layer with the binder polymer. By forming a polymer shell around the fine particles, core-shell fine particles are obtained. The core-shell fine particles preferably contain 5 to 90% by volume of a core composed of inorganic fine particles, and more preferably 15 to 80% by volume. Two or more kinds of core-shell fine particles may be used in combination. Further, inorganic fine particles having no shell and core-shell particles may be used in combination.

(3) Binder The binder polymer is preferably a polymer having a saturated hydrocarbon or polyether as the main chain, and more preferably a polymer having a saturated hydrocarbon as the main chain. The binder polymer is preferably crosslinked. The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder polymer, it is preferable to use a monomer having two or more ethylenically unsaturated groups. Examples of monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohols and (meth) acrylic acid (for example, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol). Tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and its derivatives For example, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloyl ethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylene bisacrylamide) and methacrylamide Can be mentioned. The polymer having a polyether as the main chain is preferably synthesized by a ring-opening polymerization reaction of a polyfunctional epoxy compound. Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder polymer by the reaction of a crosslinkable group. Examples of crosslinkable functional groups include isocyanate groups, epoxy groups, aziridine groups, oxazoline groups, aldehyde groups, carbonyl groups, hydrazine groups, carboxyl groups, methylol groups, and active methylene groups. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. The cross-linking group is not limited to the above compound, and may be one that exhibits reactivity as a result of decomposition of the functional group. As the polymerization initiator used for the polymerization reaction and the crosslinking reaction of the binder polymer, a thermal polymerization initiator or a photopolymerization initiator is used, and the photopolymerization initiator is more preferable. Examples of photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone. Examples of benzoins include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  The binder polymer is preferably formed by adding a monomer to the coating solution for the low refractive index layer, and at the same time as or after the coating of the low refractive index layer, by a polymerization reaction (further crosslinking reaction if necessary). Even if a small amount of polymer (for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin) is added to the coating solution for the low refractive index layer Good.

  Moreover, it is preferable to add a slipping agent to the low refractive index layer or other refractive index layers of the present invention, and scratch resistance can be improved by imparting slipperiness. As the slip agent, silicon oil or a wax-like substance is preferably used. For example, a compound represented by the following general formula is preferable.

General formula R ₁ COR ₂
In the formula, R ₁ represents a saturated or unsaturated aliphatic hydrocarbon group having 12 or more carbon atoms. An alkyl group or an alkenyl group is preferable, and an alkyl group or alkenyl group having 16 or more carbon atoms is more preferable. R ₂ represents —OM ₁ group (M ₁ represents an alkali metal such as Na or K), —OH group, —NH ₂ group, or —OR ₃ group (R ₃ represents a saturated or unsaturated group having 12 or more carbon atoms. R ₂ represents a saturated aliphatic hydrocarbon group, preferably an alkyl group or an alkenyl group, and R ₂ is preferably an —OH group, —NH ₂ group, or —OR ₃ group. Specifically, higher fatty acids such as behenic acid, stearamide, and pentacoic acid, or derivatives thereof, and carnauba wax, beeswax, and montan wax containing many of these components as natural products can also be preferably used. Polyorganosiloxane as disclosed in JP-B-53-292, higher fatty acid amide as disclosed in US Pat. No. 4,275,146, JP-B 58-33541, British patent No. 927,446 or JP-A-55-126238 and 58-90633, higher fatty acid esters (fatty acids having 10 to 24 carbon atoms and 10 to 24 carbon atoms). Esters of alcohols), and higher fatty acid metal salts as disclosed in U.S. Pat. No. 3,933,516, dicarboxylic acids having up to 10 carbon atoms as disclosed in JP-A-51-37217 A polyester compound comprising an acid and an aliphatic or cycloaliphatic diol, a dicarboxylic acid disclosed in JP-A-7-13292, It can be mentioned oligo polyester or the like from the Le.

  Particularly preferred silicone oils are the compounds listed in Table 1.

For example, the amount of slip agent to be used in the low refractive index layer is preferably ^{0.01mg / m 2 ~10mg / m 2} .

  In the present invention, in order to reduce the reflectance, it is also preferable to provide a high refractive index layer between the transparent support provided with the active ray curable resin layer and the low refractive index layer. In addition, it is more preferable to provide a middle refractive index layer between the transparent support and the high refractive index layer in order to reduce the reflectance. The refractive index of the high refractive index layer is preferably 1.55 to 2.30, and more preferably 1.57 to 2.20. The refractive index of the medium refractive index layer is adjusted to be an intermediate value between the refractive index of the transparent support and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55-1.80. The thickness of the high refractive index layer and the medium refractive index layer is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 0.1 μm. The haze of the high refractive index layer and the medium refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the high refractive index layer and the medium refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher, with a pencil hardness of 1 kg.

  Among the refractive index layers used in the present invention, the high refractive index layer was formed by applying and drying a coating solution containing a monomer, oligomer or hydrolyzate of an organic titanium compound represented by the following general formula. A layer of 55 to 2.5 is preferred.

General formula Ti (OR ¹ ) ₄
In the formula, R ¹ is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Moreover, the monomer, oligomer, or hydrolyzate thereof of an organic titanium compound reacts like -Ti-O-Ti- when an alkoxide group is hydrolyzed to form a crosslinked structure, thereby forming a cured layer.

Examples of the monomer or oligomer of the organic titanium compound used in the present invention include Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ , Ti (O-i- _{C 3 H 7) 4, Ti} (O-n-C 4 H 9) 4, Ti (O-n-C 3 H 7) 4 2-10 mer, Ti (O-i-C 3 H 7) Preferred examples include ₄ to 10 mer of ₄ and 2 to 10 mer of Ti (On-C ₄ H ₉ ) ₄ . These may be used alone or in combination of two or more. Of these _{Ti (O-n-C 3} H 7) 4, Ti (O-i-C 3 H 7) 4, Ti (O-n-C 4 H 9) 4, Ti (O-n-C 3 H 7 ) ₄ to 10-mer and Ti (On-C ₄ H ₉ ) ₄ to 10-mer are particularly preferable.

  Among the coating solutions for the high refractive index layer used in the present invention, it is preferable to add the organic titanium compound to a solution in which water and an organic solvent described later are sequentially added. When water is added later, hydrolysis / polymerization does not proceed uniformly, and white turbidity occurs or film strength decreases. After the water and the organic solvent are added, it is preferable that they are stirred and mixed and dissolved in order to mix well.

  Further, as another method, it is also a preferred embodiment that an organic titanium compound and an organic solvent are mixed and this mixed solution is added to the mixed and stirred solution of water and the organic solvent.

Moreover, it is preferable that the quantity of water is the range of 0.25-3 mol with respect to 1 mol of organic titanium compounds. When the amount is less than 0.25 mol, hydrolysis and polymerization are not sufficiently progressed and the film strength is lowered. If it exceeds 3 moles, hydrolysis and polymerization will proceed excessively, resulting in generation of coarse TiO ₂ particles and white turbidity. Therefore, the amount of water needs to be adjusted within the above range.

  Moreover, it is preferable that the content rate of water is less than 10 mass% with respect to the coating liquid total amount. If the water content is 10% by mass or more with respect to the total amount of the coating solution, it is not preferable because the stability of the coating solution with time deteriorates and white turbidity occurs.

  The organic solvent used in the present invention is preferably a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), many Monohydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyvalent Alcohol ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether) , Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol mono Phenyl ether, propylene glycol monophenyl ether, etc.), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine) , Triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclic rings (For example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (for example, dimethyl sulfoxide, etc.), sulfones (for example, , Sulfolane and the like), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable. The amount of these organic solvents used may be adjusted as described above so that the water content is less than 10% by mass with respect to the total amount of the coating solution.

  The monomer, oligomer or hydrolyzate of the organic titanium compound used in the present invention preferably occupies 50.0% by mass to 98.0% by mass in the solid content contained in the coating solution. The solid content ratio is more preferably 50% by mass to 90% by mass, and further preferably 55% by mass to 90% by mass. In addition, it is also preferable to add to the coating composition a polymer of an organic titanium compound (a product obtained by crosslinking the organic titanium compound in advance by hydrolysis) or titanium oxide fine particles.

  The high refractive index layer and medium refractive index layer used in the present invention preferably include those containing metal oxide particles as fine particles and further containing a binder polymer.

  Alternatively, when the organic titanium compound hydrolyzed / polymerized by the coating liquid preparation method and the metal oxide particles are combined, the metal oxide particles and the hydrolyzed / polymerized organic titanium compound are firmly bonded, and the hardness of the particles A strong coating film having the flexibility of a uniform film can be obtained.

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

  Examples of the metal oxide particles include at least one selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. Specific examples of the metal oxide include titanium dioxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, and zirconium oxide. Of these, titanium oxide, tin oxide, and indium oxide are particularly preferable. The metal oxide particles are mainly composed of oxides of these metals, can further contain other elements, and fine particles imparted with conductivity are also preferably used. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.

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

  Specific examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane. Methoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxy Propyltriethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, Examples include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane.

  Examples of silane coupling agents having a disubstituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, and γ-glycidyloxypropylmethyldiethoxysilane. Γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyldiethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldi Ethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimeth Shishiran, .gamma.-mercaptopropyl methyl diethoxy silane, .gamma.-aminopropyl methyl dimethoxy silane, .gamma.-aminopropyl methyl diethoxy silane, methyl vinyl dimethoxy silane, and methyl vinyl diethoxy silane.

  Of these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane having a double bond in the molecule. Γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-methacryloyloxypropylmethyldiethoxy having a disubstituted alkyl group with respect to silicon Silane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, and γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypro Pyrtrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane are particularly preferred.

  Two or more coupling agents may be used in combination. In addition to the silane coupling agents shown above, other silane coupling agents may be used. Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and its hydrolyzate.

  The surface treatment with the coupling agent can be carried out by adding the coupling agent to the fine particle dispersion and allowing the dispersion to stand at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

  These silane coupling agents are preferably hydrolyzed with a necessary amount of water in advance. When the silane coupling agent is hydrolyzed, the surfaces of the organic titanium compound and the metal oxide particles described above are easy to react and a stronger film is formed. It is also preferable to add a hydrolyzed silane coupling agent to the coating solution in advance. The water used for this hydrolysis can also be used for the hydrolysis / polymerization of the organic titanium compound.

  In the present invention, the treatment may be performed by combining two or more kinds of surface treatments. The shape of the metal oxide particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape. Two or more kinds of metal oxide particles may be used in the high refractive index layer or the middle refractive index layer.

  The ratio of the metal oxide particles in the high refractive index layer and the medium refractive index layer is preferably 5 to 65% by volume, more preferably 10 to 60% by volume, and still more preferably 20 to 55% by volume. is there.

  The metal oxide particles are supplied to a coating solution for forming a high refractive index layer and a medium refractive index layer in a dispersion state dispersed in a medium. As a dispersion medium for metal oxide particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ketone alcohol (eg, diacetone alcohol). , Esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene) Chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg, diethyl ether, dioxane, Tiger hydrofuran), ether alcohols (e.g., 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

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

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

  Examples of the anionic group include a carboxylic acid group (carboxyl), a sulfonic acid group (sulfo), and a phosphoric acid group (phosphono). Of these, sulfonic acid groups and phosphoric acid groups are preferred. Here, the anionic group may be in a salt state. The cation that forms a salt with the anionic group is preferably an alkali metal ion. Moreover, the proton of the anionic group may be dissociated. The linking group that binds the anionic group and the polymer chain is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof. The crosslinked polymer which is a preferable binder polymer is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked structure. In this case, the ratio of the repeating unit having an anionic group in the copolymer is preferably 2 to 96% by mass, more preferably 4 to 94% by mass, and most preferably 6 to 92% by mass. preferable. The repeating unit may have two or more anionic groups.

  The crosslinked polymer having an anionic group may contain other repeating units (a repeating unit having neither an anionic group nor a crosslinked structure). Other repeating units are preferably a repeating unit having an amino group or a quaternary ammonium group and a repeating unit having a benzene ring. The amino group or quaternary ammonium group has a function of maintaining the dispersed state of the inorganic fine particles, like the anionic group. The benzene ring has a function of increasing the refractive index of the high refractive index layer. The amino group, the quaternary ammonium group, and the benzene ring can obtain the same effect even if they are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure.

  In the crosslinked polymer containing a repeating unit having an amino group or a quaternary ammonium group as a constituent unit, the amino group or quaternary ammonium group may be directly bonded to the polymer chain, or may be a side chain via a linking group. May be bonded to the polymer chain, but the latter is more preferred. The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably carbon number. 1 to 6 alkyl groups. The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group that connects the amino group or quaternary ammonium group to the polymer chain is a divalent group selected from —CO—, —NH—, —O—, an alkylene group, an arylene group, and combinations thereof. Is preferred. When the crosslinked polymer includes a repeating unit having an amino group or a quaternary ammonium group, the ratio is preferably 0.06 to 32% by mass, more preferably 0.08 to 30% by mass, Most preferably, it is 0.1-28 mass%.

  The cross-linked polymer is prepared by blending a monomer for generating a cross-linked polymer to prepare a coating solution for forming a high refractive index layer and a medium refractive index layer, and is generated by a polymerization reaction simultaneously with or after coating of the coating solution. Is preferred. Each layer is formed with the production of the crosslinked polymer. The monomer having an anionic group functions as a dispersant for inorganic fine particles in the coating solution. The monomer having an anionic group is preferably used in an amount of 1 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass with respect to the inorganic fine particles. The monomer having an amino group or a quaternary ammonium group functions as a dispersion aid in the coating solution. The monomer having an amino group or a quaternary ammonium group is preferably used in an amount of 3 to 33% by mass based on the monomer having an anionic group. These monomers can be made to function effectively before application of the coating liquid by a method of forming a crosslinked polymer by a polymerization reaction simultaneously with or after application of the coating liquid.

  As the monomer used in the present invention, a monomer having two or more ethylenically unsaturated groups is most preferable, and examples thereof include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di ( (Meth) acrylate, 1,4-dichlorohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester Terpolyacrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (E.g., methylenebisacrylamide) and methacrylamide. Commercially available monomers may be used as the monomer having an anionic group and the monomer having an amino group or a quaternary ammonium group. As a commercially available monomer having a commercially available anionic group, KAYAMAPMPM-21, PM-2 (manufactured by Nippon Kayaku Co., Ltd.), Antox MS-60, MS-2N, MS-NH4 (manufactured by Nippon Emulsifier Co., Ltd.) , Aronix M-5000, M-6000, M-8000 series (manufactured by Toagosei Chemical Industry Co., Ltd.), Biscote # 2000 series (manufactured by Osaka Organic Chemical Industry Co., Ltd.), New Frontier GX-8289 (Daiichi Kogyo Seiyaku) NK ester CB-1, A-SA (manufactured by Shin-Nakamura Chemical Co., Ltd.), AR-100, MR-100, MR-200 (manufactured by Eighth Chemical Industry Co., Ltd.), and the like. It is done. Examples of commercially available monomers having a commercially available amino group or quaternary ammonium group include DMAA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), DMAEA, DMAPAA (manufactured by Kojin Co., Ltd.), and Bremer QA (Nippon Yushi Co., Ltd.). ) And New Frontier C-1615 (Daiichi Kogyo Seiyaku Co., Ltd.).

  For the polymerization reaction of the polymer, a photopolymerization reaction or a thermal polymerization reaction can be used. A photopolymerization reaction is particularly preferable. A polymerization initiator is preferably used for the polymerization reaction. For example, the thermal polymerization initiator mentioned later used in order to form the binder polymer of an actinic radiation curable resin layer, and a photoinitiator are mentioned.

  A commercially available polymerization initiator may be used as the polymerization initiator. In addition to the polymerization initiator, a polymerization accelerator may be used. The addition amount of the polymerization initiator and the polymerization accelerator is preferably in the range of 0.2 to 10% by mass of the total amount of monomers. The coating liquid (dispersion of inorganic fine particles containing monomer) may be heated to promote polymerization of the monomer (or oligomer). Moreover, it may heat after the photopolymerization reaction after application | coating, and may additionally process the thermosetting reaction of the formed polymer.

  For the medium refractive index layer and the high refractive index layer, it is preferable to use a polymer having a relatively high refractive index. Examples of the polymer having a high refractive index include polystyrene, styrene copolymer, polycarbonate, melamine resin, phenol resin, epoxy resin, and polyurethane obtained by reaction of cyclic (alicyclic or aromatic) isocyanate and polyol. . Polymers having other cyclic (aromatic, heterocyclic, alicyclic) groups and polymers having halogen atoms other than fluorine as substituents can also be used with a high refractive index.

  Each layer of the antireflection layer is formed by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, micro gravure coating, extrusion coating, spray coating, and inkjet. It can be formed by coating.

  FIG. 7 is a schematic view showing a cross section of the antiglare antireflection film according to the present invention.

  It is composed of a thermoplastic film (surface layer 102, base layer 101, surface layer 103) having a multilayer structure, and fine particles are added to the surface layer 102 or surface layer 103 to form irregularities. An active ray curable resin layer 104 and an antireflection layer 105 are laminated thereon. In particular, the fine particles added to the surface layer 102 can give an excellent antiglare effect by giving an internal scattering effect.

<Polarizer>
The polarizing plate of the present invention will be described.

  The polarizing plate can be produced by a general method. The back side of the antiglare antireflection film of the present invention is subjected to alkali saponification treatment, and the antiglare antireflection film thus treated is immersed and stretched in an iodine solution. It is preferable to bond using an aqueous polyvinyl alcohol solution. The antiglare antireflection film may be used on the other surface, or another polarizing plate protective film may be used. With respect to the antiglare antireflection film of the present invention, the polarizing plate protective film used on the other surface has an in-plane retardation Ro of 590 nm, a phase difference of 20 to 70 nm, and Rt of 100 to 400 nm. Preferably it is. These can be produced, for example, by the methods described in JP-A-2002-71957, paragraph numbers [0014] to [0078] and JP-A-2003-170492, paragraphs [0064] to [0252]. Alternatively, it is preferable to use a polarizing plate protective film that also serves as an optical compensation film having an optically anisotropic layer formed by aligning a liquid crystal compound such as a discotic liquid crystal. For example, the optically anisotropic layer can be formed by the method described in paragraph numbers [0033] to [0053] of JP-A-2003-98348. By using it in combination with the antiglare antireflection film of the present invention, a polarizing plate having excellent flatness and a stable viewing angle expansion effect can be obtained.

  As the polarizing plate protective film used on the back side, KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC8UCR-3 (manufactured by Konica Minolta Opto Co., Ltd.) and the like are preferably used as commercially available cellulose ester films.

  The polarizing film, which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction. A typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film. There are one in which iodine is dyed on a system film and one in which dichroic dye is dyed. As the polarizing film, a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound. On the surface of the polarizing film, one side of the antiglare antireflection film of the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.

  A conventional polarizing plate using an antiglare antireflection film is inferior in flatness, and when the reflected image is seen, fine wavy irregularities are observed and glare is also observed. In addition, as a result of the durability test under the conditions of 60 ° C. and 90% RH, the wavy unevenness increased. On the other hand, the polarizing plate using the antiglare antireflection film of the present invention has excellent flatness, There was little glare and the pencil hardness was excellent. In addition, even in a durability test under the conditions of 60 ° C. and 90% RH, the wavy unevenness does not increase, and even with a polarizing plate having an optical compensation film on the back surface side, the viewing angle characteristics after the durability test are It was possible to provide good visibility without fluctuation.

<Display device>
By incorporating the polarizing plate of the present invention into a display device, the display device of the present invention having various visibility can be manufactured. The anti-glare anti-reflection film of the present invention is a reflection type, transmission type, transflective LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type, etc. It is preferably used in LCDs. Further, the antiglare antireflection film of the present invention has remarkably little color unevenness and glaring of the reflected light of the antireflection layer, and is excellent in flatness, plasma display, field emission display, organic EL display, inorganic EL display, It is also preferably used for various display devices such as electronic paper. In particular, a large-screen display device with a screen of 30 or more types, particularly 30 to 54 types, has less color unevenness, glare and wavy unevenness, and has an effect that eyes are not tired even during long-time viewing.

  Hereinafter, the present invention will be described more specifically by way of examples. However, the embodiments of the present invention are not limited to these examples. Here, cellulose ester was used as the thermoplastic resin.

Example 1
[Production of cellulose ester film]
A cellulose ester solution was prepared using the cellulose ester, plasticizer, ultraviolet absorber, fine particles, and solvent described in Table 2 so as to have a dope composition as shown in Table 3.

  That is, the solvent was put into an airtight container, the remaining materials were put in order while stirring, and completely dissolved and mixed while heating and stirring. The fine particles were added dispersed in a part of the solvent. After the temperature was lowered to the temperature at which the solution was cast and allowed to stand overnight, a defoaming operation was performed, and then the solution was produced by Azumi Filter Paper No. Filtration using 244 gave each cellulose ester solution.

  The dopes A to V prepared above are combined from the two surface layer dope lines and the base layer dope line to the respective surface layer die or base layer die as shown in Table 4, and the layer after drying The film was introduced so that the film thickness was as described in Table 4, and co-casting was performed on an endless stainless steel belt having an infinite traveling length of 2 m (the surface layer was cast slightly wider than the base layer). The temperature of the stainless steel belt was set to 35 ° C. so that the surface layer 1 was on the belt surface (this surface was designated as B surface) and the surface layer 2 was on the air side surface (this surface was designated as A surface). The solvent was evaporated on the stainless steel belt, and the web was peeled off from the stainless steel belt. The tension was adjusted so that the draw ratio in the conveyance direction from immediately after peeling to the tenter was 1.1 times. Furthermore, the peeled web was cut to 1.5 m width with a slitter, the web was introduced into a tenter dryer, and both ends were gripped with clips and dried at 90 ° C. while stretching 1.1 times in the width direction. Then, drying was terminated while a large number of rolls arranged vertically were passed through a roll dryer having each drying zone at 125 ° C. alternately, and drying was completed to produce a multilayer cellulose ester film. Further, both ends of this cellulose ester film are cut off to form a 1.4 m wide film, and both ends of this film are subjected to a knurling process having a width of 10 mm and a height of 8 μm. Obtained.

  As a result of measuring the glass transition temperature of the base layer and the surface layer 1 by the measurement method, the surface layer was 5 ° C. lower than the base layer.

<< Coating of actinic radiation curable resin layer (production of antiglare hard coat film) >>
A coating solution 1 for actinic radiation curable resin layer having the following composition was prepared as a coating solution, and applied on the B surface of the cellulose ester films 1 to 24 using a microgravure coater so that the film thickness after curing was 3 μm. After evaporating and drying the solvent, an actinic radiation curable resin layer was formed by curing with 0.2 J / cm ² ultraviolet irradiation using a high pressure mercury lamp, and antiglare hard coat films 1 to 24 were produced.

<Coating liquid 1 for active ray curable resin layer>
Dipentaerythritol hexaacrylate 70 parts by weight Trimethylolpropane triacrylate 30 parts by weight Photoinitiator 4 parts by weight (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
Ethyl acetate 150 parts by mass Propylene glycol monomethyl ether 150 parts by mass Silicon compound 0.4 parts by mass (BYK-307 (by Big Chemie Japan))
Conductive fine particles (average particle diameter: 10 nm) containing tin oxide as a main component were added so that the refractive index of the film formed on the composition was 1.6. The tin oxide used was dispersed in advance using a part of the solvent added to the coating solution. Furthermore, 5 parts by mass of crosslinked polystyrene particles (SH-130H particle size 1.3 μm, manufactured by Soken Chemical) were added and uniformly mixed and dispersed.

《Coating back coat layer》
Furthermore, the following coating composition for a back coat layer was prepared by filtering with a filter having a particle capture efficiency of 3 μm of 99% or more and 0.5 μm or less and a particle capture efficiency of 10% or less. This back coat layer coating composition was applied to the surface opposite to the surface coated with the active ray curable resin layer of the antiglare hard coat film so that the wet film thickness was 15 μm using an extrusion coater. And dried at 90 ° C. for 30 seconds.

<Coating liquid for back coat layer>
Diacetyl cellulose (acetyl group substitution degree 2.4) 0.5 parts by mass Acetone 70 parts by mass Methanol 20 parts by mass Propylene glycol monomethyl ether 10 parts by mass Ultrafine silica AEROSIL 200V (manufactured by Nippon Aerosil Co., Ltd.)
0.003 parts by mass (Silica fine particles were added dispersed in methanol to be added.)
<Surface treatment and coating of low refractive index layer>
<< Preparation of antireflection layer (low refractive index layer 1) >>
First, composite particles were prepared.

(Preparation of composite particles P-1)
A reaction mother liquor was prepared by mixing 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by mass and 1900 g of pure water, and heated to 80 ° C. The pH of this reaction mother liquor is 10.5, and 9000 g of a 1.5 mass% sodium silicate aqueous solution as SiO ₂ and 9000 g of a 0.5 mass% sodium aluminate aqueous solution as Al ₂ O ₃ are simultaneously added to the mother liquor. did. Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition of sodium silicate and sodium aluminate, and hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a dispersion (A) of SiO ₂ .Al ₂ O ₃ porous particle precursor having a solid content concentration of 20% by mass. (First step)
1900 g of pure water was added to 100 g of the dispersion (A) of the porous particle precursor obtained above and heated to 95 ° C., and while maintaining this temperature, an aqueous sodium silicate solution (1.5 g in mass as SiO _2). %) And 27000 g of an aqueous sodium aluminate solution (0.5% by mass as Al ₂ O ₃ ) were gradually added at the same time, and particle growth was performed using the particles of the dispersion liquid (A) of the porous particle precursor as seed particles. . After completion of the addition, the mixture was cooled to room temperature, washed with an ultrafiltration membrane and concentrated to obtain a dispersion (B) of a SiO ₂ · Al ₂ O ₃ porous particle precursor having a solid content concentration of 20% by mass. (First step)
500 g of this porous particle precursor dispersion (B) is taken, and then the aluminum salt dissolved in the ultrafiltration membrane is separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, and a part of aluminum is removed. A dispersion (C) of SiO ₂ .Al ₂ O ₃ porous particles was prepared. (Second step)
A mixture of 1500 g of the porous particle dispersion (C), 500 g of pure water, 1750 g of ethanol and 626 g of 28% ammonia water was heated to 35 ° C., and then 104 g of ethyl silicate (SiO ₂ 28 mass%) was added. Then, the surface of the porous particles was coated with a hydrolyzed polycondensate of ethyl silicate. Next, after concentration to a solid content concentration of 5% by mass with an evaporator, ammonia water with a concentration of 15% by mass was added to adjust the pH to 10, and heat treatment was performed at 180 ° C. for 2 hours in an autoclave. A dispersion of the substituted composite particles (P-1) having a solid content concentration of 20% by mass was prepared. (Third step)
Table 5 shows the average particle diameter, SiO ₂ / MOx (molar ratio), and refractive index of the composite particles (P-1). Here, the average particle diameter was measured by a dynamic light scattering method, and the refractive index was measured by the following method using Series A, AA made by CARGILL as a standard refractive liquid.

<Measuring method of particle refractive index>
(1) The particle dispersion is taken in an evaporator and the dispersion medium is evaporated.

  (2) This is dried at 120 ° C. to obtain a powder.

  (3) A standard refraction liquid having a known refractive index is dropped on a glass plate of a few drops, and the above powder is mixed therewith.

  (4) The operation of (3) above is performed with various standard refractive liquids, and the refractive index of the standard refractive liquid when the mixed liquid becomes transparent is used as the refractive index of the colloidal particles.

(surface treatment)
The actinic radiation curable resin films 1 to 24 are immersed in a 1.5N-NaOH aqueous solution heated to 50 ° C. for 2 minutes for alkali treatment, washed with water, and then washed with a 0.5 mass% -H ₂ SO ₄ aqueous solution at room temperature. It was immersed for 30 seconds to neutralize, washed with water and dried.

(Preparation of low refractive index layer 1)
The average particle size is 60 nm and the refractive index is 1. with respect to a matrix in which Si (OC ₂ H ₅ ) ₄ is mixed at 95 mol% and CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ is mixed at 5 mol%. A low refractive index coating agent was prepared by adding 50% by mass of 38 composite particles (P-1), using 1.0N-HCl as a catalyst, and further diluting with a solvent. A coating solution is applied with a film thickness of 0.1 μm on the antiglare hard coat film subjected to the above surface treatment using a micro gravure method, dried at 120 ° C. for 1 minute, and irradiated with ultraviolet rays to have a refractive index of 1.41. The low refractive index layer 1 was formed.

  As described above, antiglare antireflection films 1 to 24 were produced.

  Subsequently, the polarizing plates 1-24 and the liquid crystal display devices 1-24 were produced by the method shown below using each anti-glare antireflection film 1-24.

<Production of polarizing plate>
A polyvinyl alcohol film having a thickness of 120 μm was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. This was washed with water and dried to obtain a polarizing film.

  Subsequently, according to the following processes 1-5, the polarizing film, the said glare-proof antireflection film, and the cellulose ester film on the back side were bonded together, and the polarizing plate was produced. As the polarizing plate protective film on the back side, a cellulose ester film R (Ro = 43 nm, Rt = 132 nm) having a retardation produced by the following method was used as a polarizing plate.

  Step 1: Soaked in a 1 mol / L sodium hydroxide solution at 50 ° C. for 60 seconds, then washed with water and dried to obtain a saponified cellulose ester film bonded to the polarizer.

  Step 2: The polarizing film was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.

  Step 3: Lightly wipe off the excess adhesive adhering to the polarizing film in Step 2, place it on the cellulose ester film treated in Step 1, and then stack and arrange so that the antireflection layer is on the outside did.

Step 4: The antiglare antireflection film, the polarizing film, and the cellulose ester film sample laminated in Step 3 were bonded at a pressure of 20 to 30 N / cm ² and a conveyance speed of about 2 m / min.

  Process 5: The sample which bonded together the polarizing film produced in the process 4, the cellulose-ester film, and the glare-proof antireflection film in the 80 degreeC dryer was dried for 2 minutes, and the polarizing plate was produced. Polarizing plates 1 to 24 were produced using the antiglare and antireflection films 1 to 24, respectively.

<Preparation of cellulose ester film R>
(Preparation of dope solution E)
Cellulose ester (cellulose acetate propionate acetyl group substitution degree 1.9, propionyl group substitution degree 0.8) 100 parts by mass (Mn = 70000, Mw = 220,000, Mw / Mn = 3.14)
Triphenyl phosphate 8 parts by weight Ethylphthalyl ethyl glycolate 2 parts by weight Methylene chloride 300 parts by weight Ethanol 60 parts by weight The above is put into a sealed container, heated and stirred, and completely dissolved. Azumi Filter Paper Co., Ltd. Azumi filter paper No. No. 24 was filtered to prepare a dope solution E.
(Silicon dioxide dispersion E)
Aerosil 972V (manufactured by Nippon Aerosil Co., Ltd.) 10 parts by mass Ethanol 75 parts by mass The above was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. 75 parts by mass of methylene chloride was added to the silicon dioxide dispersion while stirring, and the mixture was stirred and mixed for 30 minutes with a dissolver to prepare a silicon dioxide dispersion dilution E.
(Preparation of inline additive solution E)
Methylene chloride 100 parts by mass Tinuvin 109 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 4 parts by mass Tinuvin 171 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 4 parts by mass Tinuvin 326 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 2 parts by mass The solution was put into a container, heated, stirred and completely dissolved and filtered.

  To this, 20 parts by mass of silicon dioxide dispersion diluent E was added with stirring, and further stirred for 30 minutes, and then cellulose ester (cellulose acetate propionate acetyl group substitution degree 1.9, propionyl group substitution degree 0.8). 5 parts by mass was added with stirring, and the mixture was further stirred for 60 minutes, and then filtered through a polypropylene wind cartridge filter TCW-PPS-1N manufactured by Advantech Toyo Co., Ltd. to prepare an in-line additive solution E.

  Add 4 parts by mass of the filtered inline additive E to 100 parts by mass of the filtered dope solution E, mix thoroughly with an inline mixer (Toray static type in-pipe mixer Hi-Mixer, SWJ), and then belt cast Using the apparatus, it was cast uniformly on a stainless steel band support at a temperature of 35 ° C. and a width of 1800 mm. With the stainless steel band support, the solvent was evaporated until the amount of residual solvent reached 100%, and then peeled off from the stainless steel band support. The web of the peeled cellulose ester film was evaporated at 55 ° C., slit to 1650 mm width, and then stretched 1.3 times at 130 ° C. in the TD direction (direction perpendicular to the film transport direction) with a tenter. At this time, the residual solvent amount when starting stretching with a tenter was 18%. Thereafter, drying is completed while transporting the drying zone at 120 ° C. and 110 ° C. with a number of rolls, slitting to a width of 1400 mm, a knurling process with a width of 15 mm and an average height of 10 μm is applied to both ends of the film, winding, cellulose ester Film R was obtained. The amount of residual solvent was 0.1%, the average film thickness was 80 μm, and the number of turns was 4000 m. This cellulose ester film had Ro = 43 nm and Rt = 132 nm, had a slow axis in the width direction, and the deviation angle of the slow axis with respect to the width direction was within ± 0.6 degrees.

<Production of liquid crystal display device>
A liquid crystal panel was produced as follows, and the characteristics as a liquid crystal display device were evaluated.

  The both-sided polarizing plates of the 15-inch display VL-150SD manufactured by Fujitsu were peeled off, and the prepared polarizing plates 1 to 8 were each bonded to the glass surface of the liquid crystal cell.

  At that time, the direction of bonding of the polarizing plate is such that the surface of the optical compensation film (retardation film) is on the liquid crystal cell side and the absorption axis is in the same direction as the polarizing plate previously bonded. The liquid crystal display devices 1 to 24 were respectively produced. The polarizing plate used was cut out from the end of a long anti-glare antireflection film whose performance tends to vary.

  The following evaluation was performed about the obtained anti-glare antireflection film and the liquid crystal display device.

[Evaluation]
The following evaluation was performed about the obtained anti-glare antireflection film and the liquid crystal display device.

<Prevention of reflection>
Place the sample on a flat and flat table, and arrange 40W fluorescent lamps (FLR40S-EX-D / M, manufactured by Matsushita Electric) with a height of 1.5m so that the sample table can be illuminated obliquely. Reflection was judged visually.

◎: The outline of the fluorescent lamp is blurred and I don't care about the reflection at all ○: The outline of the fluorescent lamp is blurred and I don't care about the reflection △: The outline of the fluorescent lamp is slightly recognized ×: The outline of the fluorescent lamp is understood I'm worried about the reflection.
About the produced display apparatus, the glare was determined visually.

◎: Glitter is not known at all ○: Glitter is slightly understood △: Slight glaring is known ×: Glitter is quite worrisome << Flatness >>
Laser displacement meter: Keyence Corporation, Model: LT-8100, Resolution: 0.2 μm, Scan with laser displacement meter in width direction to measure fine undulations on surface, anti-glare antireflection film The flatness of was evaluated.

  The measuring method is to place the film on a flat and horizontal table, fix both ends of the width to the table with tape, and set the measuring camera parallel to the table. It set so that the space | interval of a sample film might be set to 25 mm, and it scanned and measured with the moving speed of 5 cm / min. The measurement was performed from the back side provided with an antireflection layer in order to observe deformation such as undulation of the film itself. The value obtained by the measurement is the state and size of minute irregularities on the film. The smaller the unevenness due to deformation of the film, the better the flatness.

◎: Unevenness due to film deformation is less than 1.0 ○: Unevenness due to film deformation is less than 1.0 to 2.0 μm Δ: Unevenness due to film deformation is less than 2.0 to 4.0 μm ×: Due to film deformation Unevenness is 4.0 μm or more << Evaluation of visibility >>
About each produced said liquid crystal display device, after leaving for 100 hours on 60 degreeC and 90% RH conditions, it returned to 23 degreeC and 55% RH. As a result, when the surface of the display device was observed, the one using the antiglare antireflection film of the present invention was excellent in flatness, whereas the comparative display device showed fine wavy unevenness, My eyes were easy to get tired when I was watching.

◎: No wavy unevenness is observed on the surface ○: Slight wavy unevenness is recognized on the surface △: Small wavy unevenness is slightly recognized on the surface ×: Fine wavy unevenness is recognized on the surface << Reflected light Evaluation of uneven color >>
For each liquid crystal display device, the screen was displayed in black, and the reflection unevenness of the surface was visually evaluated.

◎: Color unevenness of reflected light is not known, black appears to be blurred ○: Color unevenness of reflected light is slightly recognized △: Color unevenness of reflected light is recognized, but there is no practical problem ×: Reflected light I'm worried about the uneven color.

  The above evaluation results are summarized in the following table.

  As a result, the antiglare and antireflection films 1 to 20 of the present invention were excellent in the anti-reflection effect, and the fogging was remarkably small. Moreover, the liquid crystal display devices 1-20 of this invention were excellent in visibility, and there were also few color irregularities of reflected light. On the other hand, the comparative anti-glare antireflection films 21 to 24 and the liquid crystal display devices 21 to 24 were inferior in the anti-glare effect. The visibility was also inferior, uneven color of reflected light was recognized, and it was difficult to provide a uniform antireflection layer.

Example 2
A cellulose ester film was produced by the following method.

<Cellulose ester film>
(Silicon dioxide dispersion A)
Aerosil 972V (manufactured by Nippon Aerosil Co., Ltd.) 12 parts by mass (average primary particle diameter 16 nm, apparent specific gravity 90 g / liter)
88 parts by mass of ethanol or more was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. The liquid turbidity after dispersion was 200 ppm. 88 parts by mass of methylene chloride was added to the silicon dioxide dispersion while stirring, and the mixture was stirred and mixed for 30 minutes with a dissolver to prepare silicon dioxide dispersion dilution A.
(Preparation of inline additive solution A)
Tinuvin 109 (manufactured by Ciba Specialty Chemicals) 11 parts by mass Tinuvin 171 (manufactured by Ciba Specialty Chemicals) 5 parts by weight 100 parts by weight of methylene chloride Dissolved and filtered.

  To this, 36 parts by mass of silicon dioxide dispersion diluent A was added with stirring, and after further stirring for 30 minutes, cellulose acetate propionate (acetyl group substitution degree 1.9, propionyl group substitution degree 0.8) 6 masses. The mixture was added with stirring, and further stirred for 60 minutes, and then filtered through a polypropylene wind cartridge filter TCW-PPS-1N manufactured by Advantech Toyo Co., Ltd. to prepare an in-line additive solution A.

(Preparation of dope solution A)
Cellulose ester (cellulose triacetate synthesized from linter cotton)
100 parts by mass (Mn = 148000, Mw = 310000, Mw / Mn = 2.1, acetyl group substitution degree 2.92)
Trimethylolpropane tribenzoate (the following compound) 5.0 parts by mass Ethylphthalyl ethyl glycolate 5.5 parts by mass Methylene chloride 440 parts by mass Ethanol 40 parts by mass

  The above was put into a closed container, heated and stirred, and completely dissolved. Azumi filter paper No. 24, and the dope liquid A was prepared.

  The dope solution A was filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd. in the film production line. In-line additive solution line was filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd. Add 2 parts by mass of the filtered in-line additive A to 100 parts by mass of the filtered dope liquid A, mix well with an in-line mixer (Toray static type in-pipe mixer Hi-Mixer, SWJ), and then cast the belt. Using the apparatus, it was cast uniformly on a stainless steel band support at a temperature of 35 ° C. and a width of 1800 mm. With the stainless steel band support, the solvent was evaporated until the residual solvent amount became 120%, and then peeled off from the stainless steel band support. The peeled cellulose ester web was evaporated at 35 ° C., slit to 1650 mm width, and then stretched 1.1 times in the TD direction (direction perpendicular to the film transport direction) with a tenter, Dried at the drying temperature. At this time, the residual solvent amount when starting stretching with a tenter was 30%.

  Thereafter, drying is completed while transporting the drying zone of 110 ° C. and 120 ° C. with a number of rolls, slitting to a width of 1400 mm, a knurling process having a width of 15 mm and an average height of 10 μm is applied to both ends of the film, and an initial winding tension of 220 N / M and a final tension of 110 N / m were wound around a 6-inch inner diameter core to obtain a cellulose ester film. The draw ratio in the MD direction (same direction as the film transport direction) immediately after peeling calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.07. The residual solvent amount of the cellulose ester film was 0.2%, the average film thickness was 80 μm, and the winding number was 3000 m.

  In the process shown in FIG. 8, the following coating composition was applied to the obtained cellulose ester film with a film thickness of 1 μm with a die coater, dried at 90 ° C., and between the hot roll and back roll provided with the mold as it was. Then, a cellulose ester film 25 having an uneven surface with a center line average roughness Ra of 0.3 μm was produced on the coating layer.

<Coating composition>
Cellulose acetate propionate (acetyl group substitution degree 1.9, propionyl group substitution degree 0.8) 10 parts by mass (Mn = 70000, Mw = 220,000, Mw / Mn = 3.14)
Silicon oxide fine particles (average primary particle size 12 nm Aerosil 200V manufactured by Nippon Aerosil Co., Ltd.) 1 part by mass Methyl acetate 70 parts by mass Ethanol 30 parts by mass It was used by dispersing so as to obtain secondary particles of about 5 μm.

  An actinic radiation curable resin layer was provided in the same manner as in Example 1 on the obtained cellulose ester film having an uneven surface. Further, the following low refractive index layer 2 was formed thereon, and a back coat layer was provided on the back side of the actinic radiation curable resin layer in the same manner as in Example 1 to obtain an antiglare antireflection film 25.

<< Production of Low Refractive Index Layer 2 >>
Silica-based fine particles (cavity particles) were prepared as described below.

(Preparation of silica-based fine particles P-2)
A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by mass and 1900 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 9000 g of 0.98 mass% sodium silicate aqueous solution as SiO ₂ and 9000 g of 1.02 mass% sodium aluminate aqueous solution as Al ₂ O ₃ were simultaneously added to the mother liquor. did. Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition, and hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ .Al ₂ O ₃ core particle dispersion having a solid content concentration of 20% by mass. (Process (a))
1700 g of pure water is added to 500 g of this core particle dispersion and heated to 98 ° C., and while maintaining this temperature, a silicic acid solution (SiO ₂₎ obtained by dealkalizing a sodium silicate aqueous solution with a cation exchange resin. A dispersion of core particles in which 3000 g (concentration of 3.5% by mass) was added to form a first silica coating layer was obtained. (Process (b))
Next, 1125 g of pure water is added to 500 g of the core particle dispersion liquid that has been washed with an ultrafiltration membrane to form a first silica coating layer having a solid content concentration of 13% by mass, and concentrated hydrochloric acid (35.5%) is further added dropwise. The pH was adjusted to 1.0 and dealumination was performed. Next, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, and SiO ₂ · Al from which some of the constituent components of the core particles forming the first silica coating layer were removed. A dispersion of ₂ O ₃ porous particles was prepared (step (c)). A mixture of 1500 g of the above porous particle dispersion, 500 g of pure water, 1,750 g of ethanol, and 626 g of 28% ammonia water is heated to 35 ° C., and then 104 g of ethyl silicate (SiO ₂ 28 mass%) is added. The surface of the porous particles on which the first silica coating layer was formed was coated with a hydrolyzed polycondensate of ethyl silicate to form a second silica coating layer. Next, a dispersion of silica-based fine particles (P-2) having a solid content concentration of 20% by mass, in which the solvent was replaced with ethanol using an ultrafiltration membrane, was prepared.

Table 8 shows the thickness, average particle diameter, MOx / SiO ₂ (molar ratio), and refractive index of the first silica coating layer of the silica-based fine particles (P-2). Here, the average particle diameter was measured by a dynamic light scattering method, and the refractive index was measured in the same manner as described above.

<Surface treatment and coating of low refractive index layer>
(surface treatment)
The actinic radiation curable resin film 25 is immersed in a 1.5N-NaOH aqueous solution heated to 50 ° C. for 2 minutes for alkali treatment, washed with water, and then washed in a 0.5 mass% -H ₂ SO ₄ aqueous solution at room temperature for 30 seconds. It was immersed and neutralized, washed with water and dried.

(Preparation of low refractive index layer 2)
Si (OC ₂ H _{5) 4} to _{95mol%, C 3 F 7 -} (OC 3 F 6) 24 -O- (CF 2) 2 -C 2 H 4 -O-CH 2 Si (OCH 3) 3 to 5mol 50% by mass of silica-based fine particles (P-2) having an average particle diameter of 60 nm are added to a matrix mixed at a ratio of 1.0%, and a low refractive index coating agent further diluted with a solvent using 1.0N HCl as a catalyst. Was made. The coating solution was applied in a film thickness of 0.1 μm using a die coater method on the cellulose ester film on which the surface-treated actinic radiation curable resin layer was formed, dried at 120 ° C. for 1 minute, and then 0.2 J / A low refractive index layer 2 having a refractive index of 1.37 was formed by performing ultraviolet irradiation of cm ² .

  A polarizing plate 25 and a display device 25 were produced in the same manner as in Example 1 using the antiglare antireflection film 25 produced as described above, and the same evaluation was performed.

  As a result, Example 1 was reproduced, and an antiglare antireflection film having excellent flatness and anti-reflection properties and having extremely little blurring could be obtained. Furthermore, it was possible to obtain a display device having a wide viewing angle with a viewing angle of 170 ° with no uneven color of reflected light and excellent visibility.

The cross section of the film of 3 layer structure is shown typically. It is the figure showing the place which formed the multilayer casting web by casting and a co-casting die. It is a figure showing the web of the sequential casting die and the casted multilayer structure. It is the figure which showed the cross section of another type co-casting die. It is the figure which showed typically the dope preparation process of the solution casting film forming apparatus concerning this invention. It is the figure which showed typically from the casting process to the drying process of the solution casting film forming apparatus concerning this invention. It is the schematic diagram which showed the cross section of the anti-glare antireflection film which concerns on this invention. It is a schematic diagram of the process which has an uneven | corrugated formation part using application | coating and a mold roll.

Explanation of symbols

101 Base layer 102 Surface layer 103 Surface layer 104 Actinic radiation curable resin layer 105 Antireflection layer 106 Backcoat layer

Claims (10)

It has a high refractive index active ray curable resin layer and a low refractive index layer containing inorganic fine particles on the uneven surface of a substrate film containing a thermoplastic resin, and the inorganic fine particles contained in the low refractive index layer are porous particles. And a composite particle having a coating layer provided on the surface of the porous particle, and a hollow particle filled with a solvent, a gas, or a porous substance inside, and an antiglare antireflection film. The antiglare antireflection film according to claim 1, wherein the unevenness of the base film has a center line average roughness (Ra) of 0.03 μm or more. The anti-glare antireflection film according to claim 1, wherein the base film contains fine particles. The anti-glare antireflection film according to any one of claims 1 to 3, wherein the base film has a thermoplastic resin layer containing fine particles in a surface layer. The antiglare antireflection film according to any one of claims 1 to 4, further comprising a surface layer having a glass transition temperature lower than that of the base layer on the surface of the base film. The anti-glare antireflection film according to claim 1, wherein the base film is formed by co-casting or sequential casting. The base film is composed of an ultraviolet absorber and a plasticizer, a total acyl group substitution degree of 2.6 to 2.9, a number average molecular weight (Mn) of 80,000 to 200,000, a weight average molecular weight (Mw) / number average molecular weight ( The antiglare reflection according to any one of claims 1 to 6, which is a stretched cellulose ester film containing a cellulose ester having a value of Mn) of 1.4 to 3.0. Prevention film. A polarizing plate comprising the antiglare antireflection film according to any one of claims 1 to 7 on one surface and an optical compensation film on the other surface. A display device comprising the antiglare antireflection film according to claim 1 provided on a surface thereof. A display device comprising the polarizing plate according to claim 8.

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