JP2009288413A - Method for manufacturing hard coat film, hard coat film, antireflection film, polarizing plate, and image displaying device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a hard coat film which has a hard coat layer and is excellent both in hardness and in prevention of curling, the hard coat film being especially excellent both in high hardness and in prevention of curling after the film is stored at a high temperature and humidity for a long period of time, a hard coat film manufactured by the manufacturing method, an antireflection films using the hard coat film, a polarizing plate using the hard coat film and the antireflection film, and an image-displaying device. <P>SOLUTION: In the method for manufacturing the hard coat film having a hard coat layer, directly or via another layer, on a film base material, the film thickness of the hard coat layer is 10 μm or larger, and an alkaline solution is applied onto the surface opposite to the side at which the hard coat layer is formed. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a hard coat film, a hard coat film, an antireflection film, a polarizing plate, and an image display device.

  In recent years, display bodies such as a liquid crystal display and a plasma display provided with a film having a hard coat material as a protective layer (hereinafter referred to as a hard coat film) on the surface are rapidly spreading. In particular, since the liquid crystal display is enlarged and used by an unspecified number of consumers, the hard coat material used for the liquid crystal display is required to have higher hardness.

  However, when trying to obtain a high hardness, the hard coat layer is liable to be cracked or peeled off, and at the same time, the curl due to curing shrinkage of the hard coat layer is increased, causing a problem in practical use. As preventive measures, a technique for performing solvent treatment on the back surface of the hard coat layer (for example, see Patent Document 1), a technique for forming a back coat layer (for example, see Patent Document 2), and the like are disclosed.

  On the other hand, the hard coat layer of a hard coat film is generally formed as a coating film of about 2 to 10 μm on a film substrate using an ionizing radiation curable resin such as a thermosetting resin or an ultraviolet curable resin. However, with the above thickness, even when a hard coat resin having a pencil hardness of 4H or more when coated on glass, it was affected by the film base material as a base and formed on the film base material. The surface hardness of the hard coat layer is 2H or less in pencil hardness.

  For this reason, it is conceivable to simply increase the thickness of the hard coat layer in order to obtain higher hardness. However, when the hard coat layer is formed with a thickness of 10 μm or more, the techniques disclosed in Patent Documents 1 and 2 are particularly suitable for hardness and curl, especially under conditions assuming long-term storage such as high temperatures in summer and high humidity storage and transportation. It was difficult to balance suppression.

  For example, Patent Document 3 discloses a technique for achieving both hardness and curl suppression in a hard coat film having a hard coat layer of 10 μm or more.

  Patent Document 3 is a technique for improving the above problem by forming a hard coat layer with a specific acrylate and inorganic fine particles.

  When using a hard coat film especially as a protective film of a liquid crystal display, it is laminated | stacked on the polarizing film which is a liquid-crystal member, and is used as a polarizing plate protective film. In this case, in order to obtain adhesion with PVA which is a polarizing film base film, the hard coat film is laminated after alkali saponification treatment.

However, the hard coat film of Patent Document 3 after the alkali saponification treatment has a problem in that the inorganic fine particles react with each other due to the alkali saponification treatment, the hard coat layer is deteriorated, and high hardness cannot be obtained.
JP-A-9-218302 JP 2005-266231 A JP 2006-106427 A

  Accordingly, an object of the present invention is to provide a method for producing a hard coat film that achieves both hardness and curl suppression in a hard coat film having a hard coat layer, and in particular, high hardness after long-term storage at high temperature and high humidity. The present invention provides a method for producing a hard coat film that achieves both curl suppression. The present invention also provides a hard coat film obtained by the production method, an antireflection film using the hard coat film, a polarizing plate using the hard coat film, the antireflection film, and an image display device.

  The above object of the present invention is achieved by the following configurations.

  1. In a method for producing a hard coat film having a hard coat layer directly or via another layer on a film substrate, the thickness of the hard coat layer is 10 μm or more, opposite to the side on which the hard coat layer is provided The manufacturing method of the hard coat film characterized by apply | coating an alkaline solution to the side surface.

  2. 2. The method for producing a hard coat film according to 1 above, wherein the thickness of the hard coat layer is 12 μm or more and 20 μm or less.

  3. 3. The method for producing a hard coat film according to 1 or 2, wherein the hard coat layer has a pencil hardness of 3H or more.

  4). 4. The method for producing a hard coat film according to any one of 1 to 3, wherein the hard coat layer has a pencil hardness of 4H or more.

  5). The method for producing a hard coat film according to any one of 1 to 4, wherein the alkaline solution contains a fluorine compound or a silicone compound.

  6). The said film base material contains cellulose-ester resin, The manufacturing method of the hard coat film of any one of said 1-5 characterized by the above-mentioned.

  7. The said film base material contains a cellulose-ester resin and an acrylic resin, The manufacturing method of the hard coat film of any one of said 1-6 characterized by the above-mentioned.

  8). The said film base material contains a cellulose-ester resin, an acrylic resin, and an acrylic particle, The manufacturing method of the hard coat film of any one of said 1-7 characterized by the above-mentioned.

  9. The hard coat film produced using the manufacturing method of the hard coat film of any one of said 1-8.

  10. 10. An antireflection film, wherein a low refractive index layer is laminated directly or via another layer on the hard coat layer of the hard coat film as described in 9 above.

  11. 10. A polarizing plate comprising the hard coat film described in 9 or the antireflection film described in 10 on at least one surface of a polarizing film.

  12 10. An image display device comprising the hard coat film according to 9, the antireflection film according to 10, or the polarizing plate according to 11.

  According to the present invention, it is possible to provide a method for producing a hard coat film having both hardness and curl suppression in a hard coat film having a hard coat layer, and in particular, high hardness and curl suppression after long-term storage at high temperature and high humidity. A method for producing a compatible hard coat film can be provided.

  Moreover, the hard coat film obtained by this manufacturing method, the anti-reflective film using the same, Furthermore, the polarizing plate using this hard coat film and this anti-reflective film, and an image display apparatus can be provided.

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

  The method for producing a hard coat film of the present invention according to claim 1 has a hard coat layer directly on the film substrate or via another layer, and the film thickness of the hard coat layer is 10 μm or more, An alkaline solution is applied to the surface opposite to the side on which the hard coat layer is provided. Even when laminated on a polarizing film to form a polarizing plate protective film, it does not require alkali saponification treatment, is excellent in productivity, and has a high hardness and curl suppression even after long-term storage at high temperature and high humidity. Can provide film.

  In the present invention, in order to obtain high hardness, the curl when the thickness of the hard coat layer is 10 μm or more, particularly the curl after long-term storage at high temperature and high humidity, the surface opposite to the side on which the hard coat layer is provided. It has been found that it can be adjusted by applying an alkaline solution to the solution, and the problem of achieving both high hardness and curl suppression can be solved, and the present invention has been achieved.

  In conventional solvent treatment, etc., additives (for example, ultraviolet absorbers, plasticizers, etc. described later) contained in the base film are likely to be localized in the base film, and are stored particularly at high temperature and high humidity. In order to obtain high hardness, the above-mentioned problem is conspicuous when the thickness of the hard coat layer is 10 μm or more in order to easily curl due to the influence. It is estimated that the alkaline solution can suppress the localization of the additive in the base film, and can suppress the curling even when stored at high temperature and high humidity.

  The invention according to claim 2 is a method for producing a hard coat film, wherein the thickness of the hard coat layer is 12 μm or more and 20 μm or less, and is excellent in both high hardness and curl suppression. is there.

  The invention according to claim 3 is a method for producing a hard coat film, wherein the hard coat layer has a pencil hardness of 3H or more, and is excellent in both high hardness and curl suppression.

  The invention according to claim 4 is a method for producing a hard coat film, wherein the hard coat layer has a pencil hardness of 4H or more, and is excellent in both high hardness and curl suppression.

  The invention according to claim 5 is a method for producing a hard coat film, wherein the alkaline solution contains a fluorine-based compound or a silicone compound, and is excellent in both high hardness and curl suppression. .

  The invention according to claim 6 is a method for producing a hard coat film, wherein the film base material contains a cellulose ester resin, and is excellent in both high hardness and curl suppression.

  The invention according to claim 7 is a method for producing a hard coat film, wherein the film base material contains a cellulose ester resin and an acrylic resin, and is excellent in both high hardness and curl suppression. is there.

  The invention according to claim 8 is a method for producing a hard coat film, wherein the film substrate contains a cellulose ester resin, an acrylic resin, and acrylic particles, and is excellent in both high hardness and curl suppression. Is.

  The invention according to claim 9 is. It is the hard coat film produced using the manufacturing method of the hard coat film of any one of Claims 1-8, and is excellent in coexistence of high hardness and curl suppression.

  The invention according to claim 10 is an antireflection film characterized in that a low refractive index layer is laminated directly or via another layer on the hard coat layer of the hard coat film according to claim 9. Yes, it is excellent in achieving both high hardness and curl suppression.

  The invention according to claim 11 is. A polarizing plate having the hard coat film according to claim 9 or the antireflection film according to claim 10 on at least one surface of the polarizing film.

  An invention according to claim 12 is an image display device comprising the hard coat film according to claim 9, the antireflection film according to claim 10, or the polarizing plate according to claim 11.

  Hereinafter, the present invention will be described in detail.

<Alkaline solution>
First, the alkaline solution that is a feature of the present invention will be described. By applying the alkaline solution of the present invention to the surface opposite to the side on which the hard coat layer is provided (hereinafter also referred to as a back coat surface or a back coat layer), a good curl suppressing effect can be obtained even in a high hardness hard coat film. As a result, both high hardness and curl suppression can be achieved. First, the alkaline agent contained in the alkaline solution will be described.

  Examples of the alkaline agent include trisodium phosphate, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, ammonium, Inorganic alkaline agents such as sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium and lithium can be mentioned. Moreover, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Ethyleneimine, ethylenediamine, pyridine, DBU (1,8-diazabicyclo [4,3,0] -5-undecene), DBN (1,5-diazabicyclo [5,4,0] -7-nonene), tetramethylammonium Hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, triethylbutylammonium Organic alkali agents such as Dorokishido be used. These alkali agents can be used alone or in combination of two or more, and a part of them may be added in the form of a salt, for example, halogenated.

  Among these alkali agents, sodium hydroxide and potassium hydroxide are preferable. The reason is that the pH can be adjusted in a wide pH range by adjusting these amounts.

  Although the density | concentration of an alkaline solution is determined according to the kind and application amount of the alkali to be used, 0.1-25 mass% is preferable and, as for the alkali concentration in an alkaline solution, the alkali concentration in an alkaline solution is 1-15 mass. % Is more preferable.

  The alkaline solution preferably contains a fluorine compound or a silicone compound from the viewpoint that the object effect of the present invention is easily exhibited.

  The fluorine-based compound is a monomer, oligomer, or polymer containing a perfluoroalkyl group as a mother nucleus, and includes derivatives such as polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene, and the like. Examples of commercially available products include Surflon “S-381”, “S-382”, “SC-101”, “SC-102”, “SC-103”, and “SC-104” (all manufactured by Asahi Glass Co., Ltd.). FLORARD "FC-430", "FC-431", "FC-173" (all made by Fluorochemicals-Sumitomo 3M), F-top "EF352", "EF301", "EF303" (all Shin-Akita Kasei Co., Ltd.) Company made), Schwegaufur "8035", "8036" (both made by Schwegman), "BM1000", "BM1100" (both made by BM Himmy), Megafuck "F-114", "F -470 "," F-443 "(all manufactured by Dainippon Ink & Chemicals, Inc.) and the like.

  Examples of the fluorine compound also include a fluorine-siloxane graft polymer obtained by copolymerizing polysiloxane containing siloxane and / or organosiloxane alone and / or organopolysiloxane by grafting to a fluorine-based resin. . Examples of commercially available fluorine-siloxane graft polymers include ZX-022H, ZX-007C, ZX-049, and ZX-047-D manufactured by Fuji Chemical Industry Co., Ltd.

  The density | concentration of a fluorine-type compound is 0.01-5 mass% in an alkaline solution, Preferably it is 0.05-2 mass%. One or two or more fluorine compounds can be used in combination.

  Next, the silicone compound will be described. The silicone compound is preferably straight silicone oil or modified silicone oil.

  Here, the straight silicone oil refers to one in which a methyl group, a phenyl group, or a hydrogen atom is bonded as a substituent. A modified silicone oil is one having a component that is secondarily derived from a straight silicone oil. On the other hand, it can be classified from the reactivity of silicone oil. These are summarized as follows.

(Silicone oil)
1. Straight silicone oil 1-1. Non-reactive silicone oil: dimethyl, methylphenyl substitution, etc.

1-2. Reactive silicone oil: methyl hydrogen substitution and the like.
2. Modified silicone oil Modified silicone oil is born by introducing various organic groups into dimethyl silicone oil.

  2-1. Non-reactive modified silicone oil: alkyl, alkyl / aralkyl, alkyl / polyether, polyether, higher fatty acid ester substitution, etc.

  The alkyl / aralkyl-modified silicone oil is a silicone oil in which a part of the methyl group of dimethyl silicone oil is substituted with a long-chain alkyl group or a phenylalkyl group.

  The polyether-modified silicone oil is a surfactant in which hydrophobic dimethyl silicone is introduced into hydrophilic polyoxyalkylene.

  The higher fatty acid-modified silicone oil is a silicone oil in which a part of the methyl group of dimethyl silicone oil is replaced with a higher fatty acid ester.

  The amino-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is substituted with an aminoalkyl group.

  The epoxy-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is substituted with an epoxy group-containing alkyl group.

  The carboxyl-modified or alcohol-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is substituted with a carboxyl group or a hydroxyl group-containing alkyl group.

  Of these, polyether-modified silicone oil is preferred. The number average molecular weight of the polyether-modified silicone oil is, for example, 1,000 to 100,000, preferably 2,000 to 50,000. When the number average molecular weight is less than 1,000, the drying property of the coating film is low. Conversely, if the number average molecular weight exceeds 100,000, bleeding out to the coating surface becomes difficult.

  Specific products include L-45, L-9300, FZ-3704, FZ-3703, FZ-3720, FZ-3786, FZ-3501, FZ-3504, FZ-3508, FZ- from Toray Dow Corning. 3705, FZ-3707, FZ-3710, FZ-3750, FZ-3760, FZ-3785, FZ-3785, Y-7499, Shin-Etsu Chemical KF96L, KF96, KF96H, KF99, KF54, KF965, KF968, KF56, KF995, KF351, KF351A, KF352, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, FL100, BYK series manufactured by BYK Japan, BYK-300 / 302, BYK-306, BYK-3307 BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-340, BYK-344, BYK-370, BYK- 375, BYK-377, BYK-352, BYK-354, BYK-355 / 356, BYK-358N / 361N, BYK-357, BYK-390, BYK-392, BYK-UV3500, BYK-UV3510, BYK-UV3570, BYK-Silclean 3700, dimethyl silicone series manufactured by GE Toshiba Silicone, XC96-723, YF3800, XF3905, YF3057, YF3807, YF3802, YF3897, and the like.

  The silicone compound may be a compound in which a part of the methyl group of the silicone oil is substituted with a hydrophilic group. The position of substitution includes a side chain of silicone oil, both ends, one end, both end side chains, and the like. Examples of the hydrophilic group include polyether, polyglycerin, pyrrolidone, betaine, sulfate, phosphate, and quaternary salt.

  Specific examples include silicone surfactants SILWET L-77, L-720, L-7001, L-7002, L-7604, Y-7006, FZ-2101, FZ-2104, FZ- from Toray Dow Corning. 2105, FZ-2110, FZ-2118, FZ-2120, FZ-2122, FZ-2123, FZ-2130, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164, FZ-2166, FZ-2191, SUPERSILWET SS-2801, SS-2802, SS-2803, SS-2804, SS-2805, etc. are mentioned.

  As a preferable structure of the compound in which the hydrophobic group is composed of dimethylpolysiloxane and the hydrophilic group is composed of polyoxyalkylene, a dimethylpolysiloxane structure portion and polyoxyal. Specific examples include, for example, silicone surfactant ABN SILWET manufactured by Toray Dow Corning. FZ-2203, FZ-2207, FZ-2208, FZ-2222, etc. are mentioned.

  Moreover, as a silicone compound, you may contain the reactive modified silicone resin (it is also called reactive modified silicone oil) demonstrated below.

  2-2. Reactive modified silicone oil: amino, epoxy, carboxyl, alcohol substitution, etc.

  The reactive modified silicone resin is a reactive type modified silicone resin in which the side chain, one end or both ends of polysiloxane is substituted with amino, epoxy, carboxyl, hydroxyl group, methacryl, mercapto, phenol or the like. As amino-modified silicone resins, specifically, KF-860, KF-861, X-22-161A, X-22-161B (above, manufactured by Shin-Etsu Chemical Co., Ltd.), FM-3311, FM-3325 (above, Chisso Corporation), epoxy-modified silicone resins such as KF-105, X-22-163A, X-22-163B, KF-101, KF-1001 (above, Shin-Etsu Chemical Co., Ltd.), polyether-modified X-22-4272, X-22-4952 as silicone resins, X-22-3701E, X-22-3710 (above, manufactured by Shin-Etsu Chemical Co., Ltd.) as carboxyl-modified silicone resins, and carbinol-modified silicone resins KF-6001, KF-6003 (Shin-Etsu Chemical Co., Ltd.), methacryl-modified silicone X-22-164C (made by Shin-Etsu Chemical Co., Ltd.) as the resin, KF-2001 (made by Shin-Etsu Chemical Co., Ltd.) as the mercapto-modified silicone resin, and X-22-1821 as the phenol-modified silicone resin (The above is manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the hydroxyl group-modified silicone resin include FM-4411, FM-4421, FM-DA21, FM-DA26 (manufactured by Chisso Corporation). In addition, X-22-170DX, X-22-2426, X-22-176F (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are also included.

  The concentration of the silicone compound described above is preferably 0.01 to 5.0% by mass in the alkaline solution, more preferably 0.05 to 2% by mass. A silicone compound can use together 1 type (s) or 2 or more types.

  The alkaline solution may contain a solvent. Solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl oxide, methyl-n-amyl ketone, cyclohexanone, diacetone alcohol, diisobutyl ketone, methylcyclohexanone, methyl acetate, ethyl acetate, ethyl lactate, butyl lactate, benzoate Esters such as ethyl acetate and methyl acetoacetate, ethers such as dioxolane, dioxane, methyl cellosolve and methyl carbitol, polyhydric alcohol esters such as methyl cellosolve acetate and cellosolve acetate, furans such as tetrahydrofuran and furfural, glacial acetic acid Acids such as methylene chloride, ethylene dichloride, tetrachloroethane, nitromethane, nitroethane, pyridine, dimethylformamide, nitric acid Nitrogen compounds such as Robenzen, and sulfonic acids such as dimethyl sulfoxide and the like.

  In consideration of drying after coating, a solvent that easily volatilizes is preferable, and a solvent having a boiling point of 200 ° C. or lower is preferable. Moreover, as a solvent, you may contain a high boiling point side solvent and a low boiling point side solvent at least 1 type each.

  Examples of the high boiling point solvent include cyclohexanone (bp 155.65 ° C.), diacetone alcohol (bp 169.2 ° C.), ethyl lactate (bp 154.1 ° C.), dimethylformamide (bp 153 ° C.), and methyl cellosolve (bp 145 ° C.). , Dioxane (101.4 ° C.) and the like.

  Examples of the low boiling point solvent include acetone (bp 56.12 ° C.), methyl ethyl ketone (bp 79.6 ° C.), methyl acetate (bp 56.87 ° C.), ethyl acetate (bp 77.11 ° C.), dioxolane (bp 75.6 ° C.). And the like.

  In addition, alcohols such as methanol, ethanol, propanol, n-butanol, 2-butanol, tert-butanol, glycol ethers (propylene glycol mono (C1-C4) alkyl ether (specifically, propylene glycol monomethyl ether (PGME)) , Propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, etc.), propylene glycol mono (C1-C4) alkyl ether esters (propylene glycol monomethyl ether acetate, propylene glycol monoethyl) Ether acetate)), water and other solvents can also be used. The solvent concentration of the alkaline solution is preferably 50 to 99.8% by mass in the alkaline solution.

  Moreover, the alkaline solution may contain an acrylic resin or a cellulose ester resin. First, cellulose ester resin (hereinafter also referred to as cellulose ester) will be described. The cellulose ester has an X + Y range of 2.0 ≦ X + Y <2.4 when the average substitution degree of the acetyl group of the cellulose ester is X, and the average substitution degree of the acyl group not containing the acetyl group is Y. The thing of the range of 1 <= Y <= 2.2 is preferable. Cellulose molecules are composed of many glucose units linked together, and the glucose unit has three hydroxyl groups. The number of acyl groups derived from these three hydroxyl groups is called the degree of substitution. For example, cellulose triacetate has an acetyl group bonded to all three hydroxyl groups of the glucose unit.

  The cellulose ester is a carboxylic acid ester having about 2 to 22 carbon atoms, and may be an aromatic carboxylic acid ester, and is particularly preferably a lower fatty acid ester of cellulose. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. The acyl group bonded to the hydroxyl group may be linear or branched or may form a ring. Furthermore, another substituent may be substituted. When the degree of substitution is the same, birefringence decreases when the number of carbon atoms is large, and therefore, the number of carbon atoms is preferably selected from acyl groups having 2 to 6 carbon atoms. Further, the acyl group preferably has 2 to 4 carbon atoms, particularly preferably 2 or 3 carbon atoms, and is preferably a propionyl group or a butyryl group. In addition, the measuring method of the substitution degree of an acyl group can be measured according to the prescription | regulation of ASTM-D817-96.

  Examples of cellulose esters include cellulose acetate propionate, cellulose acetate butyrate, and cellulose acetate as described in JP-A Nos. 10-45804, 8-231761, U.S. Pat. No. 2,319,052, and the like. Examples include mixed fatty acid esters such as phthalate. Among these, cellulose acetate propionate and cellulose acetate butyrate are preferable. The cellulose ester can be synthesized by a known method.

  Moreover, diacetylcellulose, triacetylcellulose, etc. can also be used.

  As the cellulose ester, a 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 cellulose ester synthesized from cotton linter (hereinafter sometimes referred to simply as linter) alone or in combination.

  In general, when the molecular weight of the cellulose ester is large, the rate of change of the elastic modulus due to heat becomes small. However, when the molecular weight is excessively increased, the viscosity of the cellulose ester solution becomes too high and the productivity is lowered. The molecular weight of the cellulose ester is preferably 30000-200000 in terms of number average molecular weight (Mn), more preferably 40000-170000.

The measurement conditions of the number average molecular weight and the weight average molecular weight of the cellulose ester using high performance liquid chromatography are as follows.
Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (GL Science Co., Ltd.)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 100000 to 500 samples were used. It is preferable to obtain 13 samples at approximately equal intervals. Two or more types of cellulose esters may be used in combination.

  Next, the acrylic resin will be described. As the acrylic resin, a thermoplastic acrylic resin is preferable. For example, a thermoplastic acrylic resin having a molecular weight of tens of thousands to hundreds of thousands and a glass transition point of 20 to 105 ° C. is preferable. As these types of commercial products, 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 Methacrylic monomers there may be cited various homopolymers and copolymers were prepared as raw materials. The glass transition point can be determined by the method described in JIS-K7121.

  The concentration of the acrylic resin and cellulose ester resin in the alkaline solution is 0.05 to 50% by mass, more preferably 0.1 to 20% by mass. By using in these ranges, it exists stably in an alkaline solution, and the objective effect of this invention is easy to be exhibited.

  Other binders include, for example, vinyl chloride / vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, vinyl acetate / vinyl alcohol copolymer, partially hydrolyzed vinyl chloride / vinyl acetate copolymer, vinyl chloride / Vinyl polymers such as vinylidene chloride copolymer, vinyl chloride / acrylonitrile copolymer, ethylene / vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, or Copolymer, copolymer of maleic acid and / or acrylic acid, acrylate copolymer, acrylonitrile / styrene copolymer, chlorinated polyethylene, acrylonitrile / chlorinated polyethylene / styrene copolymer, methyl methacrylate / butadiene / Styrene copolymer, acrylic resin, poly Nyl 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, rubber-based resin such as butadiene / acrylonitrile resin, silicone Resin, fluorine resin and the like can be used in combination.

  Fine particles may be added to the alkaline solution in order to provide an antiblocking function. Examples of inorganic fine particles added include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, tin oxide, indium oxide, and zinc oxide. And ITO, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate.

  These fine particles include, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.), Seahoster KE-P10, KE-P30, KE- P50, KE-P100, KE-P150, and KE-P250 (above, manufactured by Nippon Shokubai Co., Ltd.) are commercially available and can be used. Among these, Aerosil 200V, Aerosil R972V, Seahoster KE-P30, KE-P50, and KE-P100 are particularly preferably used because they have a large anti-blocking effect while keeping haze low.

  The concentration of fine particles contained in the alkaline solution is preferably 0.1 to 50% by mass, more preferably 0.1 to 30% by mass.

  The increase in haze when an alkaline solution is applied is preferably 1% or less, more preferably 0.5% or less, and particularly preferably 0.0 to 0.1%.

  Further, the coefficient of dynamic friction of the surface coated with the alkaline solution is preferably 0.9 or less, particularly preferably 0.1 to 0.9.

  As an application method of the alkaline solution, a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, or spray coating, ink jet coating, etc. Although it is preferable to apply with a wet film thickness of 1 to 100 μm, it is particularly preferable that the thickness is 5 to 30 μm from the viewpoint that curl suppression is easily exhibited well.

  After application, it may be heat-dried and cured as necessary. The alkaline solution application can be applied in two or more steps.

  Moreover, you may have the process of adjusting a film base material to predetermined temperature beforehand, before apply | coating an alkaline solution. As means for adjusting the temperature of the film substrate, for example, direct heating by hot air collision (blowing), contact heat transfer by a heating roll, induction heating by microwaves, or radiant heat heating by an infrared heater can be used. Moreover, after adjusting the temperature of the film substrate, it may have a means for maintaining, specifically, collision of hot air against the opposite surface of the coating (blowing), contact heat transfer with a heating roll, induction heating with microwaves Radiant heat heating with an infrared heater can be preferably used. As the infrared heater, an electric, gas, oil or steam far infrared ceramic heater can be used.

  Moreover, you may have the process of scraping off an alkaline solution from a base film. In addition, the scraping process said here means the process of reducing the liquid quantity which exists on the film surface, diluting an alkaline solution after apply | coating an alkaline solution. Specifically, a method of applying an alkali diluent and spraying the alkali diluent can be mentioned. The alkali dilution liquid preferably has a surface tension of 20 to 60 mN / m or less at 35 ° C., more preferably 35 to 60 mN / m. If the surface tension is within this range, the surface of the base film coated with the alkaline solution tends to wet and spread, and the coated bead is stabilized.

  Furthermore, you may have the process (washing | cleaning process) of washing off the alkaline solution which could not be removed by scraping off from a base film.

  The washing step can be performed by a method of applying washing water, a method of spraying washing water, or a method of immersing the base film together in a container containing washing water. The method of applying the washing water and the method of spraying are preferable for carrying out the substrate film while carrying it continuously. The method of spraying the washing water is particularly preferable because turbulent mixing of the washing water on the base film and the alkaline coating liquid can be obtained by a jet.

  Moreover, you may perform the alkali saponification process mentioned later before and behind alkali solution application | coating.

<Hard coat layer>
Next, the hard coat layer according to the present invention will be described.

  First, the resin binder for forming the hard coat layer will be described. As the resin binder, an active energy ray curable resin is preferable. The active energy ray-curable resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams. As the active energy ray curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and the active energy ray curable resin layer is cured by irradiation with an active ray such as an ultraviolet ray or an electron beam. It is formed. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and the ultraviolet curable resin is particularly preferable from the viewpoint of excellent mechanical film strength (abrasion resistance, pencil hardness).

  As the ultraviolet curable resin, a polyfunctional acrylate is preferable. The polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. Here, the polyfunctional acrylate is a compound having two or more acryloyloxy groups and / or methacryloyloxy groups in the molecule.

  Examples of the polyfunctional acrylate monomer include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane triacrylate. , Tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerol triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Ritolol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, Tetramethylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetramethacrylate Acrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate, isobornyl acrylate and the like preferably. These compounds are used alone or in admixture of two or more. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient. The addition amount of the active energy ray-curable resin is preferably 15% by mass or more and less than 70% by mass in the solid content in the hard coat layer forming composition (hereinafter also referred to as hard coat layer coating solution).

  The hard coat layer preferably contains a photopolymerization initiator to accelerate the curing of the active energy ray curable resin. The amount of the photopolymerization initiator is preferably a mass ratio of photopolymerization initiator; energy active ray curable resin = 20: 100 to 0.01: 100.

  Specific examples of the photopolymerization initiator include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto.

  For the hard coat layer, a binder such as a thermoplastic resin, a thermosetting resin, or a hydrophilic resin such as gelatin can also be used. Further, the hard coat layer may contain particles of an inorganic compound or an organic compound in order to adjust slipperiness and refractive index.

  Inorganic particles used for the hard coat layer include silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin And calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. In particular, silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used.

  Organic particles include 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. An ultraviolet curable resin composition such as polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, or polyfluoroethylene resin powder can be added. Particularly preferred are cross-linked polystyrene particles (for example, SX-130H, SX-200H, SX-350H, manufactured by Soken Chemical), polymethyl methacrylate-based particles (for example, MX150, MX300, manufactured by Soken Chemical), and fluorine-containing acrylic resin fine particles. . Examples of the fluorine-containing acrylic resin fine particles include commercial products such as FS-701 manufactured by Nippon Paint. Examples of the acrylic particles include Nippon Paint: S-4000, and examples of the acrylic-styrene particles include Nippon Paint: S-1200, MG-251.

  The average particle diameter of these fine particle powders is preferably 0.01 to 5 μm, more preferably 0.1 to 5.0 μm, and particularly preferably 0.1 to 4.0 μm. Moreover, it is preferable to contain 2 or more types of microparticles | fine-particles from which a particle size differs. The ratio of the curable resin composition and the fine particles is desirably blended so as to be 0.1 to 30 parts by mass with respect to 100 parts by mass of the curable resin composition.

  In order to increase the heat resistance of the hard coat layer, an antioxidant that does not inhibit the photocuring reaction can be selected and used. Examples include hindered phenol derivatives, thiopropionic acid derivatives, phosphite derivatives, and the like. Specifically, for example, 4,4′-thiobis (6-tert-3-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) mesitylene, di-octadecyl-4- Examples thereof include hydroxy-3,5-di-tert-butylbenzyl phosphate.

  The hard coat layer forming composition may contain a solvent, or may be appropriately contained and diluted as necessary. Examples of the organic solvent contained in the coating solution include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), It can be appropriately selected from esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents, or a mixture thereof can be used. 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%.

  The hard coat layer has a center line average roughness (Ra) defined by JIS B 0601 of 0.001 to 0.1 μm, or a fine hard coat layer and Ra is adjusted to 0.1 to 1 μm. An antiglare hard coat layer may also be used. The center line average roughness (Ra) is preferably measured by an optical interference type surface roughness measuring instrument, and can be measured, for example, using a non-contact surface fine shape measuring device WYKO NT-2000 manufactured by WYKO.

  Further, in the antiglare hard coat layer, an uneven shape may be formed on the hard coat surface by embossing with a roll or a master.

  The hard coat layer may contain the fluorine compound or the silicone compound. Moreover, you may contain the surfactant shown below. Specifically, Kao Corporation make: Emulgen 102KG (6.3), Emulgen 103 (8.1), Emulgen 104P (9.6), Emulgen 105 (9.7), Emulgen 106 (10.5), Emulgen 108 (12.1), Emulgen 109P (13.6), Emulgen 120 (15.3), Emulgen 123P (16.9), Emulgen 147 (16.3), Emulgen 210P (10.7), Emulgen 220 (14.2), Emulgen 306P (9.4), Emulgen 320P (13.9), Emulgen 404 (8.8), Emulgen 408 (10.0), Emulgen 409PV (12.0), Emulgen 420 (13 .6), Emulgen 430 (16.2), Emulgen 705 (10.5), Emulgen 707 (12.1), Margen 709 (13.3), Emulgen 1108 (13.5), Emulgen 1118S-70 (16.4), Emulgen 1135S-70 (17.9), Emulgen 2020G-HA (13.0), Emulgen 2025G (15 .7), Emulgen LS-106 (12.5), Emulgen LS-110 (13.4), Emulgen LS-114 (14.0), Emulgen MS-110 (12.7), Emulgen A-60 (12) .8), Emulgen A-90 (14.5), Emulgen A-500 (18.0), Emulgen B-66 (13.2), Latemul PD-420 (12.6), Latemulu PD-430 (14 .4), Latemul PD-430S (14.4), Latemul PD-450 (16.2), Rheodor SP-L10 (8.6), Leo SP-P10 (6.7), Rhedol SP-S10V (4.7), Rhedol SP-S20 (4.4), Rhedol SP-O10V (4.3), Rhedol Super SP-L10 (8. 6), Rheodor AS10V (4.7), Rheodor AO-10V (4.3), Rhedol AO-15V (3.7), Emazole L-10V (8.6), Emazole P-10V (6.7) , Emazole S-10V (4.7), Emazole O-10V (4.3), Rhedol TW-L120 (16.7), Rhedol TW-L106 (13.3), Rhedol TW-P120 (15.6) , Rhedol TW-S120V (14.9), Rheodor TW-S106V (9.6), Rhedol TW-S320V (10.5), Rhedol TW-O120V (1 5.0), Rheodor TW-O106V (10.0), Rheodor TW-O320V (11.0), Rheodor Super TW-L120 (16.7), Rheodor 430V (10.5), Rheodor 440V (11. 8), Rhedol 460V (13.8), Rhedol MS-60 (3.5), Rhedol MS-165V (11.0), Excel T-95 (3.8), Excel VS-95 (3.8) , Excel O-95R (3.5), Excel 200 (3.5), Excel 122V (3.5), Emanon 1112 (13.7), Emanon 4110 (11.6), Emanon CH-25 (10. 7), Emanon CH-40 (12.5), Emanon CH-60 (K) (14.0), Emanon CH-80 (15.0), Amite 102 ( .3), Amit 105 (9.8), Amit 105A (10.8), Amit 302 (5.1), Amit 320 (15.4), Aminone PK-02S (5.5), Aminone L-02 (5.8), manufactured by Nissin Chemical Industry Co., Ltd .: Surfinol 104E (4), Surfinol 104H (4), Surfinol 104A (4), Surfinol 104BC (4), Surfinol 104DPM (4), Surfy Nord 104PA (4), Surfinol 104PG-50 (4), Surfinol 104S (4), Surfinol 420 (4), Surfinol 440 (8), Surfinol 465 (13), Surfinol 485 (17), Surfinol SE (6), Surfinol SE-F (6), Surfinol 61 (6), Sir Inol 604 (8), Surfinol 2502 (8), Surfinol 82 (4), Surfinol DF110D (3), Surfinol CT111 (8-11), Surfinol CT121 (11-15), Surfinol CT136 (13 ), Surfinol TG (9), Surfinol GA (13), Orphine STG (9-10), Orphin E1004 (7-9), Orphin E1010 (13-14), Shin-Etsu Chemical Co., Ltd .: X-22 -4272 (7), X-22-6266 (8), KF-351 (12), KF-352 (7), KF-353 (10), KF-354L (16), KF-355A (12), KF-615A (10), KF-945 (4), KF-618 (11), KF-6011 (12), KF-601 5 (4), KF-6004 (5), and the like. Figures in parentheses indicate HLB values. The HLB value is Hydrophile-Lipophile-Balance, hydrophilic-lipophilic-balance, and is a value indicating the hydrophilicity or lipophilicity of a compound. The smaller the HLB value, the higher the lipophilicity, and the higher the value, the higher the hydrophilicity.

  The fluorine compound, silicone compound and surfactant have a mass ratio of the fluorine compound, silicone compound and surfactant: active energy ray curable resin = 0.05: 100 to 5 with respect to the active energy ray curable resin. It is stably used in the hard coat layer forming composition and in the hard coat layer.

  The hard coat layer further has a vinyl group and a carboxyl group in the side chain of the polyurethane resin as a curing aid, has a weight average molecular weight of 10,000 to 30,000, and a double bond equivalent of 500 to 2,000. An acrylic polymer having a vinyl group in a polymer or a side chain of the polymer, having a weight average molecular weight (Mw) of 10,000 or more and 100,000 or less, a double bond equivalent of 1,000 or less, and a polymer Tg of −50 ° C. or more and 120 ° C. or less, Other functional thiol compounds may be included. Examples of other functional thiol compounds include 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like. Commercially available products include Showa Denko Co., Ltd., trade name Karenz MT series, and the like.

  Moreover, you may contain a fluorine-acrylic copolymer resin. The fluorine-acrylic copolymer resin is a copolymer resin composed of a fluorine monomer and an acrylic monomer, and a block copolymer composed of a fluorine monomer segment and an acrylic monomer segment is particularly preferable. The molecular weight of the fluorine-acrylic copolymer resin may be 5,000 to 1,000,000, preferably 10,000 to 300,000, and more preferably 10,000 to 100,000 in terms of number average molecular weight. In the production of the fluorine-acrylic copolymer resin, polymeric peroxide was used as a polymerization initiator. It can be produced by a known production process (for example, Japanese Patent Publication No. 5-41668 and Japanese Patent Publication No. 5-59942). Polymeric peroxide is a compound having two or more peroxy bonds in one molecule. As the polymer peroxide, one or more of various polymer peroxides described in JP-B-5-59942 can be used. As a commercial item of fluorine-acrylic copolymer resin, the brand name of Nippon Oil & Fat Co., Ltd. Modiper F-200, Modiper F-600, Modiper F-2020, etc. are mentioned.

  Moreover, it is preferable that the refractive index of a hard-coat layer is adjusted to the range of 1.4-2.2 by 23 degreeC and wavelength 550nm measurement. The means for adjusting the refractive index can be achieved by adding metal oxide fine particles and the like. Metal oxide The metal oxide fine particles used preferably have a refractive index of 1.80 to 2.60, more preferably 1.85 to 2.50.

  The kind of metal oxide fine particles is not particularly limited, and Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S A metal oxide having at least one element selected from the group consisting of Al, In, Sn, Sb, Nb, a halogen element, Ta and the like is doped with a minute amount of atoms. May be. A mixture of these may also be used. In the present invention, at least one metal oxide fine particle selected from among zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium-tin oxide (ITO), antimony-doped tin oxide (ATO), and zinc antimonate is used. It is particularly preferable to use it as the main component. In particular, it is preferable to contain zinc antimonate particles.

  The average particle diameter of the primary particles of these metal oxide fine particles is in the range of 10 nm to 200 nm, particularly preferably 10 to 150 nm. The average particle diameter of the metal oxide fine particles can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc. If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze is remarkably increased, which is not preferable. The shape of the metal oxide fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape.

  The metal oxide fine particles may be surface-treated with an organic compound. By modifying the surface of the metal oxide fine particles with an organic compound, the dispersion stability in an organic solvent is improved, the dispersion particle size can be easily controlled, and aggregation and sedimentation over time can be suppressed. . For this reason, the surface modification amount with a preferable organic compound is 0.1 mass%-5 mass% with respect to metal oxide particle, More preferably, it is 0.5 mass%-3 mass%. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, silane coupling agents are preferred. Two or more kinds of surface treatments may be combined.

  The hard coat layer may contain a π-conjugated conductive polymer. The π-conjugated conductive polymer can be used as long as it is an organic polymer having a main chain composed of a π-conjugated system. Examples thereof include polythiophenes, polypyrroles, polyanilines, polyphenylenes, polyacetylenes, polyphenylene vinylenes, polyacenes, polythiophene vinylenes, and copolymers thereof. From the viewpoint of ease of polymerization and stability, polythiophenes, polyanilines, and polyacetylenes are preferable.

  The π-conjugated conductive polymer can provide sufficient conductivity and solubility in a binder resin even if it is not substituted, but in order to further improve conductivity and solubility, an alkyl group, a carboxy group, a sulfo group, an alkoxy group. A functional group such as a group, a hydroxy group, or a cyano group may be introduced.

Moreover, you may contain an ionic compound. The ionic compounds, imidazolium, pyridinium-based, alicyclic amine-based, aliphatic amine, cations and _BF ⁴ aliphatic phosphonium -, PF ₆ ^- inorganic ion system such, _CF 3 SO ₂ ^- , (CF ₃ SO ₂ ) ₂ N ⁻ , CF ₃ CO ₂ ^—, etc. Examples of the ionic compound include anionic polymer compounds such as those described in JP-B-49-23828, JP-A-49-23827, and JP-A-47-28937, JP-B-55-734, and JP-A-50-54672. Ionene type polymer having a dissociating group in the main chain, as shown in JP-B-59-14735, JP-B-57-18175, JP-B-57-18176, 57-56059, etc. No. 57-15376, No. 53-45231, No. 55-145783, No. 55-65950, No. 55-67746, No. 57-11342, No. 57-19735, No. 58-56858. No., JP-A 61-27853, 62-9346, and a cationic pendant type having a cationic dissociation group in the side chain And the like can be given Rimmer. It is also desirable to contain an ionene conductive polymer described in JP-A-9-203810 or a quaternary ammonium cation conductive polymer having intermolecular crosslinking (for example, P-1 shown below). The polymer compounds described above are generally in the particle size range of about 0.05 μm to 0.5 μm, preferably in the range of 0.05 μm to 0.2 μm. The ratio of the polymer to the binder is preferably 10 to 400 parts by mass of the binder with respect to 100 parts by mass of the polymer, particularly preferably 100 parts by mass of the binder with respect to 100 parts by mass of the polymer. -200 parts by mass.

  In addition, as a color correction filter for various display elements, a color tone adjusting agent (dye or pigment) having a color tone adjusting function, an electromagnetic wave blocking agent, an infrared absorbing agent, or the like may be included.

  Examples of the coating method of the hard coat layer coating liquid include a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, spray coating, and inkjet coating.

  It is preferable to apply a wet film thickness of 0.1 to 100 μm on one surface of the base film using the coating method.

  In the present invention, the film thickness (dry film thickness) of the hard coat layer is not less than 10 μm, preferably not less than 10 μm and not more than 40 μm, more preferably not less than 12 μm and not more than 20 μm, because high hardness and curl suppression are satisfactorily exhibited. It is as follows.

  High hardness is also desired from the use on the surface of a display device such as an LCD, and because it is difficult to be scratched in the polarizing plate forming step, and as a high hardness condition in the present invention, a pencil hardness which is an index of hardness is preferably 3H or more, more preferably 4H or more.

  For the pencil hardness, the prepared hard coat film is conditioned at a temperature of 23 ° C. and a relative humidity of 55% for 2 hours or more, and then using a test pencil specified by JIS S 6006, the pencil hardness specified by JIS K 5400. It is the value measured according to the evaluation method.

The hard coat layer of the present invention may be formed by heating and drying after application by the above-described method, and curing as necessary. The curing step is preferably performed by heat treatment or UV curing treatment. As a light source for UV curing treatment, any light source that generates ultraviolet rays can be used without 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. Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 5 to 1000 mJ / cm ² , preferably 50 to 500 mJ / cm 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 500 N / m. The method for applying tension is not particularly limited, and tension may be applied in the conveying direction on the back roll, or tension may be applied in the width direction or biaxial direction by a tenter. This makes it possible to obtain a film with further excellent flatness. The hard coat layer may be a single layer or a multilayer structure of two or more layers.

  The heat treatment is 40 ° C. or higher, more preferably 60 ° C. or higher. Further, the upper limit temperature is appropriately set from the characteristics of the base film.

  The heat treatment is preferably performed while applying a tension in the film transport direction or the width direction, and the applied tension is preferably 50 to 500 N / m, and more preferably 250 to 500 N / m.

  The width tension applying method is not particularly limited, and may be a free span, a back roll or the like. In addition, a method of applying tension using a width regulating device in the width direction is also effective, preferably stretching by 3.0% or less, more preferably by stretching by 0.05% to 1.0%. Is more effective. Thereby, a film excellent in blocking resistance can be obtained.

  The hard coat layer may be subjected to the following surface treatment. Examples of the surface treatment method include a cleaning method, an alkali saponification treatment method, a plasma treatment method, an electron beam method, an ion beam method, a sputtering method, an acid treatment, a corona treatment method, and an atmospheric pressure glow discharge plasma method.

  The alkali saponification treatment is generally carried out in a cycle in which the film is immersed in an alkali solution, washed with water and dried. Further, after the alkali treatment, neutralization in an acidic water step may be performed, followed by washing with water and drying. Examples of the alkaline solution include a potassium hydroxide solution and a sodium hydroxide solution, and the prescribed concentration of hydroxide ions is preferably 0.1 to 3N, and more preferably 0.5N to 2N. Adhesiveness between the hard coat layer and the low refractive index layer can be obtained by setting the content in the above range. The temperature of the alkaline solution is preferably in the range of 25 to 90 ° C., more preferably 40 to 70 ° C., from the viewpoint of precipitation of the alkaline solution. The alkali treatment time is 5 seconds to 5 minutes, preferably 30 seconds to 3 minutes.

  The alkali saponification treatment may be performed by applying an alkali solution to the hard coat layer surface, and for example, the methods described in JP-A Nos. 2003-313326 and 2007-332253 may be used.

  Examples of the plasma treatment include flame plasma treatment, atmospheric pressure plasma treatment, and atmospheric pressure plasma treatment.

  As plasma treatment, plasma treatment techniques disclosed in Japanese Patent Application Laid-Open Nos. 2004-352777, 2004-352777, 2007-314707, and the like can also be referred to.

  Moreover, the pure water contact angle of the hard coat layer surface after the surface treatment is 60 ° or less, for example, when a low refractive index layer is provided on the hard coat layer, the adhesion between the hard coat layer and the hard coat layer is improved. preferable. The contact angle can be measured based on JIS K 2396.

<Antireflection film>
In the hard coat film according to the present invention, a low refractive index layer is laminated on the hard coat layer directly or via another layer to form an antireflection film, in order to increase the visibility when incorporated in an image display device. This is a preferred embodiment.

(Low refractive index layer)
A low refractive index layer means a layer lower than the refractive index of a film base material. A specific refractive index is preferably in the range of 1.20 to 1.45 at 23 ° C. and a wavelength of 550 nm. Further, the film thickness of the low refractive index layer is preferably 5 nm to 0.5 μm, more preferably 10 nm to 0.3 μm, and further preferably 30 nm to 0.2 μm, from the characteristics as an optical interference layer.

  The low refractive index layer is composed of an organic silicon compound or a hydrolyzate thereof or a polycondensate thereof, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin, It is formed from fluoroacrylate, fluorine-containing polymer or the like. Examples of the fluoropolymer include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.) (meta ) A part of acrylic acid or a fully fluorinated alkyl ester derivative (for example, Biscoat 6FM (manufactured by Osaka Organic Chemical) or M-2020 (manufactured by Daikin)), a fully or partially fluorinated vinyl ether or the like. Among these, an organic silicon compound having 1 to 4 carbon atoms, a hydrolyzate thereof, or a polycondensate thereof, specifically, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, etc., or these A hydrolyzate or a polycondensate is mentioned.

  The low refractive index layer contains magnesium fluoride or at least one inorganic particle selected from the group consisting of hollow silica-based particles having an outer shell layer and porous or hollow inside. Is preferred.

  Examples of magnesium fluoride include isopropanol-dispersed magnesium fluoride sol manufactured by Nissan Chemical Industries, Nanotech series manufactured by CI Kasei.

  Specific examples of hollow silica-based particles having an outer shell layer and having a porous or hollow interior include (1) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles, or ( 2) Cavity particles having a cavity inside and filled with a solvent, gas or porous substance.

  A hollow particle is a particle having a cavity inside, and the cavity is surrounded by a particle wall. The cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation. The average particle size of such hollow silica-based particles is 5 to 200 nm, preferably 10 to 70 nm. The particle size of the hollow silica particles is preferably monodispersed with a coefficient of variation of 1 to 40%.

  The average particle diameter of the hollow silica particles used in the present invention can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc.

  The average particle diameter of the hollow silica-based particles is appropriately selected according to the thickness of the transparent film of the low refractive index layer to be formed, and is 3/2 to 1/10, preferably 2/3, of the film thickness of the transparent film. 1/10 is desirable. These hollow silica 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), ketone alcohol (for example, diacetone alcohol), propylene monomethyl ether, propylene glycol monomethyl ether acetate and the like are preferable. .

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is 1 to 40 nm, preferably 1 to 20 nm, more 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 the coating liquid component can easily enter the composite particles to reduce the internal porosity. However, the effect of lowering the refractive index may not be obtained sufficiently. In addition, when the thickness of the coating layer exceeds 20 nm, the coating liquid component does not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of lowering the refractive index cannot be sufficiently obtained. Sometimes.

  In the case of hollow particles, when the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even when the thickness exceeds 20 nm, the effect of lowering the 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.

Moreover, components other than silica may be contained, specifically, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , _{sb 2 O 5, SbO 2,} 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 , Sb ₂ O ₅ , SbO ₂ and MoO _3. , ZnO ₂ , WO ₃ or one or more of them can be mentioned. In such porous particles, the molar ratio when the silica is represented by SiO ₂ and the inorganic compound other than silica is represented by oxide (MOx): MOx / SiO ₂ is 0.0001 to 1.0, preferably Is preferably in the range of 0.001 to 0.3.

A porous particle having a molar ratio of MOx / SiO ₂ of less than 0.0001 is difficult to obtain, and even if obtained, a pore volume is small and particles having a low refractive index cannot be obtained. Further, when the molar ratio of the porous particles: MOx / SiO ₂ exceeds 1.0, the ratio of silica decreases, so that the pore volume increases and it may be difficult to obtain a material having a lower refractive index.

  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. When the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained, and when the pore volume exceeds 1.5 ml / g, the strength of the 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 determined by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous substance used at the time of preparing the particles. The solvent may contain an unreacted particle precursor used when preparing the hollow particles, the catalyst used, and the like.

  Moreover, what consists of the compound illustrated by the 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 hollow particles, for example, the method for preparing composite oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is preferably employed. Specifically, when the composite particles are composed of silica and an inorganic compound other than silica, hollow particles can be produced by carrying out 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 mixed aqueous solution of a silica raw material and an inorganic compound raw material other than silica is prepared in advance. According to the composite ratio of the target composite oxide, a porous particle precursor is prepared by gradually adding it to an alkaline aqueous solution having a pH of 10 or more while stirring.

  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 And salts and quaternary ammonium salts. More specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium acid, 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, and usually these sols are used. be able to. 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 an aqueous solution of the above compound is added to the alkaline aqueous solution while stirring. Also in this case, it is not always necessary to control the pH of the dispersion. When seed particles are used in this way, it is easy to control the particle size of the porous particles to be prepared, and particles with uniform particle sizes 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 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 particles.

The composite ratio of silica and an 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 silica proportion 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 compounds other than silica from porous particles)
In the second step, at least a part of inorganic compounds other than silica (elements other than silicon and oxygen) is selectively removed from the porous particle precursor obtained in the first step. 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, fluorine-substituted, obtained by dealkalizing an alkali metal salt of silica into the porous particle precursor dispersion obtained in the first step. It is preferable to add a silicic acid solution containing an alkyl group-containing silane compound or a hydrolyzable organosilicon compound to form a silica protective film. The thickness of the silica protective film may be 0.5 to 40 nm, preferably 0.5 to 15 nm. Even if a silica protective film is formed, the protective film in this step is porous and thin, so it is possible to remove inorganic compounds other than silica from the porous particle precursor. is there.

  By forming such a silica protective film, inorganic compounds other than 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. be able to. 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.

  Further, 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 body, 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.

  As the hydrolyzable organosilicon compound used for forming the silica protective film, an alkoxysilane represented by the following general formula (1) can be used.

R ″ _m Si (OR ′) _4-m (1)
(In the formula, R ″ and R ′ represent a hydrocarbon group such as an alkyl group, an aryl group, a vinyl group, and an acrylic group, and m represents 0, 1, 2, or 3.)
In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane substituted with fluorine are preferably used.

  As a method of addition, 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 porous particles, and then alkoxysilane, pure water, and alcohol are added. A solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of the above is added to a dispersion of porous particles, and a silicic acid polymer produced by hydrolyzing alkoxysilane is deposited on the surface of 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.

(3rd process: Formation of a silica coating layer)
In the third step, a hydrolyzable organosilicon compound or silica containing a fluorine-substituted alkyl group-containing silane compound is added to the porous particle dispersion (in the case of hollow particles, a hollow particle precursor dispersion) prepared in the second step. By adding an acid solution or the like, the surface of the particles is coated with a hydrolyzable organosilicon compound or a polymer such as a silicic acid solution to form a silica coating layer.

  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 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 40 nm, Preferably, it is added in an amount of 1 to 20 nm in a dispersion of porous particles (in the case of hollow particles, hollow particle precursor). 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 40 nm, preferably 1 to 20 nm. The

  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 lowering the refractive index may not be obtained.

  The refractive index of the hollow silica particles thus obtained is as low as less than 1.42. Such hollow silica-based particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow.

  Further, from the viewpoint of stability at the time of the coating composition, the hollow silica-based particles are preferably those in which a polymer having a hydrocarbon main chain is covalently bonded to the surface.

  Next, hollow silica particles in which a polymer having a hydrocarbon main chain is covalently bonded will be described.

  The polymer having a hydrocarbon main chain is a direct covalent bond, or a binder is interposed between the silica on the surface of the hollow silica-based particle and the polymer having the hydrocarbon main chain, and the silica and the binder are covalently bonded. It also refers to those in which the binder and the polymer are covalently bonded. As the binder, a coupling agent is preferably used.

  Hollow particles to which a polymer having a hydrocarbon main chain is covalently bonded (1) Forms a covalent bond with the surface of the hollow silica particle in the state where the surface of the hollow silica particle is untreated or treated with a coupling agent or the like. A method in which a polymer having a functional group is reacted and the polymer is grafted on the surface of the hollow silica particle; or (2) the hollow silica system in a state where the surface of the hollow silica particle is untreated or treated with a coupling agent or the like. It can be produced by a method of polymerizing a monomer from the particle surface to grow a polymer chain and surface grafting. As a specific manufacturing method, the method described in JP-A-2006-257308 can be used.

  In the above production method, from the viewpoint of improving the surface modification rate, a method of polymerizing a monomer from the surface of the hollow silica-based particle to grow a polymer chain and grafting the surface is preferable. More preferred is a method in which hollow silica-based particles are surface-treated with a coupling agent containing a functional group having a polymerization initiating ability or a chain transfer ability, monomers are polymerized therefrom, polymer chains are grown, and surface grafting is performed. As a surface treatment agent (coupling agent) for introducing a functional group having a polymerization initiating ability or a chain transfer ability into hollow silica particles, an alkoxy metal compound (for example, a titanium coupling agent, an alkoxysilane compound (silane coupling) Agent)) is preferably used.

  The hollow silica particles may contain two or more kinds of hollow silica particles having different average particle diameters.

  Further, among the hollow silica-based particles, hollow silica-based particles having a conductive metal oxide coating layer are preferable in that the object and effects of the present invention are better exhibited. The metal oxide for forming the conductive metal oxide coating layer is not particularly limited. For example, tin oxide, antimony tin oxide, indium tin oxide, antimony oxide, aluminum zinc oxide, gallium zinc oxide, and these The thing chosen from the mixture of these is mentioned. Among these, hollow silica particles coated with antimony oxide are particularly preferable.

  The average thickness of the conductive metal oxide coating layer is in the range of 1 to 40 nm, more preferably 1 to 20 nm, the hollow silica-based particles can be sufficiently coated, and the resulting conductive metal oxide-coated hollow silica system The thickness of the coating layer is preferably 1 nm or more in that the conductivity of the particles is sufficient. The thickness of the coating layer is preferably 40 nm or less in that the effect of improving the conductivity is sufficient and the refractive index is sufficient even when the average particle size of the conductive metal oxide-coated hollow silica-based particles is small.

  Among the hollow silica particles having a conductive metal oxide coating layer, hollow silica particles having an antimony oxide coating layer are particularly preferable. Next, hollow silica-based particles having an antimony oxide coating layer will be described.

The antimony oxide may be any of Sb ₂ O ₃ , Sb ₂ O ₅ , SbO _2, etc., and the antimony oxide coating layer may contain tin oxide or the like. The total content of these antimony oxides in the antimony oxide coating layer is preferably 10% or more. The antimony oxide coating layer may be further coated with silica or the like.

  The volume resistance value of the antimony oxide-coated hollow silica particles is preferably 10 to 5000 Ω / cm, and more preferably 10 to 2000 Ω / cm. By setting the volume resistance value within this range, the surface resistance of the low refractive index coating film can be lowered while keeping the refractive index of the particles low. The volume resistance value can be controlled by adjusting the particle size of the core particles, the film thickness of the surface-coated metal oxide layer, and the composition.

  The volume resistance value can be measured by the following method.

Using a ceramic cell with a cylindrical hollow (cross-sectional area 0.5 cm ² ) inside, place the cell on the gantry electrode, fill it with 0.6 g of sample powder, By inserting protrusions, pressurizing the upper and lower electrodes with a hydraulic machine, measuring the resistance value (Ω) and the sample height (cm) when 100 kg / cm ^{2 is} applied, and multiplying the resistance value by the height Asked.

  A method for producing antimony oxide-coated hollow silica particles will be described.

  First, a dispersion of porous silica-based particles or silica-based particles having cavities inside is prepared by the method described above. The solid content concentration of the dispersion is preferably in the range of 0.1 to 40% by mass, more preferably 0.5 to 20% by mass. When the solid content concentration is less than 0.1% by mass, the production efficiency is low, and when the solid content concentration exceeds 40% by mass, the resulting antimony oxide-coated hollow silica-based particles may agglomerate, and the transparency of the film May decrease or haze may deteriorate.

  Also, an antimonic acid dispersion (aqueous solution) is prepared. The antimonic acid preparation method is not particularly limited as long as the antimony oxide coating layer can be formed on the particle surface without filling the pores and cavities of the porous silica particles or the silica particles having cavities inside. However, the following method is preferable because a uniform and thin antimony oxide coating layer can be formed.

  Specifically, an alkali antimonate aqueous solution is treated with a cation exchange resin to prepare an antimonic acid (gel) dispersion, and then treated with an anion exchange resin. As the alkali antimonate aqueous solution, for example, an alkali antimonate aqueous solution used in a method for producing an antimony oxide sol described in JP-A-2-180717 is suitable.

The alkali antimonate aqueous solution is preferably obtained by reacting antimony trioxide (Sb ₂ O ₃ ), an alkali substance and hydrogen peroxide, and the molar ratio of antimony oxide, alkali substance and hydrogen peroxide is 1: 2.0 to 2.5: 0.8 to 1.5, preferably 1: 2.1 to 2.3: 0.9 to 1.2, and the system containing antimony trioxide and an alkaline substance is peroxidized. It is obtained by adding hydrogen at a rate of 0.2 mol / hr or less per mol of antimony trioxide.

The antimony trioxide used at this time is preferably a powder, particularly a fine powder having an average particle size of 10 μm or less, and examples of the alkaline substance include LiOH, KOH, NaOH, Mg (OH) ₂ , and Ca (OH). _2, etc. Among them, alkali metal hydroxides such as KOH and NaOH are preferable. These alkaline substances have the effect of stabilizing the resulting antimonic acid solution.

  First, a predetermined amount of an alkaline substance and antimony trioxide are added to water to prepare an antimony trioxide suspension. The antimony trioxide concentration of the antimony trioxide suspension is desirably in the range of 3 to 15% by mass as Sb2O3. Next, this suspension is heated to 50 ° C. or higher, preferably 80 ° C. or higher, and hydrogen peroxide water having a concentration of 5 to 35% by mass is added to antimony trioxide at 0.2 mol / hr or less per mol. Add at a rate of When the hydrogen peroxide solution is added at a rate higher than 0.2 mol / hr, the particle size of the obtained antimony oxide particles is increased, and the particle size distribution is widened, which is not preferable. Moreover, since productivity is bad when the addition rate of hydrogen peroxide water is very slow, a preferable addition rate range is 0.04 to 0.2 mol / hr.

The alkali antimonate aqueous solution (when MHSbO ₃ : M is an alkali metal) obtained by the above reaction is separated from an undissolved residue as necessary, and further diluted as necessary, and treated with a cation exchange resin. Then, an antimonic acid gel (HSbO ₃ ⁻ ) n dispersion is prepared by removing alkali ions.

  The alkali antimonate aqueous solution may contain an aqueous solution containing a doping agent such as an alkali stannate aqueous solution or a sodium phosphate aqueous solution. When such a doping agent is contained, antimony oxide-coated hollow silica-based particles having higher conductivity can be obtained.

Here, antimonic acid can be represented by (HSbO ₃ ⁻ ) n (polymer of n = 2 or more), and is composed of a polymer of antimonic acid (HSbO ₃ ⁻ ) having a particle diameter of about 1 to 5 nm, and is a fine particle Are aggregated to form a gel state.

  The concentration of the alkali antimonate aqueous solution when it is treated with the cation exchange resin is preferably in the range of 0.01 to 5% by mass, more preferably 0.1 to 3% by mass as the solid content Sb2O5. If the solid content is less than 0.01% by mass, the production efficiency is low, and if it exceeds 5% by mass, large aggregates of antimonic acid may be formed, and it is difficult to coat the hollow silica particles with antimonic acid. In some cases, it may become non-uniform.

  The amount of the cation exchange resin used is preferably such that the pH of the resulting antimonic acid dispersion is in the range of 1 to 4, and more preferably in the range of 1.5 to 3.5. When the pH is less than 1, there is a tendency that aggregated particles are generated instead of chain particles, and when the pH exceeds 4, monodispersed particles tend to be generated. In addition, when the pH is less than 1, the solubility of antimony oxide is high, so that it is difficult to coat a predetermined amount of antimony oxide. When the pH exceeds 4, the obtained antimony oxide-coated hollow silica-based particles may be aggregated. In some cases, the dispersibility in the film may be reduced, and the antistatic effect may be insufficient.

  Next, the antimonic acid dispersion and porous silica-based particles or a dispersion of silica-based particles having cavities inside are mixed and aged at 50 to 250 ° C., preferably 70 to 120 ° C., usually for 1 to 24 hours. By performing this, an antimony oxide-coated hollow silica-based particle dispersion can be obtained.

The mixing ratio of the antimonic acid dispersion and the silica-based particle dispersion is 1 to 200 parts by weight, preferably ₅ to 100 parts by weight, with silica-based particles as solids and 100 parts by weight, and antimonic acid as Sb ₂ O _5. Add as follows. When the mixing ratio of antimonic acid is less than 1 part by mass, the coating is uneven or the thickness of the coating layer is insufficient, and the effect of coating with antimony oxide, sand splitting, and the effect of imparting and improving conductivity are obtained. You may not get enough. Even when the mixing ratio of antimonic acid exceeds 200 parts by mass, the antimony oxide that does not contribute to the coating does not increase, and the conductivity of the obtained antimony oxide-coated hollow silica-based particles is not further improved. May be higher than 60.

  It is preferable that the density | concentration of the mixed dispersion exists in the range of 1-40 mass% as solid content, and also 2-30 mass%. When the concentration of the mixed dispersion is less than 1% by mass, the coating efficiency of antimony oxide is insufficient or the production efficiency is lowered. On the other hand, when it exceeds 40 mass%, when the amount of antimonic acid used is large, the resulting antimony oxide-coated hollow silica-based particles may aggregate.

  In addition, the low refractive index layer may contain the following colloidal silica.

  Colloidal silica is obtained by dispersing silicon dioxide in water or an organic solvent in a colloidal form, and is not particularly limited, and is spherical, acicular or beaded.

  The average particle size of the colloidal silica is preferably in the range of 50 to 300 nm, and is preferably monodispersed with a coefficient of variation of 1 to 40%. The average particle diameter can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc.

  Colloidal silica is commercially available, and examples thereof include the Snowtex series of Nissan Chemical Industries, the Cataloid-S series of Catalytic Chemical Industry, and the Lebasil series of Bayer. Further, bead-like colloidal silica in which primary particles of colloidal silica or silica cation-modified with alumina sol or aluminum hydroxide are bonded to each other with metal ions having a valence of 2 or more and connected in a bead shape is also preferably used. There are beaded colloidal silicas such as SNOWTEX-AK series, SNOWTEX-PS series, SNOWTEX-UP series of NISSAN CHEMICAL INDUSTRIES, and specifically IPS-ST-L (isopropanol dispersion, particle size 40-50 nm, Solid content 30%), MEK-ST-MS (methyl ethyl ketone dispersion, particle diameter 17-23 nm, solid content 35) and the like.

  The low refractive index layer preferably contains a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as oxalic acid, acetic acid, formic acid and methanesulfonic acid, inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia, and organic acids such as triethylamine and pyridine. Examples include bases, metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium, metal chelate compounds described later, and the like. Among them, acid catalysts and metal chelate compounds are preferably used.

  As the acid catalyst, hydrochloric acid, sulfuric acid, oxalic acid, acetic acid, phthalic acid and the like are preferably used. As the metal chelate compound, a chelate compound having a metal selected from Zr, Ti, and Al as a central metal can be suitably used without particular limitation.

  Specific examples include tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethyl acetoacetate) zirconium, n-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (n-propyl acetoacetate) zirconium, tetrakis ( Zirconium chelate compounds such as acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetate) titanium, diisopropoxybis (acetylacetone) titanium, etc. Titanium chelate compound, diisopropoxyethyl acetoacetate aluminum, diisopropoxyacetylacetonate aluminum , Isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonatobis (ethylacetoacetate) aluminum, etc. Examples of the aluminum chelate compound.

  Of these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are particularly preferably used. These metal chelate compounds can be used either alone or in combination.

  The low refractive index layer preferably contains an organosilicon compound represented by the following general formula (2), a hydrolyzate thereof, or a polycondensate thereof.

R2 _m SiX2 _4-m (2)
In the formula, R2 is a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, X2 is a hydroxyl group or a hydrolyzable substituent, and m is an integer of 0 to 3.

  Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, s-butyl group, hexyl group, decyl group, hexadecyl group and the like. Examples of the aryl group include a phenyl group and a naphthyl group.

  Examples of the hydrolyzable substituent for X2 include an alkoxy group, a halogen group, and a carboxyl group.

  Specific examples include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane. , Hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, isobutyltrimethoxysilane, trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltri Methoxyethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-glycidoxypropi Trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltrimeth Sisilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-1,3-dimethylbutylidenepropylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercapto Examples thereof include propyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane, p-styryltrimethoxysilane, diethylsilane and the like, and these are used alone or in admixture of two or more.

  The coating composition for forming the low refractive index layer preferably contains an organic solvent. Specific examples of organic solvents include alcohols (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), 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 Group hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate. Of these, toluene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, isopropanol, and propylene glycol monomethyl ether are particularly preferable.

  The solid content concentration in the coating composition for forming the low refractive index layer is preferably 1 to 4% by mass. By setting the solid content concentration to 4% by mass or less, coating unevenness is less likely to occur, and 1% by mass. By setting it as% or more, the drying load is reduced.

  The coating composition for forming the low refractive index layer preferably contains a fluorine compound or a silicone surfactant. Inclusion of the surfactant is effective for reducing coating unevenness and improving the antifouling property of the film surface.

  The fluorine-based compound is a monomer, oligomer, or polymer containing a perfluoroalkyl group as a mother nucleus, and includes derivatives such as polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene, and the like. Examples of commercially available products include Surflon “S-381”, “S-382”, “SC-101”, “SC-102”, “SC-103”, and “SC-104” (all manufactured by Asahi Glass Co., Ltd.). FLORARD "FC-430", "FC-431", "FC-173" (all made by Fluorochemicals-Sumitomo 3M), F-top "EF352", "EF301", "EF303" (all Shin-Akita Kasei Co., Ltd.) Company made), Schwegower "8035", "8036" (both made by Schwegman), "BM1000", "BM1100" (both made by BM Himmy), Megafuck "F-171", "F -470 "(all manufactured by Dainippon Ink & Chemicals, Inc.).

  The content rate of a fluorine-type compound is 0.05-5 mass% in a coating composition, Preferably it is 0.1-2 mass%. One or two or more fluorine compounds can be used in combination.

  Next, the silicone surfactant will be described.

  Silicone surfactants can be broadly classified into straight silicone oils and modified silicone oils depending on the type of organic group bonded to the silicon atom.

  Here, the straight silicone oil refers to one in which a methyl group, a phenyl group, or a hydrogen atom is bonded as a substituent. A modified silicone oil is one having a component that is secondarily derived from a straight silicone oil. On the other hand, it can be classified from the reactivity of silicone oil. These are summarized as follows.

(Silicone oil)
1. Straight silicone oil 1-1. Non-reactive silicone oil: dimethyl, methylphenyl substitution, etc.

1-2. Reactive silicone oil: methyl hydrogen substitution and the like.
2. Modified silicone oil Modified silicone oil is born by introducing various organic groups into dimethyl silicone oil.

  2-1. Non-reactive modified silicone oil: alkyl, alkyl / aralkyl, alkyl / polyether, polyether, higher fatty acid ester substitution, etc.

  The alkyl / aralkyl-modified silicone oil is a silicone oil in which a part of the methyl group of dimethyl silicone oil is substituted with a long-chain alkyl group or a phenylalkyl group.

  The polyether-modified silicone oil is a surfactant in which hydrophobic dimethyl silicone is introduced into hydrophilic polyoxyalkylene.

  The higher fatty acid-modified silicone oil is a silicone oil in which a part of the methyl group of dimethyl silicone oil is replaced with a higher fatty acid ester.

  The amino-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is substituted with an aminoalkyl group.

  The epoxy-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is substituted with an epoxy group-containing alkyl group.

  The carboxyl-modified or alcohol-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is substituted with a carboxyl group or a hydroxyl group-containing alkyl group.

  Of these, polyether-modified silicone oil is preferably added. The number average molecular weight of the polyether-modified silicone oil is, for example, 1,000 to 100,000, preferably 2,000 to 50,000. When the number average molecular weight is less than 1,000, the drying property of the coating film is low. Conversely, if the number average molecular weight exceeds 100,000, bleeding out to the coating surface becomes difficult.

  Specific products include L-45, L-9300, FZ-3704, FZ-3703, FZ-3720, FZ-3786, FZ-3501, FZ-3504, FZ-3508, FZ- from Toray Dow Corning. 3705, FZ-3707, FZ-3710, FZ-3750, FZ-3760, FZ-3785, FZ-3785, Y-7499, Shin-Etsu Chemical KF96L, KF96, KF96H, KF99, KF54, KF965, KF968, KF56, KF995, KF351, KF351A, KF352, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, FL100, surfactants BYK series manufactured by BYK Japan, BYK-300 / 302, BYK-306, BYK-307, BY -310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-340, BYK-344, BYK-370 BYK-375, BYK-377, BYK-352, BYK-354, BYK-355 / 356, BYK-358N / 361N, BYK-357, BYK-390, BYK-392, BYK-UV3500, BYK-UV3510, BYK -UV3570, BYK-Silklean 3700, dimethyl silicone series manufactured by GE Toshiba Silicone, XC96-723, YF3800, XF3905, YF3057, YF3807, YF3802, YF3897 and the like.

  The silicone surfactant is a surfactant obtained by substituting a part of the methyl group of the silicone oil with a hydrophilic group. The position of substitution includes a side chain of silicone oil, both ends, one end, both end side chains, and the like. Examples of the hydrophilic group include polyether, polyglycerin, pyrrolidone, betaine, sulfate, phosphate, and quaternary salt.

  As the silicone surfactant, a nonionic surfactant having a hydrophobic group composed of dimethylpolysiloxane and a hydrophilic group composed of polyoxyalkylene is preferable.

  A nonionic surfactant is a generic term for surfactants that do not have a group capable of dissociating into ions in an aqueous solution. Oxyethylene) or the like as a hydrophilic group. Hydrophilicity increases as the number of alcoholic hydroxyl groups increases and as the polyoxyalkylene chain (polyoxyethylene chain) becomes longer. When a nonionic surfactant composed of dimethylpolysiloxane as a hydrophobic group and polyoxyalkylene as a hydrophilic group is used, unevenness of the low refractive index layer and antifouling property of the film surface are improved. It is thought that the hydrophobic group made of polymethylsiloxane is oriented on the surface and forms a film surface that is not easily soiled.

  Specific examples of the nonionic surfactant include silicone surfactants SILWET L-77, L-720, L-7001, L-7002, L-7604, Y-7006, FZ-2101 from Toray Dow Corning, FZ-2104, FZ-2105, FZ-2110, FZ-2118, FZ-2120, FZ-2122, FZ-2123, FZ-2130, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ- 2164, FZ-2166, FZ-2191, SUPERSILWET SS-2801, SS-2802, SS-2803, SS-2804, SS-2805, and the like.

  Preferred structures of these nonionic surfactants comprising a hydrophobic group of dimethylpolysiloxane and a hydrophilic group of polyoxyalkylene include linear structures in which dimethylpolysiloxane structural portions and polyoxyalkylene chains are alternately and repeatedly bonded. A block copolymer is preferred. It is preferable from unevenness suppression and leveling properties when a coating composition for forming a low refractive index layer is applied. Specific examples thereof include silicone surfactants ABN SILWET FZ-2203, FZ-2207, FZ-2208, and FZ-2222 manufactured by Toray Dow Corning.

  The coating composition for forming the low refractive index layer has a reactive modified silicone resin (reactive modified silicone oil) to be described below from the viewpoint of easily exerting the object effect of the present invention after a durability test under more severe conditions. (Also referred to as).

  2-2. Reactive modified silicone oil: amino, epoxy, carboxyl, alcohol substitution, etc.

  The reactive modified silicone resin is a reactive type modified silicone resin in which the side chain, one end or both ends of polysiloxane is substituted with amino, epoxy, carboxyl, hydroxyl group, methacryl, mercapto, phenol or the like. As amino-modified silicone resins, specifically, KF-860, KF-861, X-22-161A, X-22-161B (above, manufactured by Shin-Etsu Chemical Co., Ltd.), FM-3311, FM-3325 (above, Chisso Corporation), epoxy-modified silicone resins such as KF-105, X-22-163A, X-22-163B, KF-101, KF-1001 (above, Shin-Etsu Chemical Co., Ltd.), polyether-modified X-22-4272, X-22-4952 as silicone resins, X-22-3701E, X-22-3710 (above, manufactured by Shin-Etsu Chemical Co., Ltd.) as carboxyl-modified silicone resins, and carbinol-modified silicone resins KF-6001, KF-6003 (Shin-Etsu Chemical Co., Ltd.), methacryl-modified silicone X-22-164C (made by Shin-Etsu Chemical Co., Ltd.) as the resin, KF-2001 (made by Shin-Etsu Chemical Co., Ltd.) as the mercapto-modified silicone resin, and X-22-1821 as the phenol-modified silicone resin (The above is manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the hydroxyl group-modified silicone resin include FM-4411, FM-4421, FM-DA21, FM-DA26 (manufactured by Chisso Corporation). In addition, X-22-170DX, X-22-2426, X-22-176F (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are also included.

  The above-mentioned surfactants may be used in combination with other surfactants. Also, for example, anionic surfactants such as sulfonate, sulfate, phosphate, etc. You may use together with nonionic surfactants, such as an ether type | mold and ether ester type | mold which have as an oxyethylene chain hydrophilic group. The addition amount of the surfactant described above is 0.05 to 5.0% by mass in the low refractive index layer coating composition, not only improving the water repellency, oil repellency and antifouling property of the coating film. From the viewpoint of exerting an effect also on the scratch resistance of the surface.

  The low refractive index layer is a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, a known method such as an inkjet method, and the above coating composition for forming the low refractive index layer is applied, and after coating, It is formed by heat drying and curing treatment with UV or the like as necessary.

  The coating amount is suitably 0.05 to 100 μm, preferably 0.1 to 50 μm, as the wet film thickness. Further, the solid content concentration of the coating composition is adjusted so that the dry film thickness becomes the above film thickness.

Examples of the curing method include a method of thermosetting by heating, a method of curing by irradiation with light such as ultraviolet rays, and the like. When thermosetting, the heating temperature is preferably 50 to 300 ° C, preferably 60 to 250 ° C, and more preferably 80 to 150 ° C. When curing by light irradiation, exposure of the irradiation light is ^{preferably, 100mJ / cm 2 ~500mJ / cm} 2 and more preferably ^{10mJ / cm 2 ~10J / cm 2} .

Here, the wavelength range of the irradiated light is not particularly limited, but light having a wavelength in the ultraviolet region is preferably used. Specifically, 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. Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 5 to 500 mJ / cm ² , preferably 5 to 150 mJ / cm ² , and particularly preferably 20 to 100 mJ / cm ² .

  Moreover, you may include the process of heat-processing at the temperature of 50-160 degreeC after forming a low-refractive-index layer. The period of the heat treatment may be appropriately determined depending on the set temperature. For example, if it is 50 ° C., it is preferably a period of 3 days or more and less than 30 days, and if it is 160 ° C., a range of 10 minutes or more and 1 day or less is preferable .

  Further, when the low refractive index layer is laminated on the hard coat layer, it is preferable that the hard coat layer is subjected to the alkali saponification treatment, the alkali solution coating described above, or the plasma treatment described later.

(Conductive layer)
The conductive layer can be applied between the film base and the low refractive index layer, or on the surface opposite to the low refractive index layer.

  The conductive layer imparts a function of preventing charging when the film is handled. Specifically, the conductive layer is formed by providing a layer containing a conductive compound.

The refractive index of the conductive layer is preferably in the range of 1.45 to 1.60 as measured at a wavelength of 550 nm. The conductive layer is preferably a layer whose surface specific resistance is adjusted to 1013 Ω / cm ² (25 ° C., 55% RH) or less. More preferably, it is 1010 Ω / cm ² (25 ° C., 55% RH) or less, and particularly preferably 109 Ω / cm ² (25 ° C., 55% RH) or less.

  Here, the measurement of the surface specific resistance is a value measured using a resistivity meter after conditioning the sample for 24 hours under the conditions of 25 ° C. and 55% RH. Moreover, as a resistivity meter device, for example, Hiresta UP MCP-HT450 manufactured by Mitsubishi Chemical Corporation can be used.

  In addition, the measurement of the surface specific resistance value when the overcoat layer is provided on the conductive layer is substantially the same as the surface specific resistance value of the outermost surface layer on the side where the conductive layer is provided. Define as a value.

  As the conductive compound, metal oxide fine particles or π-conjugated conductive polymers are preferable compounds.

  The metal oxide fine particles are not particularly limited, and are selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S Metal oxides having at least one element can be used, and these metal oxide fine particles may be doped with a trace amount of atoms such as Al, In, Sn, Sb, Nb, halogen elements, Ta, etc. Good. A mixture of these may also be used. In the present invention, at least one metal oxide fine particle selected from among zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium-tin oxide (ITO), antimony-doped tin oxide (ATO), and zinc antimonate is used. An antimony compound such as antimony-doped tin oxide (ATO) or zinc antimonate is particularly preferred from the viewpoint of the object and effects of the present invention.

  The average particle size of primary particles of these metal oxide fine particles is preferably 10 to 200 nm, more preferably 10 to 150 nm. The average particle diameter of the metal oxide fine particles can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc. If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze is remarkably increased, which is not preferable. The shape of the metal oxide fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape.

  The π-conjugated conductive polymer can be used as long as it is an organic polymer having a main chain composed of a π-conjugated system. Examples thereof include polythiophenes, polypyrroles, polyanilines, polyphenylenes, polyacetylenes, polyphenylene vinylenes, polyacenes, polythiophene vinylenes, and copolymers thereof. Polythiophenes, polyanilines, and polyacetylenes are preferred from the standpoints of ease of polymerization, stability, and object effects of the present invention.

  The π-conjugated conductive polymer can provide sufficient conductivity and solubility in a binder resin even if it is not substituted, but in order to further improve conductivity and solubility, an alkyl group, a carboxy group, a sulfo group, an alkoxy group. A functional group such as a group, a hydroxy group, or a cyano group may be introduced.

  Specific examples of such π-conjugated conductive polymers include polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), poly (3-hexylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-bromothiophene), poly (3-chlorothiophene), poly (3 -Cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythio) ), Poly (3-octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3,4-dihydroxythiophene), poly (3,4-dimethoxythiophene) , Poly (3,4-diethoxythiophene), poly (3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyloxythiophene), poly (3,4 -Dioctyloxythiophene), poly (3,4-didecyloxythiophene), poly (3,4-didodecyloxythiophene), poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedi) Oxythiophene), poly (3,4-butenedioxythiophene), poly (3-methyl-4-methoxythiophene), poly Li (3-methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl -4-carboxybutylthiophene), polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-N-propylpyrrole), poly (3-butylpyrrole) ), Poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3- Carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole) Poly (3-methyl-4-carboxybutylpyrrole), poly (3-hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexyl) Oxypyrrole), poly (3-methyl-4-hexyloxypyrrole), polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-anilinesulfonic acid), poly (3-anilinesulfone) Acid), polyphenylacetylene and the like. Each of these may be used alone, or two types of copolymers can be suitably used.

  A dopant component may be added to these π-conjugated conductive polymers. Examples of the dopant component include low molecular weight dopants such as halogens, Lewis acids, proton acids, transition metal halides, and polymers such as polyanions.

  A polyanion is a polymer having an anionic group that functions as a dopant for a π-conjugated conductive polymer, and is a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted Substituted polyamides, substituted or unsubstituted polyesters, and copolymers thereof, comprising a structural unit having an anionic group and a structural unit having no anionic group.

  Polyalkylene is a polymer whose main chain is composed of repeating methylene, and examples thereof include polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyvinyl alcohol, polyvinylphenol, polyacrylonitrile, polyacrylate, polystyrene, and the like.

  Polyalkenylene is a polymer composed of structural units containing one or more unsaturated bonds in the main chain. For example, propenylene, 1-methylpropenylene, 1-butylpropenylene, 1-decylpropenylene, 1-cyanopropene. Nylene, 1-phenylpropenylene, 1-hydroxypropenylene, 1-butenylene, 1-methyl-1-butenylene, 1-ethyl-1-butenylene, 1-octyl-1-butenylene, 2-methyl-1-butenylene, 2-ethyl-1-butenylene, 2-butyl-1-butenylene, 2-hexyl-1-butenylene, 2-octyl-1-butenylene, 2-decyl-1-butenylene, 2-phenyl-1-butenylene, 2- Butenylene, 1-methyl-2-butenylene, 1-ethyl-2-butenylene, 1-octyl-2-butenylene, 2 Methyl-2-butenylene, 2-ethyl-2-butenylene, 2-butyl-2-butenylene, 2-hexyl-2-butenylene, 2-octyl-2-butenylene, 2-decyl-2-butenylene, 2-phenyl- 2-butenylene, 2-propylenephenyl-2-butenylene, 2-pentenylene, 4-ethyl-2-pentenylene, 4-propyl-2-pentenylene, 4-butyl-2-pentenylene, 4-hexyl-2-pentenylene, 4 Examples include polymers containing one or more structural units selected from -cyano-2-pentenylene, 3-methyl-2-pentenylene, 3-phenyl-2-pentenylene, 4-hydroxy-2-pentenylene, hexenylene, and the like.

  As polyimide, pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-tetracarboxydiphenyl ether dianhydride, 2,2 ′-[4 , 4′-di (dicarboxyphenyloxy) phenyl] propane dianhydride and the like, and polyimides composed of diamines such as oxydiamine, paraphenylenediamine, metaphenylenediamine, and benzophenonediamine.

  Examples of the polyamide include polyamide 6, polyamide 6,6, polyamide 6,10 and the like.

  Examples of the polyester include polyethylene terephthalate and polybutylene terephthalate.

  The anion group of the polyanion may be a functional group that can undergo chemical oxidation doping to the π-conjugated conductive polymer. From the viewpoint of ease of production and stability, a monosubstituted sulfate group and a monosubstituted phosphate ester Group, phosphoric acid group, carboxy group, sulfo group and the like are preferable. Furthermore, from the viewpoint of the doping effect of the functional group on the π-conjugated conductive polymer, a sulfo group, a monosubstituted sulfate group, and a carboxy group are more preferable.

  Specific examples of polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly (2-acrylamido-2-methylpropane sulfonic acid), polyisoprene. Sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly (2-acrylamido-2-methylpropane carboxylic acid), polyisoprene carboxylic acid, polyacrylic acid, etc. Can be mentioned. These homopolymers may be used, or two or more types of copolymers may be used. Among these, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethyl sulfonic acid, and polyacrylic acid butyl sulfonic acid are preferable. These polyanions have high compatibility with the binder resin, and can further increase the conductivity of the obtained conductive layer.

  In addition to the polyanion, the following donor or acceptor dopant can be used as long as the π-conjugated conductive polymer can be oxidized and reduced.

  Donor dopants include alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, quaternary compounds such as tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, methyltriethylammonium and dimethyldiethylammonium. An amine compound etc. are mentioned.

  Acceptable dopants include halogen compounds such as Cl2, Br2, I2, ICl, IBr and IF, Lewis acids such as PF5, AsF5, SbF5, BF5, BCl5, BBr5 and SO3, tetracyanoethylene, tetracyanoethylene oxide, tetra Use organic cyano compounds such as cyanobenzene, dichlorodicyanobenzoquinone, tetracyanoquinodimethane, tetracyanoazanaphthalene, proton acids, organometallic compounds, fullerene, hydrogenated fullerene, hydroxylated fullerene, carboxylated fullerene, sulfonated fullerene, etc. it can.

  Examples of the protonic acid include inorganic acids and organic acids. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, perchloric acid and the like. Examples of organic acids include organic carboxylic acids and organic sulfonic acids.

  As organic carboxylic acid, what contains 1 or 2 or more of carboxy groups in aliphatic, aromatic, cycloaliphatic, etc. can be used. For example, formic acid, acetic acid, oxalic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, nitroacetic acid, And triphenylacetic acid.

  As the organic sulfonic acid, aliphatic, aromatic, cycloaliphatic or the like containing one or more sulfo groups or a polymer containing sulfo groups can be used.

  Examples of those containing one sulfo group include methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, 1-octanesulfonic acid, 1-nonanesulfonic acid, 1-decanesulfonic acid, 1-pentadecanesulfonic acid, 2-bromoethanesulfonic acid, 3-chloro-2-hydroxypropanesulfonic acid, trifluoromethanesulfonic acid, trifluoroethanesulfonic acid, colistin methanesulfone Acid, 2-acrylamido-2-methylpropanesulfonic acid, aminomethanesulfonic acid, 1-amino-2-naphthol-4-sulfonic acid, 2-amino-5-naphthol-7-sulfonic acid, 3-aminopropanesulfonic acid N-cyclohexyl-3-aminopropanesulfone Benzenesulfonic acid, alkylbenzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzene Sulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, 2,4-dimethylbenzenesulfonic acid, dipropylbenzenesulfonic acid, 4-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m- Aminobenzenesulfonic acid, 4-amino-2-chlorotoluene-5-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4-amino-5-methoxy-2-methylbenze Sulfonic acid, 2-amino-5-methylbenzene-1-sulfonic acid, 4-amino-2-methylbenzene-1-sulfonic acid, 5-amino-2-methylbenzene-1-sulfonic acid, 4-amino-3 -Methylbenzene-1-sulfonic acid, 4-acetamido-3-chlorobenzenesulfonic acid, 4-chloro-3-nitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, butyl Naphthalenesulfonic acid, pentylnaphthalenesulfonic acid, 4-amino-1-naphthalenesulfonic acid, 8-chloronaphthalene-1-sulfonic acid, naphthalenesulfonic acid formalin polycondensate, melaminesulfonic acid formalin polycondensate, anthraquinonesulfonic acid, pyrene Examples include sulfonic acid It is done. These metal salts can also be used.

  Examples of those containing two or more sulfo groups include ethanedisulfonic acid, butanedisulfonic acid, pentanedisulfonic acid, decanedisulfonic acid, o-benzenedisulfonic acid, m-benzenedisulfonic acid, p-benzenedisulfonic acid, and toluenedisulfonic acid. Xylene disulfonic acid, chlorobenzene disulfonic acid, fluorobenzene disulfonic acid, dimethylbenzene disulfonic acid, diethylbenzene disulfonic acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, 3,4-dihydroxy-1,3 Benzene disulfonic acid, naphthalene disulfonic acid, methyl naphthalene disulfonic acid, ethyl naphthalene disulfonic acid, pentadecyl naphthalene disulfonic acid, 3-amino-5-hydroxy-2,7-naphthalene disulfonic acid, 1- Cetamide-8-hydroxy-3,6-naphthalenedisulfonic acid, 2-amino-1,4-benzenedisulfonic acid, 1-amino-3,8-naphthalenedisulfonic acid, 3-amino-1,5-naphthalenedisulfonic acid, 8-amino-1-naphthol-3,6-disulfonic acid, 4-amino-5-naphthol-2,7-disulfonic acid, 4-acetamido-4′-isothiocyanotostilbene-2,2′-disulfonic acid, Examples include 4-acetamido-4′-maleimidyl stilbene-2,2′-disulfonic acid, naphthalene trisulfonic acid, dinaphthylmethane disulfonic acid, anthraquinone disulfonic acid, and anthracene sulfonic acid. These metal salts can also be used.

Moreover, you may contain an ionic compound as a conductive compound. The ionic compounds, imidazolium, pyridinium-based, alicyclic amine-based, aliphatic amine, cations and _BF ⁴ aliphatic phosphonium -, PF ₆ ^- inorganic ion system such, _CF 3 SO ₂ ^- , (CF ₃ SO ₂ ) ₂ N ⁻ , CF ₃ CO ₂ ^—, etc.

  The conductive compound is preferably 0.01 part by weight to 300 parts by weight, and more preferably 0.1 part by weight to 100 parts by weight with respect to 100 parts by weight of the resin used as the conductive layer binder described later.

  Next, the resin will be described. As the resin binder of the conductive layer, a curable resin is preferable, and an active energy ray curable resin is preferable from the viewpoint of excellent film-forming properties and physical characteristics of the coating film and adhesion to the laminated film. The active energy ray-curable resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams. As the active energy ray curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and the active energy ray curable resin layer is cured by irradiation with an active ray such as an ultraviolet ray or an electron beam. It is formed. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and an ultraviolet curable resin is particularly 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. Of these, ultraviolet curable acrylate resins are preferred.

  The UV curable urethane acrylate resin generally includes 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate) in addition to a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, as described in JP-A-59-151110, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Chemical Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) is preferably used. It is done.

  Examples of UV curable polyester acrylate resins include those which are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyols. JP-A-59-151112 Those described in the publication can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photopolymerization initiator added thereto, and reacted to form an oligomer. Those described in US Pat. No. 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. Can be mentioned.

  These ultraviolet curable resins are preferably used in combination with a photopolymerization initiator from the viewpoint of promoting the reaction.

  Specific examples of the photopolymerization initiator include benzoin and derivatives thereof, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and the like. You may use with a photosensitizer. The photopolymerization initiator can also be used as a photosensitizer.

  In addition, when using an epoxy acrylate photopolymerization initiator, a sensitizer such as n-butylamine, triethylamine, tri-n-butylphosphine can be used. The photopolymerization initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 20 parts by mass, preferably 1 to 15 parts by mass with respect to 100 parts by mass of the curable resin.

  Examples of other monomers include, for example, general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene. As monomers having two or more unsaturated double bonds, ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, isobornyl acrylate, etc. Can be mentioned. Moreover, the monomer etc. of Unexamined-Japanese-Patent No. 2006-3647 can also be used preferably.

  Commercially available UV curable resins include Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (manufactured by Asahi Denka Co., Ltd.); 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), PHCX-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, RM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (manufactured by Daicel UC 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 (Dainippon Ink Chemical Co., Ltd.); 340 clear (manufactured by China Paint Co., Ltd.); Sun Rad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (Sanyo Chemical Industries Co., Ltd.); 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.); NK Hard B-420 , NK ester A-IB, B-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like can be appropriately selected and used.

  The curable resin also includes a thermosetting resin. Examples of the thermosetting resin include unsaturated polyester resins, epoxy resins, vinyl ester resins, phenol resins, thermosetting polyimide resins, thermosetting polyamide imides, and the like.

  As unsaturated polyester resin, for example, orthophthalic acid resin, isophthalic acid resin, terephthalic acid resin, bisphenol resin, propylene glycol-maleic acid resin, dicyclopentadiene or derivatives thereof are introduced into the unsaturated polyester composition. Low-shrinkage resin with low styrene volatile resin and thermoplastic resin (polyvinyl acetate resin, styrene / butadiene copolymer, polystyrene, saturated polyester, etc.) with low molecular weight or film-forming wax compound added Reactive types such as direct bromination of unsaturated polyester with Br2 or copolymerization of heptic acid and dibromoneopentyl glycol, halides such as chlorinated paraffin and tetrabromobisphenol, antimony trioxide, and phosphorus compounds Combination Addition-type flame retardant resin that uses aluminum or aluminum hydroxide as an additive, toughness resin that is hybridized with polyurethane or silicone, or IPN (high strength, high elastic modulus, high elongation), etc. .

  Examples of the epoxy resin include glycidyl ether type epoxy resins including bisphenol A type, novolak phenol type, bisphenol F type, brominated bisphenol A type, glycidyl amine type, glycidyl ester type, cyclic aliphatic type, and heterocyclic epoxy type. The special epoxy resin containing etc. can be mentioned.

  Examples of vinyl ester resins include those obtained by dissolving an oligomer obtained by a ring-opening addition reaction between an ordinary epoxy resin and an unsaturated monobasic acid such as methacrylic acid in a monomer such as styrene. There are also special types such as vinyl monomers having vinyl groups at the molecular ends and side chains.

  Examples of vinyl ester resins of glycidyl ether type epoxy resins include bisphenol type, novolak type, brominated bisphenol type, etc., and special vinyl ester resins include vinyl ester urethane type, isocyanuric acid vinyl type, side chain vinyl ester type, etc. There is. The phenol resin is obtained by polycondensation using phenols and formaldehydes as raw materials, and there are a resol type and a novolac type.

  Examples of thermosetting polyimide resins include maleic acid-based polyimides such as polymaleimide amine, polyamino bismaleimide, bismaleimide / O, O′-diallyl bisphenol-A resin, bismaleimide / triazine resin, nadic acid-modified polyimide, And acetylene-terminated polyimide.

  The conductive layer may contain the inorganic particles or organic particles. The average particle size of these particles is preferably 0.01 to 5 μm, more preferably 0.1 to 5.0 μm, and particularly preferably 0.1 to 4.0 μm. Moreover, you may contain 2 or more types of particle | grains from which a particle size differs. The particles are desirably blended so as to be 0.1 to 30 parts by mass with respect to 100 parts by mass of the curable resin.

  The conductive layer has a vinyl group and a carboxyl group in the side chain of the polyurethane resin as a curing aid, a weight average molecular weight of 10,000 to 30,000, and a double bond equivalent of 500 to 2,000. And an acrylic polymer having a vinyl group in the side chain of the polymer, a weight average molecular weight (Mw) of 10,000 to 100,000, a double bond equivalent of 1,000 or less, and a polymer Tg of −50 ° C. to 120 ° C. A functional thiol compound or the like may be included. Examples of other functional thiol compounds include 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like. Commercially available products include Showa Denko Co., Ltd., trade name Karenz MT series, and the like.

  Moreover, you may contain the said fluorine-acryl copolymer resin. The fluorine-acrylic copolymer resin is a copolymer resin composed of a fluorine monomer and an acrylic monomer, and a block copolymer composed of a fluorine monomer segment and an acrylic monomer segment is particularly preferable. The molecular weight of the fluorine-acrylic copolymer resin may be 5,000 to 1,000,000 in terms of number average molecular weight, preferably 10,000 to 300,000, and more preferably 10,000 to 100,000. In the production of the fluorine-acrylic copolymer resin, polymeric peroxide was used as a polymerization initiator. It can be produced by a known production process (for example, Japanese Patent Publication No. 5-41668 and Japanese Patent Publication No. 5-59942).

  Polymeric peroxide is a compound having two or more peroxy bonds in one molecule. As the polymer peroxide, one or more of various polymer peroxides described in JP-B-5-59942 can be used.

  As a commercial item of fluorine-acrylic copolymer resin, the brand name of Nippon Oil & Fat Co., Ltd. Modiper F-200, Modiper F-600, Modiper F-2020, etc. are mentioned.

  Further, the conductive layer contains the silicone surfactant, fluorine compound, polyoxyether compound, etc. described in the low refractive index layer, so that the surface uniformity is improved and high-speed coating suitability is imparted. This is preferable in that the productivity can be improved.

  Preferable examples of the fluorine-based compound include a fluoroaliphatic group-containing copolymer, specifically, compounds described in paragraphs 0053 to 0082 of JP-A-2007-45142. In addition, the compounds described in paragraphs 0008 to 0031 of JP 2000-119354 A can also be used. These components are preferably added in the range of 0.01 to 5% by mass with respect to the solid component in the conductive layer composition, from the viewpoint that surface defects such as coating unevenness, drying unevenness, and point defects can be improved. .

  As the fluorine-based compound, a polymer obtained by copolymerizing a fluororesin with siloxane (including polysiloxane) and / or organosiloxane (including organopolysiloxane) by grafting or the like can be preferably used. Specific examples include ZX-022H, ZX-007C, ZX-049, and ZX-047-D manufactured by Fuji Chemical Industry Co., Ltd. These compounds may be used as a mixture.

  Examples of the polyoxyether compound include polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ether compounds such as polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Polyoxyalkyl phenyl ether compounds such as ethylene octyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octyldodecyl ether and the like can be mentioned. Commercially available products of polyoxyethylene alkyl ether include Emulgen 1108, Emulgen 1118S-70 (above, manufactured by Kao Corporation), and commercially available products of polyoxyethylene lauryl ether include Emulgen 103, Emulgen 104P, Emulgen 105, Emulgen 106, Emulgen 108, Emulgen 109P, Emulgen 120, Emulgen 123P, Emulgen 147, Emulgen 150, Emulgen 130K (above, manufactured by Kao Corporation), and polyoxyethylene cetyl ether are commercially available products of Emulgen 210P, Emulgen 220 (above, manufactured by Kao Corporation) As commercially available products of polyoxyethylene stearyl ether, Emulgen 220, Emulgen 306P (above, manufactured by Kao Corporation), and commercially available products of polyoxyalkylene alkyl ether include Examples of commercially available products of Rugen LS-106, Emulgen LS-110, Emulgen LS-114, Emulgen MS-110 (manufactured by Kao Corporation) polyoxyethylene higher alcohol ether include Emulgen 705, Emulgen 707, and Emulgen 709. .

  Among these polyoxyether compounds, a polyoxyethylene oleyl ether compound is preferable, and a compound represented by the following general formula (3).

_{C 18 H 35 -O (C 2} H 4 O) nH ··· (3)
In the formula, n represents 2 to 40.

  The average addition number (n) of ethylene oxide with respect to the oleyl part is 2 to 40, preferably 2 to 10. Moreover, the compound of the said general formula (H) is obtained by making ethylene oxide and oleyl alcohol react. Specific products include Emulgen 404 [polyoxyethylene (4) oleyl ether], Emulgen 408 [polyoxyethylene (8) oleyl ether], Emulgen 409P [polyoxyethylene (9) oleyl ether], Emulgen 420 [polyoxy Ethylene (13) oleyl ether], Emulgen 430 [polyoxyethylene (30) oleyl ether] (above, manufactured by Kao Corporation), NOFBLEEAO-9905 (polyoxyethylene (5) oleyl ether), and the like. Note that () represents the number n. The polyoxyether compounds may be used alone or in combination of two or more.

  Moreover, you may use together an acetylene glycol type compound, a nonionic surfactant, a radically polymerizable nonionic surfactant, etc.

  Nonionic surfactants include polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyalkyl ester compounds such as polyoxyethylene monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, etc. Sorbitan ester compounds, and the like. Examples of the acetylene glycol compounds include Surfinol 104E, Surfinol 104PA, Surfinol 420, Surfinol 440, and Dynal 604 (manufactured by Nissin Chemical Industry Co., Ltd.). Examples of the radical polymerizable nonionic surfactant include polyoxyalkylene alkyl such as “RMA-564”, “RMA-568”, “RMA-1114” [trade name, manufactured by Nippon Emulsifier Co., Ltd.]. Examples include phenyl ether (meth) acrylate polymerizable surfactants.

  The conductive layer may contain a color tone adjusting agent (dye or pigment, etc.) having a color tone adjusting function as a color correction filter for various display elements, an electromagnetic wave blocking agent, an infrared absorber, or the like.

  The conductive layer preferably contains a cellulose ester resin or an acrylic resin in order to maintain easy adhesion with the overcoat layer.

  Examples of the cellulose ester resin include cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose nitrate.

  Examples of the acrylic resin include Acrypet MD, VH, MF, V (Mitsubishi Rayon Co., Ltd.), Hyperl M4003, 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.) Various homopolymers and copolymers to produce Le and methacrylic monomer as a raw material is preferably used.

  The resin used here is preferably 60% by mass or more, more preferably 80% by mass or more of the total resin used in the conductive layer, and an actinic ray curable resin or thermosetting resin is used as necessary. It can also be added. These resins are coated as a binder in a state dissolved in the following solvent.

  For the coating composition for coating the conductive layer, the following solvents are preferably used. As the solvent, hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents (methylene chloride) can be appropriately mixed and used, but are not particularly limited thereto.

  Examples of the hydrocarbons include benzene, toluene, xylene, hexane, cyclohexane and the like, and examples of alcohols include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, 2-butanol, tert- Examples include butanol, pentanol, 2-methyl-2-butanol, and cyclohexanol. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of esters include methyl formate, ethyl formate, Examples thereof include methyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, ethyl lactate, and methyl lactate. Examples of glycol ethers (C1 to C4) include methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ester. As terrestrial (PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, or propylene glycol mono (C1-C4) alkyl ether esters, propylene glycol monomethyl Examples of ether acetate, propylene glycol monoethyl ether acetate, and other solvents include methylene chloride and N-methylpyrrolidone. Although not particularly limited to these, a solvent in which these are appropriately mixed is also preferably used.

  As a coating method of the conductive layer coating composition, using a gravure coater, dip coater, wire bar coater, reverse coater, extrusion coater, etc., the coating solution film thickness (sometimes referred to as wet film thickness) is 1 to 100 μm. In particular, 5 to 30 μm is preferable.

<High refractive index layer>
The antireflection film is preferably provided with a high refractive index layer having a higher refractive index than that of the film substrate, from the point that an external light reflection preventing function can be more obtained between the film substrate and the low refractive index layer.

  The high refractive index layer preferably contains metal oxide fine particles in terms of refractive index adjustment. The kind of metal oxide fine particles is not particularly limited, and Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S A metal oxide having at least one element selected from the group consisting of Al, In, Sn, Sb, Nb, a halogen element, Ta and the like is doped with a minute amount of atoms. May be. A mixture of these may also be used. In the present invention, at least one metal oxide fine particle selected from among zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium-tin oxide (ITO), antimony-doped tin oxide (ATO), and zinc antimonate is used. It is particularly preferable to use it as the main component. In particular, it is preferable to contain zinc antimonate particles.

  The average particle diameter of the primary particles of these metal oxide fine particles is in the range of 10 nm to 200 nm, particularly preferably 10 to 150 nm. The average particle diameter of the metal oxide fine particles can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc. If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze is remarkably increased, which is not preferable. The shape of the metal oxide fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape.

  Specifically, the refractive index of the high refractive index layer is higher than the refractive index of the base film, and is preferably in the range of 1.5 to 2.2 when measured at 23 ° C. and a wavelength of 550 nm. The means for adjusting the refractive index of the high refractive index layer is that the kind and addition amount of the metal oxide fine particles are dominant, so that the refractive index of the metal oxide fine particles is preferably 1.80 to 2.60, More preferably, it is 1.85 to 2.50.

  The metal oxide fine particles may be surface-treated with an organic compound. By modifying the surface of the metal oxide fine particles with an organic compound, the dispersion stability in an organic solvent is improved, the dispersion particle size can be easily controlled, and aggregation and sedimentation over time can be suppressed. . For this reason, the surface modification amount with a preferable organic compound is 0.1 mass%-5 mass% with respect to metal oxide particle, More preferably, it is 0.5 mass%-3 mass%. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, silane coupling agents are preferred. Two or more kinds of surface treatments may be combined.

  Specifically, the refractive index of the high refractive index layer is higher than the refractive index of the base film, and is preferably in the range of 1.5 to 2.2 when measured at 23 ° C. and a wavelength of 550 nm. The means for adjusting the refractive index of the high refractive index layer is that the kind and addition amount of the metal oxide fine particles are dominant, so that the refractive index of the metal oxide fine particles is preferably 1.80 to 2.60, More preferably, it is 1.85 to 2.50.

  The ratio of the metal oxide fine particles to be used and a binder such as actinic ray curable resin to be described later varies depending on the kind of metal oxide fine particles, the particle size, etc., but the volume ratio of the former 1 to the latter 2 to the former 2 The latter one is preferable.

  The amount of the metal oxide fine particles used is preferably 5% by mass to 85% by mass, more preferably 10% by mass to 80% by mass, and most preferably 20% by mass to 75% by mass in the high refractive index layer. If the amount used is small, the desired refractive index and the effect of the present invention cannot be obtained, and if it is too large, the film strength deteriorates.

  The metal oxide fine particles are supplied to a coating solution for forming a high 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), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate. Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The metal oxide fine 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. It is also preferable to contain a dispersant.

  Furthermore, metal oxide fine particles having a core / shell structure may be contained. One layer of the shell may be formed around the core, or a plurality of layers may be formed in order to further improve the light resistance. The core is preferably completely covered by the shell.

  For the core, titanium oxide (rutile type, anatase type, amorphous type, etc.), zirconium oxide, zinc oxide, cerium oxide, indium oxide doped with tin, tin oxide doped with antimony, etc. can be used. Titanium may be the main component.

  The shell is preferably formed of a metal oxide or sulfide containing an inorganic compound other than titanium oxide as a main component. For example, an inorganic compound mainly composed of silicon dioxide (silica), aluminum oxide (alumina) zirconium oxide, zinc oxide, tin oxide, antimony oxide, indium oxide, iron oxide, zinc sulfide, or the like is used. Of these, alumina, silica, and zirconia (zirconium oxide) are preferable. A mixture of these may also be used.

  The coating amount of the shell with respect to the core is 2 to 50% by mass as an average coating amount. Preferably it is 3-40 mass%, More preferably, it is 4-25 mass%. When the coating amount of the shell is large, the refractive index of the fine particles is lowered, and when the coating amount is too small, the light resistance is deteriorated. Two or more inorganic fine particles may be used in combination.

  The titanium oxide used as a core can use what was produced by the liquid phase method or the gaseous-phase method. As a method for forming the shell around the core, for example, U.S. Pat. No. 3,410,708, JP-B-58-47061, U.S. Pat. No. 2,885,366, and U.S. Pat. No. 1, British Patent No. 1,134,249, US Pat. No. 3,383,231, British Patent No. 2,629,953, No. 1,365,999, etc. Can do.

  The high refractive index layer or the low refractive index layer described above can contain a compound represented by the following general formula (CL1) or a chelate compound thereof, and can improve physical properties such as hardness.

General formula (CL1) AnMBx-n
In the formula, M represents a metal atom, A represents a hydrolyzable functional group or a hydrocarbon group having a hydrolyzable functional group, and B represents an atomic group covalently or ionically bonded to the metal atom M. x represents the valence of the metal atom M, and n represents an integer of 2 or more and x or less.

  Examples of the hydrolyzable functional group A include halogens such as alkoxyl groups and chloro atoms, ester groups and amide groups. The metal compound belonging to the general formula (CL1) includes an alkoxide having two or more alkoxyl groups directly bonded to a metal atom, or a chelate compound thereof. Preferable metal compounds include titanium alkoxide, zirconium alkoxide, or chelate compounds thereof. Titanium alkoxide has a high reaction rate and a high refractive index and is easy to handle. However, since it has a photocatalytic action, its light resistance deteriorates when added in a large amount. Zirconium alkoxide has a high refractive index but tends to become cloudy, so care must be taken in dew point management during coating. Moreover, since titanium alkoxide has the effect of promoting the reaction of the ultraviolet curable resin and metal alkoxide, the physical properties of the coating film can be improved by adding a small amount.

  Examples of the titanium alkoxide include tetramethoxy titanium, tetraethoxy titanium, tetra-iso-propoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy titanium, and the like. Is mentioned.

  Examples of the zirconium alkoxide include tetramethoxy zirconium, tetraethoxy zirconium, tetra-iso-propoxy zirconium, tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetra-sec-butoxy zirconium, tetra-tert-butoxy zirconium and the like. Is mentioned.

  Preferred chelating agents for coordination with free metal compounds to form chelate compounds include alkanolamines such as diethanolamine and triethanolamine, glycols such as ethylene glycol, diethylene glycol and propylene glycol, acetylacetone and acetoacetate Examples thereof include ethyl and the like having a molecular weight of 10,000 or less. By using these chelating agents, it is possible to form a chelate compound that is stable against water mixing and is excellent in the effect of reinforcing the coating film.

  The addition amount of the metal compound is preferably adjusted so that the content of the metal oxide derived from the metal compound contained in the high refractive index layer is 0.3 to 5% by mass. If it is less than 0.3% by mass, the scratch resistance is insufficient, and if it exceeds 5% by mass, the light resistance tends to deteriorate.

  The high refractive index layer preferably contains an actinic ray curable resin as a binder for the metal oxide fine particles in order to improve the film formability and physical properties of the coating film. Examples of the actinic ray curable resin include monomers or oligomers having two or more functional groups that cause polymerization reaction directly by irradiation of actinic rays such as ultraviolet rays and electron beams or indirectly by the action of a photopolymerization initiator. Can be used. Polyol acrylate, epoxy acrylate, urethane acrylate, polyester acrylate or a mixture thereof is preferable, for example, the polyfunctional acrylate compound described in the hard coat layer is preferable.

  The addition amount of the actinic ray curable resin is preferably 15% by mass or more and less than 50% by mass in the solid content in the high refractive index composition.

  In order to accelerate the curing of the actinic ray curable resin, it may contain a photopolymerization initiator and an acrylic compound having two or more polymerizable unsaturated bonds in the molecule in a mass ratio of 3: 7 to 1: 9. preferable.

  Specific examples of the photopolymerization initiator include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto.

  Examples of the organic solvent used for coating the high refractive index layer include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol). , Benzyl alcohol, etc.), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thio Diglycol, etc.), polyhydric alcohol ethers (eg, ethylene glycol monomethyl ether, ethylene glycol) Cole 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 monophenyl ether, propylene glycol monophenyl ether, etc.), amines (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenedi) Mines, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.) Heterocycles (for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (for example, dimethyl sulfoxide, etc.), Examples include sulfones (for example, sulfolane), urea, acetonitrile, acetone, and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable.

  As a coating method of the high refractive index layer, the coating composition for forming the high refractive index layer is applied using a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and an ink jet method. After the coating, it is dried by heating and, if necessary, is cured. The coating amount is suitably 0.05 to 100 μm, preferably 0.1 to 50 μm, as the wet film thickness. Further, the solid content concentration of the coating composition is adjusted so that the dry film thickness becomes the above film thickness. Two or more high refractive index layers may be used.

(Reflectance)
The reflectance of the antireflection film (the reflectance of the antireflection layer) can be measured with a spectrophotometer or a spectrocolorimeter. At that time, after the surface on the measurement side of the sample is roughened, the light absorption treatment is performed by attaching a black spray, a black acrylic plate, etc., and then the reflected light in the visible light region (400 to 700 nm) is measured. To do.

  The lower the reflectivity, the better. However, the average value in the visible light region wavelength of 1.5% or less suitably obtains an external light antireflection function when used on the outermost surface of an image display device such as an LCD. It is preferable from the point of being. Further, the minimum reflectance is preferably 0.8% or less.

  Moreover, it is preferable to have a flat reflection spectrum in the visible light wavelength region. In addition, the reflection hue on the surface of the display device that has been subjected to the antireflection treatment is often colored red or blue because the reflectance in the short wavelength region and the long wavelength region is high in the visible light region due to the design of the antireflection film. The color tone of the reflected light varies depending on the application, and when used on the outermost surface of a flat-screen television or the like, a neutral color tone is preferred. In this case, generally preferred reflection hue ranges are 0.17 ≦ x ≦ 0.27 and 0.07 ≦ y ≦ 0.17 on the XYZ color system (CIE1931 color system). Further, the range in which the distance Δxy of (x, y) = (0.31, 0.31) on the xy plane is 0.05 or less is preferable because it is closer to neutral with no color, and 0.03 or less is preferable. Further preferred.

  The color tone can be achieved by calculating and adjusting the film thickness according to a conventional method in consideration of the reflectance and the color of reflected light from the refractive index of each layer.

(Surface treatment and coating)
It is preferable to perform a surface treatment before applying each layer. Surface treatment methods include cleaning methods, alkali saponification methods, alkaline solution coating, plasma treatment methods (eg flame plasma treatment method, radio frequency discharge plasma method), electron beam method, ion beam method, sputtering method, acid treatment, corona Examples thereof include a treatment method and an atmospheric pressure glow discharge plasma method.

<Base film>
The base film used in the present invention is preferably easy to produce, easy to adhere to the hard coat layer, and optically isotropic. Any of these may be used, for example, cellulose ester films such as triacetyl cellulose film, cellulose acetate propionate ionate film, cellulose diacetate film, cellulose acetate butyrate film, polyethylene terephthalate, polyethylene naphthalate, etc. Polyester film such as phthalate, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene film, polypropylene film, cellophane, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, Shinji Otectic polystyrene film, norbornene resin film, polymethylpentene Examples include, but are not limited to, film, polyether ketone film, polyether ketone imide film, polyamide film, fluororesin film, nylon film, cycloolefin polymer film, polymethyl methacrylate film or acrylic film. Absent. Among these, cellulose ester films (for example, Konica Minoltak KC8UX2M, KC4UX2M, KC4UY, KC8UT, KC5UN, KC12UR, KC8UCR-3, KC8UCR-4 (above, manufactured by Konica Minolta Opto), polycarbonate film, cycloolefin A polymer film and a polyester film are preferred, and a cellulose ester film is particularly preferred from the viewpoint of production, cost, isotropy, adhesiveness, and the object effects of the present invention.

(Cellulose ester film)
Next, a cellulose ester film (hereinafter also referred to as a cellulose ester film) will be described.

  The cellulose ester resin (hereinafter also referred to as cellulose ester) is preferably a lower fatty acid ester of cellulose. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. For example, cellulose acetate, cellulose propionate, cellulose butyrate and the like, and JP-A Nos. 10-45804 and 08-231761. , Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate as described in US Pat. No. 2,319,052 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 alone or in combination.

  In the case of cellulose triacetate, those having an average degree of acetylation (bound acetic acid amount) of 54.0 to 62.5% are preferably used, and more preferably an average degree of acetylation of 58.0 to 62.5%. Cellulose triacetate. When the average degree of acetylation is small, the dimensional change is large, and the polarization degree of the polarizing plate is lowered. When the average acetylation degree is large, the solubility in a solvent is lowered and the productivity is lowered.

  Preferred cellulose esters other than cellulose triacetate have an acyl group having 2 to 4 carbon atoms as a substituent, the substitution degree of acetyl group is X, and the substitution degree of propionyl group or butyryl group is Y, the following formula ( It is a cellulose ester containing the cellulose ester which satisfy | fills I) and (II) simultaneously.

Formula (I) 2.6 ≦ X + Y ≦ 3.0
Formula (II) 0 ≦ X ≦ 2.5
Of these, cellulose acetate propionate is preferably used, and it is particularly preferable that 1.9 ≦ X ≦ 2.5 and 0.1 ≦ Y ≦ 0.9. The portion that is not substituted with an acyl group usually exists as a hydroxyl group. These can be synthesized by known methods. The measuring method of the substitution degree of an acyl group can be measured according to ASTM-D817-96.

  The molecular weight of the cellulose ester is preferably a number average molecular weight (Mn) of 60,000 to 300,000, more preferably 70,000 to 200,000, particularly preferably 100,000 to 200,000. The cellulose ester used in the present invention preferably has a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio of 4.0 or less, more preferably 1.4 to 2.3.

  Since the average molecular weight and molecular weight distribution of the cellulose ester can be measured using high performance liquid chromatography, the number average molecular weight (Mn) and the weight average molecular weight (Mw) can be calculated using this, and the ratio can be calculated.

  The measurement conditions are as follows.

Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (GL Science Co., Ltd.)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation)
A calibration curve with 13 samples from Mw = 100000 to 500 was used. The 13 samples are preferably used at approximately equal intervals.

  As the cellulose ester, a cellulose ester synthesized using 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 cellulose ester synthesized from cotton linter (hereinafter sometimes simply referred to as linter) alone or in combination.

  In addition, the cellulose ester film preferably contains an acrylic resin from the viewpoint that the object and effects of the present invention are better exhibited and that the pencil hardness is also excellent.

(Acrylic resin, acrylic particles)
Acrylic resin also includes methacrylic resin. Although it does not restrict | limit especially as resin, What consists of 50-99 mass% of methyl methacrylate units and 1-50 mass% of other monomer units copolymerizable with this is preferable.

  Other monomers that can be copolymerized include alkyl methacrylates having 2 to 18 carbon atoms, alkyl acrylates having 1 to 18 carbon atoms, acrylic acid, methacrylic acid, and the like. Saturated acids, maleic acids, fumaric acids, unsaturated divalent carboxylic acids such as itaconic acid, aromatic vinyl compounds such as styrene, α-methylstyrene, and nucleus-substituted styrene, α, β- such as acrylonitrile, methacrylonitrile, etc. Examples thereof include unsaturated nitrile, maleic anhydride, maleimide, N-substituted maleimide, glutaric anhydride, and the like. These can be used alone or in combination of two or more.

  Among these, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable from the viewpoint of thermal decomposition resistance and fluidity of the copolymer. n-Butyl acrylate is particularly preferably used.

  The acrylic resin preferably has a weight average molecular weight (Mw) of 80000 to 1000000 from the viewpoint of mechanical strength as a film and fluidity when producing the film. A weight average molecular weight (Mw) can be measured using said high performance liquid chromatography.

  There is no restriction | limiting in particular as a manufacturing method of an acrylic resin, You may use any well-known methods, such as suspension polymerization, emulsion polymerization, block polymerization, or solution polymerization. Here, as a polymerization initiator, a normal peroxide type and an azo type can be used, and a redox type can also be used. Regarding the polymerization temperature, suspension or emulsion polymerization may be performed at 30 to 100 ° C, and bulk or solution polymerization may be performed at 80 to 160 ° C. Further, in order to control the reduced viscosity of the produced copolymer, polymerization can be carried out using alkyl mercaptan or the like as a chain transfer agent. With this molecular weight, both heat resistance and brittleness can be achieved. A commercially available thing can also be used as an acrylic resin. For example, Delpet 60N, 80N (Asahi Kasei Chemicals Co., Ltd.), Dialal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd.), KT75 (Electrochemical Industry Co., Ltd.) and the like can be mentioned. .

  Next, since the cellulose ester film exhibits the objective effect of the present invention well and is particularly excellent in pencil hardness, it is preferable to contain an acrylic resin and further acrylic particles.

  Acrylic particles, for example, a PTFE membrane having a pore diameter less than the average particle diameter of acrylic particles when a predetermined amount of the prepared acrylic resin-containing film is collected, dissolved in a solvent, stirred, and sufficiently dissolved and dispersed. It is preferable that the weight of the insoluble matter filtered and collected using a filter is 90% by mass or more of the acrylic particles added to the acrylic resin-containing film.

  The acrylic particles are not particularly limited, but are preferably acrylic particles having a layer structure of two or more layers, and particularly preferably the following multilayer structure acrylic granular composite.

  The multilayer structure acrylic granular composite is formed by laminating the innermost hard layer polymer, the cross-linked soft layer polymer exhibiting rubber elasticity, and the outermost hard layer polymer from the central portion toward the outer peripheral portion. This refers to a particulate acrylic polymer having a structure.

  Preferred embodiments of the multilayer structure acrylic granular composite used in the acrylic resin composition include the following. (A) Monomer comprising 80 to 98.9% by mass of methyl methacrylate, 1 to 20% by mass of alkyl acrylate having 1 to 8 carbon atoms in the alkyl group, and 0.01 to 0.3% by mass of polyfunctional grafting agent An innermost hard layer polymer obtained by polymerizing the body mixture, (b) in the presence of the innermost hard layer polymer, 75 to 98.5% by mass of an alkyl acrylate having an alkyl group with 4 to 8 carbon atoms, A crosslinked soft layer polymer obtained by polymerizing a monomer mixture composed of 0.01 to 5% by mass of a multifunctional crosslinking agent and 0.5 to 5% by mass of a multifunctional grafting agent, (c) the innermost hard In the presence of a polymer comprising a layer and a crosslinked soft layer, a monomer mixture composed of 80 to 99% by mass of methyl methacrylate and 1 to 20% by mass of alkyl acrylate having 1 to 8 carbon atoms in the alkyl group is polymerized. Outermost hard layer polymer obtained by And the obtained three-layer structure polymer has an innermost hard layer polymer (a) of 5 to 40% by mass, a soft layer polymer (b) of 30 to 60% by mass, and an outermost layer polymer. The hard granular polymer (c) comprises 20 to 50% by mass, has an insoluble part when fractionated with acetone, and an acrylic granular composite having a methyl ethyl ketone swelling degree of 1.5 to 4.0 in the insoluble part. Can be mentioned.

  As disclosed in Japanese Patent Publication No. 60-17406 or Japanese Patent Publication No. 3-39095, not only the composition and particle diameter of each layer of the multilayer acrylic granular composite are defined, but also the multilayer acrylic granular composite. By setting the tensile modulus of the body and the degree of swelling of methyl ethyl ketone in the acetone-insoluble part within a specific range, it becomes possible to realize a further sufficient balance between impact resistance and stress whitening resistance.

  Here, the innermost hard layer polymer (a) constituting the multi-layer structure acrylic granular composite is 80 to 98.9% by mass of methyl methacrylate and 1 to 20% of alkyl acrylate having 1 to 8 carbon atoms in the alkyl group. % And a polyfunctional grafting agent obtained by polymerizing a monomer mixture consisting of 0.01 to 0.3% by mass.

  Here, examples of the alkyl acrylate having 1 to 8 carbon atoms in the alkyl group include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like. And n-butyl acrylate are preferably used.

  The proportion of the alkyl acrylate unit in the innermost hard layer polymer (a) is 1 to 20% by mass. When the unit is less than 1% by mass, the thermal decomposability of the polymer is increased, while the unit is 20% by mass. If it exceeds 50%, the glass transition temperature of the innermost hard layer polymer (c) is lowered, and the impact resistance imparting effect of the three-layer structure acrylic granular composite is lowered.

  Examples of the polyfunctional grafting agent include polyfunctional monomers having different polymerizable functional groups, such as allyl esters of acrylic acid, methacrylic acid, maleic acid, and fumaric acid, and allyl methacrylate is preferably used. . The polyfunctional grafting agent is used to chemically bond the innermost hard layer polymer and the soft layer polymer, and the ratio used during the innermost hard layer polymerization is 0.01 to 0.3% by mass. .

  The crosslinked soft layer polymer (b) constituting the acrylic granular composite is an alkyl acrylate 75-98.5 having 1 to 8 carbon atoms in the presence of the innermost hard layer polymer (a). What is obtained by polymerizing a monomer mixture consisting of mass%, polyfunctional crosslinking agent 0.01 to 5 mass% and polyfunctional grafting agent 0.5 to 5 mass% is preferable.

  Here, as the alkyl acrylate having 4 to 8 carbon atoms in the alkyl group, n-butyl acrylate or 2-ethylhexyl acrylate is preferably used.

  In addition to these polymerizable monomers, it is possible to copolymerize 25% by mass or less of other monofunctional monomers capable of copolymerization.

  Examples of other monofunctional monomers that can be copolymerized include styrene and substituted styrene derivatives. As the ratio of the alkyl acrylate having 4 to 8 carbon atoms in the alkyl group and styrene increases, the glass transition temperature of the produced polymer (b) decreases as the former increases, that is, it can be softened. On the other hand, from the viewpoint of the transparency of the resin assembly, the refractive index of the soft layer polymer (b) at room temperature is set to the innermost hard layer polymer (a), the outermost hard layer polymer (c), and the hard heat. It is more advantageous to make it closer to the plastic acrylic resin, and the ratio between them is selected in consideration of these.

  For example, in applications where the coating layer thickness is small, it is not always necessary to copolymerize styrene.

  As the polyfunctional grafting agent, those mentioned in the item of the innermost layer hard polymer (a) can be used. The polyfunctional grafting agent used here is used to chemically bond the soft layer polymer (b) and the outermost hard layer polymer (c), and the proportion used during the innermost hard layer polymerization is impact resistance. 0.5-5 mass% is preferable from a viewpoint of the property provision effect.

  As the polyfunctional crosslinking agent, generally known crosslinking agents such as divinyl compounds, diallyl compounds, diacrylic compounds, and dimethacrylic compounds can be used, and polyethylene glycol diacrylate (molecular weight 200 to 600) is preferably used.

  The polyfunctional cross-linking agent used here is used to generate a cross-linked structure at the time of polymerization of the soft layer (b) and develop an effect of imparting impact resistance. However, if the above-mentioned polyfunctional grafting agent is used during the polymerization of the soft layer, the polyfunctional crosslinking agent is not an essential component because the crosslinked structure of the soft layer (b) is generated to some extent. Is preferably 0.01 to 5% by mass from the viewpoint of imparting impact resistance.

  In the presence of the innermost hard layer polymer (a) and the soft layer polymer (b), the outermost hard layer polymer (c) constituting the multilayer structure acrylic granular composite is 80 to 99 mass% of methyl methacrylate. % And a monomer mixture comprising 1 to 20% by mass of an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group is preferred.

  Here, as the acrylic alkylate, those described above are used, and methyl acrylate and ethyl acrylate are preferably used. The ratio of the alkyl acrylate unit in the outermost hard layer (c) is preferably 1 to 20% by mass.

  Further, for the purpose of improving the compatibility with the acrylic resin during the polymerization of the outermost hard layer (c), an alkyl mercaptan or the like can be used as a chain transfer agent to adjust the molecular weight.

  In particular, it is preferable to provide the outermost hard layer with a gradient such that the molecular weight gradually decreases from the inside toward the outside in order to improve the balance between elongation and impact resistance. As a specific method, the monomer mixture for forming the outermost hard layer is divided into two or more, and the molecular weight is increased from the inside by a method of sequentially increasing the amount of chain transfer agent added each time. It is possible to make it smaller toward the outside. The molecular weight formed at this time can also be examined by polymerizing the monomer mixture used each time under the same conditions and measuring the molecular weight of the obtained polymer. The particle diameter of the acrylic granular composite that is a multilayer structure polymer is not particularly limited, but is preferably 10 nm or more and 1000 nm or less, and more preferably 20 nm or more and 500 nm or less. In particular, the thickness is most preferably from 50 nm to 400 nm.

  In the acrylic granular composite which is a multilayer structure polymer, the mass ratio of the core and the shell is not particularly limited, but when the total multilayer structure polymer is 100 parts by mass, the core layer is 50 parts by mass. The content is preferably 90 parts by mass or less, and more preferably 60 parts by mass or more and 80 parts by mass or less.

  Examples of such commercially available multilayered acrylic granular composites include, for example, “Metablene” manufactured by Mitsubishi Rayon Co., “Kane Ace” manufactured by Kaneka Chemical Co., Ltd., “Paraloid” manufactured by Kureha Chemical Co., Ltd., Rohm and Haas “Acryloid” manufactured by KK, “Staffyroid” manufactured by Ganz Kasei Kogyo Co., Ltd., “Parapet SA” manufactured by Kuraray Co., Ltd., and the like can be used.

  Specific examples of acrylic particles (c-1) which are graft copolymers suitably used as acrylic particles include unsaturated carboxylic acid ester monomers and unsaturated carboxylic acids in the presence of a rubbery polymer. Examples thereof include a graft copolymer obtained by copolymerizing a monomer mixture comprising a monomer, an aromatic vinyl monomer, and, if necessary, other vinyl monomers copolymerizable therewith.

  Although there is no restriction | limiting in particular in the rubbery polymer used for the acrylic particle (c-1) which is a graft copolymer, Diene rubber, acrylic rubber, ethylene rubber, etc. can be used. Specific examples include polybutadiene, styrene-butadiene copolymer, block copolymer of styrene-butadiene, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, polyisoprene, butadiene-methyl methacrylate copolymer. , Butyl acrylate-methyl methacrylate copolymer, butadiene-ethyl acrylate copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-isoprene copolymer, and ethylene-acrylic acid Examples thereof include a methyl copolymer. These rubbery polymers can be used alone or in a mixture of two or more.

  Moreover, since the transparency of a base film can be obtained when each refractive index of an acrylic resin and an acrylic particle is approximated, it is preferable. Specifically, the refractive index difference between the acrylic particles and the acrylic resin is preferably 0.05 or less, more preferably 0.02 or less, and particularly preferably 0.01 or less.

  In order to satisfy such a refractive index condition, a method for adjusting the composition ratio of each monomer unit of the acrylic resin and / or a composition ratio of the rubbery polymer or monomer used for the acrylic particles is prepared. Depending on the method, the difference in refractive index can be reduced, and an acrylic resin-containing film excellent in transparency can be obtained.

  The difference in refractive index referred to here means that the acrylic resin-containing film is sufficiently dissolved in a solvent in which the acrylic resin is soluble to obtain a cloudy solution, which is then subjected to an operation such as centrifugation, to obtain a solvent-soluble portion. And the soluble part (acrylic resin) and the insoluble part (acrylic particles) are purified respectively, and the difference in the measured refractive index (23 ° C., measurement wavelength: 550 nm) is shown.

  There is no restriction | limiting in particular in the method of mix | blending an acrylic particle with an acrylic resin, After blending an acrylic resin and another arbitrary component previously, it is a single screw or a twin screw extruder, adding an acrylic particle normally at 200-350 degreeC. Thus, a method of uniformly melting and kneading is preferably used.

  A commercially available thing can also be used as an acrylic particle. For example, metabrene W-341 (C2) (manufactured by Mitsubishi Rayon Co., Ltd.), Chemisnow MR-2G (C3), MS-300X (C4) (manufactured by Soken Chemical Co., Ltd.) and the like can be mentioned.

  The acrylic particles preferably contain 0.5 to 45% by mass of acrylic particles with respect to the total mass of the cellulose ester resin and the acrylic resin.

  Moreover, the film which consists of a cellulose-ester resin and an acrylic resin (henceforth a cellulose-ester resin and an acrylic resin film) has a tension softening point of 105-145 degreeC, and a film with which ductile fracture does not occur is preferable. Ductile fracture is caused by the application of a greater stress than the strength of a certain material, and is defined as a fracture that involves significant elongation or drawing of the material before final fracture. As a specific measurement method of the tension softening point temperature, for example, using a Tensilon tester (ORIENTEC Co., RTC-1225A), the acrylic resin-containing film is cut out at 120 mm (length) × 10 mm (width), and 10N The temperature can be raised at a rate of 30 ° C./min while pulling with tension, and the temperature at 9 N is measured three times, and the average value can be obtained.

  Moreover, it is preferable that the film consisting of a cellulose ester resin and an acrylic resin has a glass transition temperature (Tg) of 110 ° C. or higher. More preferably, it is 120 ° C. or higher. Especially preferably, it is 150 degreeC or more.

  The glass transition temperature is determined by using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer) at a heating rate of 20 ° C./min, and determined in accordance with JIS K7121 (1987). Tmg).

  A film composed of a cellulose ester resin and an acrylic resin preferably has a breaking elongation in at least one direction of 10% or more, more preferably 20% or more, in the measurement based on JIS-K7127-1999. The upper limit of the elongation at break is not particularly limited, but is practically about 250%. In order to increase the elongation at break, it is effective to suppress defects in the film caused by foreign matter and foaming. The thickness of the film made of cellulose ester resin and acrylic resin is preferably 20 μm or more.

  More preferably, it is 30 μm or more. The upper limit of the thickness is not particularly limited, but in the case of forming a film by a solution casting method, the upper limit is about 250 μm from the viewpoint of applicability, foaming, solvent drying, and the like. The thickness of the film can be appropriately selected depending on the application.

  The film comprising a cellulose ester resin and an acrylic resin preferably contains an acrylic resin and a cellulose ester resin in a mass ratio of 95: 5 to 30:70 from the viewpoint of both workability and heat resistance. The total substitution degree (T) of the acyl group is 2.00 to 3.00, the acetyl group substitution degree (ac) is 0 to 1.89, the number of carbons of the acyl group other than the acetyl group is 3 to 7, and the weight The average molecular weight (Mw) is preferably 75,000 to 280000. Moreover, the total mass of an acrylic resin and a cellulose-ester resin is 55-100 mass% of an acrylic resin containing film, Preferably it is 60-99 mass%.

  A film made of a cellulose ester resin and an acrylic resin may contain other acrylic resins.

  A cellulose ester film or a film made of a cellulose ester resin and an acrylic resin may be produced by a solution casting method or a melt casting method, but preferably at least stretched in the width direction. In particular, when the amount of residual peeling is 3 to 40% by mass in the solution casting step, it is preferably stretched 1.01 to 1.5 times in the width direction. More preferably, it is biaxially stretched in the width direction and the lengthwise direction, and when the amount of residual dissolution is 3 to 40% by mass, it is stretched by 1.01 to 1.5 times in the width direction and the lengthwise direction, respectively. It is desirable that The draw ratio at this time is particularly preferably 1.03 to 1.45.

  The length of the base film is preferably 100 m to 5000 m, and the width is preferably 1.2 m or more, more preferably 1.4 to 4 m. By making the length and width of the base film within the above ranges, the handleability and productivity are excellent.

  The cellulose ester film is preferably a transparent support having a light transmittance of 90% or more, more preferably 93% or more.

(Plasticizer)
The cellulose ester film or cellulose ester resin / acrylic resin film preferably contains the following plasticizer. Examples of plasticizers include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, glycolate plasticizers, citrate ester plasticizers, and polyesters. A plasticizer, a polyhydric alcohol ester plasticizer, and the like can be preferably used.

  For phosphate plasticizers, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenylbiphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. For phthalate ester plasticizers, diethyl phthalate, dimethoxy For trimellitic acid plasticizers such as ethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, tributyl trimellitate, triphenyl trimellitate, triethyl For pyromellitic acid ester plasticizers such as trimellitate, tetrabutylpyromellitate, In the case of glycolate plasticizers such as lupyromelitate and tetraethylpyromellitate, triacetin, tributyrin, ethylphthalylethyl glycolate, methylphthalylethyl glycolate, butylphthalylbutyl glycolate, etc. Citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n- (2-ethylhexyl) citrate and the like can be preferably used. Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters.

  As the polyester plasticizer, a copolymer of a dibasic acid and a glycol such as an aliphatic dibasic acid, an alicyclic dibasic acid, or an aromatic dibasic acid can be used. The aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyl dicarboxylic acid, and the like can be used. As glycol, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol and the like can be used. These dibasic acids and glycols may be used alone or in combination of two or more.

  The polyhydric alcohol ester plasticizer comprises an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid. 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, 2-n-butyl-2-ethyl-1, 3-propanediol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, xylitol, and the like can be raised. 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 polyhydric alcohol ester, 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. It is more preferable that it is C1-C20, and it is especially preferable that it is C1-C10. 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-hexanecarboxylic 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, and laccelic acid, undecylenic acid, olein Unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid and arachidonic acid can be raised. Examples of preferable alicyclic monocarboxylic acid 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 biphenyl carboxylic acid, naphthalene carboxylic acid, and tetralin carboxylic acid. Aromatic monocarboxylic acids or derivatives thereof can be raised. Particularly preferred is benzoic acid. The molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably in the range of 300 to 1500, and more preferably in the range of 350 to 750. The larger one is preferable in terms of improving the retention, and the smaller one is preferable in terms of moisture permeability and compatibility with the 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 with carboxylic acid, or a part of the OH groups may be left as they are. These plasticizers are preferably used alone or in combination. The amount of these plasticizers used is preferably from 1 to 20% by mass, particularly preferably from 3 to 13% by mass, based on the cellulose ester, in terms of film performance, processability and the like.

(UV absorber)
You may make a base film contain a ultraviolet absorber. Next, the ultraviolet absorber will be described.

  As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.

  Specific examples include, but are not limited to, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, and the like.

  Although the following specific examples are given as a benzotriazole type ultraviolet absorber, 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 Japan Co., Ltd.)
UV-9: Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- Mixture of 4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba Japan Co., Ltd.)
Moreover, although the following specific examples are shown as a benzophenone series ultraviolet absorber, this invention is not limited to these.

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)
As the UV absorber, a benzotriazole UV absorber and a benzophenone UV absorber, which are highly transparent and excellent in preventing the deterioration of polarizing plates and liquid crystals, are preferable, and benzotriazole UV absorption with less unnecessary coloring is preferable. An agent is particularly preferably used.

  In addition, an ultraviolet absorber having a distribution coefficient of 9.2 or more described in Japanese Patent Application No. 11-295209 can be used, and in particular, an ultraviolet absorber having a distribution coefficient of 10.1 or more is the surface quality of the base film. Is preferable from the standpoint of maintaining good.

  Further, the polymer ultraviolet absorber (or ultraviolet ray) described in the general formula (1) or general formula (2) of JP-A-6-148430 and the general formulas (3), (6), and (7) of Japanese Patent Application No. 2000-156039. Absorbable polymers) are also preferably used. As a polymer ultraviolet absorber, PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) and the like are commercially available.

  Moreover, you may give an internal haze to a base film.

(particle)
Internal haze, for example, by adding particles with a refractive index different from that of the base film to the base film, and controlling the addition amount and particle size of the particles, generating haze due to internal scattering, and adjusting this Can be achieved. The particles are classified into inorganic particles and organic particles. The inorganic particles are not particularly limited, and examples thereof include silicon oxide, titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate. The organic particles are not particularly limited. For example, fluorinated acrylic resin powder, polystyrene resin powder, polymethacrylic acid methyl acrylate resin powder, silicone resin powder, polycarbonate resin powder, acrylic styrene resin powder, benzoguanamine resin Examples thereof include powder, melamine resin powder, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, and polyfluoroethylene resin powder. These inorganic particles and organic particles may be used in combination of two or more different types and average particle diameters, and those obtained by surface-treating the surface of the particles with an organic substance are also preferably used.

  Particularly preferred inorganic particles are silicon dioxide. Specific examples of silicon dioxide include Aerosil 200V, Aerosil R972V, Aerosil R972, R974, R812, 200, 300, R202, OX50, TT600 (above Nippon Aerosil Co., Ltd.), Sea Hoster KEP-10, Sea Hoster KEP-30, Commercial products having trade names such as Seahoster KEP-50 (above, made by Nippon Shokubai Co., Ltd.), Silo Hovic 100 (made by Fuji Silysia), Nip Seal E220A (made by Nippon Silica Kogyo), Admafine SO (made by Admatechs), etc. Can be preferably used. The shape of the particles can be used without any particular limitation, such as indefinite shape, needle shape, flat shape, spherical shape, etc. However, the use of spherical particles is particularly preferable because it is easy to adjust the haze. As the organic particles, fluorine-containing acrylic resin particles are particularly suitable.

  The fluorine-containing acrylic resin particles are, for example, particles formed from a fluorine-containing acrylic ester or methacrylic ester monomer or polymer. Specific examples of the fluorine-containing acrylic ester or methacrylic ester include 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H- Dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (Meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2-perfluorodecylethyl (Meth) acrylate, 3-perf Orobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 2- (perfluoro-3-methylbutyl ) Ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) 2-hydroxypropyl (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) Acrylate, 1H-1- ( (Rifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, perfluorooctylethyl acrylate, 2- (perfluorobutyl) ethyl In addition, among the fluorine-containing acrylic resin particles, particles made of 2- (perfluorobutyl) ethyl-α-fluoroacrylate, fluorine-containing polymethyl methacrylate particles, and fluorine-containing methacrylic acid are cross-linked. Particles copolymerized with a vinyl monomer in the presence of an agent are preferred, and fluorine-containing polymethyl methacrylate particles are more preferred.

  The vinyl monomer copolymerizable with fluorine-containing (meth) acrylic acid is not particularly limited as long as it has a vinyl group. Specifically, alkyl methacrylates such as methyl methacrylate and butyl methacrylate, and methyl acrylate. , Alkyl acrylates such as ethyl acrylate, and styrenes such as styrene and α-methylstyrene. These may be used alone or in combination. The crosslinking agent used in the polymerization reaction is not particularly limited, but those having two or more unsaturated groups are preferably used. For example, bifunctional dimethacrylates such as ethylene glycol dimethacrylate and polyethylene glycol dimethacrylate are used. And trimethylolpropane trimethacrylate, divinylbenzene and the like.

  The polymerization reaction for producing the fluorine-containing polymethyl methacrylate particles may be either random copolymerization or block copolymerization. Specifically, for example, the method described in JP-A No. 2000-169658 can also be mentioned.

  As a commercial item, commercial items, such as Negami Industries make: MF-0043, are mentioned. In addition, these fluorine-containing acrylic resin particles may be used alone or in combination of two or more. Moreover, the state of these fluorine-containing acrylic resin particles may be added in any state such as powder or emulsion.

  Moreover, you may use the fluorine-containing crosslinked particle of Paragraphs 0028-0055 of Unexamined-Japanese-Patent No. 2004-83707.

  Examples of polystyrene particles include commercially available products such as those manufactured by Soken Chemicals; SX-130H, SX-200H, SX-350H), Sekisui Plastics, SBX series (SBX-6, SBX-8).

  Examples of the melamine-based particles include a product made by Nippon Shokubai: benzoguanamine / melamine / formaldehyde condensate (trade name: eposter, grade; M30, product name: eposter GP, grade; H40 to H110), and made by Nippon Shokubai: melamine / formaldehyde condensation. Commercial products such as products (trade name: eposter, grade; S12, S6, S, SC4) can be mentioned. Moreover, the core-shell type spherical composite cured melamine resin particles in which the core is made of a melamine resin and the shell is filled with silica are also exemplified. Specifically, it can be produced by the method described in JP-A-2006-171033, and commercially available products such as melamine resin / silica composite particles (trade name: Opto Beads) manufactured by Nissan Chemical Industries, Ltd. can be mentioned.

  Examples of the poly ((meth) acrylate) particles and the crosslinked poly ((meth) acrylate) particles include, for example, Soken Chemicals; MX150, MX300, Nippon Shokubai; Eposta MA, Grades; MA1002, MA1004, MA1006, MA1010, Epostor MX (Emulsion), grade: MX020W, MX030W, MX050W, MX100W, manufactured by Sekisui Plastics: MBX series (MBX-8, MBX12), and other commercial products.

  Specific examples of the crosslinked poly (acryl-styrene) particles include commercial products such as FS-201 and MG-351 manufactured by Nippon Paint. Examples of the benzoguanamine-based particles include a product manufactured by Nippon Shokubai Co., Ltd .: benzoguanamine / formaldehyde condensate (trade name: eposter, grade; L15, M05, MS, SC25).

  The average particle size of the particles added to the support is preferably from 0.3 to 1 μm, more preferably from 0.4 to 0.7 μm.

  The average particle size can be determined by visual observation from an image photograph of secondary electron emission obtained by scanning electron microscope (SEM) or the like of 500 particles or by image processing, or by dynamic light scattering, static It can be measured by a particle size distribution meter using an automatic light scattering method or the like. The average particle diameter here refers to the number average particle diameter. In addition, an average particle diameter means the average particle diameter of an aggregate, when particle | grains are the aggregates of a primary particle. Moreover, when a particle is not spherical, it means the diameter of a circle corresponding to the projected area.

  The refractive index of the particles is preferably 1.45 to 1.70, more preferably 1.45 to 1.65. In addition, the refractive index of the particles is measured by measuring the turbidity by dispersing the same amount of particles in the solvent in which the refractive index is changed by changing the mixing ratio of two kinds of solvents having different refractive indexes. The refractive index of the solvent can be measured by measuring with an Abbe refractometer.

  In addition, the refractive index difference between the resin used for the support and the particles is preferably 0.02 or more and 0.20 or less in order to increase the internal haze using the light scattering effect. A more preferable range of the refractive index difference is 0.05 or more and 0.15 or less.

  The content of the inorganic or organic particles is preferably 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the resin for producing the film base material, and more preferably 5 parts by mass to 25 parts by mass for obtaining the internal haze. Part.

  The particles may be dispersed together with cellulose ester, other additives and an organic solvent when preparing the composition (dope) for producing the base film, or may be dispersed alone in the solution. . As a method for dispersing the particles, it is preferable that the particles are preliminarily dispersed in an organic solvent and then finely dispersed by a disperser (high pressure disperser) having a high shearing force.

  As a dope preparation method, it is preferable to disperse particles in a large amount of an organic solvent, merge with a cellulose ester solution, and mix with an in-line mixer to form a dope. In this case, an ultraviolet absorbent may be added to the particle dispersion to form an ultraviolet absorbent liquid.

  In addition, in the preparation of a solution composed of cellulose ester or cellulose ester resin and an acrylic resin, the above-mentioned deterioration inhibitor and ultraviolet absorber may be added together with a solvent, cellulose ester, cellulose ester resin and acrylic resin, It may be added during or after solution preparation.

(Organic solvent)
The dope preferably contains an organic solvent from the viewpoint of film forming properties and productivity. Any organic solvent can be used without limitation as long as it dissolves cellulose ester and other additives simultaneously. For example, methylene chloride, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3 , 3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3 , 3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane and the like. Among these organic solvents, methylene chloride, methyl acetate, ethyl acetate, and acetone are preferably used.

  The dope preferably contains 1 to 40% by mass of an alcohol having 1 to 4 carbon atoms in addition to the organic solvent. When the proportion of alcohol in the dope increases, the web gels, facilitating peeling from the metal support, and when the proportion of alcohol is small, the role of promoting dissolution of cellulose esters in non-chlorine organic solvent systems There is also. Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Ethanol is preferred because of the stability, boiling point of these inner dopes, relatively good drying, and no toxicity.

  The concentration of the cellulose ester in the dope is preferably adjusted to 15 to 40% by mass, and the dope viscosity is preferably adjusted to a range of 100 to 500 poise (P) in order to obtain good film surface quality.

(Solution casting method)
Cellulose ester film, and cellulose ester resin / acrylic resin film are produced by a solution casting method. A step of preparing a dope by dissolving cellulose ester or cellulose ester resin / acrylic resin and an additive in a solvent, and belting the dope A step of casting on a metal support in the form of a drum or a drum, a step of drying the cast 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 finished film It is performed by a winding process.

  The concentration of cellulose ester in the dope, and the concentration of cellulose ester resin / acrylic resin is preferably higher because the drying load after casting on a metal support can be reduced. The load increases, and the filtration accuracy deteriorates. As a density | concentration which makes these compatible, 10-35 mass% is preferable, More preferably, it is 15-25 mass%.

  The metal support in the casting (casting) step preferably has a mirror-finished surface. As the metal support, a stainless steel belt or a drum whose surface is plated with a casting is preferably used. 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 the 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%.

  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.

  Further, in the drying step of the cellulose ester film or the film made of cellulose ester resin / acrylic resin, it is preferable that the web is peeled off from the metal support and further dried to make the residual solvent amount 1% by mass or less. Preferably it is 0.1 mass% or less, Most preferably, it is 0-0.01 mass%.

  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 tenter method is used while drying the web.

  In the film drying step, it is preferable to carry out the treatment while transporting in an atmosphere with an atmosphere substitution rate of 12 times / hour or more, preferably 12 to 45 times / hour.

The atmosphere substitution rate is defined as follows. When the atmosphere capacity of the heat treatment chamber is V (m ³ ) and the fresh air flow rate is FA (m ³ / hr), the atmosphere of the heat treatment chamber per unit time determined by the following formula is Fresh-air. Is the number of replacements by. “Fresh-air” means that the wind blown into the heat treatment chamber is not a wind that is recycled and reused, and it means a fresh wind that does not contain volatilized solvent or plasticizer or has been removed. Yes.

Atmosphere replacement rate = FA / V (times / hour)
An atmosphere substitution rate of 12 times / hour or more is preferable because the plasticizer concentration in the atmosphere due to the plasticizer volatilized from the cellulose ester film can be sufficiently reduced, and reattachment to the film can be reduced.

(Melting method)
The cellulose ester film and the cellulose ester resin / acrylic resin film are also preferably formed by a melt film forming method. In the melt film-forming method, a composition containing a cellulose ester, a cellulose ester resin / acrylic resin, and an additive such as a plasticizer is heated and melted to a temperature showing fluidity, and then a melt containing a fluid cellulose ester. It means to cast.

  More specifically, the heat melting molding method can be classified into a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, a stretch molding method, and the like. Among these, in order to obtain a cellulose ester film excellent in mechanical strength and surface accuracy, and a cellulose ester resin / acrylic resin film, the melt extrusion method is excellent.

  It is preferable that a plurality of raw materials used for melt extrusion are usually kneaded in advance and pelletized.

  Pelletization may be performed by a known method. For example, dry cellulose ester, plasticizer, and other additives are fed to an extruder with a feeder and kneaded using a single-screw or twin-screw extruder, and formed into a strand from a die. It can be done by extrusion, water cooling or air cooling and cutting.

  The additives may be mixed before being supplied to the extruder, or may be supplied by individual feeders. A small amount of additives such as particles and antioxidants are preferably mixed in advance in order to mix uniformly.

  The extruder is preferably processed at as low a temperature as possible so as to be able to be pelletized so that the shear force is suppressed and the resin does not deteriorate (decrease in molecular weight, coloring, gel formation, etc.). For example, in the case of a twin screw extruder, it is preferable to rotate in the same direction using a deep groove type screw. From the uniformity of kneading, the meshing type is preferable.

  A film is formed using the pellets obtained as described above. Of course, the raw material powder can be directly fed to the extruder by a feeder without being pelletized to form a film as it is.

  Using a single or twin screw extruder, the pellets are melted at a temperature of about 200 to 300 ° C., filtered through a leaf disk filter, etc. to remove foreign matter, and then formed into a film from a T die. And solidified on a cooling roll.

  When introducing from the supply hopper to the extruder, it is preferable to prevent oxidative decomposition or the like under vacuum, reduced pressure, or inert gas atmosphere.

  The extrusion flow rate is preferably performed stably by introducing a gear pump or the like. Further, a stainless fiber sintered filter is preferably used as a filter used for removing foreign substances.

  The stainless steel fiber sintered filter is a united stainless steel fiber body that is intricately intertwined and compressed, and the contact points are sintered and integrated. The density of the fiber is changed depending on the thickness of the fiber and the amount of compression, and the filtration accuracy is improved. Can be adjusted.

  Additives such as plasticizers and particles may be mixed with the resin in advance, or may be kneaded in the middle of the extruder. In order to add uniformly, it is preferable to use a mixing apparatus such as a static mixer.

  The film temperature on the touch roll side when the film is nipped between the cooling roll and the elastic touch roll is preferably Tg or more and Tg + 110 ° C. or less of the film. A well-known roll can be used for the roll which has the elastic body surface used for such a purpose.

  When peeling the film from the cooling roll, it is preferable to control the tension to prevent deformation of the film.

  Moreover, it is preferable that the film obtained as described above is stretched by the stretching operation after passing through the step of contacting the cooling roll.

  As a method of stretching, a known roll stretching machine or tenter can be preferably used. The stretching temperature is usually preferably performed in the temperature range of Tg to Tg + 60 ° C. of the resin constituting the film. Before winding, the end may be slit and cut to the width to be the product, and knurling (embossing) may be applied to both ends to prevent sticking and scratching during winding. The knurling method can process a metal ring having an uneven pattern on its side surface by heating or pressing. In addition, since the film has deform | transformed and cannot use as a product normally, the holding part of the clip of both ends of a film is cut out and reused.

(Polarizing plate protective film)
When the hard coat film produced using the production method of the present invention is used as a polarizing plate protective film, the thickness of the protective film is preferably 10 to 500 μm. In particular, it is preferably 20 μm or more, and more preferably 35 μm or more. Moreover, 150 micrometers or less, Furthermore 120 micrometers or less are preferable. Most preferably, it is 25 or more and 90 micrometers. If the antireflection film is thicker than the above region, the polarizing plate after polarizing plate processing becomes too thick, and is not suitable for the purpose of thin and light in liquid crystal displays used for notebook personal computers and mobile electronic devices. On the other hand, if it is thinner than the above-mentioned region, it is not preferable because it becomes difficult to develop retardation, the moisture permeability of the film becomes high, and the ability to protect the polarizer from humidity decreases.

(Polarizer)
A hard coat film produced by the production method of the present invention and a polarizing plate using an antireflection film in which a low refractive index layer is laminated on the hard coat layer of the hard coat film will be described. When a polarizing plate is produced by a general method, a completely saponified polyvinyl alcohol aqueous solution is formed on at least one surface of a polarizing film produced by immersing and stretching an alkali saponified hard coat film or antireflection film in an iodine solution. In the antireflection film in which the low refractive index layer is laminated on the hard coat layer of the hard coat film and the hard coat layer of the hard coat film, an alkali saponification treatment is performed. Since it can be bonded to the polarizing film without causing any adhesion of foreign matter that occurs in the alkali saponification step, it is preferable from the viewpoint of suppressing the occurrence of display defects due to foreign matter when used in an image display device.

  In addition, in alkali saponification treatment, in order to prevent foreign matter adhesion and deterioration of the hard coat layer or the low refractive index layer, a protective film that can be peeled off is previously applied to the hard coat layer and the low refractive index layer for protection. In general, a hard coat film produced by the production method of the present invention and an antireflection film in which a low refractive index layer is laminated on the hard coat layer of the hard coat film are coated with a peelable protective film. Since no attaching process or peeling process is required, there is no equipment load and the productivity is excellent.

  Moreover, a polarizing plate protective film is usually affixed on the other surface which bonded the hard coat film or the antireflection film. As the polarizing plate protective film, an optical compensation film (retardation film) having an in-plane retardation Ro of 590 nm, a retardation of 20 to 70 nm, and an Rt of 70 to 400 nm is preferably used. These can be prepared, for example, by the methods described in JP-A No. 2002-71957 and Japanese Patent Application No. 2002-155395. 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 JP-A-2003-98348. Alternatively, a non-oriented film having a retardation Ro of 590 nm of 0 to 5 nm and an Rt of -20 to +20 nm described in JP-A No. 2003-12859 is also preferably used. The produced polarizing plate of the present invention has a stable viewing angle expansion effect.

  Commercially available polarizing plate protective films include KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC4UEW, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1, KC4FR-2, KC8UE, K4T For example).

  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 ones in which iodine is dyed on a system film and ones in which a dichroic dye is dyed, but it is not limited to this. 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. A polarizing film having a thickness of 5 to 30 μm, preferably 8 to 15 μm, is preferably used. On the surface of the polarizing film, one side of the 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.

(Image display device)
By incorporating the polarizing plate of the present invention into a display device, various image display devices with excellent visibility can be produced.

  Specifically, a reflective type, a transmissive type, a transflective type liquid crystal display device, or various driving methods such as a TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type, OCB type, etc. Embedded in various image display devices such as liquid crystal display devices, plasma displays, field emission displays, organic EL displays, inorganic EL displays, and electronic paper.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1
(Base film 1; production of cellulose ester film 1)
(Dope solution composition 1)
The following materials were sequentially put into a sealed container, the temperature in the container was raised from 20 ° C. to 80 ° C., and the mixture was stirred for 3 hours while maintaining the temperature at 80 ° C. to completely dissolve the cellulose ester. . The silicon oxide fine particles were added dispersed in a solution of a solvent to be added in advance and a small amount of cellulose ester. This dope was filtered using filter paper (Azumi filter paper No. 244, manufactured by Azumi Filter Paper Co., Ltd.) to obtain a dope solution composition 1.

Cellulose triacetate (acetyl group substitution degree 2.95) 100 parts by weight Trimethylolpropane tribenzoate 5 parts by weight Ethylphthalylethyl glycolate 5 parts by weight Fine particles of silicon oxide 0.2 parts by weight (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.)
Tinuvin 109 (manufactured by Ciba Japan) 1 part by weight Tinuvin 171 (manufactured by Ciba Japan) 1 part by weight Methylene chloride 300 parts by weight Ethanol 40 parts by weight Butanol 5 parts by weight Next, the obtained dope The liquid composition 1 was cast through a casting die kept at a temperature of 35 ° C. onto a support having a temperature of 35 ° C. made of a stainless steel endless belt to form a web. Next, the web was dried on the support, and the web was peeled from the support with a peeling roll when the residual solvent amount of the web reached 80% by mass.

  The web after peeling is transported while being dried with 90 ° C drying air in a transport drying process using a plurality of rolls arranged on the top and bottom, and then grips both ends of the web with a tenter and then stretches in the width direction at a temperature of 130 ° C. The film was stretched to 1.1 times the previous size. After stretching with a tenter, the web was dried with a drying air at a temperature of 135 ° C. in a transport drying process using a plurality of rolls arranged vertically. After heat-treating for 15 minutes in an atmosphere with an atmosphere substitution rate of 15 (times / hour) in the drying step, the film was cooled to room temperature and wound up. A long cellulose ester film 1 was produced. Further, the film was wound by applying a knurling process with a width of 2 cm and an average height of 20 μm at both ends. The draw ratio in the web conveyance direction immediately after peeling calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.1 times.

<Atmosphere replacement rate>
The atmosphere replacement rate is defined as the atmosphere of the heat treatment chamber per unit time determined by the following formula when the atmosphere capacity of the heat treatment chamber is V (m ³ ) and the fresh air flow rate is FA (m ³ / hr). The number of replacements with -air. “Fresh-air” means that the wind blown into the heat treatment chamber is not a wind that is recycled and reused, and it means a fresh wind that does not contain volatilized solvent or plasticizer or has been removed. Yes.

Atmosphere replacement rate = FA / V (times / hour)
(Preparation of hard coat film 1)
A hard coat film 1 was produced on the produced cellulose ester film 1 by the following procedure.

(Preparation of hard coat film 1)
On the cellulose ester film 1, the following hard coat layer composition 1 is filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a hard coat layer coating solution, which is extruded using a coater, and the cellulose ester film After coating on the surface of 1 and drying at a temperature of 80 ° C. for 50 seconds, the irradiance of the irradiated part is 300 mW / cm ² using an ultraviolet lamp, the irradiation amount is 0.3 J / cm ² and the coating layer is cured, After forming a hard coat layer having a dry film thickness of 10 μm, a wet film is formed on the surface opposite to the side on which the hard coat layer is provided with the following alkaline solution 1 by continuous coating (in Table 1, it is described as a back coat layer). The surface of the cellulose ester film 1 is coated on the surface opposite to the surface on which the hard coat layer is coated with an extrusion coater so that the thickness is 8 μm, and the temperature is 100 ° C. for 50 seconds. In dried, taken up in a roll form to prepare a hard coat film 1.

(Hard coat layer composition 1)
The following materials were stirred and mixed to obtain hard coat layer composition 1.

180 parts by mass of dipentaerythritol hexaacrylate (NK ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Irgacure 184 6 parts by mass (Ciba Japan Co., Ltd.)
Irgacure 907 8 parts by mass (Ciba Japan Co., Ltd.)
Polyether-modified silicone compound (trade name: KF-355A, manufactured by Shin-Etsu Chemical Co., Ltd.) 9 parts by mass Propylene glycol monomethyl ether 10 parts by mass Ethyl acetate 80 parts by mass Methyl ethyl ketone 100 parts by mass (Alkaline solution 1)
Potassium hydroxide 8.6 parts by weight Pure water 24.4 parts by weight Acetone 56.0 parts by weight Isopropanol 10.0 parts by weight Ultrafine silica 2% acetone dispersion 0.2 parts by weight (Aerosil 200V manufactured by Nippon Aerosil Co., Ltd.)
(Preparation of hard coat films 2-5)
In the production of the hard coat film 1, hard coat films 2 to 5 were produced in the same manner except that the dry film thickness of the hard coat layer was changed as described in Table 1.

(Preparation of hard coat film 6 and hard coat film 7)
In the production of the hard coat film 1, the hard coat film 6 and the hard coat film were similarly prepared except that the dry film thickness of the hard coat layer was as shown in Table 1 and the alkaline solution 1 was changed to the following alkaline solution 2. 7 was produced.

(Alkaline solution 2)
Sodium hydroxide 8.6 parts by weight Pure water 24.4 parts by weight Acetone 56.0 parts by weight Isopropanol 10.0 parts by weight Cellulose acetate propionate 0.6 parts by weight (acetyl group substitution degree 1.9, propionyl group substitution degree) 0.8)
0.2 parts by mass of ultrafine silica 2% acetone dispersion (Aerosil 200V manufactured by Nippon Aerosil Co., Ltd.)
(Preparation of hard coat films 8-11)
In the production of the hard coat film 1, the hard coat films 6 to 11 were similarly formed except that the dry film thickness of the hard coat layer was described in Table 1 and the alkaline solution 1 was changed to the following back coat solution 1. Produced.

(Backcoat solution 1)
Acetone 89.0 parts by mass Isopropanol 10.0 parts by mass Cellulose acetate propionate 0.6 parts by mass (acetyl group substitution degree 1.9, propionyl group substitution degree 0.8)
0.2 parts by mass of ultrafine silica 2% acetone dispersion (Aerosil 200V manufactured by Nippon Aerosil Co., Ltd.)
(Preparation of hard coat films 12-16)
In the production of the hard coat film 1, the hard coat films 12 to 16 were similarly formed except that the dry film thickness of the hard coat layer was described in Table 1 and the alkaline solution 1 was changed to the following back coat solution 2. Produced.

(Backcoat solution 2)
Acetone 89.0 parts by mass Isopropanol 10.8 parts by mass (Preparation of hard coat film 17)
In the production of the hard coat film 1, a hard coat film 17 was produced in the same manner except that the dry film thickness of the hard coat layer was changed to 8 μm.

(Preparation of hard coat film 18)
In the production of the hard coat film 1, a hard coat film 18 was produced in the same manner except that the dry film thickness of the hard coat layer was changed to 8 μm and the alkaline solution 1 was changed to the back coat solution 1.

(Preparation of hard coat film 19)
In the production of the hard coat film 1, the hard coat film 19 was produced in the same manner except that the dry film thickness of the hard coat layer was changed to 8 μm and the alkaline solution 1 was changed to the back coat solution 2.

<Evaluation>
About the produced said hard coat films 1-19, the wet heat processing was implemented on the conditions which assumed long-term storage, such as high temperature and high humidity storage of summer, and transportation, and the following method evaluated. The obtained results are shown in Table 1.

(Humid heat treatment)
It was stored for 7 days under conditions of 50 ° C. and 80%, and wet heat treatment was performed. Next, 5 m was cut out from a 3500 m hard coat film roll that had been heat-moisture treated, and the cut out hard coat film was conditioned for 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 55%, and then evaluated for the following pencil hardness and curl. .

(Pencil hardness)
Using the test pencil specified by JIS-S6006, according to the pencil hardness evaluation method specified by JIS-K5400, the surface of the hard coat layer was scratched 5 times with a pencil of each hardness using a weight of 500 g, and one scratch was found. The hardness was measured. The higher the number, the higher the hardness, and the hardness of 3H or higher is the high hardness in the present invention, and 4H or higher is practically preferable.

(curl)
1. Curl The curl of the hard coat film was measured using the curl measurement template of Method A in “Measurement Method of Curling of Photographic Film” of JIS K7619-1988. Here, “curl plus” means a curl where the hard coat layer coating side of the film is inside the curve, and “minus” means a curl where the coating side is outside the curve. Further, the curl is expressed by the following formula A.

(Formula A) Curl = 1 / R R is the radius of curvature (m)
The ranking was as follows according to the curl amount of the measurement result.

Minus 5 to plus 5: ◎ (very good)
Minus 10 to minus 5, plus 5 to plus 10: ○ (excellent)
Minus 15 to minus 10, plus 10 to plus 15: x (somewhat inferior, there is a problem in practical use)
Minus 15 or less, plus 15 or more: XX (Inferior)
2. End curl Place the hard coat layer face up on a horizontal base, pull out 2m from the 5m hard coat film, tape the end of the 2m pull out end, tape it to the part, and head out from there The distance (lifting distance) was measured from the horizontal platform at both ends at a position of 1 m. The total length of the lifting distance was evaluated as ◎, less than 30 mm, ○, 30 mm, less than 50 mm, ５０, 50 mm, less than 70 mm (practically problematic), and 70 mm or more as xx.

In addition, as a comprehensive evaluation, the compatibility between the high hardness of the target effect and curl suppression was evaluated as a standard below and shown in Table 1.
◎: Curling and end curl with hardness 3H or higher (high hardness) ◎
○: Hardness is 3H or higher (high hardness) and either curl or end curl is ○
X: Hardness is less than 3H, or either curl or end curl is less than x

  As can be seen from Table 1, in the case of a high-hardness hard coat film having a hard coat layer thickness of 10 μm or more and a pencil hardness of 3H or more, the backcoat coating solution is a curl-free solution (backcoat solution 1 or 2). The deterioration of the hardness is deteriorated, and both high hardness and curl suppression cannot be achieved (hard coating film Nos. 8 to 16 of comprehensive evaluation). In contrast, the hard coat film of the present invention using an alkali-containing solution for back coat application is excellent in both high hardness and curl suppression (Hard coat film Nos. 8 to 16 of comprehensive evaluation ◯).

  In particular, in the hard coat film (hard coat film Nos. 2 to 4) of the present invention having a hard coat layer thickness of 12 μm or more and 20 μm or less and a pencil hardness of 4H or more (hard coat film No. 2 to 4), a comparative hard coat film (hard coat film no. .8 to 10 and 13 to 15), particularly excellent hardness and curl suppressing effect can be obtained. When the thickness of the hard coat layer is 24 μm, a particularly excellent high hardness and curling suppression effect can be obtained as compared with the comparative hard coat film of the same film thickness, but the hard coat film in the present invention has the curling suppression effect. Somewhat weak.

Example 2
(Preparation of hard coat film 20)
In the production of the hard coat film 2, a hard coat film 20 was produced in the same manner except that the alkaline solution 1 was changed to the following alkaline solution 3.

(Alkaline solution 3)
Sodium hydroxide 8.6 parts by weight Pure water 24.4 parts by weight Acetone 56.0 parts by weight Isopropanol 10.0 parts by weight Cellulose acetate propionate 0.6 parts by weight (acetyl group substitution degree 1.9, propionyl group substitution degree) 0.8)
0.2 parts by mass of ultrafine silica 2% acetone dispersion (Aerosil 200V manufactured by Nippon Aerosil Co., Ltd.)
Fluorine compound (perfluoroalkyl group / hydrophilic group / lipophilic group-containing oligomer, trade name: F-477, manufactured by DIC Corporation) 1.5 parts by mass (production of hard coat film 21)
In the production of the hard coat film 2, a hard coat film 21 was produced in the same manner except that the alkaline solution 1 was changed to the following alkaline solution 4.

(Alkaline solution 4)
Sodium hydroxide 8.6 parts by weight Pure water 24.4 parts by weight Acetone 56.0 parts by weight Isopropanol 10.0 parts by weight Cellulose acetate propionate 0.6 parts by weight (acetyl group substitution degree 1.9, propionyl group substitution degree) 0.8)
0.2 parts by mass of ultrafine silica 2% acetone dispersion (Aerosil 200V manufactured by Nippon Aerosil Co., Ltd.)
Polyether-modified silicone compound (trade name; KF-351A, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.5 parts by mass << Evaluation >>
The produced hard coat films 2, 20 and 21 were evaluated in the same manner as in Example 1 except that the wet heat treatment was changed to the following conditions. The obtained results are shown in Table 2.

(Humid heat treatment)
It was stored for 14 days under conditions of 50 ° C. and 80%, and was subjected to wet heat treatment. Next, 5 m was cut out from a 3500 m hard coat film roll that had been heat-moisture treated, and the cut out hard coat film was conditioned for 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 55%, and then evaluated for the following pencil hardness and curl. .

As can be seen from the results in Table 2, in a hard coat film subjected to more severe wet heat treatment, a particularly excellent curling suppression effect can be obtained by including a fluorine compound or a silicone compound in the back coat layer. I understand.

Example 3
In the production of the hard coat film 2, hard coat films 22 and 23 were produced in the same manner except that the base film was changed to the following base film 2 and 3.

<Preparation of base film 2>
<Production of Cellulose Ester Resin / Acrylic Resin Film 1>
(Dope solution composition 2)
Acrylic resin Dianal BR80 (Mitsubishi Rayon Co., Ltd.) 70 parts by mass (MW95000)
CAP482-20 (acyl group total substitution degree 2.75, acetyl group substitution degree 0.19, propionyl group substitution degree 2.56, Mw = 200000 manufactured by Eastman Chemical Co., Ltd.)
30 parts by weight Tinuvin 109 (manufactured by Ciba Japan) 1 part by weight Tinuvin 171 (manufactured by Ciba Japan) 1 part by weight Methylene chloride 300 parts by weight Ethanol 40 parts by weight Butanol 5 parts by weight The above composition is heated. While fully dissolved, a dope solution was prepared. In addition, CAP is a cellulose acetate propionate resin.

(Film formation of cellulose ester resin / acrylic resin film 1)
The produced dope solution was uniformly cast on a stainless steel band support at a temperature of 22 ° C. and a width of 2 m using a belt casting apparatus. With the stainless steel band support, the solvent was evaporated until the amount of residual solvent reached 100%, and peeling was performed from the stainless steel band support with a peeling tension of 162 N / m.

  The peeled acrylic resin web was evaporated at 35 ° C., slit to 1.6 m width, and then dried at a drying temperature of 135 ° C. while being stretched 1.1 times in the width direction by a tenter. At this time, the residual solvent amount when starting stretching with a tenter was 10%.

  After stretching with a tenter and relaxing at 130 ° C. for 5 minutes, drying is completed while transporting a drying zone at 120 ° C. and 130 ° C. with many rolls, slitting to a width of 1.5 m, and a height of 2 cm on both ends of the film. A knurling process having a thickness of 20 μm was applied and wound up to obtain a cellulose ester resin / acrylic resin film 1 having a film thickness of 40 μm, a length of 3500 m, and a refractive index of 1.50.

  The draw ratio in the MD direction calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.1 times.

<Preparation of base film 3>
A base film 3 (cellulose ester resin / acrylic resin film 2) was prepared in the same manner except that the base film 2 was changed to the following dope solution composition 3 in the preparation of the base film 2.

<Preparation of acrylic particles>
A reactor with a reflux condenser with an internal volume of 60 liters was charged with 38.2 liters of ion-exchanged water and 111.6 g of sodium dioctylsulfosuccinate, and the temperature was raised to 75 ° C. under a nitrogen atmosphere while stirring at a rotational speed of 250 rpm. The effect of oxygen was virtually eliminated. 0.36 g of APS was added, and after stirring for 5 minutes, a monomer mixture consisting of 1657 g of MMA, 21.6 g of BA, and 1.68 g of ALMA was added all at once. Completed. Next, 3.48 g of APS was added, and after stirring for 5 minutes, a monomer mixture consisting of BA 8105 g, PEGDA (200) 31.9 g, and ALMA 264.0 g was continuously added over 120 minutes. Hold for a minute to complete the soft layer polymerization.

  Next, 1.32 g of APS was added, and after stirring for 5 minutes, a monomer mixture consisting of 2106 g of MMA and 201.6 g of BA was continuously added over 20 minutes. The polymerization of was completed.

  Next, 1.32 g of APS was added, and after 5 minutes, a monomer mixture consisting of 3148 g of MMA, 201.6 g of BA, and 10.1 g of n-OM was continuously added over 20 minutes, and the mixture was held for another 20 minutes after the addition was completed. Next, the temperature was raised to 95 ° C. and held for 60 minutes to complete the polymerization of the outermost hard layer 2.

  A small amount of the polymer latex thus obtained was collected, and the flat particle diameter was determined by the absorbance method. As a result, it was 0.10 μm. The remaining latex was put into a 3% by mass aqueous solution of sodium sulfate, salted out and coagulated, and then repeatedly dehydrated and washed, and then dried to obtain acrylic particles having a three-layer structure.

  The above abbreviations are the following materials.

MMA; methyl methacrylate MA; methyl acrylate BA; n-butyl acrylate ALMA; allyl methacrylate PEGDA; polyethylene glycol diacrylate (molecular weight 200)
n-OM; n-octyl mercaptan APS; ammonium persulfate <Preparation of acrylic ester film-containing cellulose ester resin / acrylic resin film 2>
(Dope solution composition 3)
Dianar BR80 (manufactured by Mitsubishi Rayon Co., Ltd.) 70 parts by mass CAP482-20 30 parts by mass The above prepared acrylic particles 20 parts by mass Tinuvin 109 (manufactured by Ciba Japan) 1 part by mass Tinuvin 171 (Ciba Japan Co., Ltd.) 1 part by mass Methylene chloride 300 parts by mass Ethanol 40 parts by mass Butanol 5 parts by mass The above composition was sufficiently dissolved while heating to prepare a dope solution.

<Evaluation>
The produced hard coat films 2, 22 and 23 were subjected to the same wet heat treatment as in Example 2 and evaluated in the same manner as in Example 1. The obtained results are shown in Table 3.

  As can be seen from the results in Table 3, the hard coat film subjected to more severe wet heat treatment is particularly excellent in curling suppression effect by making the base film a film made of cellulose ester resin / acrylic resin rather than cellulose ester film. It can be seen that Further, the base film 3 made of cellulose ester resin / acrylic resin and containing acrylic particles can achieve particularly excellent curling suppression and high hardness.

Example 4
<Preparation of antireflection films 1 and 2>
Plasma treatment was performed on the hard coat layers of the hard coat films 2 and 8 under the following conditions. Next, on the surface of the hard coat layer, the following low refractive index layer coating composition 1 was applied by an extrusion coater, dried at 100 ° C. for 1 minute, and then irradiated with ultraviolet rays at an irradiation intensity of 100 mW / cm ² and 0.3 J / It was cured by irradiating cm ² , a low refractive index layer was provided so as to have a thickness of 85 nm, and the film was wound into a roll. Subsequently, the film was subjected to heat aging treatment at 60 ° C. for 2 days to produce antireflection films 1 and 2.

  The refractive index of the low refractive index layer of the obtained antireflection film was 1.37.

(Plasma treatment)
The distance between electrodes was set to 1.8 mm using the plasma processing apparatus shown in FIG. A DC voltage of 210 to 230 V is applied to the DC power supply of the power supply circuit 10 that generates a pulsed electric field, the following discharge gas is supplied to the discharge space, and a pulse electric field of 10 kHz frequency and Vpp 16.09 kV is applied between the electrodes. Processed.

(Low refractive index layer coating composition 1)
Propylene glycol monomethyl ether 200 parts by mass Isopropyl alcohol 660 parts by mass Tetraethoxysilane hydrolyzate A 120 parts by mass γ-methacryloxypropyltrimethoxysilane 4 parts by mass (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.)
30 parts by mass of isopropyl alcohol-dispersed hollow silica particle sol (solid content 20%, silica sol manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name: ELCOM V-8209)
Aluminum ethyl acetoacetate / diisopropylate 2 parts by mass Silicone surfactant (FZ-2207, manufactured by Nippon Unicar Co., Ltd.) 10% propylene glycol monomethyl ether solution 3 parts by mass Acetic acid 4 parts by mass << Evaluation >>
The antireflection films 1 and 2 produced above were subjected to wet heat treatment and evaluation in the same manner as in Example 1. The results obtained are shown in Table 4.

  As can be seen from the results in Table 4, the antireflection film of the present invention can achieve both excellent curl suppression and high hardness.

Example 5
Using the hard coat films 1 to 19 produced in Example 1 and the antireflection films 1 and 2 produced in Example 4, polarizing plates were prepared as follows, and these polarizing plates were used as liquid crystal display panels (image display). The device was incorporated into a device, and the flatness and visibility were evaluated.

  According to the following method, the hard coat films 1 to 19 produced in Example 1 and the antireflection films 1 and 2 produced in Example 4 were each one of KC8UCR5 (manufactured by Konica Minolta Opto), which is a cellulose ester-based optical compensation film. Were used as polarizing plate protective films to prepare polarizing plates 101 to 121, respectively.

(A) Production of Polarizing Film What was impregnated with 10 parts by mass of glycerin and 170 parts by mass of water in 100 parts by mass of polyvinyl alcohol (hereinafter abbreviated as PVA) having a saponification degree of 99.95 mol% and a polymerization degree of 2400. After melt-kneading and defoaming, it was melt-extruded from a T-die onto a metal roll to form a film. Then, it dried and heat-processed and obtained the PVA film. The obtained PVA film had an average thickness of 25 μm, a moisture content of 4.4%, and a film width of 3 m.

Next, the obtained PVA film was continuously processed in the order of preliminary swelling, dyeing, uniaxial stretching by a wet method, fixing treatment, drying, and heat treatment to prepare a polarizing film. That is, the PVA film was pre-swelled by immersing in water at a temperature of 30 ° C. for 30 seconds, and immersed in an aqueous solution having an iodine concentration of 0.4 g / liter and a potassium iodide concentration of 40 g / liter at a temperature of 35 ° C. for 3 minutes. Subsequently, the film was uniaxially stretched 6 times in a 50% aqueous solution with a boric acid concentration of 4% under the condition that the tension applied to the film was 700 N / m, and the potassium iodide concentration was 40 g / liter and the boric acid concentration was 40 g / liter. Then, it was immersed in an aqueous solution having a zinc chloride concentration of 10 g / liter and a temperature of 30 ° C. for 5 minutes for fixing. Thereafter, the PVA film was taken out, dried with hot air at a temperature of 40 ° C., and further heat-treated at a temperature of 100 ° C. for 5 minutes. The obtained polarizing film had an average thickness of 13 μm, a polarizing performance of a transmittance of 43.0%, a polarization degree of 99.5%, and a dichroic ratio of 40.1.
(B) Production of Polarizing Plate Next, according to the following steps 1 to 4, the polarizing film and the protective film for polarizing plate were bonded together, and the hard coat films 1 to 19 produced in Example 1 and the reflection produced in Example 4 were used. Polarizing plates 101 to 121 corresponding to the prevention films 1 and 2 were produced.

  Process 1: The above-mentioned polarizing film was immersed for 1 to 2 seconds in the storage tank of the polyvinyl alcohol adhesive agent solution of 2 mass% of solid content.

  Step 2: Excess adhesive adhered to the polarizing film in Step 1 is lightly removed, immersed in this polarizing film and 2 mol / L sodium hydroxide solution at a temperature of 60 ° C. for 90 seconds, then washed with water and dried, The saponified optical compensation film, the hard coat films 1 to 19 prepared in Example 1, and the antireflection films 1 and 2 prepared in Example 4 were sandwiched and laminated.

Step 3: The laminate was bonded at a speed of about 2 m / min at a pressure of ^{20 to} 30 N / cm ² with two rotating rollers. At this time, it was carried out with care to prevent bubbles from entering.

  Step 4: The sample prepared in Step 3 was dried in a dryer at a temperature of 80 ° C. for 2 minutes to prepare polarizing plates 101 to 121.

  Next, the polarizing plate on the outermost surface of a commercially available liquid crystal display panel (VA type) was carefully peeled off, and the polarizing plates 101 to 121 whose polarization directions were matched were pasted in the configuration shown in FIG. The liquid crystal panels 201 to 221 thus obtained were placed on a desk 80 cm high from the floor, and a daylight direct fluorescent lamp (FLR40S • D / MX Matsushita Electric) was placed on the ceiling 3 m high from the floor. Sangyo Co., Ltd.) 40W × 2 were set as one set, and 10 sets were arranged at intervals of 1.5 m. In this case, when the evaluator is in front of the display surface of the liquid crystal display panel, the fluorescent lamp is arranged so that the fluorescent lamp comes to the ceiling portion from the evaluator's overhead to the rear. Each liquid crystal panel was tilted by 25 ° from the vertical direction with respect to the desk, and was evaluated according to the following ranks so that a fluorescent lamp was reflected.

  About the polarizing plate which bonded the hard coat film, the deterioration of the planarity by curl was evaluated on the following references | standards.

◎: Fluorescent lamp looks straight ○: Fluorescent lamp appears to be slightly bent △: Fluorescent lamp appears to be bent

  X: A fluorescent lamp appears to swell greatly.

  About the polarizing plate which bonded the anti-reflective film, the following reference | standard evaluated the visibility (visibility) of a screen.

A: I don't care about the reflection of the nearest fluorescent lamp, and I can clearly read characters with a font size of 8 or less. B: The reflection of a nearby fluorescent lamp is a little anxious, but I don't care about the distance. Can manage to read characters with a font size of 8 or less C: It is difficult to read characters with a font size of 8 or less. The part of the reflection is anxious and cannot read characters with a font size of 8 or less. As a result of evaluation, a liquid crystal panel using a polarizing plate of a comparative example in which a hard coat film and an antireflection film of a comparative example are bonded Whereas the above evaluation is that the flatness evaluation is x to Δ, and the visibility evaluation is C or less, the liquid crystal panel using the polarizing plate on which the hard coat film and the antireflection film of the present invention are bonded, Both have flatness evaluation , And the visibility evaluation was good and the evaluation result of A.

It is another schematic diagram of an atmospheric pressure plasma processing apparatus. It is the schematic which shows the structure of the liquid crystal display device preferable for this invention.

Explanation of symbols

A discharge space 101a atmospheric pressure plasma processing apparatus 101 high frequency high voltage power supply 102 roll electrode 103 curved surface electrode 104 plasma gas supply apparatus 104b plasma gas supply port 104d plasma gas temperature adjustment apparatus 105a first temperature measurement apparatus 105b second temperature measurement apparatus 106 control Means 122 Film 123 Nip roll 300 Viewing-side polarizing plate 301 Hard coat film or antireflection film 302 Dichroic polarizer 303 Polarizing plate protective film 304 Light diffusing plate 305 Light guide plate 306 Backlight 307 Reflecting plate 308 Liquid crystal display Cell 309 Backlight side polarizing plate

Claims (12)

In a method for producing a hard coat film having a hard coat layer directly or via another layer on a film substrate, the thickness of the hard coat layer is 10 μm or more, opposite to the side on which the hard coat layer is provided The manufacturing method of the hard coat film characterized by apply | coating an alkaline solution to the side surface. The method for producing a hard coat film according to claim 1, wherein the hard coat layer has a thickness of 12 μm or more and 20 μm or less. The method for producing a hard coat film according to claim 1 or 2, wherein the hard coat layer has a pencil hardness of 3H or more. The method for producing a hard coat film according to any one of claims 1 to 3, wherein the hard coat layer has a pencil hardness of 4H or more. The said alkaline solution contains a fluorine-type compound or a silicone compound, The manufacturing method of the hard coat film of any one of Claims 1-4 characterized by the above-mentioned. The said film base material contains cellulose-ester resin, The manufacturing method of the hard coat film of any one of Claims 1-5 characterized by the above-mentioned. The said film base material contains a cellulose-ester resin and an acrylic resin, The manufacturing method of the hard coat film of any one of Claims 1-6 characterized by the above-mentioned. The said film base material contains a cellulose-ester resin, an acrylic resin, and an acrylic particle, The manufacturing method of the hard coat film of any one of Claims 1-7 characterized by the above-mentioned. A hard coat film produced using the method for producing a hard coat film according to claim 1. An antireflection film, wherein a low refractive index layer is laminated directly or via another layer on the hard coat layer of the hard coat film according to claim 9. A polarizing plate comprising the hard coat film according to claim 9 or the antireflection film according to claim 10 on at least one surface of a polarizing film. An image display device comprising the hard coat film according to claim 9, the antireflection film according to claim 10, or the polarizing plate according to claim 11.

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