JP5217906B2 - Polarizing plate, liquid crystal display device, and IPS (in-plane switching) mode liquid crystal display device - Google Patents

Description

  The present invention relates to a polarizing plate, a liquid crystal display device, and an IPS (in-plane switching) mode liquid crystal display device.

  Since the outermost surface of the liquid crystal display device is easily damaged by physical damage, and the display image quality is deteriorated when it is damaged, it is desired to enhance the surface hardness of the protective film for protecting the outermost surface. In addition, the surface of a polarizing plate (a laminated product in which a protective film is bonded to one or both sides of a polarizing film having polarizing ability) constituting a liquid crystal display device is easily damaged when transported or cut out. There was a problem. Also from this fact, a high surface hardness (high hardness) is required. Moreover, a polarizing plate is generally manufactured in a roll form, and is manufactured by punching so as to be a polarizing plate having a predetermined size.

  In recent years, the liquid crystal display device has been increased in screen size, and the polarizing plate needs to have a large size. However, when manufacturing a polarizing plate with a particularly large size, a polarizing plate using a protective film having a hard coating film with high hardness causes quality problems such as cracking and flaking of the punched end portion in the punching process. It was easy and caused a decrease in productivity. In addition, there is a problem that the quality such as the plane characteristics of the polarizing plate deteriorates.

  In particular, the above-described problems are easily manifested in a polarizing plate of an in-plane switching mode (IPS) liquid crystal display device to which optical compensation means is added.

  Patent Document 1 discloses a method for producing a polarizing plate which is excellent in smoothness in the polarizing plate punching process, is inexpensive and has high productivity. In Patent Document 1, a polarizing plate having a transparent protective film, a polarizing film, and an optical compensation layer in this order, the optical compensation layer including a transparent support and an optically anisotropic layer, It contains liquid crystal molecules and is characterized in that the absorption axis of the polarizing film is neither parallel nor perpendicular to the slow axis of the transparent support.

With the above-described technique, a certain level of smoothness and high productivity can be obtained, but with a protective film using a hard coat film with a hard surface hardness on the outermost surface, a sufficient improvement effect cannot be obtained, and punching is performed. Quality issues such as cracking and rolling at the edge of the polarizing plate were not improved.
JP 2005-513521 Gazette

  As a result of examining the above problems, the hardness of the optically anisotropic layer comprising the hard coat layer of the outermost hard coat film as the first protective film and the polymerizable liquid crystal compound of the second protective film ( Martens hardness) and found that it can be solved by adjusting the elastic modulus in the width direction (TD) of the transparent film of the second protective film, leading to the present invention.

  Therefore, the object of the present invention is to improve the quality problems such as cracking and flaking of the end portion of the polarizing plate using a hard coat film having high hardness, excellent productivity, and flatness. An excellent in-plane switching mode (IPS) liquid crystal display polarizing plate is provided.

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

1. In the polarizing plate in which the first protective film, the polarizing film, and the second protective film are laminated in this order, the second protective film is composed of a vertically aligned polymerizable liquid crystal compound layer and a transparent film. at least Martens hardness from the polarizing film of the protective film of the first on the far side (HMS) is, 400 N / mm ² or more, has a 800 N / mm ² or less hard coat layer, the polymerizable liquid crystal compound layer The Martens hardness (HMs) is 100 N / mm ² or more and 200 N / mm ² or less, and the elastic modulus in the direction parallel to the transmission axis of the polarizing film of the transparent film at 23 ° C. and 55% RH is A polarizing plate having a viscosity of 4.0 to 6.0 kN / mm ² .

  2. 2. The polarizing plate according to 1 above, wherein the hard coat layer contains a cationic polymerizable compound.

  3. 3. A liquid crystal display device comprising the polarizing plate according to 1 or 2 on at least one surface of a liquid crystal cell.

  4). 3. An IPS (in-plane switching) mode liquid crystal display device comprising the polarizing plate according to 1 or 2 on at least one surface of an IPS (in-plane switching) mode liquid crystal cell.

  According to the present invention, quality problems such as cracking and scoring of the edge portion of the polarizing plate using a hard coat film having high hardness are improved, and productivity is excellent and flatness is also excellent. In addition, a polarizing plate for an in-plane switching mode (IPS) liquid crystal display 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 polarizing plate of the present invention is a polarizing plate in which at least a first protective film, a polarizing film, and a second protective film are laminated in this order, and the second protective film is substantially vertically aligned. the polymeric is a liquid crystal compound layer and the transparent film, at least Martens hardness from the polarizing film of the first protective film on the far side (HMS) is, 400 N / mm ² or more, 800 N / mm ² or less of the hard coat The polarizing film of the transparent film at 23 ° C. and 55% RH when the polymerizable liquid crystal compound layer has a Martens hardness (HMs) of 100 N / mm ² or more and 200 N / mm ² or less . The elastic modulus in the direction parallel to the transmission axis is 4.0 to 6.0 kN / mm ² .

  As a result of intensive studies on the above problems, the inventors of the present invention have adjusted the hardness of the hard coat layer of the first protective film to a specific range, and further an optical made of a polymerizable liquid crystal compound of the second protective film. By adjusting the hardness of the anisotropic layer and the elastic modulus in the width direction (TD) of the transparent film, the quality issues such as cracking and flaking of the end portion in punching are improved, and the productivity is excellent. In addition, the present inventors have found that a polarizing plate for in-plane switching mode (IPS) liquid crystal display having excellent flatness can be obtained, and the present invention has been achieved.

  This is because the hard coat layer of the hard coat film of the first protective film and the hardness (Martens hardness) of the optically anisotropic layer made of the polymerizable liquid crystal compound of the second protective film and the base material used therefor By adjusting the elastic modulus to the above specific range and making it a polarizing plate, the stress applied to the surface of the polarizing plate is made constant, which makes it difficult to apply shear strain locally when punching out the polarizing plate. It is presumed that surface quality such as suppression of phenomena such as cracking and rolling of the end portion punched by the polarizing plate and surface quality such as flatness will be improved.

  Hereinafter, the present invention will be described in detail.

《Martens hardness》
Martens hardness (Vickers hardness) is a microhardness meter using a Vickers indenter and a triangular pyramid indenter with an accuracy of 115 degrees between ridges. The hard coat surface of the film is approximately 1 / th of the film thickness of the hard coat layer. In the load test force-indentation depth curve when the indenter is pushed down to a thickness of 10, indentation from 50% to 90% of the maximum load test force (Fmax) obtained from the load test force-indentation depth curve From the slope (m) in which the depth is proportional to the square root of the load test force, it is a value defined by the following equation.

1HMs = 1 / (26.4m ² )
<< first protective film >>
The first protective film is at least Martens hardness (HMS) is 400 N / mm ² or more, it is characterized by having a 800 N / mm ² or less hard coat layer.

  In order to adjust Martens hardness to the said range, it can adjust by selection of the hard-coat layer composition described below and hardening conditions.

<Hard coat layer>
First, the hard coat layer of the present invention will be described.

(Radically polymerizable compound)
In the present invention, it is preferable to use a radical polymerizable compound as a binder.

  Examples of the radical polymerizable group include ethylenically unsaturated groups such as a (meth) acryloyl group, a vinyloxy group, a styryl group, and an allyl group, and among them, a compound having a (meth) acryloyl group is preferable. Moreover, as a radically polymerizable compound, it is preferable to contain the polyfunctional monomer which contains a 2 or more radically polymerizable group in a molecule | numerator. The polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. 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 Lithol 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.

  Commercially available polyfunctional acrylates include Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (Asahi Denka Co., Ltd.); Hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT-102Q8 MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP-10, DP-20 DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (manufactured by Dainichi Seika Kogyo Co., Ltd.); KRM7033, RM 7039, KRM 7130, KRM 7131, UVECRYL 29201, UVECRYL 29202 (manufactured by Daicel UCB); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120, RC- 5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.); 340 clear (manufactured by China Paint Co., Ltd.); Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (manufactured by Sanyo Chemical Industries); SP -1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.); RCC-15C (manufactured by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.); B420 (manufactured by Shin-Nakamura Chemical Co., Ltd.) or the like can be appropriately selected and used.

  In the hard coat composition, the addition amount of the radical polymerizable compound is preferably 15% by mass or more and less than 70% by mass in the solid content from the viewpoint of the stability of the hard coat composition.

(Radical polymerization accelerator)
In order to accelerate the curing of the radical polymerizable compound, it is preferable to use a photopolymerization initiator in combination with the radical polymerizable compound. When the photopolymerization initiator and the radical polymerizable compound are used in combination, it is preferable to contain the photopolymerization initiator and the radical polymerizable compound in a mass ratio of 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.

  Furthermore, in order to make the Martens hardness of a hard-coat layer into the said range, it is preferable that a hard-coat layer contains the following cationically polymerizable compound.

(Cationically polymerizable compound)
Any cationically polymerizable compound can be used as long as it undergoes cationic polymerization by irradiation with energy active rays or heat to form a resin. Specific examples include an epoxy group, a cyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester compound, and a vinyloxo group. Among them, a compound having a functional group such as an epoxy group or a vinyl ether group is preferably used in the present invention. Examples of the cationically polymerizable compound having an epoxy group or a vinyl ether group include phenyl glycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, vinylcyclohexene dioxide, limonene dioxide, 3,4-epoxycyclohexylmethyl-3 ′. , 4'-epoxycyclohexanecarboxylate, bis- (6-methyl-3,4-epoxycyclohexyl) adipate, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, 1 , 4-cyclohexanedimethanol divinyl ether and the like. Moreover, as an epoxy compound, a polymer compound can also be used, for example, it is compoundable by the method currently disclosed by Unexamined-Japanese-Patent No. 7-247313.

  Among them, it is preferable to use an oxetane compound as the cationic polymerizable compound. As the oxetane compound, any compound having at least one oxetane ring in the molecule may be used. As such an oxetane compound, various compounds can be used. As preferred compounds, the following general formula (I) These are compounds of general formula (II) and general formula (III).

(Wherein R ⁷ represents hydrogen, fluorine, an alkyl group, a fluoroalkyl group, an allyl group, an aryl group or a furyl group, m represents an integer of 1 to 4, Z represents oxygen or sulfur, and R ⁸ Represents a monovalent to tetravalent organic group depending on the value of m.)

(Wherein R ⁹ and R ¹⁰ each independently represent hydrogen, fluorine, an alkyl group, a fluoroalkyl group, an allyl group, an aryl group, or a furyl group.)

(In the formula, R ¹¹ represents hydrogen, fluorine, an alkyl group, a fluoroalkyl group, an allyl group, an aryl group or a furyl group, R ¹² represents hydrogen or an inert monovalent organic group, and R ¹³ represents water. Represents a decomposable functional group, n represents an integer of 1 to 5, and p represents an integer of 0 to 2.)
In the above general formulas (I) to (III), when R ⁷ , R ⁹ , R ¹⁰ and R ¹¹ are alkyl groups, the carbon number thereof can be about 1 to 6, specifically, methyl, Examples include ethyl, propyl, butyl and the like. The fluoroalkyl group can also have about 1 to 6 carbon atoms. Furthermore, the aryl group is typically phenyl or naphthyl, which may be substituted with other groups.

In addition, the organic group represented by R ⁸ in the general formula (I) is not particularly limited. For example, when m is 1, an alkyl group, a phenyl group, or the like, and when m is 2, the number of carbon atoms is In the case where 1 to 12 linear or branched alkylene groups, linear or branched poly (alkyleneoxy) groups, and the like is 3 or 4, a similar polyfunctional group is exemplified.

The inactive monovalent organic group represented by R ¹² in the general formula (II) typically includes an alkyl group having 1 to 4 carbon atoms, and is hydrolyzable represented by R ^13. Examples of the functional group include an alkoxy group having 1 to 5 carbon atoms including methoxy and ethoxy, and a halogen atom such as a chlorine atom and a bromine atom.

  Furthermore, if necessary, a (co) polymer containing a monomer having a hydrogen bond-forming group and a reactive polymer having an oxetanyl group in the main chain or side chain and having a number average molecular weight of 20,000 or more can also be used.

  Moreover, you may use the fluorine-containing vinyl ether compound as shown by the following general formula.

_{CH 2 = CH-O- (CH} 2) a-O- (CH 2) b-Rf- (CH 2) b-O- (CH 2) a-O-CH = CH 2
(In the formula, Rf represents a fluorine-containing alkyl group, a represents an integer of 1 to 2, and b represents an integer of 0 to 3. Rf may be a linear or branched alkyl group.)
Specific compounds are as follows.

_{CH 2 = CH-O-CH} 2 -O- (CF 2) k-O-CH 2 -O-CH = CH 2
_{CH 2 = CH-O-CH} 2 -O-CH 2 - (CF 2) k-CH 2 -O-CH 2 -O-CH = CH 2
_{CH 2 = CH-O-CH} 2 -O- (CH 2) 2 - (CF 2) k- (CH 2) 2 -O-CH 2 -O-CH = CH 2
_{CH 2 = CH-O-CH} 2 -O- (CH 2) 3 - (CF 2) k- (CH 2) 3 -O-CH 2 -O-CH = CH 2
_{CH 2 = CH-O- (CH} 2) 2 -O- (CF 2) k-O- (CH2) 2 -O-CH = CH 2
_{CH 2 = CH-O- (CH} 2) 2 -O-CH 2 - (CF 2) k-CH 2 -O- (CH 2) 2 -O-CH = CH 2
_{CH 2 = CH-O- (CH} 2) 2 -O- (CH 2) 2 - (CF 2) k- (CH 2) 2 -O- (CH 2) 2 -O-CH = CH 2
_{CH 2 = CH-O- (CH} 2) 2 -O- (CH 2) 3 - (CF 2) k- (CH 2) 3 -O- (CH 2) 2 -O-CH = CH 2
In the above, k is preferably an integer of 2 or more and 12 or less, and more preferably, k is 4 or more and 10 or less. The fluorine-containing vinyl ether compound can be produced by reacting a fluorine-containing dialcohol and a vinyl ether having a halogen group in the presence of an alkali catalyst. Moreover, you may contain a fluorine-containing epoxy compound, for example, the compound as described in General formula (1)-(4) of Unexamined-Japanese-Patent No. 11-309830 can be used. Specific examples thereof include, but are not limited to, the following fluorine-containing epoxy compounds 1 to 4.

  Fluorine-containing epoxy compound 1

  Fluorine-containing epoxy compound 2

  Fluorine-containing epoxy compound 3

  Fluorine-containing epoxy compound 4

  In addition, the compounds described in JP-A-2007-254650, paragraph numbers [116] to [126] can also be mentioned.

  From the viewpoint of stability of the hard coat composition, the above-mentioned cationically polymerizable compound is preferably 15% by mass or more and less than 70% by mass in the solid content in the hard coat composition.

(Cationic polymerization accelerator)
Examples of the compound that accelerates the polymerization of the cationic polymerizable compound include known acids and photoacid generators. Examples of the photoacid generator include a cationic polymerization photoinitiator, a dye photodecoloring agent, a photochromic agent, a known compound used in a microresist, and a mixture thereof. Specific examples include onium compounds, organic halogen compounds, and disulfone compounds, and onium compounds are preferable. As the onium compound, diazonium salts, sulfonium salts, iodonium salts and the like represented by the following formulas are preferably used.

ArN ₂ ⁺ Z ⁻ ,
(R) ₃ S ⁺ Z ⁻ ,
(R) ₂ I ⁺ Z ⁻
In the formula, Ar represents an aryl group, R represents an aryl group or an alkyl group having 1 to 20 carbon atoms, and when R appears multiple times in one molecule, they may be the same or different, and Z ⁻ Represents a non-basic and non-nucleophilic anion.

In each of the above formulas, the aryl group represented by Ar or R is also typically phenyl or naphthyl, and these may be substituted with an appropriate group. Specific examples of the anion represented by Z ⁻ include tetrafluoroborate ion (BF ₄ ⁻ ), tetrakis (pentafluorophenyl) borate ion (B (C ₆ F ₅ ) ₄ ⁻ ), and hexafluorophosphate ion. (PF ₆ ⁻ ), hexafluoroarsenate ion (AsF ₆ ⁻ ), hexafluoroantimonate ion (SbF ₆ ⁻ ), hexachloroantimonate ion (SbCl ₆ ⁻ ), hydrogen sulfate ion (HSO ₄ ⁻ ), perchloric acid Ion (ClO ₄ ⁻ ) and the like.

  Examples of other onium compounds include ammonium salts, iminium salts, phosphonium salts, arsonium salts, selenonium salts, boron salts, and the like. For example, compounds described in paragraph numbers [0058] to [0059] of JP-A-2002-29162 Etc.

  Of these, diazonium salts, iodonium salts, sulfonium salts, and iminium salts are preferable from the viewpoint of the material stability of the compound.

  Specific examples of onium salts that can be suitably used include, for example, an amylated sulfonium salt described in paragraph No. [0035] of JP-A No. 9-268205, and paragraph Nos. Of JP-A No. 2000-71366. Diaryl iodonium salts or triarylsulfonium salts described in [0010] to [0011], sulfonium salts of thiobenzoic acid S-phenyl ester described in paragraph [0017] of JP-A-2001-288205, JP-A-2001-133696 Onium salts and the like described in paragraph numbers [0030] to [0033] of the publication.

  Other examples of the acid generator include organometallic / organic halides described in JP-A-2002-29162, paragraphs [0059] to [0062], and a photoacid generator having an o-nitrobenzyl type protecting group. And compounds such as compounds that generate photosulfonic acid to generate sulfonic acid (iminosulfonate, etc.). Since many of these compounds are commercially available, such commercially available products can be used. Commercially available initiators include, for example, “Syracure UVI-6990” (trade name) sold by Dow Chemical Japan Co., Ltd., and “Adekaoptomer SP-150” (available from ADEKA Corporation) Product name), “Adekaoptomer SP-300” (trade name), “RHODORSIL PHOTOINITIAOR 2074” (trade name) sold by Rhodia Japan Co., Ltd., and the like.

  As the acid, Bronsted acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like, or organic acid such as acetic acid, formic acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, dibutyltin dilaurate, Examples thereof include Lewis acids such as dibutyltin diacetate, dibutyltin dioctate, triisopropoxyaluminum, tetrabutoxyzirconium, and tetrabutoxytitanate.

  Aromatic polycarboxylic acids such as pyromellitic acid, pyromellitic anhydride, trimellitic acid, trimellitic anhydride, phthalic acid, phthalic anhydride, or anhydrides thereof, maleic acid, maleic anhydride, succinic acid, succinic anhydride Aliphatic polyvalent carboxylic acid or anhydride thereof such as

  As an acid, only 1 type may be used and 2 or more types may be used together.

  These acids and photoacid generators are preferably added in a proportion of 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, with respect to 100 parts by mass of the cationic polymerizable compound. is there. When the addition amount is in the above range, it is preferable from the viewpoint of stability of the curable composition, polymerization reactivity, and the like.

(Silicon compound)
Further, the hard coat layer preferably contains an organosilicon compound represented by the following general formula (A), a hydrolyzate thereof, or a polycondensate thereof.

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

  R2 of the alkoxysilane compound having an epoxy group represented by the general formula (A) is not particularly limited, but examples thereof include 2-glycidoxyethyl group, 3-glycidoxypropyl group, 3-glycidoxybutyl group and the like. Glycidoxy C1-C4 alkyl group, preferably glycidoxy C1-C3 alkyl group, glycidyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group, 2- (3 Oxiranes such as 4-epoxycycloheptyl) ethyl group, 2- (3,4-epoxycyclohexyl) propyl group, 2- (3,4-epoxycyclohexyl) butyl group, 2- (3,4-epoxycyclohexyl) pentyl group And a C1-C3 alkyl group substituted with a C5-C8 cycloalkyl group having a group. Among these, a 2-glycidoxyethyl group, a 3-glycidoxypropyl group, and a 2- (3,4-epoxycyclohexyl) ethyl group are preferable. Preferred specific examples of the compound that can be used as the compound of the general formula (1) having these substituents R2 include 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, and 3-glycidide. Xylpropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4) -epoxycyclohexylethyltriethoxysilane and the like. These may be used alone or in combination of two or more.

The alkoxysilane compound can be produced, for example, by the method described in JP-A-10-324749 and JP-A-6-298940. As described in JP-A-2006-348061, it can also be obtained by (co) condensation of an alkoxysilane compound of the general formula (1) under a base catalyst. In that case, water can be added as needed to promote (co) condensation. The amount of water added is usually 0.05 to 1.5 mol, preferably 0.1 to 1.2 mol, with respect to 1 mol of alkoxy groups in the entire reaction mixture. The catalyst used for the condensation reaction is not particularly limited as long as it is basic, but an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. Organic bases such as ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used. Among these, an inorganic base or ammonia is preferable because the catalyst can be easily removed from the product. The addition amount of the catalyst is usually 5 × 10 ^{−4 to} 7.5 mass%, preferably 1 × 10 ^{−3 to} 5 mass%, based on the amount of the alkoxysilane compound. The condensation reaction can be carried out without a solvent or in a solvent. There is no restriction | limiting in particular as a solvent in the case of using a solvent, if it is a solvent which melt | dissolves an alkoxysilane compound. Examples of such solvents include nonpolar solvents such as dimethylformamide, dimethylacetamide, tetrahydrofuran, methyl ethyl ketone, and methyl isobutyl ketone, and aromatic hydrocarbons such as toluene and xylene, preferably methyl ethyl ketone and methyl isobutyl ketone. .

  Furthermore, you may contain the fluorine substituted alkyl group containing silane compound represented by the following general formula (OSi-2).

  The fluorine-substituted alkyl group-containing silane compound represented by the general formula (OSi-2) will be described.

In the formula, R ^{1 to} R ⁶ are alkyl groups having 1 to 16 carbon atoms, preferably 1 to 4 carbon atoms, halogenated alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and 6 to 12 carbon atoms, preferably 6 carbon atoms. 10 to 10 aryl groups, 7 to 14 carbon atoms, preferably 7 to 12 alkylaryl groups, arylalkyl groups, 2 to 8 carbon atoms, preferably 2 to 6 alkenyl groups, or 1 to 6 carbon atoms, preferably 1 to 3 alkoxy groups, a hydrogen atom or a halogen atom.

Rf represents-(CaHbFc)-, a is an integer of 1 to 12, b + c is 2a, b is an integer of 0 to 24, and c is an integer of 0 to 24. Such Rf is preferably a group having a fluoroalkylene group and an alkylene group. Specifically, examples of such fluorine-containing silicone compounds include (MeO) ₃ SiC ₂ H ₄ C ₂ F ₄ C ₂ H ₄ Si (MeO) ₃ , (MeO) ₃ SiC ₂ H ₄ C ₄ F ₈ C _{2 H 4 Si (MeO) 3} , (MeO) 3 SiC 2 H 4 C 6 F 12 C 2 H 4 Si (MeO) 3, (H 5 C 2 O) 3 SiC 2 H 4 C 4 F 8 C 2 H _{4 Si (OC 2 H 5)} 3, include methoxy disilane compound or the like represented by _{(H 5 C 2 O) 3} SiC 2 H 4 C 6 F 12 C 2 H 4 Si (OC 2 H 5) 3.

  The hard coat layer may contain a silane coupling agent. Silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane. Ethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltri Acetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltri Ethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ- Acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N- Examples include β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane.

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

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

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

In addition, the hard coat layer may contain a silicon compound represented by CF ₃ (CF ₂ ) nCH ₂ CH ₂ Si (OR ₁ ) ₃ . (In the formula, R1 represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 12.) Specific examples of the compound include trifluoropropyltrimethoxysilane and trifluoropropyl. Examples include triethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, and these are used alone or in combination of two or more. Can be used. _{It may} also contain H 2 NCONH (CH) mSi ( OR2) silicon compound in the terminal position represented by ₃ having a ureido group _(H 2 NCONH-). (In the formula, R2 represents an alkyl group having 1 to 5 carbon atoms, and m represents an integer of 1 to 5.) Specific compounds include γ-ureidopropyltrimethoxysilane and γ-ureido. Examples thereof include propyltriethoxysilane and γ-ureidopropyltripropoxysilane. Among these, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, and the like are particularly preferable.

  In addition, the hard coat layer can use, for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, fluoroacrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin, or the like as a binder.

  It is preferable that a hard-coat layer contains 5-95 mass% binder on the whole.

(Other)
Further, a binder such as a known thermoplastic resin, thermosetting resin or hydrophilic resin such as gelatin may be added to the hard coat layer. These resins preferably have a polar group in the molecule. Examples of the polar _{group, -COOM, -OH, -NR2, -NR3X} , -SO 3 M, -OSO 3 M, -PO 3 M2, -OPO 3 M ( wherein, M represents a hydrogen atom, an alkali metal or an ammonium group X represents an acid that forms an amine salt, and R represents a hydrogen atom or an alkyl group.

  Further, the hard coat layer may contain fine particles of an inorganic compound or an organic compound in order to adjust the scratch resistance, slipperiness and refractive index.

  Examples of inorganic fine particles used in 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, and 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. Further, it is preferable to contain two or more kinds of fine particles having different particle diameters. The proportion of the ultraviolet 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 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 coating solution 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%.

  Further, the hard coat layer preferably contains a silicone surfactant or a polyoxyether compound. As the silicone surfactant, polyether-modified silicone is preferable. Specifically, BYK-UV3500, BYK-UV3510, BYK-333, BYK-331, BYK-337 (manufactured by BYK-Chemical Japan), TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (GE Toshiba Silicone), KF-351, KF-351A, KF-352, KF-353, KF-354, KF-355, KF-615, KF-618, KF-945, KF- 6004 (polyether-modified silicone oil; manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are exemplified, but not limited thereto.

  Of the polyoxyether compounds, the polyoxyethylene oleyl ether compound is preferable, and is generally a compound represented by the general formula (α).

Formula (α) C ₁₈ H ₃₅ —O (C ₂ H ₄ O) nH
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, more preferably 2 to 9, and further preferably 2 to 8. The compound of the general formula (α) can be obtained by reacting ethylene oxide with oleyl alcohol.

  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) or more, Kao Corporation, NOFBLEEAO-9905 (polyoxyethylene (5) oleyl ether) manufactured by NOF Corporation.

  Note that () represents the number n. Nonionic polyoxyether compounds may be used alone or in combination of two or more.

  These improve applicability | paintability and it is preferable to add these components in 0.01-3 mass% with respect to the solid content component in a coating liquid.

  Further, the hard coat layer may contain a fluorine-siloxane graft polymer.

  The fluorine-siloxane graft polymer refers to a copolymer polymer obtained by grafting polysiloxane containing siloxane and / or organosiloxane alone and / or organopolysiloxane to at least a fluorine-based resin. Examples of commercially available products include ZX-022H, ZX-007C, ZX-049, and ZX-047-D manufactured by Fuji Kasei Kogyo Co., Ltd. These compounds may be used as a mixture. Fluorine-siloxane graft polymer should be used in a coating solution that has a mass ratio of actinic ray curable resin to fluorine-siloxane graft polymer: energy-active radiation curable resin = 0.05: 100 to 5.00: 100. To preferred.

  The hard coat layer may have a multilayer structure of two or more layers. One or both of them may be a so-called conductive layer containing, for example, conductive fine particles, a π-conjugated conductive polymer, or an ionic polymer. Examples of the π-conjugated conductive polymer include polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), and 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-hexyloxythiophene), poly (3 Octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3,4-dihydroxythiophene), poly (3,4-dimethoxythiophene), poly (3,4-di Ethoxythiophene), 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-propylenedioxythiophene), poly (3,4 4-butenedioxythiophene), poly (3-methyl-4-methoxythiophene), poly (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-octyl) Pyrrole), 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-hexyloxypyrrole), poly ( 3-methyl-4-hexyloxypyrrole), polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-anilinesulfonic acid), poly (3-anilinesulfonic acid) and the like. . Each of these may be used alone or two types of copolymers can be suitably used.

  Further, as a color correction filter for various display elements, a color tone adjusting agent (dye or pigment, etc.) having a color tone adjusting function may be included, or an electromagnetic wave blocking agent or an infrared absorbing agent may be added to each function. It is preferable to have it.

  As the coating method of the hard coat layer coating solution, the above-described methods can be used. The coating amount is suitably 0.1 to 40 μm, preferably 0.5 to 30 μm, as the wet film thickness. Moreover, as a dry film thickness, it is an average film thickness of 0.1-30 micrometers, Preferably it is 1-20 micrometers.

  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.

(Coating process)
In the formation of the hard coat layer, the step of adjusting the Martens hardness to the range of the present invention and easily exhibiting the object effect of the present invention is preferably performed by applying a light to the hard coat layer after coating and drying, and further performing a heat treatment. .

  An example of the heat treatment step is as shown in FIG. In addition, the heat treatment step needs to be performed in a place where the temperature and humidity can be adjusted, and is preferably performed in a clean room without dust.

  A preferable temperature for the heat treatment is 80 ° C. or higher, more preferably 120 ° C. or higher, from the viewpoint that the target effect is better exhibited. Further, the heat treatment time is preferably 20 minutes or less. Even if the heat treatment is carried out for a time longer than 20 minutes, the objective effect obtained better is not changed, and the film tends to be deteriorated in appearance such as discoloration or deformation due to heat.

  The heat treatment time here refers to a time during which the temperature is kept constant at a desired temperature, and does not include the time when the temperature is raised and the time when the temperature is lowered.

  The temperature to be held is preferably in the range of ± 5 ° C. of the set temperature. There may be a plurality of heat treatment steps. In that case, it may be designed so that each temperature can be changed.

  FIG. 1 is a schematic view showing a step of performing heat treatment continuously after irradiation. The long film Y is fed out from the feed roll 1, transported by the transport roller 2, and a hard coat layer is applied by the extrusion coater 3. At this time, the hard coat layer may be a single layer structure or a plurality of layers. Next, the long film Y coated with the hard coat layer is dried in the drying zone 5. The temperature of the drying zone 5 is preferably 50 to 150 ° C. Drying is performed by blowing warm air whose temperature and humidity are controlled from the front surface, back surface, or both surfaces of the long film Y. After drying, the film is cured by irradiating actinic rays such as ultraviolet rays with an air-cooled actinic ray lamp 6 a in the light irradiation lamp unit 6. Alternatively, the half-cure state can be achieved by controlling the irradiation amount and irradiation conditions. Actinic ray irradiation can also be performed in a state in which the long film Y is wound around the opposing roll 4 whose temperature is controlled to 20 to 120 ° C. in advance.

At that time, it is also preferable to send cooling air from the air cooling air vent 6b to adjust the temperature of the actinic ray irradiating unit, and N ₂ gas is supplied from the N ₂ supply chamber to promote hardening of the hard coat layer. It is also preferable to do.

As examples of the light irradiation lamp, 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. These light sources are preferably air-cooled or water-cooled. The irradiation conditions vary depending on individual lamps, the dose of active ray is preferably a ^{50mJ / cm 2 ~1J / cm 2} , particularly preferably 50 to 500 mJ / cm ^2. Further, it is preferable to reduce the oxygen concentration to 0.01% to 5% by nitrogen purge in the irradiated portion.

  Next, after the light irradiation, heat treatment is performed in the heating zone 7. In the heating zone 7, the long film Y is heated at a predetermined temperature for a predetermined time by the transport rollers 2 arranged above and below.

  In the heat treatment step, it 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. At 250 to 500 N / m, the objective effect of the present invention is better exhibited after a more severe durability test. When it exceeds 500 N / m, it becomes difficult to maintain the flatness of the film. 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 long film Y subjected to the heat treatment is taken up as a take-up roll 9 in the take-up chamber 8. In that case, it is also preferable to carry out while blowing hot air of a predetermined temperature from the hot air outlet 10. As a measure for preventing electrification and dust adhesion, the hot air is preferably adjusted to a relative humidity in the range of 10 to 70% RH, preferably 20 to 70% RH, particularly 40 to 60% RH. Moreover, it is preferable that warm air is an ion wind, and it is preferable to install a static elimination apparatus and an air cleaner in the vicinity of the winding part.

  As shown in FIG. 2, the heat treatment may be performed by applying a roll of the hard coat film wound on the movable carriage 12 after the application, drying, and light irradiation, and performing the heat treatment in the heat treatment chamber A.

  In the heat treatment A, the temperature difference between the inside and outside of the roll of the film roll due to a rapid temperature increase is increased, and it is preferable to gradually increase or decrease the temperature in order to prevent wrinkles and the like from entering near the winding core. . Specifically, the rate of temperature increase and the rate of temperature decrease are preferably 0.3 to 5 ° C./hour.

  Moreover, in order to prevent blocking and to keep a winding form favorable, it is preferable to give a knurling process. The knurling process should just be formed in the at least one surface of the film, and may be formed in both surfaces. The thickness of the knurling part is preferably larger than the film thickness of the hard coat layer, and the thickness of the knurling part is preferably in the range of 5 to 30 μm. Preferably it is the range of 10-25 micrometers.

  In addition, as the winding core when winding the hard coat film in a roll shape, any material may be used as long as it is a cylindrical core, preferably a hollow plastic core, and a plastic material As long as it is a heat-resistant plastic that can withstand the heat treatment temperature, examples thereof include resins such as phenol resin, xylene resin, melamine resin, polyester resin, and epoxy resin. A thermosetting resin reinforced with a filler such as glass fiber is preferred. The number of windings on these winding cores is preferably 100 windings or more, more preferably 500 windings or more, and the winding thickness is preferably 5 cm or more.

  Moreover, when performing the said heat processing in the state which wound up the hard coat film wound up in roll shape, you may rotate this roll.

  The rotation is preferably performed at a speed of 1 rotation or less per minute, and may be continuous or intermittent. Moreover, it is also preferable to perform the roll rewinding once or more during the heating period.

  In order to rotate the long hard coat film wound around the core during the heat treatment, it is preferable to provide a dedicated turntable in the heat treatment chamber. More preferably, the hard coat film is set on a dedicated carriage having a heat-resistant rotation function and rotated during the heat treatment in the heating chamber.

  It is also preferable that the hard coat film roll after the heat treatment is carried, for example, to a rewinding step (not shown) and cooled to room temperature while the hard coat film is rewinded to obtain a rewind roll. Further, in the rewinding step, it is preferable to pass through an atmosphere having a relative humidity of 10 to 70% RH or to wind in the atmosphere. When the relative humidity is preferably 20 to 70% RH, particularly 40 to 60% RH, a good hard coat film roll can be obtained without static electricity failure or collapse of the winding shape. The film rewinding speed is 1 to 200 m / min, preferably 10 to 100 m / min. At the time of rewinding, it is also preferable to bring the film into contact with at least one roller while being drawn out in order to lower the film temperature.

  When rotating or rewinding these rolls, there is a possibility that static electricity failure or scratches may occur on the film. It is preferable to install a static eliminator or in a clean room. The surface of the contact roller during rewinding is smooth. It is preferable to use one having a high value.

  As the heating means in the heat treatment step, hot air blowing, contact heat transfer using a heating roll, induction heating using a microwave, radiant heat heating using an infrared heater, or the like can be used. As the infrared heater, an electric, gas, oil or steam far infrared ceramic heater can be used. A commercially available infrared heater (for example, manufactured by Noritake Company Limited) may be used. An oil-type or steam-type infrared heater using oil or steam as the heat medium is preferable from the viewpoint of explosion prevention in an atmosphere in which an organic solvent coexists.

  Moreover, the film temperature and heating temperature at the time of a heating can be measured with the non-contact-type infrared thermometer generally marketed. Further, feedback control may be performed on the heating means in order to control the temperature range.

  As a coating method of these hard coat layers, it can be applied by a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, or an ink jet method.

<Film base>
As a film base used in the first protective film of the present invention, preferable requirements include ease of production, optical isotropy, optical transparency, and the like.

  The term “transparent” as used herein means that the visible light transmittance is 60% or more, preferably 80% or more, and particularly preferably 90% or more.

  Although it will not specifically limit if it has said property, For example, cellulose ester-type films, such as a cellulose diacetate film, a cellulose triacetate film, a cellulose acetate propionate film, a cellulose acetate butyrate film, a polyester-type film, a polycarbonate Film, polyarylate film, polysulfone (including polyethersulfone) film, polyester film such as polyethylene terephthalate and polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol Film, syndiotactic polystyrene film, cycloolefin polymer fill (Arton (manufactured by JSR)), ZEONEX, ZEONOR (manufactured by Nippon Zeon), polyvinyl acetal, polymethylpentene film, polyether ketone film, polyether ketone imide film, polyamide film, fluororesin film, nylon film A polymethyl methacrylate film, an acrylic film, a glass plate, etc. can be mentioned.

  Among these, a cellulose ester film, a polycarbonate film, a polysulfone (including polyether sulfone) film, and a cycloolefin polymer film are preferable.

  In particular, it is preferable to use a cellulose ester film (hereinafter also referred to as a cellulose ester film) as the film substrate. Among these, a cellulose triacetate film is preferably used from the viewpoint of production, cost, transparency, adhesiveness, and the like.

The elastic modulus of cellulose triacetate film at 23 ° C. and 55% RH is generally 2.5 to 4.0 kN / mm ² in the film forming direction (MD), and the width direction (TD) varies depending on the stretching conditions. 2.5 to 5.5 kN / mm ² . In addition, the above-mentioned elastic modulus was conditioned for 24 hours in an environment of 23 ° C. and 55% RH, and in accordance with the method described in JIS K7127, Tensilon RTA-100 manufactured by Tensile Tester Orientec Co., Ltd. was used. Measured value.

  As a commercially available cellulose triacetate film, for example, Konica Minoltack, product names KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, KC12UR (above, manufactured by Konica Minolta Opto) .

  Hereinafter, the cellulose ester film which is a preferable film substrate will be described in detail.

  The cellulose ester film may be a film produced by melt casting film formation or a film produced by solution casting film formation.

  As the cellulose ester, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferable. Among them, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose acetate propionate are preferably used.

  In particular, when the substitution degree of the acetyl group is X and the substitution degree of the propionyl group or butyryl group is Y, it is preferable to use a cellulose ester film in which X and Y are in the following ranges.

2.3 ≦ X + Y ≦ 3.0
0.1 ≦ Y ≦ 2.0
In particular,
2.5 ≦ X + Y ≦ 2.9
0.1 ≦ Y ≦ 1.2
It is preferable that

  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.

  The number average molecular weight of the cellulose ester is preferably 50000 to 250,000, since it has a high mechanical strength when molded and an appropriate dope viscosity, and more preferably 80000 to 150,000.

  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 mass 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 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 1,000,000-500 calibration curves with 13 samples were used. The 13 samples are preferably used at approximately equal intervals.

  The raw material cellulose of the cellulose ester may be wood pulp or cotton linter, and the wood pulp may be softwood or hardwood, but softwood is more preferable. A cotton linter is preferably used from the viewpoint of peelability during film formation. The cellulose ester made from these can be mixed suitably or can be used independently.

  For example, the ratio of cellulose ester derived from cellulose linter: cellulose ester derived from wood pulp (coniferous): cellulose ester derived from wood pulp (hardwood) is 100: 0: 0, 90: 10: 0, 85: 15: 0, 50:50: 0, 20: 80: 0, 10: 90: 0, 0: 100: 0, 0: 0: 100, 80:10:10, 85: 0: 15, 40:30:30.

  Moreover, a cellulose-ester film may contain the acrylic resin mentioned later.

(acrylic resin)
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 (A), 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.), Dianal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd.), KT75 (Electrochemical Industry Co., Ltd.) and the like can be mentioned. .

  Furthermore, it is preferable to contain acrylic particles from the viewpoint of the brittleness resistance and surface hardness of the film substrate.

  Next, the acrylic particles will be described. 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.

  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. For example, when cellulose ester is used as a film base material In the case of cellulose ester, the solvent used for dissolution tends to remain. The elastic modulus of the film is lowered due to the influence of the remaining solvent, and plastic deformation is likely to occur. Therefore, it is preferable to prepare the film by a melt casting method. Methods formed by melt casting can be classified into melt extrusion molding methods, press molding methods, inflation methods, injection molding methods, blow molding methods, stretch molding methods, and the like. Among these, the melt extrusion method is preferable, in which a film having excellent mechanical strength and surface accuracy can be obtained.

  In the present invention, a method of forming a film after the film forming material is heated to exhibit its fluidity and then extruded onto a drum or an endless belt is also included as a melt casting film forming method.

  Further, in film formation of the film substrate, it is preferable to stretch at least in the width direction (TD). Especially in the solution casting step, when the amount of residual peeling is 3 to 40% by mass, 1.01 to 1.0 in the width direction. It is preferable to stretch 1.5 times. More preferably, the film is biaxially stretched in the width direction and the film forming direction (MD), and 1.01 to 1.5 in the width direction and the film forming direction, respectively, when the amount of residual peeling is 3 to 40% by mass. It is to be stretched twice.

  In particular, the above stretching operation is preferably used to adjust the retardation.

  Although the film thickness of a film base material is not specifically limited, the thing of the range of 10-200 micrometers is used. In particular, the film thickness is particularly preferably 10 to 100 μm. More preferably, it is 20-80 micrometers.

  The length of the film substrate 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 film base within the above ranges, the handleability and productivity are excellent. The film substrate is preferably a transparent support having a light transmittance of 90% or more, more preferably 93% or more.

(Plasticizer)
The film substrate 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 Ethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, etc. For pyromellitic acid ester plasticizers such as trimellitate, tetrabutylpyromellitate, In the case of glycolate plasticizers such as lupyromelitate and tetraethylpyromellitate, triacetin, tributyrin, ethylphthalylethyl glycolate, methylphthalylethylglycolate, butylphthalylbutylglycolate, 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- Examples include 1,3-propanediol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, xylitol, and the like. 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 Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid. Examples of preferred alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, or 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. And aromatic monocarboxylic acids possessed by them, or derivatives thereof. 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 improvement in retention, and the smaller one is preferable in terms of moisture permeability and compatibility with cellulose ester.

  The carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified 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)
The film substrate may contain an 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)
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)
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.

  Further, 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 film substrate. Is preferable from the standpoint that it can be maintained well.

  Moreover, the polymer ultraviolet absorber (or the general formula (1) or the general formula (2) of JP-A-6-148430 and the general formulas (3), (6) and (7) described in Japanese Patent Application No. 2000-156039 (or A UV-absorbing polymer) is 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 film base material.

(particle)
Internal haze, for example, by adding particles with a refractive index different from that of the film base to the film base 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 Sea Hoster KEP-50 (above, Nippon Shokubai Co., Ltd.), Silo Hovic 100 (Fuji Silysia), Nip Seal E220A (Nihon Silica Kogyo), Admafine SO (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.

  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. Note that the refractive index of the particles is measured by measuring the turbidity by dispersing the same amount of particles in a solvent in which the refractive index is changed by changing the mixing ratio of two types 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 at the time of preparing a composition (dope) for producing a film substrate, or may be dispersed alone in a 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, the above plasticizer and ultraviolet absorber may be added together with a solvent in the preparation of a solution composed of cellulose ester or cellulose ester resin and an acrylic resin. It may be added during or after preparation.

(Organic solvent)
When the cellulose ester film is produced by a solution casting method, the dope preferably contains an organic solvent from the viewpoint of film forming property 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 10 to 50 Pa · s in order to obtain good film surface quality.

<< second protective film >>
Next, the second protective film will be described. Hereinafter, it is also referred to as a retardation film.

  The second protective film of the present invention is a protective film disposed opposite to the first protective film with respect to the polarizing film, and includes at least a transparent film and a substantially vertically aligned polymerizable liquid crystal compound. Consists of sex layers. In particular, the polymerizable liquid crystal compound is preferably a rod-like liquid crystal compound for an IPS liquid crystal display device.

In the second protective film, the Martens hardness (HMs) of the optically anisotropic layer containing the polymerizable liquid crystal compound is in the range of 100 N / mm ² or more and 200 N / mm ² . The Martens hardness can be adjusted by adjusting materials such as a polymerizable liquid crystal material and a photopolymerization initiator described later, curing conditions, and the like.

  The second protective film of the present invention preferably has a thickness of 20 to 80 μm and preferably has the following characteristics as a retardation value.

0nm ≦ Ro ≦ 330nm
−150 nm ≦ Rt ≦ 150 nm
Ro and Rt are the total of Ro and Rt of the transparent film, the optically anisotropic layer in which the rod-like liquid crystal is vertically aligned and the alignment is fixed, and in some cases, other intermediate layers.

  The retardation value was measured by adjusting the humidity to a wavelength of 590 nm and 23 ° C. and 55% RH using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments).

  In order to obtain the 2nd protective film of this invention, it is preferable to be comprised by the transparent film and vertical alignment liquid crystal layer as described at least below.

  The transparent film of the present invention preferably has the following characteristics.

Transmittance: 80% or more Film thickness: 20-80 μm
0nm ≦ Ro ≦ 330nm
−100 nm ≦ Rt ≦ 340 nm
Ro = (nx−ny) × d
Rt = ((nx + ny) / 2−nz) × d
(Where nx is the refractive index in the slow axis direction in the plane of the transparent film, ny is the refractive index in the direction perpendicular to the slow axis in the plane, nz is the refractive index in the thickness direction, and d is transparent) Represents the thickness (nm) of the film, and the measurement wavelength of the refractive index is 590 nm.)
The refractive index can be obtained at a wavelength of 590 nm under an environment of 23 ° C. and 55% RH using, for example, KOBRA-21ADH (Oji Scientific Instruments).

  For the second protective film, the transparent film described in the first protective film can be used, and among them, it is particularly preferable to use a cellulose ester film.

In this invention, it is one characteristic that the elastic modulus of the width direction (TD) of the transparent film used for a 2nd protective film is 4.0-6.0 kN / mm < ² >. The elastic modulus of TD can be achieved by controlling drawing conditions such as drawing temperature and draw ratio, and the elastic modulus can be measured by the method described below. The stretching ratio is 1% to 250%, more preferably 5% to 100%, and still more preferably 5% to 80% in at least one side. Although it may be stretched evenly in the vertical and horizontal directions, it is more preferable to stretch one of the stretch ratios more than the other and stretch the same.

  The film forming direction / longitudinal direction (MD) and the width direction / transverse direction (TD) may be increased, but the smaller stretching ratio is preferably 0% to 30%, more preferably 0% to 25%. Yes, more preferably from 0% to 20%. The larger draw ratio is 1% to 250%, more preferably 10% to 200%, and still more preferably 30% to 150%.

Stretch ratio (%) = 100 × {(Length after stretching) − (Length before stretching)} / (Length before stretching)
These longitudinal stretching and lateral stretching may be performed independently (uniaxial stretching) or may be performed in combination (biaxial stretching). In the case of biaxial stretching, it may be carried out in the longitudinal and transverse sequential manners (sequential stretching) or simultaneously (simultaneous stretching).

  Following such stretching, it is preferable to relax 0% to 10% in the longitudinal or transverse direction. Furthermore, it is also preferable to heat-fix at 150-250 degreeC for 1 second-3 minutes following extending | stretching.

(Measurement of elastic modulus)
The elastic modulus measurement in the TD direction and the MD direction is performed according to JIS K 7127.

  Specifically, the elastic modulus is conditioned at 23 ° C. and 55% RH for 24 hours, and Tensilon RTA-100 manufactured by Orient Test Co., Ltd. is used according to the method described in JIS K7127. The shape of the test piece is a No. 1 type test piece, and the test speed is measured under the condition of 10 mm / min.

<Optically anisotropic layer in which rod-like liquid crystal is vertically aligned and fixed in alignment>
The optically anisotropic layer preferably has the following characteristics.

0 ≦ Ro ≦ 10
−500 ≦ Rt ≦ −100
Here, Ro is the in-plane retardation, Rt is the thickness direction retardation (Rt), the main refractive index of the optically anisotropic layer is nx (slow axis), and the refractive index in the direction orthogonal to the main refractive index is When ny is the fast axis, the refractive index in the thickness direction of the layer is nz, and the thickness of the layer is d (nm), Ro = (nx−ny) × d, Rt = (( nx + ny) / 2−nz) × d.

  The optically anisotropic layer of the present invention is obtained by applying a liquid crystal material or a liquid crystal solution directly on the cellulose ester film or on an intermediate layer, drying and heat-treating (also referred to as orientation treatment), ultraviolet curing or thermal polymerization. It is preferably a retardation layer made of rod-like liquid crystal in which liquid crystal alignment is fixed and aligned in the vertical direction (hereinafter, the optically anisotropic layer is also referred to as a retardation layer).

  Here, “orienting in the vertical direction” means that the rod-like liquid crystal is in the range of 70 to 90 ° (the vertical direction is 90 °) with respect to the film surface serving as the support.

  The rod-like liquid crystal may be oriented obliquely or the orientation angle may be gradually changed. Preferably it is the range of 80-90 degrees.

  The optically anisotropic layer of the present invention is a retardation layer made of a rod-like liquid crystal oriented in the vertical direction with Ro in the range of 0 to 10 nm and Rt in the range of −500 to −100 nm. Further, Ro is more preferably in the range of 0 to 5 nm. The phase difference measurement of the layer on which the liquid crystal alignment is fixed on these supports can be measured using AxoScan manufactured by Opto Science Co., Ltd.

  When forming a retardation layer by aligning rod-shaped liquid crystals, an alignment film coated with a vertical alignment agent that aligns so-called liquid crystal materials in the vertical direction is used as an intermediate layer, and the liquid crystal material is vertically aligned and fixed. You can take a method.

  When the liquid crystal material itself is aligned in the vertical direction at the air interface, the alignment regulating force extends to the interface opposite to the air interface, and the alignment film is not particularly necessary, and this is also preferable from the viewpoint of simplifying the configuration. preferable.

  As a specific method for vertically aligning the liquid crystal material, an alignment film composed of a cross-linked product of a block polymer composition containing a (meth) acrylic block polymer described in JP-A-2005-148473 and the like is used. Known methods such as a method of using, a method of using a vertical alignment film described in JP 2005-265889 A, and a method of using an air interface vertical alignment agent can be used.

  In order to make the retardation layer in the above range, it is preferable to control the orientation of the rod-like liquid crystal layer, the film thickness control, the temperature during UV curing, the tilt angle control, and the control of the pretilt angle at the support / air interface.

  The retardation layer is formed by curing a liquid crystal material capable of forming a liquid crystal phase at a predetermined temperature with a predetermined liquid crystal regularity. The upper limit of the temperature showing the liquid crystal phase is not particularly limited as long as the cellulose ester film of the base material is not damaged.

  Specifically, a temperature of 120 ° C. or lower is preferable from the viewpoint of easy control of process temperature and maintenance of dimensional accuracy, and a liquid crystal material that becomes a liquid crystal phase at a temperature of 100 ° C. or lower is preferably used. On the other hand, the lower limit of the temperature showing the liquid crystal phase can be said to be a temperature at which the liquid crystal material can maintain the alignment state when used as a polarizing plate.

  As the liquid crystal material used for the retardation layer, a polymerizable liquid crystal material is preferably used. The polymerizable liquid crystal material can be used by being polymerized by irradiating with predetermined actinic radiation. In the polymerized state, the vertical alignment state is fixed.

  As the polymerizable liquid crystal compound, any of a polymerizable liquid crystal monomer, a polymerizable liquid crystal oligomer, and a polymerizable liquid crystal polymer can be used, and they can be used by mixing with each other.

  Among the above, a polymerizable liquid crystal monomer is preferably used as the polymerizable liquid crystal compound because of its high sensitivity during alignment and easy vertical alignment.

  Specific examples of the polymerizable liquid crystal monomer include a rod-like liquid crystal compound (I) represented by the following general formula (1) and a rod-like liquid crystal compound (II) represented by the following general formula (2). be able to. As the compound (I), two or more compounds included in the general formula (1) can be mixed and used. Similarly, the compound (II) is included in the general formula (2). Two or more kinds of compounds may be mixed and used. In addition, one or more compounds (I) and one or more compounds (II) may be mixed and used.

In the general formula (1) representing the compound (I), R ¹ and R ² each represent hydrogen or a methyl group, but R ¹ and R ² must be both hydrogen because of the wide temperature range showing the liquid crystal phase. preferable.

  X may be hydrogen, chlorine, bromine, iodine, an alkyl group having 1 to 4 carbon atoms, a methoxy group, a cyano group, or a nitro group, but is preferably chlorine or a methyl group.

  Moreover, a and b which show the chain length of the alkylene group which is a spacer with the (meth) acryloyloxy group of both ends of the molecular chain of a compound (I), and an aromatic ring are respectively arbitrary integers in the range of 2-12. Although it can take, it is preferable that it is the range of 4-10, and it is more preferable that it is the range of 6-9.

  In addition to the above, in the present invention, conventionally known materials can be appropriately selected and used as the polymerizable liquid crystal oligomer and the polymerizable liquid crystal polymer.

  For example, as a polymerizable rod-like liquid crystal compound, Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. Nos. 4,683,327, 5,622,648, and 5,770,107, International Publication No. 95/22586. Pamphlet, 95/24455, 97/00600, 98/23580, 98/52905, JP-A-1-272551, 6-16616, 7-110469, 11 JP-A-80081, JP-A 2001-328773, JP-A 2004-240188, JP-A 2005-99236, JP-A 2005-99237, JP-A 2005-121827, JP-A 2002-30042. The compounds described in the Japanese Patent Publication No. can be used.

  As commercially available compounds, UCL-018 (Dainippon Ink Chemical Co., Ltd.), Palio Color LC242 (BASF Co., Ltd.), etc. can be used.

  In the present invention, a photopolymerization initiator is used as required in addition to the polymerizable liquid crystal compound. When polymerizing a polymerizable liquid crystal compound by electron beam irradiation, a photopolymerization initiator may not be necessary. However, in the case of curing by, for example, ultraviolet (UV) irradiation, which is generally used, photopolymerization is usually performed. An initiator is used to promote polymerization.

  Photopolymerization initiators include benzyl (also called bibenzoyl), benzoin isobutyl ether, benzoin isopropyl ether, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylamino Methylbenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 3,3′-dimethyl-4-methoxybenzophenone, methylobenzoylformate, 2-methyl-1- (4 -(Methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 1- (4-dodecylphenyl) -2- Droxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2- Examples include methylpropan-1-one, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, or 1-chloro-4-propoxythioxanthone. it can.

  In general, the addition amount of the photopolymerization initiator is preferably 0.01% to 20%, more preferably 0.1% to 10%, and still more preferably 0.5% to 5%. Can be added to the polymerizable liquid crystal material of the present invention.

  In addition to the photopolymerization initiator, a sensitizer can be added as long as the object of the present invention is not impaired.

  The film thickness of the optically anisotropic layer in the present invention is preferably in the range of 0.1 μm to 10 μm, and more preferably in the range of 0.2 to 5 μm.

  The polymerizable liquid crystal compound is prepared by using a composition for forming an optically anisotropic layer by blending a photopolymerization initiator, a sensitizer, etc., if necessary, and coating it on a substrate. A layer forming layer is formed.

  As a method of forming a layer in which the orientation of liquid crystal is fixed, for example, a method in which a dry film or the like is formed in advance and a layer in which the orientation of liquid crystal is fixed is laminated on a substrate, or a liquid crystal composition is dissolved. Alternatively, it is possible to use a method of melting and coating on a substrate, but in the present invention, a liquid crystal composition is added with a solvent and a coating composition in which other components are dissolved is used. It is preferable to form a layer in which the orientation of the liquid crystal is fixed by coating on the substrate and removing the solvent. This is simple in terms of process as compared with other methods.

  The solvent is not particularly limited as long as it is a solvent capable of dissolving the above-described polymerizable liquid crystal material and the like and does not deteriorate the properties of the transparent resin film. Specifically, benzene, Hydrocarbons such as toluene, xylene, n-butylbenzene, diethylbenzene, tetralin; ethers such as methoxybenzene, 1,2-dimethoxybenzene, diethylene glycol dimethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, or 2,4- Ketones such as pentanedione; ethyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, or γ-butyrolactone Amides solvents such as 2-pyrrolidone, N-methyl-2-pyrrolidone, dimethylformamide or dimethylacetamide; chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, tritrichloroethylene, tetrachloroethylene, chlorobenzene, or orthodichlorobenzene Halogen solvents such as t-butyl alcohol, diacetone alcohol, glycerin, monoacetin, ethylene glycol, triethylene glycol, hexylene glycol, ethylene glycol monomethyl ether, ethyl cellosolve, or butyl cellosolve; phenols, One or more of phenols such as parachlorophenol can be used.

  If only a single type of solvent is used, the solubility of the polymerizable liquid crystal material or the like may be insufficient, or the substrate may be eroded as described above. However, this inconvenience can be avoided by using a mixture of two or more solvents.

  Of the above-mentioned solvents, preferred as a single solvent are a hydrocarbon solvent and a glycol monoether acetate solvent, and a preferred mixed solvent is a mixed system of ethers or ketones and glycols. It is.

  The concentration of the solution depends on the solubility of the polymerizable liquid crystal material and the like and the film thickness of the optically anisotropic layer to be produced, but cannot be defined unconditionally, but is usually preferably 1% to 60%, more preferably It is adjusted in the range of 3% to 40%.

  Compounds other than those described above can be added to the composition for forming an optically anisotropic layer used in the present invention within a range not impairing the object of the present invention.

  Examples of compounds that can be added include polyester (meth) acrylate obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by condensing polyhydric alcohol and monobasic acid or polybasic acid; A polyurethane (meth) acrylate obtained by reacting a compound having two isocyanate groups with each other and then reacting the reaction product with (meth) acrylic acid; bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak Type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ether, aliphatic or cycloaliphatic epoxy resin, amine epoxy resin, triphenolmethane type epoxy resin, dihydroxybenzene type epoxy resin and the like (meth) Ak A photopolymerizable compound such as epoxy (meth) acrylate obtained by reacting phosphoric acid, a photopolymerizable liquid crystal compound having an acrylic group or a methacryl group, an onium salt described in JP-A-2007-45993, and a fluorine compound. Acrylate polymers and the like.

  The amount of these compounds added to the composition for forming an optically anisotropic layer of the present invention is selected within a range that does not impair the object of the present invention, and in general, the composition for forming an optically anisotropic layer of the present invention. Is preferably 40% or less, more preferably 20% or less.

  Addition of these compounds improves the curability of the liquid crystal material in the present invention, increases the mechanical strength of the resulting optically anisotropic layer, and improves its stability.

  In addition, a surfactant or the like can be added to the composition for forming an optically anisotropic layer containing a solvent in order to facilitate coating.

  Examples of surfactants that can be added include cationic surfactants such as imidazoline, quaternary ammonium salts, alkylamine oxides and polyamine derivatives; polyoxyethylene-polyoxypropylene condensates, primary or secondary Alcohol ethoxylates, alkylphenol ethoxylates, polyethylene glycol and esters thereof, sodium lauryl sulfate, ammonium lauryl sulfate, lauryl sulfate amines, alkyl-substituted aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonic acid formalin condensates, etc. Anionic surfactants; amphoteric surfactants such as laurylamidopropylbetaine and laurylaminoacetic acid betaine; nonionics such as polyethylene glycol fatty acid esters and polyoxyethylene alkylamine Surfactant: Perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl trimethyl ammonium salt, perfluoroalkyl group / hydrophilic group-containing oligomer, perfluoroalkyl / lipophilic group Fluorosurfactants such as containing oligomer perfluoroalkyl group-containing urethanes.

  The amount of surfactant added depends on the type of surfactant, the type of liquid crystal material, the type of solvent, and the type of alignment film on which the solution is applied. 10 ppm to 10% is preferable, more preferably 100 ppm to 5%, and most preferably 0.1 to 1%.

  As a method of coating the composition for forming an optically anisotropic layer, a spin coating method, a roll coating method, a printing method, a dip pulling method, a die coating method, a casting method, a bar coating method, a blade coating method, a spray coating method, Examples include a gravure coating method, a reverse coating method, and an extrusion coating method.

  As a method for removing the solvent after coating the composition for forming an optically anisotropic layer, for example, air drying, heat removal, or reduced pressure removal, and a combination of these methods are performed. By removing the solvent, a layer in which the alignment of the liquid crystal is fixed is formed.

  In the step of curing the polymerizable liquid crystal material, energy for curing the polymerizable liquid crystal material is given, and thermal energy may be used, but it is usually performed by irradiation with ionizing radiation capable of causing polymerization.

  If necessary, a polymerization initiator may be contained in the polymerizable liquid crystal material. The ionizing radiation is not particularly limited as long as it is a radiation capable of polymerizing the polymerizable liquid crystal material. Usually, ultraviolet light or visible light is used from the viewpoint of the ease of the apparatus, and the wavelength is The light of 150-500 nm is preferable, More preferably, it is 250-450 nm, More preferably, it is an ultraviolet-ray with a wavelength of 300-400 nm.

  In the present invention, a method of performing radical polymerization by irradiating ultraviolet rays (UV) as actinic radiation and generating radicals from the polymerization initiator with ultraviolet rays is preferable. Since the method using UV as the actinic radiation is an already established technique, it can be easily applied to the present invention including the polymerization initiator to be used.

  As a light source for irradiating ultraviolet rays, a low-pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), a high-pressure discharge lamp (high-pressure mercury lamp, metal halide lamp), or a short arc discharge lamp (ultra-high-pressure mercury lamp, xenon) Lamp, mercury xenon lamp) and the like.

  In particular, the use of metal halide lamps, xenon lamps, high-pressure mercury lamps, etc. is recommended. The irradiation intensity may be appropriately adjusted depending on the composition of the polymerizable liquid crystal material used for forming the layer in which the alignment of the liquid crystal is fixed and the amount of the photopolymerization initiator.

  The alignment fixing step by irradiation with actinic radiation may be performed at the processing temperature in the step of forming the optically anisotropic layer forming layer described above, that is, a temperature condition in which the polymerizable liquid crystal material becomes a liquid crystal phase. The temperature may be lower than the temperature at which

(Middle layer)
It is preferable to provide an intermediate layer between the optically anisotropic layers in which the transparent film and the rod-shaped liquid crystal are aligned vertically to fix the alignment.

  The intermediate layer of the present invention is made of a transparent resin. The transparent resin is preferably a binder polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a binder polymer having a saturated hydrocarbon chain as a main chain.

  Particularly preferred is a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams, or a mixed composition of a crosslinking agent and a resin having a reactive site.

  Examples of the curable resin include UV curable urethane acrylate resins, UV curable polyester acrylate resins, UV curable epoxy acrylate resins, UV curable polyol acrylate resins, and UV curable epoxy resins. A type acrylate resin is preferably used.

  The UV curable urethane acrylate resin generally includes a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and further includes 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter, acrylate includes methacrylate). It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate.

  For example, those described in JP 59-151110 A can be used. For example, a mixture of purple light UV-7510B (manufactured by Nippon Synthetic Chemical Co., Ltd.), Unidic 17-806 (manufactured by Dainippon Ink Co., Ltd.) and 1 part of Coronate L (manufactured by Nippon Polyurethane Co., Ltd.) Preferably used.

  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 Japanese Patent 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.

  Specific examples of photopolymerization initiators for these curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer.

  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 curable resin composition is 0.1 to 25 parts by mass, preferably 1 to 15 parts by mass with respect to 100 parts by mass of the composition.

  Examples of the mixed composition of the resin having a crosslinking agent and a reactive site include polyvinyl alcohol and glyoxal, gelatin and glyoxal, and the like.

  Further, the intermediate layer 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 intermediate layer of the present invention may be two or more layers.

<Method for producing intermediate layer>
The intermediate layer is coated with a coating composition for forming the intermediate layer using a known method such as a gravure coater, dip coater, reverse coater, wire bar coater, die coater, ink jet method, etc., coated on a support, and then dried by heating. And UV curing treatment is preferred.

  The coating amount is suitably 0.1 to 40 μm, preferably 0.5 to 30 μm, as the wet film thickness.

  Moreover, as a dry film thickness, it is an average film thickness of 0.01-1 micrometer, Preferably it is 0.02-0.7 micrometer.

  As the light source for the 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 500 mJ / cm ² , preferably 5 to 150 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 300 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 having further excellent flatness.

  The coating composition for forming the intermediate layer may contain a solvent. Examples of the organic solvent contained in the coating composition include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone). , Esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents may be appropriately selected or mixed for use.

  As the organic solvent, propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate (1 to 4 carbon atoms of the alkyl group) is preferable. Moreover, as content of an organic solvent, 5-80 mass% is preferable in a coating composition.

<Antireflection layer>
On the hard coat layer of the hard coat film of the present invention, at least a low refractive layer may be laminated directly or via another layer to form an antireflection film with a hard coat layer.

  Further, in addition to the low refractive index layer, an antireflection layer may be configured by further combining a high refractive index layer having a higher refractive index than the support. Further, a medium refractive index layer (a layer having a higher refractive index than the support and a lower refractive index than the high refractive index layer) may be laminated. Moreover, you may provide a backcoat layer in the film back surface.

  Specific examples of the layer structure of the antireflection film include the following, but are not limited thereto.

Transparent film / Hard coat layer / Medium refractive index layer / Low refractive index layer Transparent film / Hard coat layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Transparent film / Hard coat layer / Low refractive index layer Transparent film / Hard coat layer / conductive layer / low refractive index layer Transparent film / hard coat layer / high refractive index layer (conductive layer) / low refractive index layer Transparent film / hard coat layer / antiglare layer / low refractive index layer Back coat layer / transparent film / hard coat layer / low refractive index layer Back coat layer / transparent film / hard coat layer / medium refractive index layer / low refractive index layer Back coat layer / transparent film / hard coat layer / antiglare layer / Low refractive index layer Back coat layer / Transparent film / Hard coat layer / Conductive layer / Low refractive index layer Back coat layer / Transparent film / Hard coat layer / High refractive index layer (conductive layer) / Low refractive index layer [ Refractive index layer]
The low refractive index layer in the present invention means a layer lower than the refractive index of the transparent film as the support, and the refractive index is preferably in the range of 1.30 to 1.45 at 23 ° C. and wavelength of 550 nm. .

  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 most preferably 30 nm to 0.2 μm.

  The composition for forming a low refractive index layer used in the present invention may contain at least one kind of particles having an outer shell layer and porous or hollow inside as silica-based fine particles. The particles having a layer and porous or hollow inside are preferably hollow silica fine particles.

(Hollow silica fine particles)
The hollow silica-based fine particles are (I) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles, or (II) having cavities inside, and the contents are solvent, gas or porous It is a hollow particle filled with a porous material. Note that the low refractive index layer only needs to contain either (I) composite particles or (II) hollow particles, or both.

  Note that the cavity particles are particles having a cavity inside, and the cavity is covered with a coating layer (also referred to as 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. It is desirable that the average particle size of such hollow fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm. The average particle diameter of the hollow fine particles to be used is desirably 3/2 to 1/10, preferably 2/3 to 1/10, of the average film thickness of the low refractive index layer to be formed. These hollow fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol) and ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), ketone alcohol (for example, diacetone alcohol), or a mixed solvent containing these is preferable.

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

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, and 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. , 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. Among these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly preferable. Examples of inorganic compounds other than silica include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ and WO _3. 1 type or 2 types or more can be mentioned. In such porous particles, the molar ratio MO _X / SiO ₂ when the silica is expressed by SiO ₂ and the inorganic compound other than silica is expressed in terms of oxide (MO _X ) is 0.0001 to 1.0, Preferably it is in the range of 0.001 to 0.3. It is difficult to obtain a porous particle having a molar ratio MO _X / SiO ₂ of less than 0.0001. Even if it is obtained, a pore volume is small and particles having a low refractive index cannot be obtained. In addition, when the molar ratio MO _X / SiO _{2 of} the porous particles exceeds 1.0, the ratio of silica decreases, so that the pore volume increases and it is difficult to obtain a material having a lower refractive index. is there.

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

  In addition, 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 said porous particle as a porous substance is mentioned. These contents may be composed of a single component or may be a mixture of a plurality of components.

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

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

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

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

Although the pH value of the mixed aqueous solution changes simultaneously with the addition of these aqueous solutions, an operation for controlling the pH value within a predetermined range is not particularly required. The aqueous solution finally has a pH value determined by the type of inorganic oxide and the mixing ratio thereof. There is no restriction | limiting in particular in the addition rate of the aqueous solution at this time. Further, in the production of composite oxide particles, a dispersion of seed particles can be used as a starting material. The seed particles are not particularly limited, but inorganic oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or fine particles of these composite oxides are used. Usually, these sols are used. Can do. Furthermore, the porous particle precursor dispersion obtained by the above production method may be used as a seed particle dispersion. When using a seed particle dispersion, the pH of the seed particle dispersion is adjusted to 10 or higher, and then an aqueous solution of the compound is added to the above-mentioned 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 fine particles, or seed particles. It grows on the top and particle growth occurs. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of fine particles.

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

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

  The porous particle precursor obtained in the first step is a particle having a network structure in which silicon and an inorganic compound constituent element are bonded through 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 15 nm. Even if the silica protective film is formed, the protective film in this step is porous and thin, so that it is possible to remove inorganic compounds other than silica described above from the porous particle precursor.

  By forming such a silica protective film, inorganic compounds other than 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. Can do. Note that when the amount of the inorganic compound to be removed is small, the particles are not broken, and thus it is not always necessary to form a protective film.

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

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

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

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

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

The hydrolyzable organic silicon compound used for the silica coating layer formed, the above-mentioned such general formula _{R n Si (OR ') 4} -n [R, R': an alkyl group, an aryl group, a vinyl group, An alkoxysilane represented by a hydrocarbon group such as an acryl group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

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

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

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

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

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

  The refractive index of the inorganic fine particles thus obtained is as low as less than 1.42. Such inorganic fine particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow. As the hollow silica-based fine particles, those commercially available from Catalyst Kasei Co., Ltd. can be preferably used.

  The content of the hollow silica-based fine particles having an outer shell layer and porous or hollow inside is preferably 10 to 50% by mass. In order to obtain the effect of a low refractive index, the content is preferably 15% by mass or more, and when it exceeds 50% by mass, the binder component is decreased and the film strength becomes insufficient. Most preferably, it is 20-50 mass%.

  As a method of adding to the low refractive index layer, for example, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of the tetraalkoxysilane, pure water, and alcohol is added to the dispersion of the hollow silica fine particles. The silicic acid polymer produced by hydrolyzing tetraalkoxysilane is deposited on the surface of the hollow silica fine particles. At this time, tetraalkoxysilane, 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. The silica-based fine particles may be those produced by the production method described in WO2007 / 099814.

(binder)
Moreover, it is preferable that the low refractive index layer contains the above-described cationic polymerizable compound as a binder from the viewpoint that the objective effect can be better exhibited. As the cationic polymerizable compound, the compounds described in the hard coat layer described above can be used. In addition, it is also preferable to use the above acid or photoacid generator as a compound that accelerates the polymerization of the cationic polymerizable compound. These acids and photoacid generators are preferably added in a proportion of 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the cationic polymerizable compound. From the viewpoint of stability in the composition for forming a low refractive index layer, polymerization reactivity, and the like.

  Moreover, you may use a radically polymerizable compound as a binder. As the radical polymerizable compound, the compounds described in the hard coat layer described above can be used.

  In order to accelerate curing of the radical polymerizable compound, it is preferable to use a photopolymerization initiator, and it is preferable to contain the photopolymerization initiator and the radical polymerizable compound in a mass ratio of 20: 100 to 0.01: 100.

  Furthermore, the fluorine substituted alkyl group containing silane compound represented by the said general formula (OSi-2) can also be contained.

  If the fluorine-containing alkyl group-containing silane compound is included as a binder, the transparent film itself is hydrophobic, so the transparent film is not sufficiently densified and is porous or cracked. Even if it has a void or a void, entry into the transparent film by chemicals such as moisture, acid and alkali is suppressed. Furthermore, fine particles such as metals contained in the conductive layer which is the substrate surface or the lower layer do not react with chemicals such as moisture, acid and alkali. For this reason, such a transparent film has excellent chemical resistance.

  In addition, when a fluorine-substituted alkyl group-containing silane compound is included as a binder, not only the hydrophobic property but also the slipperiness (low contact resistance) is obtained, and thus a transparent film having excellent scratch strength can be obtained. Can do. Further, when the binder contains a fluorine-substituted alkyl group-containing silane compound having such a structural unit, when the conductive layer is formed in the lower layer, the shrinkage rate of the binder is equivalent to that of the conductive layer. Therefore, it is possible to form a transparent film having excellent adhesion to the conductive layer. Furthermore, when the transparent film is heat-treated, the conductive layer is not peeled off due to the difference in shrinkage rate, and a portion having no electrical contact is not generated in the transparent conductive layer. For this reason, sufficient electroconductivity can be maintained as a whole film.

  A transparent film containing a fluorine-substituted alkyl group-containing silane compound and hollow silica-based fine particles having the outer shell layer and being porous or hollow inside has high scratch strength and is evaluated by eraser strength or nail strength. The film strength is high, the pencil hardness is high, and a transparent film excellent in strength can be formed.

  The low refractive index layer may contain a silane coupling agent. Silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane. Ethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltri Acetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltri Ethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ- Acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N- Examples include β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane.

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

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

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

The low refractive index layer may contain a silicon compound represented by CF ₃ (CF ₂ ) nCH ₂ CH ₂ Si (OR ₁ ) ₃ . (In the formula, R1 represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 12.) Specific examples of the compound include trifluoropropyltrimethoxysilane and trifluoropropyl. Examples include triethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, and these are used alone or in combination of two or more. Can be used. _{It may} also contain H 2 NCONH (CH) mSi ( OR2) silicon compound in the terminal position represented by ₃ having a ureido group _(H 2 NCONH-). (In the formula, R2 represents an alkyl group having 1 to 5 carbon atoms, and m represents an integer of 1 to 5.) Specific compounds include γ-ureidopropyltrimethoxysilane and γ-ureido. Examples thereof include propyltriethoxysilane and γ-ureidopropyltripropoxysilane. Among these, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, and the like are particularly preferable.

  In addition, the low refractive index layer can use, for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, fluoroacrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin, etc. as a binder. .

  In addition, examples of the binder include polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, fluoroacrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, and alkyd resin.

  The low refractive index layer preferably contains 5 to 80% by mass of binder as a whole. The binder has a function of maintaining the structure of the low refractive index layer including voids. The usage-amount of a binder is suitably adjusted so that the intensity | strength of a low refractive index layer can be maintained, without filling a space | gap.

(solvent)
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). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

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

  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 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.

Moreover, after forming a low refractive index layer, you may include the process of heat-processing at the temperature of 50-160 degreeC. 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 100 ° C., a range of 1 minute or more and 1 day or less is preferable. . 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. In the case of thermosetting, the heating temperature is preferably 50 to 300 ° C, preferably 60 to 250 ° C, 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 .

(High refractive index layer)
The antireflection layer may have the following high refractive index layer in addition to the above-described low refractive index layer.

  The high refractive index layer preferably contains metal oxide fine particles. 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 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. 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 film as the support, 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.

  The thickness of the high refractive index layer containing the metal oxide fine particles is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 0.1 μm.

  The 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 in the present invention is preferably 5% by mass to 85% by mass in the high refractive index layer, more preferably 10% by mass to 80% by mass, and most preferably 20% to 75% by mass. preferable. 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.

Formula (CL1) _An MB _x-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 forming a chelate compound by coordination with a free metal compound include alkanolamines such as diethanolamine and triethanolamine, glycols such as ethylene glycol, diethylene glycol and propylene glycol, acetylacetone and acetoacetic acid. 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 a radical polymerizable compound as a binder for the metal oxide fine particles in order to improve the film forming property and physical properties of the coating film. As the radically polymerizable compound, a monomer or oligomer having two or more functional groups that cause a polymerization reaction directly by irradiation with actinic rays such as ultraviolet rays or electron beams or indirectly by the action of a photopolymerization initiator is used. Specifically, 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 described above is preferable.

  The addition amount of the radical polymerizable compound 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 curing of the radically polymerizable compound, it is preferable to contain a photopolymerization initiator. The addition amount of the photopolymerization initiator is preferably contained in a mass ratio of photopolymerization initiator: radically polymerizable compound = 3: 7 to 1: 9.

  As the photopolymerization initiator, specifically, the compounds described in the hard coat layer described above can be used.

  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, Lenglycol 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, ether) Range amine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.) ), Heterocyclic rings (for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone), sulfoxides (for example, dimethyl sulfoxide) , Sulfones (e.g., sulfolane), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable.

  The high refractive index layer is obtained by applying the above composition to a transparent resin film or hard coat layer surface using a gravure coater, dip coater, reverse coater, wire bar coater, die coater, spray coating, ink jet coating or the like. It is applied at 1 to 100 μm, and after application, it is heated and dried, and is cured as necessary. The content described in the low refractive index layer can be used in the curing step. The dry film thickness is adjusted to the above film thickness by adjusting the solid content concentration of the coating composition.

[Conductive layer]
The conductive layer can be provided on a transparent film. For example, the conductive layer is provided between the hard coat layer and the antireflection layer or on the transparent film on the side opposite to the side on which the antireflection layer is provided. Can do.

  The conductive layer imparts a function of preventing the hard coat film from being charged when the support (resin film or the like) is handled. Specifically, the above-described π-conjugated conductivity is applied to the hard coat layer. An ionic polymer, an ionic polymer compound, a metal oxide and the like are preferably used.

The surface specific resistance of the conductive layer is preferably adjusted to 10 ¹¹ Ω / □ (25 ° C., 55% RH) or less, more preferably 10 ¹⁰ Ω / □ (25 ° C., 55% RH) or less. Particularly preferably, it is 10 ⁹ Ω / □ (25 ° C., 55% RH) or less.

  Here, although details of the measurement of the surface specific resistance value are described in the Examples, the sample was conditioned for 24 hours under the conditions of 25 ° C. and 55% RH, and a terraohm meter model VE-30 manufactured by Kawaguchi Electric Co., Ltd. was used. Use to measure.

  An overcoat layer may be further provided on the conductive layer as the outermost surface layer, but the surface specific resistance value is measured by measuring the surface specific resistance value on the outermost surface layer on the side where the conductive layer is provided. It is defined as the surface specific resistance value of the conductive layer.

  Furthermore, examples of the ionic polymer 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, JP-A-50 Ionene type polymers having a dissociation group in the main chain as seen in JP-B-54672, JP-B-59-14735, JP-A-57-18175, JP-A-57-18176, JP-A-57-56059, etc .; No. -13223, No. 57-15376, No. 53-45231, No. 55-145578, No. 55-65950, No. 55-67746, No. 57-11342, No. 57-19735, No. 58 No. 56568, Japanese Patent Application Laid-Open Nos. 61-27853 and 62-9346, and cationic penders having a cationic dissociation group in the side chain Preparative polymer; and the like. Among them, a quaternary ammonium cationic polymer having molecular crosslinking is particularly preferable, and a quaternary ammonium cationic polymer not containing chlorine ions and having molecular crosslinking is particularly preferably used from the viewpoint of environmental safety such as prevention of dioxin generation.

The ionic polymer compound may be used alone, or several types of ionic polymer compounds may be used in combination. The content of the ionic polymer compound used in the present invention in the resin film is preferably 0.02 g to 1.0 g / m ² , particularly preferably 0.02 g to 0.5 g / m ² .

  Further, fine particles may be added to the conductive layer. Examples thereof include fine particles containing silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate and the like as constituent components.

  The average particle diameter of the fine particles described above is preferably 0.01 μm to 10 μm, more preferably 0.01 μm to 5 μm, and the addition amount is 0.05 part to 10 parts by mass with respect to the solid content in the coating agent. Parts are preferred, with 0.1 to 5 parts being particularly preferred.

  Moreover, in order for a conductive layer to show sufficient antistatic effect and to maintain easy adhesion with an overcoat layer, it is preferable to contain a cellulose ester resin or an acrylic resin.

  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 acrylic resins include Acrypet MD, VH, MF, V (manufactured by 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. (manufactured by 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 added as necessary. You can also 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.

[Back coat layer]
It is preferable to provide a backcoat layer on the surface opposite to the side on which the hardcoat layer is provided. The back coat layer is provided in order to correct curling caused by providing a hard coat layer or other layers. That is, the degree of curling can be balanced by imparting the property of being rounded with the surface on which the backcoat layer is provided facing inward. The back coat layer is preferably applied also as an anti-blocking layer. In this case, it is preferable that fine particles are added to the back coat layer coating composition in order to provide an anti-blocking function.

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

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

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

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

  Examples of the solvent used for coating the backcoat layer include dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, methyl acetate, ethyl acetate, trichloroethylene, methylene chloride, ethylene chloride, tetrachloroethane, trichloroethane, Chloroform, water, methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butanol, cyclohexanone, cyclohexanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, or hydrocarbons (toluene, xylene) Are used in appropriate combinations.

  It is preferable to apply these coating compositions on the surface of the hard coat film with a gravure coater, dip coater, reverse coater, wire bar coater, die coater, spray coating, ink jet coating or the like with a wet film thickness of 1 to 100 μm. Is particularly preferably 5 to 30 μm.

  Examples of the resin used as the binder of the backcoat layer include vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, vinyl acetate-vinyl alcohol copolymer, partially hydrolyzed vinyl chloride-vinyl acetate copolymer. Polymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, etc. Vinyl polymer or copolymer, nitrocellulose, cellulose acetate propionate (preferably acetyl group substitution degree 1.8-2.3, propionyl group substitution degree 0.1-1.0), diacetyl cellulose, cellulose Cellulose derivatives such as acetate butyrate resin, maleic acid and / or Or acrylic acid copolymer, acrylic ester copolymer, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin , Polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, urethane resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene-butadiene resin, butadiene-acrylonitrile Examples thereof include, but are not limited to, rubber resins such as resins, silicone resins, fluorine resins, and the like. As the acrylic resin, the above-described compounds can be used for the conductive layer.

  As the resin used as the binder, it is preferable to use a blend of acetylated cellulose and acrylic resin such as cellulose diacetate and cellulose acetate prothionate, and the refractive index difference between the fine particles and the binder using fine particles made of acrylic resin. By setting the value to less than 0 to 0.02, a highly transparent back coat layer can be obtained.

  The order in which the backcoat layer is applied may be before or after the hardcoat layer is applied, but when the backcoat layer also serves as an anti-blocking layer, it is preferably applied first. Alternatively, the backcoat layer can be applied in two or more steps. Moreover, it is also preferable that the backcoat layer also serves as an easy-adhesion layer for improving the adhesion with the polarizer.

(Reflectivity of antireflection layer)
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 is 2.0% or less, and an external light antireflection function when used on the outermost surface of an image display device such as an LCD is suitably obtained. It is preferable from the point which is made. The minimum reflectance is preferably 0.8% or less.

  Moreover, it is preferable to have a flat reflection spectrum in the wavelength region of visible light. 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 calculated from the refractive index of each layer in accordance with a conventional method in consideration of the reflectance and the color of reflected light.

"Polarizer"
A polarizing plate using the first protective film and the second protective film of the present invention will be described.

  The polarizing plate can be produced by a general method. The first and second protective films of the present invention are subjected to alkali saponification treatment on the back side, and the treated protective film is immersed and stretched in an iodine solution on at least one surface of the polarizing film, and completely saponified polyvinyl It is preferable to bond using an aqueous alcohol solution. At that time, in the first protective film, the hard coat layer is preferably bonded to the side far from the polarizing film, and in the second protective film, the optically anisotropic layer is preferably bonded to the side far from the polarizing film.

  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 surface of the protective 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.

<Liquid crystal display device>
By incorporating the polarizing plate of the present invention on the viewing surface side of the liquid crystal display device, the liquid crystal display device of the present invention having various visibility in addition to excellent planar characteristics can be produced.

  As the liquid crystal display device, a reflective type, a transmissive type, a transflective type LCD, or a TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), or IPS type LCD is preferable. Although it is used, it is particularly preferably used in an IPS liquid crystal ideographic apparatus.

  FIG. 3 is a schematic view of an IPS mode liquid crystal display device according to the present invention.

  A light guide plate, a prism sheet (not shown), and a backlight side polarizing plate L-12 are arranged adjacent to the backlight L-13 from below. The polarizing film L-8 of the backlight side polarizing plate L-12 is sandwiched between the polarizing plate protective film L-7 and the polarizing plate protective film L-9. Next, there is an IPS liquid crystal cell L-6 having a configuration of an electrode side cell glass substrate L-6-2, an IPS type liquid crystal cell L-6-3, and a non-electrode type cell glass substrate L-6-1. There is a polarizing film L-2 constituting the plate L-10, a first protective film L-1 of the present invention, and a second protective film L-11.

  Other polarizing plate protective films L-7 and L-9 are not particularly limited. For example, polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyethylene films, polypropylene films, polycycloolefin films, cellophane, and cellulose. Acetate film, cellulose acetate butyrate film, cellulose acetate phthalate film, cellulose acetate propionate film, cellulose triacetate, film made of cellulose esters such as cellulose nitrate or derivatives thereof, polyvinylidene chloride film, polyvinyl alcohol film, ethylene Vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film , Cycloolefin polymer film (for example, ARTON (manufactured by JSR), ZEONEX, ZEONOR (manufactured by ZEON)), polymethylpentene film, polyetherketone film, polyethersulfone film, polysulfone film, polyetherketoneimide Examples thereof include a film, a polyamide film, an acrylic film, and a polyacrylate film.

  Cellulose ester films such as cellulose acetate propionate film and cellulose triacetate film (TAC film) are commercially available films, such as Konica Minolta Op KONICA MINOLTATAC KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY KC4UY, KC12UR, KC16UR, KC4UE, KC8UE, KC4FR-1, KC4FR-2, etc. are preferably used. In addition, a cycloolefin polymer film, a polycarbonate film, a polyester film, or a polyacrylic film can also be preferably used in terms of transparency, mechanical properties, and lack of optical anisotropy. These resin films may be films formed by a melt casting method or a solution casting method.

  In the case of an IPS mode liquid crystal display device, the polarizing plate protective films 7 and 9 have a retardation value Rt value in the range of -20 to 20 nm, more preferably -10 to 10 nm, and a Ro value of 0 to 10 nm. It is also preferred to use a range of films.

<IPS horizontal electric field switching mode type liquid crystal display device>
By incorporating a polarizing plate using the polarizing plate protective film of the present invention into a commercially available IPS (In Plane Switching) mode type liquid crystal display device, it has excellent visibility, excellent color shift, corner unevenness, and front contrast characteristics. The liquid crystal display device of the present invention can be manufactured.

  The IPS mode of the present invention includes a fringe-field switching (FFS) mode in the present invention, and the polarizing plate of the present invention can be incorporated in the same manner as the IPS mode. A liquid crystal display device can be manufactured.

(IPS mode liquid crystal cell)
The liquid crystal layer of the liquid crystal panel in the IPS mode type liquid crystal display device is homogeneously aligned parallel to the substrate surface in the initial state, and the director of the liquid crystal layer is parallel to the electrode wiring direction when no voltage is applied. The direction of the director of the liquid crystal layer shifts to a direction perpendicular to the electrode wiring direction when a voltage is applied, and the director direction of the liquid crystal layer is the direction of the director when no voltage is applied. When tilted in the direction of the electrode wiring by 45 ° compared to the liquid crystal layer when the voltage is applied, the azimuth angle of the polarization is rotated by 90 ° like a half-wave plate, and the transmission axis and polarization of the output side polarizing plate are rotated. The azimuth angles of the two coincide with each other to display white.

  In general, the thickness of the liquid crystal layer is constant, but since it is driven by a lateral electric field, it is considered that a slight unevenness in the thickness of the liquid crystal layer can increase the response speed to switching. Even if the thickness of the layer is not constant, the effect can be maximized.

  In this invention, there is little influence with respect to the change of the thickness of a liquid crystal layer. The thickness of the liquid crystal layer capable of greatly exerting the effect in the present invention is 2 to 6 μm, and preferably 3 to 5.5 μm.

  The liquid crystal display device of the present invention is used for a large liquid crystal television. As a screen size, it can be used for 17 or more types, preferably 26 to 100 types.

  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
<< Production of Cellulose Triacetate Film 1 which is a Base Film of the First Protective Film >>
(Preparation of dope solution A)
The following materials were sequentially put into a sealed container, the temperature in the container was raised from 20 ° C. to 80 ° C., and then stirred for 3 hours while maintaining the temperature at 80 ° C. to completely dissolve the cellulose triacetate. . The silicon oxide fine particles were dispersed and added in a solution of a solvent to be added in advance and a small amount of cellulose triacetate. This dope was filtered using a filter paper (Azumi filter paper No. 244, manufactured by Azumi Filter Paper Co., Ltd.) to obtain a dope solution A.

(Preparation of dope solution A)
Cellulose triacetate (acetyl group substitution degree 2.9) 100 parts by weight Trimethylolpropane tribenzoate 5 parts by weight Ethylphthalylethyl glycolate 5 parts by weight Silicon oxide fine particles (Aerosil R972V, Nippon Aerosil Co., Ltd.) 0.1 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 400 parts by weight Ethanol 40 parts by weight Butanol 5 parts by weight The above materials are mixed to prepare a dope solution A The obtained dope liquid A was passed through a casting die kept at a temperature of 35 ° C. and cast on a support 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.

Next, the web is transported while being dried with a drying air of 90 ° C. in a drying process of transporting by a plurality of rolls arranged on the upper and lower sides. Subsequently, both ends of the web are gripped by a tenter, and then in the width direction (TD) at 140 ° C. It extended | stretched so that it might be 1.2 times before extending | stretching. After stretching with a tenter, the web was dried with a drying air of 145 ° C. in a transport drying process using a plurality of rolls arranged vertically. After heat treatment for 15 minutes in an atmosphere with an atmosphere substitution rate of 15 (times / hour) in the drying step, the sample was cooled to room temperature and wound by applying a knurling process with a width of 2 cm and an average height of 20 μm at both ends. A cellulose triacetate film 1 having a refractive index of 1.49 having a thickness of 5 m, a thickness of 40 μm, and a length of 4000 m was produced. Moreover, the draw ratio of the web conveyance direction (MD) immediately after peeling computed from the rotational speed of a stainless steel band support body and the driving speed of a tenter was 1.1 times. The elastic modulus of the cellulose triacetate film 1 is conditioned for 24 hours in an environment of 23 ° C. and 55% RH, and Tensilon RTA-100 manufactured by Orient Test Co., Ltd. is used according to the method described in JIS K7127. The shape of the test piece was a No. 1 type test piece, and the test speed was measured under the condition of 10 mm / min. Result, the elastic modulus of the MD elastic modulus of 3.2kN / ^mm 2, TD was 3.3kN / mm ^2.

<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 triacetate film 1 by the following procedure.

The following hard coat layer coating 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 coated on the cellulose triacetate film 1 using a microgravure coater, and 80 ° C. After drying, an ultraviolet ray lamp was used to cure the coating layer with an irradiance of 200 mW / cm ² and an irradiation dose of 0.3 J / cm ² to form a hard coat layer having a dry film thickness of 25 μm, and then the following back The coating layer coating composition 1 was applied to the surface opposite to the surface coated with the hard coating layer so as to have a wet film thickness of 18 μm using an extrusion coater, and dried at 80 ° C. to prepare a hard coating film 1. .

(Hard coat layer composition 1)
<Preparation of fluorine-siloxane graft polymer I>
Hereinafter, commercial product names of materials used for preparing the fluorine-siloxane graft polymer I are shown.

○ Radical polymerizable fluororesin (A):
Cefalcoat CF-803 (hydroxyl value 60, number average molecular weight 15,000; manufactured by Central Glass Co., Ltd.)
○ One-end radical polymerizable polysiloxane (B):
Silaplane FM-0721 (number average molecular weight 5,000; manufactured by Chisso Corporation)
○ Radical polymerization initiator:
Perbutyl O (t-butylperoxy-2-ethylhexanoate; manufactured by NOF Corporation)
○ Hardener:
Sumidur N3200 (biuret type prepolymer of hexamethylene diisocyanate; manufactured by Sumika Bayer Urethane Co., Ltd.)
(Synthesis of radical polymerizable fluororesin (A))
In a glass reactor equipped with a mechanical stirrer, thermometer, condenser and dry nitrogen gas inlet, cefal coat CF-803 (1554 parts by mass), xylene (233 parts by mass), and 2-isocyanatoethyl methacrylate (6 3 parts by mass) and heated to 80 ° C. in a dry nitrogen atmosphere. After reacting at 80 ° C. for 2 hours and confirming that the absorption of isocyanate disappeared by the infrared absorption spectrum of the sample, the reaction mixture was taken out and 50% by mass of radically polymerizable fluororesin (A) via a urethane bond. Got.

(Preparation of fluorine-siloxane graft polymer I)
In a glass reactor equipped with a mechanical stirrer, a thermometer, a condenser and a dry nitrogen gas inlet, the synthesized radical polymerizable fluororesin (A) (26.1 parts by mass), xylene (19.5 parts by mass) ), N-butyl acetate (16.3 parts by mass), methyl methacrylate (2.4 parts by mass), n-butyl methacrylate (1.8 parts by mass), lauryl methacrylate (1.8 parts by mass), 2-hydroxyethyl Add methacrylate (1.8 parts by mass), FM-0721 (5.2 parts by mass), and perbutyl O (0.1 parts by mass), heat to 90 ° C. in a nitrogen atmosphere, and hold at 90 ° C. for 2 hours. did. Perbutyl O (0.1 part) was added, and the solution was further maintained at 90 ° C. for 5 hours to obtain a 35 mass% fluorine-siloxane graft polymer I solution having a weight average molecular weight of 171,000.

  The weight average molecular weight was determined by GPC. Moreover, the mass% of the fluorine-siloxane graft polymer I was calculated | required by HPLC (liquid chromatography).

  The following materials were stirred and mixed to obtain hard coat layer coating composition 1.

Pentaerythritol triacrylate 20.0 parts by mass Pentaerythritol tetraacrylate 50.0 parts by mass Dipentaerythritol hexaacrylate 30.0 parts by mass Dipentaerythritol pentaacrylate 30.0 parts by mass Irgacure 184 (manufactured by Ciba Japan) 5.0 Parts by mass Irgacure 907 (manufactured by Ciba Japan) 10.0 parts by mass The adjusted fluorine-siloxane graft polymer I (35% by mass) 5.0 parts by mass Seahoster KEP-100 (manufactured by Nippon Shokubai Co., Ltd.) 8.0 parts by mass Parts propylene glycol monomethyl ether 10 parts by weight methyl acetate 20 parts by weight acetone 20 parts by weight methyl ethyl ketone 60 parts by weight cyclohexanone 20 parts by weight (Backcoat layer coating composition 1)
Diacetyl cellulose 0.6 parts by weight Acetone 35 parts by weight Methyl ethyl ketone 35 parts by weight Methanol 35 parts by weight 2% methanol dispersion of silica particles (KE-P30, manufactured by Nippon Shokubai Co., Ltd.) 16 parts by weight <Measurement of Martens hardness>
The Martens hardness (HMs) of the hard coat layer surface of the hard coat film 1 was measured using a micro hardness meter. That is, using a microhardness meter (trade name, DUH-212, manufactured by Shimadzu Corporation) using a Vickers indenter and a triangular pyramid indenter having an angle of 115 degrees, first, a hard coat layer on the surface of the hard coat film The indenter was pushed to a thickness of about 1/10 of the film thickness, and a load test force-indentation depth curve when the indenter was pushed in was created. Next, from the created load test force-indentation depth curve, the indentation depth from the 50% value to the 90% value of the maximum load test force (Fmax) is as follows from the slope (m) proportional to the square root of the load test force. The value of Martens hardness (HMs) on the hard coat layer surface defined by the formula was calculated.

1HMs = 1 / (26.4m ² )
As a result, the Martens hardness (HMs) of the hard coat layer surface of the hard coat film 1 was 450 N / mm ² .

<Preparation of hard coat films 2-4>
Hard coat films 2 to 4 were prepared by appropriately adjusting the hard coat film thickness and curing conditions so that the Martens hardness (HMs) of the hard coat layer surface of the hard coat film was the value described in Table 1.

<< Production of Cellulose Ester Film 1 which is Transparent Film of Second Protective Film >>
<Synthesis of cellulose ester>
With reference to Example B of JP-A-6-501040, the amount of propionic acid and acetic acid was adjusted to synthesize cellulose ester A having an acetyl group substitution degree of 2.5 and a propionyl group substitution degree of 0.9. . The substitution degree of the obtained cellulose ester was calculated based on ASTM-D817-96.

(Preparation of dope solution B)
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 a filter paper (Azumi filter paper No. 244, manufactured by Azumi Filter Paper Co., Ltd.) to obtain a dope solution B.

(Preparation of dope solution A)
Cellulose ester A (acetyl group substitution degree 2.5) 100 parts by weight Monopet SB (sugar ester compound) 9 parts by weight Acrylic polymer X1 3 parts by weight Silicon oxide fine particles (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.) 0. 1 part by weight Methylene chloride 400 parts by weight Ethanol 40 parts by weight Butanol 5 parts by weight (Synthesis of acrylic polymer X1)
Bulk polymerization was performed by the polymerization method described in JP-A No. 2000-344823. That is, the contents were heated to 70 ° C. while introducing the following methyl acrylate and ruthenocene into a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, an inlet, and a reflux condenser.

  Next, half of the following β-mercaptopropionic acid which had been sufficiently purged with nitrogen gas was added to the flask under stirring. After the addition of β-mercaptopropionic acid, the contents in the stirring flask were maintained at 70 ° C. and polymerization was carried out for 2 hours.

  Further, after adding the other half of β-mercaptopropionic acid substituted with nitrogen gas, the temperature of the content being stirred was maintained at 70 ° C., and polymerization was carried out for 4 hours. The temperature of the reaction product was returned to room temperature, and 20 parts by mass of a 5% by mass benzoquinone tetrahydrofuran solution was added to the reaction product to stop the polymerization.

  While gradually heating the polymer to 80 ° C. under reduced pressure with an evaporator, the tetrahydrofuran, residual monomer and residual thiol compound were removed to obtain an acrylic polymer X1. The weight average molecular weight Mw was 1000.

Methyl acrylate 100 parts by mass Ruthenocene (metal catalyst) 0.05 parts by mass β-mercaptopropionic acid 12 parts by mass The above materials are mixed to prepare a dope solution B, and the resulting dope solution B is kept at a temperature of 35 ° C. The cast die was cast on a support made of stainless steel endless belt and having a temperature of 35 ° C. 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.

  Next, the web is transported while being dried with 120 ° C. drying air in a transport and drying process using a plurality of rolls arranged on the upper and lower sides. Subsequently, both ends of the web are gripped by a tenter and then stretched in the width direction (TD) at 170 ° C. It extended | stretched so that it might become 1.4 times before. After stretching with a tenter, the web was dried with a drying air at 170 ° C. in a conveying and drying step using a plurality of rolls arranged vertically. After cooling to room temperature, a knurling process having an average height of 10 μm was performed and wound up, and a cellulose ester film 1 having a width of 1.5 m, a film thickness of 40 μm, a length of 4000 m, and a length was prepared. The draw ratio of the web conveyance direction (MD) 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.

In addition, the elastic modulus of the cellulose ester film 1 is conditioned for 24 hours in an environment of 23 ° C. and 55% RH, and according to the method described in JIS K7127, Tensilon RTA-100 manufactured by Tensile Tester Orientec Co., Ltd. The shape of the test piece was No. 1 type test piece and the test speed was measured under the condition of 10 mm / min. As a result, the elastic modulus of MD was 3.2 kN / mm ² , and the elastic modulus of TD was 4. It was 7 kN / mm ² .

  The retardation of the cellulose ester film 1 was Ro = 69 nm and Rt = 170 nm. The retardation is a value measured at a wavelength of 590 nm using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments) after humidity adjustment to 23 ° C. and 55% RH. Moreover, the result of the retardation described in the Example is a value measured under the above conditions.

(Preparation of retardation film 1)
On the cellulose ester film 1 produced above, the following intermediate layer coating solution is applied by die coating after corona discharge, dried at 80 ° C. for 30 seconds, and then irradiated with ultraviolet rays at 120 mJ / cm ² and an illuminance of 200 mW / cm ^2. Cured. The film thickness of the intermediate layer after curing was 1.5 μm. Next, a rod-like liquid crystal compound coating liquid, which is the following polymerizable liquid crystal compound, was applied on the intermediate layer by die coating to a thickness of 8 μm. After coating, the mixture is heated at 100 ° C. for 2 minutes to align the rod-like liquid crystal compound, to provide a polymerizable liquid crystal compound layer (optically anisotropic layer 1), and the optically anisotropic layer 1 has an oxygen concentration of 0.2% and a temperature. Retardation film 1 was obtained by curing at 28 ° C. by irradiation at 180 mJ / cm ² and an illuminance of 200 mW / cm ² . The thickness of the optically anisotropic layer 1 was 1.2 μm. The retardation of the retardation film 1 as a whole was 69 nm for Ro and -11 nm for Rt.

Further, the Martens hardness of the optically anisotropic layer 1 of the retardation film 1 was measured as follows. The Martens hardness (HMs) of the optically anisotropic layer surface on which the rod-like liquid crystal compound of the retardation film 1 was aligned was measured using a micro hardness meter. Using the microhardness meter used in the measurement of the hard coat film, the optical anisotropic layer 1 of the retardation film 1 was similarly pushed into the thickness of about 1/10 of the film thickness, and the optical anisotropic layer 1 The Martens hardness was determined. As a result, the Martens hardness (HMs) of the optically anisotropic layer 1 of the retardation film 1 was 150 N / mm ² .

(Interlayer coating solution)
25 parts by mass of polyester acrylate (Laromar LR8800 manufactured by BASF Japan Ltd.)
Propylene glycol monomethyl ether 290 parts by mass Isopropyl alcohol 685 parts by mass Photopolymerization initiator (Irgacure 184, manufactured by Ciba Japan Co., Ltd.) 0.05 parts by mass (rod-like liquid crystal compound coating solution)
UV-polymerizable liquid crystal material 20 parts by mass (UCL-018 manufactured by Dainippon Ink & Chemicals, Inc.)
Propylene glycol monomethyl ether 80 parts by mass Hindered amine LS-765 (Sankyo Lifetech Co., Ltd.) 0.02 parts by mass Sensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.) 0.10 parts by mass The following air interface side vertical Alignment agent 1 0.01 parts by mass

(Preparation of retardation film 2)
A retardation film 2 was produced in the same manner as the retardation film 1 except that the cellulose ester film 2 produced in the same manner as the cellulose ester film 1 was used except that the dope liquid was changed to the dope liquid C.

  The retardation of the retardation film 2 as a whole was 68 nm for Ro and -11 nm for Rt.

Moreover, the Martens hardness (HMs) of the anisotropic layer surface of the retardation film 2 was 150 N / mm ² .

(Preparation of dope solution C)
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 a filter paper (Azumi filter paper No. 244 manufactured by Azumi Filter Paper Co., Ltd.) to obtain a dope solution C.

(Preparation of dope solution C)
Cellulose ester A (acetyl group substitution degree 2.5) 100 parts by mass Monopet SB (sugar ester compound) 9 parts by mass Aromatic polyester compound (14 below) 3 parts by mass Silicon oxide fine particles (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.) ) 0.1 parts by mass Methylene chloride 400 parts by mass Ethanol 40 parts by mass Butanol 5 parts by mass (production of retardation films 3 to 6)
In producing the cellulose ester film 1, cellulose ester films 3 to 6 were produced in the same manner except that the stretching ratio of TD was changed as described in Table 1, and a retardation film was formed on these cellulose ester films 3 to 6. In the same manner as in Example 1, except that the intermediate layer 1 and the optically anisotropic layer 1 were applied and laminated in this order, retardation films 3 to 6 were produced. The retardation values of the retardation films 3 to 6 as a whole and the Martens hardness of the optically anisotropic layer are shown in Table 1.

(Production of retardation film 7)
In the preparation of the retardation film 1, the oxygen concentration in the curing conditions of the optically anisotropic layer 1 20%, 80mJ / cm ² at a temperature 28 ° C., and then cured by irradiation illuminance 80 mW / cm ^2, optical anisotropy A retardation film 7 was produced in the same manner except that the layer 2 was provided. The retardation value as a whole of the retardation film 7 and the Martens hardness of the optically anisotropic layer 2 are shown in Table 1.

(Production of retardation film 8)
In the production of the retardation film 1, the optical anisotropic layer 1 is cured by irradiation with an oxygen concentration of 0.2%, a temperature of 28 ° C., 250 mJ / cm ² , and an illuminance of 300 mW / cm ^2. A retardation film 8 was produced in the same manner except that the anisotropic layer 3 was provided. The retardation value of the retardation film 8 as a whole and the Martens hardness of the optically anisotropic layer 3 are shown in Table 1.

(Production of retardation film 9)
In the preparation of the phase difference film 1, the anisotropic layer 1 is cured by irradiation with an oxygen concentration of 0.2%, a temperature of 28 ° C., 400 mJ / cm ² , and an illuminance of 300 mW / cm ^2. A retardation film 9 was produced in the same manner except that the conductive layer 4 was provided. The retardation value of the retardation film 7 as a whole and the Martens hardness of the optically anisotropic layer 4 are shown in Table 1.

<Preparation of cellulose ester film 10>
(Adjustment of dope solution D)
Triacetylcellulose (acetylation degree 61.0%) 85 parts by mass 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) bezotriazole
1.5 parts by mass Methyl methacrylate-2-hydroxyethyl acrylate copolymer (80/20 (mass ratio)) Mw; 8000 8 parts by mass Methyl acrylate polymer (*) Mw; 1000 5 parts by mass Methylene chloride 475 parts by mass Ethanol 50 parts by mass (*) A methyl acrylate monomer was polymerized by the polymerization method described in Example 3 of JP-A No. 2000-128911 to obtain polymers of Mw1000 and Mn700. The reaction product had a hydroxyl value (OHV; mg / g KOH) of 50.

(Matting agent solution composition)
Silica particle dispersion having an average particle size of 16 nm 11.0 parts by mass Methylene chloride (first solvent) 76.1 parts by mass Ethanol (second solvent) 3.5 parts by mass Acetyl propionyl cellulose (acetyl substitution degree 2.06, propionyl substitution) Degree 0.79) 1.9 parts by mass (Preparation of matting agent solution)
20 parts by mass of silica particles having an average particle diameter of 16 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) and 80 parts by mass of methanol were mixed well for 30 minutes to obtain a silica particle dispersion. This dispersion was put into a disperser together with the above composition, and further stirred for 30 minutes or more to dissolve each component to prepare a matting agent solution. The dope solution D having the above formulation was put into a sealed container, heated to 70 ° C., and stirred to completely dissolve cellulose triacetate (TAC) to obtain a dope. The time required for dissolution was 4 hours. After filtering the dope liquid D, 6.5 parts by mass of the matting agent solution was mixed, and the mixed liquid was uniformly cast on a stainless band support having a dope temperature of 35 ° C. and a temperature of 22 ° C. . The temperature of the stainless steel band support was 20 ° C.

  Then, after making it dry to the range which can be peeled, dope was peeled from the stainless steel band support body. The residual solvent amount of the dope at this time was 25% by mass. The time required from casting the dope to peeling was 3 minutes. Peel from the stainless steel band support with a tension of 10 kg / m, stretch 2% in the width direction with a tenter at 140 ° C, and then finish drying in a drying zone at 120 ° C and 135 ° C while transporting with many rolls. Then, a knurling process having a width of 10 mm and a height of 10 μm was applied to both ends of the film, and the cellulose ester film 10 having a thickness of 40 μm was wound up. The winding tension was an initial tension of 10 kg / m and a final winding tension of 8 kg / m. The film width was 1500 mm and the winding length was 500 m. The retardation was Ro = 0.5 nm and Rt = −1 nm.

<Preparation of Polarizing Plate 101>
(Alkaline saponification treatment)
An alkali saponification treatment was performed on the retardation film 1 and the hard coat film 1 each having a peelable protective film (PET) attached to the optically anisotropic layer 1 under the conditions described below. Further, after the alkali saponification treatment, the protective film of the retardation film 1 was peeled off and bonded to the polarizing film as described below to produce the polarizing plate 101.

Saponification step 2.5M-NaOH 50 ° C. 90 seconds Water washing step Water 30 ° C. 45 seconds Neutralization step 10 parts HCl 30 ° C. 45 seconds Water washing step Water 30 ° C. 45 seconds Water treatment, neutralization, water washing in this order And then dried at 80 ° C.

<Preparation and bonding of polarizing film>
A 120 μm-thick long roll polyvinyl alcohol film is immersed in 100 parts by mass of an aqueous solution containing 1 part by mass of iodine and 4 parts by mass of boric acid, and stretched 6 times at 50 ° C. in the film forming direction to form the polarizing film L-2. Produced.

  Next, using a polyvinyl alcohol-based adhesive, the hard coat film 1 is saponified on one surface L-1 of the polarizing film so that the transmission axis of the polarizing film L-2 and the in-plane slow axis of the film are parallel to each other. A long polarizing plate was prepared such that the opposite side of the hard coat layer and the retardation film 1 were combined as shown in FIG.

  Next, as shown in FIG. 8 of JP 2004-70106 A, a polarizing plate 101 was produced by cutting (punching) into a size of 576 × 324 mm.

<Preparation of polarizing plates 102-112>
In the production of the polarizing plate 101, a long polarizing plate was produced in the same manner except that the hard coat film of the first protective film and the retardation film of the second protective film were used in combination as described in Table 1. Then, polarizing plates 102 to 112 were produced by punching.

<Evaluation>
The following evaluation was performed about the produced polarizing plates 101-112.

(Surface hardness: pencil hardness)
The surface hardness of the polarizing plates 101 to 112 was evaluated by a pencil hardness test.

  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 of the polarizing plates 101 to 112 is repeated 5 times with a pencil of each hardness using a weight of 500 g. The hardness of scratches and scratches was measured. 4H or higher is high hardness, and the higher the number, the higher the hardness.

(Evaluation of cracks and cracks)
About the edge part of the punched polarizing plates 101-112, the state of the edge part was observed using a 10 times loupe, and the crack and the crack were evaluated according to the following criteria.

◎: Level at which no cracking / crushing occurs ○: Cracking / crushing is slightly observed but there is no practical problem △: Cracking / crushing is slightly observed ×: Cracking・ The level at which the occurrence of sawdust is seen (overall evaluation)
The balance between high hardness and cracking / crushing was evaluated as a comprehensive evaluation based on the following criteria and shown in Table 1.

◎: Hardness is 4H or higher (high hardness) and cracks and crush are ◎
○: Hardness is 4H or higher (high hardness) with cracks and crusts ○
X: Hardness of 4H or higher (high hardness) and cracks / throws are △ or less XX: Hardness is less than 4H, and cracks / throws are △ or less Table 1 shows the results obtained.

<Production of Liquid Crystal Display Device 501>
The polarizing plate 101 of the 26-inch liquid crystal television manufactured by Panasonic Corporation and the liquid crystal panel of TH-26LX60 is peeled off, and the above-prepared polarizing plate 101 is applied to the polarizing plate on the viewing side (L-10) as shown in FIG. Liquid crystal cell glass L-6-1 was bonded using an adhesive having a thickness of 5 μm. Further, on the backlight side, a cellulose ester film 10 and a cellulose triacetate film 1 that have been subjected to alkali saponification treatment in the same manner as described above, and a polarizing plate 201 in which a polarizing film is bonded in a configuration as shown in FIG. The liquid crystal cell glass L-6-2 was used for bonding to prepare a liquid crystal panel 401. Next, the liquid crystal panel 401 was set on a liquid crystal television, and a liquid crystal display device 501 was manufactured.

<Production of liquid crystal display devices 502 to 512>
Liquid crystal panels 402 to 412 are produced in the same manner except that the polarizing plate (L-10) on the viewing side of the liquid crystal display device 501 is changed to 102 to 112, set on a liquid crystal television, and the liquid crystal display devices 502 to 512 are attached. Produced.

<Evaluation>
The liquid crystal display devices 501 to 512 manufactured as described above were evaluated as follows.

(Smoothness (flatness) evaluation)
The liquid crystal display devices 501 to 512 produced above are placed on a desk 80 cm high from the floor, and a daylight direct fluorescent lamp (FLR40S • D / MX Panasonic ( 10 sets) were arranged at 1.5 m intervals, with 40W × 2 pieces as one set. 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.

  Next, the smoothness (flatness) of the liquid crystal panels 401 to 412 of the liquid crystal display devices 501 to 512 was evaluated according to the following criteria.

◎: Fluorescent lamp looks straight ○: Fluorescent lamp appears to be slightly bent △: Fluorescent lamp appears to be bent ×: Fluorescent lamp appears to be greatly bent Table 2 shows the results obtained above. .

From the results of Tables 1 and 2, Martens hardness of the hard coat layer of the hard coat film is a first protective film, 400 N / mm ² or more, 800 N / mm ² or less, rod-like liquid crystal compound of the second protective film The Martens hardness (HMs) of the oriented optically anisotropic layer is 100 N / mm ² or more and 200 N / mm ² or less, and the TD elastic modulus of the transparent film of the second protective film is 4.0 to 6.0 kN / The polarizing plate of the present invention consisting of mm ² is excellent in both high hardness and cracking / crushing, and has excellent flatness when used in an image display device.

Example 2
(Preparation of hard coat film 5)
In producing the hard coat film 1, a hard coat film 5 was produced in the same manner except that the hard coat layer composition 1 was changed to the hard coat layer composition 2. It was 440 N / mm < ² > as a result of measuring the Martens hardness (HMs) of the hard-coat layer which consists of a cation polymeric compound similarly to the hard-coat film 1. FIG.

  The following materials were stirred and mixed to obtain hard coat layer composition 2.

(Hard coat layer composition 2)
Cationic polymerizable compound: [1- (3-ethyl-3-oxetanyl) methyl] ether
170 parts by mass Cationic polymerizable compound: fluorine-containing epoxy compound 1 10 parts by mass (photocation polymerization initiator)
4-Methylphenyl [4- (1-methylethyl) phenyl] iodonium tetrakis (pentafluorophenyl) borate (Lordosyl 2074, Rhodia Japan Co., Ltd.) 6 parts by mass Seahoster KEP-50 (Nippon Shokubai Co., Ltd.) 9 mass Part 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 <Preparation of fluorine-containing epoxy compound 1>
81.03 g of 1,3-dihydroxyhexafluoroisopropylbenzene and 185 g of epichlorohydrin were mixed, 16.27 g of sodium hydroxide and 40 ml of water were added, and the mixture was heated to reflux with stirring. After reacting at 130 ° C. for 3 hours, the mixture was naturally cooled, and the produced sodium chloride was removed by suction filtration. The obtained filtrate was extracted with chloroform-water, and the organic layer was dried, filtered and concentrated to obtain 95.7 g of fluorine-containing epoxy compound 1.

(Preparation of polarizing plate 113)
In the production of the polarizing plate 101, a polarizing plate 113 was produced in the same manner except that the hard coat film 5 was used. As a result of testing the pencil hardness of the polarizing plate 113 in the same manner as in Example 1, it was 4H.

<Preparation of Liquid Crystal Display Device 513>
A liquid crystal panel 413 and a liquid crystal display device 513 were produced in the same manner except that the polarizing plate (L-10) on the viewing side was changed to the polarizing plate 113 in the production of the liquid crystal display device 501. Next, the backlights of the liquid crystal display device 501 and the liquid crystal display device 513 are turned on and left in a black display state for 2000 hours. The smoothness (flatness) after the storage and the intensity of occurrence of unevenness based on the following criteria, light The leak was evaluated.

(Evaluation of unevenness)
The intensity of unevenness was visually observed and evaluated according to the following criteria.

Situation evaluation No occurrence of unevenness ◎
Slightly weak cloudy unevenness occurs ○
Weak cloudy unevenness occurs △
Strong unevenness occurs at the four corners ×
(Light leakage evaluation)
Light leakage was evaluated by observing from an oblique direction of 70 °.

Situation evaluation There was very little light leakage.
Although there is a slight light leak, there is no problem in terms of actual damage ○
Some light leakage is observed △
Light leakage is observed on the entire surface ×
The obtained results are shown in Table 3.

  From the results in Table 3, under the conditions assuming long-term use, an excellent effect is exhibited when the hard coat layer coating composition is made into a cationically polymerizable compound and used in an image display device.

Reference example 1
Using the hard coat film 1 produced in Example 1, an antireflection film 1 was produced.

(Atmospheric pressure plasma treatment)
A hard coat film 6 was produced in the same manner as in the production of the hard coat film 1 of Example 1. Next, an atmospheric pressure plasma treatment apparatus is used on the surface of the hard coat layer of the hard coat film 6, the electrode gap is set to 0.5 mm, the following discharge gas is supplied to the discharge space, and discharge is performed at 100 kHz. Surface treatment by plasma treatment was performed.

(Discharge gas)
Nitrogen gas 80.0% by volume
Oxygen gas 20.0% by volume
(Formation of high refractive index layer)
In coating a high refractive index layer on the hard coat layer of the hard coat film 6 subjected to atmospheric pressure plasma treatment, a particle dispersion A was prepared, and then a coating composition for the high refractive index layer was prepared.

Next, the following coating composition for a high refractive index layer is die-coated on the hard coat layer of the hard coat film 6 that has been subjected to atmospheric pressure plasma treatment, dried at a temperature of 70 ° C., and then the oxygen concentration is 1.0 vol%. A high refractive index layer was provided so that the film thickness after curing was 120 nm by irradiating ultraviolet rays of 0.2 J / cm ² with a high-pressure mercury lamp while purging with nitrogen to the following atmosphere. The refractive index of the high refractive index layer was 1.60.

(Preparation of fine particle dispersion A)
Methanol-dispersed antimony double oxide colloid (zinc antimonate sol, solid content 60%, trade name: Celnax CX-Z610M-F2, manufactured by Nissan Chemical Industries, Ltd.) 6.0 kg and gradually stirring 12.0 kg of isopropyl alcohol To prepare a fine particle dispersion A.

(Coating composition for high refractive index layer)
PGME (propylene glycol monomethyl ether) 40 parts by mass Isopropyl alcohol 25 parts by mass Methyl ethyl ketone 25 parts by mass Pentaerythritol triacrylate 0.9 parts by mass Pentaerythritol tetraacrylate 1.0 part by mass Urethane acrylate (trade name: U-4HA, Shin Nakamura Chemical) 0.6 mass parts Fine particle dispersion A 20 mass parts Irgacure 184 (manufactured by Ciba Japan) 0.4 mass parts Irgacure 907 (manufactured by Ciba Japan) 0.2 mass parts FZ-2207 0.4 Part by mass (10% propylene glycol monomethyl ether solution, manufactured by Nihon Unicar)
(Formation of a low refractive index layer)
In forming the low refractive index layer on the high refractive index layer of the hard coat film 6 coated with the high refractive index layer, first, the isopropyl alcohol dispersion of the hollow silica fine particles 1 and the tetraethoxysilane hydrolyzate A are added. The coating composition 1 for low refractive index layers was prepared.

(Preparation of isopropyl alcohol dispersion of hollow silica fine particles 1)
Step (a): A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by mass and 1900 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 9000 g of 0.98 mass% sodium silicate aqueous solution as SiO ₂ and 9000 g of 1.02 mass% sodium aluminate aqueous solution as Al ₂ O ₃ were added to the mother liquor. Added simultaneously. Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition and hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ .Al ₂ O ₃ core particle dispersion having a solid content concentration of 20% by mass.

Step (b): Obtained by adding 1700 g of pure water to 500 g of this core particle dispersion and heating to 98 ° C., and maintaining the temperature while dealkalizing the sodium silicate aqueous solution with a cation exchange resin. Further, 3000 g of a silicic acid solution (SiO ₂ concentration: 3.5% by mass) was added to obtain a dispersion of core particles in which a first silica coating layer was formed.

Step (c): Next, 1125 g of pure water was added to 500 g of the core particle dispersion formed with the first silica coating layer washed with an ultrafiltration membrane to a solid content concentration of 13% by mass, and concentrated hydrochloric acid (35. 5%) was added dropwise to adjust the pH to 1.0, and dealumination was performed. Next, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, and SiO ₂ · Al from which some of the constituent components of the core particles forming the first silica coating layer were removed. A dispersion of ₂ O ₃ porous particles was prepared.

Step (d): A mixture of 1500 g of the above porous particle dispersion, 500 g of pure water, 1,750 g of ethanol, and 626 g of 28% ammonia water was heated to a temperature of 35 ° C., and then ethyl silicate ( SiO _{2 (} 28% by mass) 104 g was added, and the surface of the porous particles on which the first silica coating layer was formed was coated with a hydrolyzed polycondensate of ethyl silicate to form a second silica coating layer. Next, a dispersion of hollow silica fine particles 1 having a solid content concentration of 20% by mass was prepared by replacing the solvent with isopropyl alcohol using an ultrafiltration membrane. The thickness of the first silica coating layer of the hollow silica fine particles was 3 nm, the average particle size was 45 nm, MO _X / SiO ₂ (molar ratio) was 0.0017, and the refractive index was 1.28. Here, the average particle diameter and the coefficient of variation of the particle diameter were measured by a dynamic light scattering method.

(Preparation of tetraethoxysilane hydrolyzate A)
After mixing 230 g of tetraethoxysilane (trade name: KBE04, manufactured by Shin-Etsu Chemical Co., Ltd.) and 440 g of ethanol and adding 120 g of a 2% aqueous acetic acid solution thereto, the mixture is stirred for 28 hours at room temperature (25 ° C.). Silane hydrolyzate A was prepared.

(Coating composition 1 for low refractive index layer)
Propylene glycol monomethyl ether 430 parts by mass Isopropyl alcohol 430 parts by mass Tetraethoxysilane hydrolyzate A (solid content 21% conversion) 120 parts by mass γ-methacryloxypropyltrimethoxysilane 3.0 parts by mass (trade name: KBM503, Shin-Etsu) (Made by Chemical Industries)
60 parts by mass of isopropyl alcohol dispersion of hollow silica fine particles 1 (average particle size 45 nm, particle size variation coefficient 30%)
Aluminum ethyl acetoacetate / diisopropylate 3.0 parts by mass (manufactured by Kawaken Fine Chemical Co., Ltd.)
3.0 parts by mass of FZ-2207 (10% propylene glycol monomethyl ether solution, manufactured by Nihon Unicar Company)
Next, the coating composition 1 for low refractive index layer is die-coated on the high refractive index layer, dried at a temperature of 80 ° C., and then nitrogen is added so that the oxygen concentration becomes 1.0 vol% or less. While purging, ultraviolet rays of 0.15 J / cm ² were irradiated with a high-pressure mercury lamp, a low refractive index layer was provided so that the film thickness was 86 nm, and the antireflection film 1 was produced. The refractive index of the low refractive index layer was 1.38.

(Measurement of reflectance)
As a result of measuring the reflectance of the produced antireflection film using CM-3700d (manufactured by Konica Minolta Sensing Co., Ltd.), it was 0.83% and had good performance.

<Preparation of Polarizing Plate 114>
(Alkaline saponification treatment)
In the production of the polarizing plate 101, the retardation film 1 and the antireflection film 1 were similarly subjected to alkali saponification treatment, except that a peelable protective film (PET) was laminated to the low refractive index layer of the antireflection film. After the treatment, the protective film was peeled off and bonded to the polarizing film to produce a long polarizing plate. Next, the polarizing plate 114 was produced by punching. As a result of testing the pencil hardness of the polarizing plate 114 in the same manner as in Example 1, it was 4H.

<Preparation of Liquid Crystal Display Device 514>
A liquid crystal panel 414 and a liquid crystal display device 514 were produced in the same manner except that the viewing side polarizing plate (L-10) was changed to the polarizing plate 114 in the production of the liquid crystal display device 501. As a result of evaluating the smoothness (flatness) in the same manner as in Example 1, it was evaluated as ◎.

It is the schematic which showed the process of heat-processing continuously after actinic light irradiation. It is the schematic which heat-processes the hard coat film roll or antireflection film after winding in the heat processing chamber A. 1 is a schematic view of a liquid crystal display device according to a preferred embodiment of the present invention.

Explanation of symbols

Y long film 1 feed roll 2 transport roller 3 extrusion coater 4 counter roll 5 drying zone 6 actinic ray irradiation lamp unit 6a air cooling actinic ray lamp 6b air cooling air vent 6c N2 supply chamber 7 heating zone 8 winding chamber 9 winding Take-up roll 10 Hot air outlet 12 Movable carriage 15 Winding core A Heat treatment chamber L-1 First protective film L-2, L-8 Polarizing film L-3 Transparent film (cellulose ester film 1)
L-4 Intermediate layer L-5 Optically anisotropic layer in which rod-like liquid crystal is vertically aligned and fixed in alignment L-6 IPS liquid crystal cell L-6-1 Non-electrode side cell glass substrate L-6-2 Electrode Side cell glass substrate L-6-3 IPS liquid crystal cell L-7 Polarizing plate protective film (cellulose ester film 10)
L-9 Polarizing plate protective film (cellulose triacetate film 1)
L-10 1st polarizing plate (viewing side polarizing plate)
L-11 Second protective film (retardation film)
L-12 Second polarizing plate (backlight side polarizing plate)
L-13 Backlight

Claims (4)

In the polarizing plate in which the first protective film, the polarizing film, and the second protective film are laminated in this order, the second protective film is composed of a vertically aligned polymerizable liquid crystal compound layer and a transparent film. at least Martens hardness from the polarizing film of the protective film of the first on the far side (HMS) is, 400 N / mm ² or more, has a 800 N / mm ² or less hard coat layer, the polymerizable liquid crystal compound layer The Martens hardness (HMs) is 100 N / mm ² or more and 200 N / mm ² or less, and the elastic modulus in the direction parallel to the transmission axis of the polarizing film of the transparent film at 23 ° C. and 55% RH is A polarizing plate having a viscosity of 4.0 to 6.0 kN / mm ² . The polarizing plate according to claim 1, wherein the hard coat layer contains a cationic polymerizable compound. A liquid crystal display device comprising the polarizing plate according to claim 1 or 2 on at least one surface of a liquid crystal cell. An IPS (in-plane switching) mode liquid crystal display device comprising the polarizing plate according to claim 1 or 2 on at least one surface of an IPS (in-plane switching) mode liquid crystal cell.

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