JP5033454B2 - Optical film, polarizing plate, image display device, and optical film manufacturing method - Google Patents

Description

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

  In recent years, display devices have been used at home and demanded toughness for handling of general users. For example, in various image display devices such as liquid crystal display (LCD), plasma display panel (PDP), electroluminescence display (ELD), cathode ray tube display (CRT), SED (Surface-Conduction Electron-emitter Display) The optical film used on the surface is required to have high physical strength (such as scratch resistance), transparency, chemical resistance, and weather resistance (such as moist heat resistance and light resistance). Further, in order to prevent a decrease in contrast due to reflection of external light or reflection of an image, antiglare performance and antireflection performance are required. In addition, antifouling properties and dust proofing properties are required such that the surface is not easily contaminated with dirt and dust.

  Patent Document 1 describes a photosensitive resin composition for a hard coat agent containing a mixture of dipentaerythritol, tripentaerythritol and tetrapentaerythritol and a reaction product of (meth) acrylic acid as a material exhibiting high hard coat properties. Has been. Although these materials have a certain effect, further increase in hardness and curl reduction have been desired.

Patent Document 2 describes a laminate in which alkali resistance is improved by further providing a clear cured resin layer on the antiglare layer. An optical thin film is formed on the laminate by vapor deposition to improve light resistance and heat and humidity resistance. Although the laminate exhibits a certain scratch resistance, further improvement has been desired when it is assumed to be used on the display surface.
JP 2002-233501 A JP 2004-50535 A

  An object of the present invention is to provide an optical film having high hardness, excellent scratch resistance, and less curling. Furthermore, it is providing the optical film which was excellent in antifouling property, was provided with anti-glare property with low reflection. Furthermore, it is providing the polarizing plate and display apparatus using such an optical film.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have completed the present invention by adopting the following configuration. That is, the present invention has the following configuration.
[1]
A coating composition for a hard coat layer containing a compound having a plurality of polymerizable functional groups in one molecule and a coating composition for an overcoat layer containing a compound having at least three polymerizable functional groups on a support. A method for producing an optical film to be applied simultaneously,
The optical film is formed by curing the hard coat layer coating composition on the support and the overcoat layer coating composition, and the film thickness is 0.15 μm or more. And an overcoat layer of 10 μm or less in this order,
Weight average molecular weight (MOC) of a compound having a plurality of polymerizable functional groups in one molecule contained in the overcoat layer coating composition and polymerization in one molecule contained in the hardcoat layer coating composition The ratio (MOC / MHC) to the weight average molecular weight (MHC) of the compound having a plurality of functional functional groups is 1.1 or more and 6.0 or less,
At least one of the hard coat layer coating composition and the overcoat layer coating composition contains inorganic fine particles,
The method for producing an optical film, wherein the overcoat layer contains inorganic fine particles mainly composed of silica having an average particle diameter of 1 nm or more and 1 μm or less.
[2]
The method for producing an optical film according to [1], wherein the MOC is 300 to 3600, and the MHC is 300 to 600.
[3]
The manufacturing method of the optical film as described in [1] or [2] whose film thickness of the said hard-coat layer is 1.5-30 micrometers.
[4]
The method for producing an optical film according to any one of [1] to [3], wherein the compound having a plurality of polymerizable functional groups in one molecule is a monomer having a hydrogen bonding group.
[5]
The method for producing an optical film according to any one of [1] to [4], wherein the compound having a plurality of polymerizable functional groups in one molecule is isocyanuric acid ethoxy-modified diacrylate.
[6]
The compound having a plurality of polymerizable functional groups in one molecule is a curable multi-branch having a multi-branched polymer (HB) as a nucleus and a photo-curing and / or thermo-setting reactive group bonded to the end of the branch The method for producing an optical film according to any one of [1] to [5], which is a polymer (RHB).
[7]
The method for producing an optical film according to any one of [1] to [6], wherein the inorganic fine particles contained in the overcoat layer coating composition have pores on the surface and / or inside of the particles.
[8]
The method for producing an optical film according to any one of [1] to [7], wherein the inorganic fine particles are conductive particles.
[9]
Any one of [1] to [8], wherein the coating composition for a hard coat layer or the coating composition for an overcoat layer contains an organosilane compound and / or a hydrolyzate thereof and / or a condensate thereof. The manufacturing method of the optical film of description.
[10]
The method for producing an optical film according to any one of [1] to [9], wherein the coating composition for an overcoat layer contains at least one of a reactive silicone and a reactive fluorine compound.
[11]
The method for producing an optical film according to any one of [1] to [10], wherein the hard coat layer contains light diffusing particles.
[12]
The method for producing an optical film according to any one of [1] to [11], wherein the thickness of the support is from 15 μm to 60 μm.
[13]
The optical film manufactured by the manufacturing method of any one of [1]-[12].
[14]
A polarizing plate having a polarizing film and protective films provided on both sides of the polarizing film, wherein at least one of the protective films is the optical film according to [13].
[15]
The image display apparatus which has an optical film as described in [13], or a polarizing plate as described in [14].
Although this invention is invention which concerns on said [1]-[15], below, other matters are also described.

(1) An optical film having a hard coat layer formed by curing a hard coat layer coating composition and an overcoat layer formed by curing an overcoat layer coating composition in this order on a support. The hard coat layer coating composition and the overcoat layer coating composition contain a compound having a plurality of polymerizable functional groups in one molecule, and at least the overcoat layer coating composition is 1 An optical film containing a compound having at least three polymerizable functional groups in a molecule.
(2) Weight average molecular weight (MOC) of a compound having a plurality of polymerizable functional groups in one molecule contained in the overcoat layer coating composition and one molecule contained in the hardcoat layer coating composition 2. The optical film as described in 1 above, wherein the ratio (MOC / MHC) of the compound having a plurality of polymerizable functional groups to the weight average molecular weight (MHC) is from 1.0 to 100.
(3) The optical film as described in 1 or 2 above, wherein the overcoat layer has a thickness of 0.15 μm or more and 10 μm or less.
(4) The optical film as described in any one of 1 to 3, wherein the compound having a plurality of polymerizable functional groups in one molecule is a monomer having a hydrogen bonding group.
(5) The optical film as described in any one of 1 to 4, wherein the compound having a plurality of polymerizable functional groups in one molecule is an isocyanuric acid ethoxy-modified diacrylate.
(6) Curing in which the compound having a plurality of polymerizable functional groups in one molecule has a multi-branched polymer (HB) as a nucleus, and a photo-curing and / or thermo-setting reactive group is bonded to the branch branch end. 6. The optical film as described in any one of 1 to 5 above, which is a conductive multi-branched polymer (RHB).
(7) The optical film as described in any one of 1 to 6, wherein at least one of the hard coat layer coating composition and the overcoat layer coating composition contains inorganic fine particles.
(8) The optical film as described in 7 above, wherein the overcoat layer contains inorganic fine particles mainly composed of silica having an average particle diameter of 1 nm or more and 1 μm or less.
(9) The optical film as described in 7 or 8 above, wherein the inorganic fine particles contained in the overcoat layer coating composition have pores on the surface and / or inside of the particles.
(10) The optical film as described in any one of 7 to 9, wherein the inorganic fine particles are conductive particles.
(11) The coating composition for a hard coat layer or the coating composition for an overcoat layer according to any one of 1 to 10 above, containing an organosilane compound and / or a hydrolyzate thereof and / or a condensate thereof. Optical film.
(12) The optical film as described in any one of 1 to 11, wherein the coating composition for an overcoat layer contains at least one kind of a reactive silicone and a reactive fluorine compound.
(13) The optical film as described in any one of 1 to 12 above, wherein the surface free energy of the overcoat layer is 30 mN / m or less.
(14) The optical film as described in any one of 1 to 13 above, wherein the composition of the polymerizable compound and / or inorganic fine particles forming both layers is gradually changed at the interface between the overcoat layer and the hardcoat layer.
(15) The optical film as described in any one of 1 to 14, wherein the overcoat layer and the hard coat layer further form another interface mixed layer at the interface.
(16) The optical film as described in any one of 1 to 15 above, wherein the overcoat layer has a refractive index of 1.25 to 1.49.
(17) The optical film as described in any one of 1 to 16, wherein an average refractive index from the surface of the overcoat layer to a depth of 100 nm is from 1.25 to 1.49.
(18) The optical film as described in any one of 1 to 17, wherein the hard coat layer contains light diffusing particles.
(19) The optical film as described in any one of 1 to 18 above, which has antiglare properties.
(20) The optical film as described in any one of 1 to 19, wherein the support has a thickness of 15 μm or more and 60 μm or less.
(21) The optical film as described in any one of 1 to 20, further having a low refractive index layer on a layer formed by curing the coating composition for an overcoat layer of the optical film.
(22) A polarizing plate having a polarizing film and protective films provided on both sides of the polarizing film, wherein at least one of the protective films is the optical film according to any one of 1 to 21 Board.
(23) An image display device comprising the optical film as described in 1 to 21 or the polarizing plate as described in 22 above.
(24) A step of applying a hard coat layer coating composition containing a compound having a plurality of polymerizable functional groups in one molecule on a support, and the reaction rate of the compound is 0% or more and 50% or less. An optical film having a step of curing in this order, a step of applying a coating composition for an overcoat layer containing a compound having at least three polymerizable functional groups, and a step of curing the coating composition for an overcoat layer in this order. Production method.
(25) The method for producing an optical film as described in 24 above, wherein the coating composition for overcoat layer is applied on the support without winding up the coated support after coating the coating composition for hard coat layer. .
(26) An overcoat layer coating comprising a hard coat layer coating composition containing a compound having a plurality of polymerizable functional groups in one molecule and a compound having at least three polymerizable functional groups on a support. The manufacturing method of the optical film which apply | coats a composition simultaneously.

  According to the present invention, an optical film excellent in high hardness, excellent scratch resistance, and low curl can be provided. In one embodiment, an optical film having excellent antifouling properties and low reflection can be provided. A polarizing plate and an image display device (display device) using the optical film of the present invention are excellent in optical characteristics such as little external light and background reflection, and high visibility.

  Hereinafter, the present invention will be described in detail. In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”. . In the present specification, the description “(meth) acrylate” means “at least one of acrylate and methacrylate”. The same applies to “(meth) acrylic acid” and the like.

  The optical film of the present invention is an optical film having, on a support, a layer formed by curing a coating composition for a hard coat layer and a layer formed by curing a coating composition for an overcoat layer in this order. The hard coat layer coating composition and the overcoat layer coating composition contain a compound having a plurality of polymerizable functional groups in one molecule, and at least the overcoat layer coating composition is 1 It is an optical film containing a compound having at least three polymerizable functional groups in the molecule.

  It is essential that at least one of the polymerizable compounds in the coating composition for the overcoat layer contains three or more polymerizable functional groups in one molecule, and more preferably, the polymerizable functional group in one molecule. 4 or more and 250 or less, and most preferably 6 or more and 64 or less in one molecule of a polymerizable functional group.

  At least one of the polymerizable compounds in the hard coat layer preferably contains 2 or more and 32 or less, more preferably 2 or more and 6 or less polymerizable functional groups in one molecule. Thereby, in the hard coat layer and the overcoat layer, the respective layers themselves and the interface can be strongly chemically bonded, and a high hardness optical film can be obtained.

1. Material used for hard coat layer and overcoat layer of the present invention 1-1. Compound having a plurality of polymerizable functional groups in the molecule A plurality of hard coat layers and overcoat layers of the present invention are present in each molecule. It can be formed by coating and curing a coating composition containing a compound having a polymerizable functional group. The polymerizable functional group is not particularly limited, but is preferably a radical polymerizable group or a cationic polymerizable group, particularly preferably a radical polymerizable group. A radically polymerizable group and a cationically polymerizable group can also be contained in one molecule. The number of polymerizable groups in one molecule is at least 2, more preferably 2 or more and 6 or less in the hard coat layer, and 6 or more and 64 or less in the overcoat layer.

  As a combination of a compound that reacts with a hydroxyl group of a compound having a hydroxyl group, it is also preferable to use various amino compounds as a curing agent for the hydroxyl group-containing oligomer or polymer.

1-1-1. {Radically polymerizable monomer (M _A1 )}
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. Among them, a (meth) acryloyl group is preferable. Moreover, as a radically polymerizable monomer, it is preferable to contain the polyfunctional monomer which has a 2 or more radically polymerizable group in a molecule | numerator. Two or more kinds of polyfunctional monomers having a radical polymerizable group may be used in combination. The molecular weight of the radical polymerizable monomer is preferably 290 to 800, more preferably 290 to 600 when used in the hard coat layer, and 350 to 1000, more preferably 400 to 800 when used in the overcoat layer. is there.

  The radical polymerizable polyfunctional monomer is preferably selected from compounds having at least two terminal ethylenically unsaturated bonds. Preferably, it is a compound having 2 to 6 terminal ethylenically unsaturated bonds in the molecule. Such a compound group is widely known in the polymer material field, and these can be used without particular limitation in the present invention.

Examples of the radical polymerizable monomer (M _A1 ) include unsaturated carboxylic acids (for example, (meth) acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof and amides. Preferably, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound can be used. In addition, unsaturated carboxylic acid esters having nucleophilic substituents such as hydroxyl group, amino group, mercapto group, amides, monofunctional or polyfunctional isocyanates, addition products of epoxies, polyfunctional A dehydration condensation reaction product with a carboxylic acid is also preferably used. A reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent, such as an isocyanate group or an epoxy group, and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. . As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene or the like instead of the unsaturated carboxylic acid.

  Examples of the aliphatic polyhydric alcohol compound include alkanediol, alkanetriol, cyclohexanediol, cyclohexanetriol, inositol, cyclohexanedimethanol, pentaerythritol, sorbitol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin and the like. Polymerizable ester compounds (monoesters or polyesters) of these aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids, for example, compounds described in JP-A No. 2001-139663, paragraph numbers [0026] to [0027]. .

  Examples of other polymerizable esters include, for example, vinyl (meth) acrylate, allyl (meth) acrylate, JP-B-46-27926, JP-B-51-47334, and JP-A-57-196231. The aliphatic alcohol esters described above, those having an aromatic skeleton described in JP-A-2-226149, and those having an amino group described in JP-A-1-165613 are also preferably used.

  Specific examples of polymerizable amides formed from an aliphatic polyvalent amine compound and an unsaturated carboxylic acid include methylene bis- (meth) acrylamide, 1,6-hexamethylene bis- (meth) acrylamide, diethylenetriamine tris ( Examples include meth) acrylamide, xylylene bis (meth) acrylamide, and those having a cyclohexylene structure described in JP-B No. 54-21726.

Also, vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule (Japanese Patent Publication No. 48-41708), urethane acrylates (Japanese Patent Publication No. 2-16765, Japanese Patent Application Laid-Open No. 2005-272702). Exemplified compounds PETA-IPDI-PETA, PETA-TDI-PETA, HEA-IPDI-HEA, U-15HA, etc.), urethane compounds having an ethylene oxide-based skeleton (JP-B-62-39418, etc.), polyester acrylates (special Further, photocurable monomers and oligomers described in “Journal of Japan Adhesion Association”, Vol. 20, No. 7, pages 300 to 308 (1984) can also be used.
In particular, examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like.

  In order to reduce curl, compounds of isocyanuric acid ethoxy-modified diacrylate (described in JP-A No. 2005-109773) described below are also preferable.

  The above compound can form a coating film having low curl and excellent scratch resistance when used in combination with a trifunctional or higher functional acrylate. A mixture (I) and (meth) acrylic of dipentaerythritol (a), tripentaerythritol (b), tetrapentaerythritol (c) and pentaerythritol (d) as an optional component described in JP-A-2002-2335018 It is also preferable to use a (meth) acrylic acid ester mixture (compounds of Synthesis Examples 1 and 2) which is an acid reaction product.

  Monomers having a hydrogen bonding group are preferred because they tend to be effective in curling reduction even at the same hardness. Examples of the hydrogen bonding functional group include amide group, amino group, urethane group, acyl group, acylamino group, acyloxy group, sulfamoyl group, hydroxyl group, silanol group and the like. Particularly preferred are compounds containing urethane-bondable groups.

1-1-2. {Cationically polymerizable monomer (M _A2 )}
Next, the compound (cation polymerizable monomer) (M _A2 ) containing a cationic polymerizable group will be described.

The cationically polymerizable monomer (M _A2 ) used in the present invention is any compound that causes a polymerization reaction and / or a crosslinking reaction when irradiated with an active energy ray in the presence of an active energy ray-sensitive cationic polymerization initiator. Representative examples include epoxy compounds, cyclic thioether compounds, cyclic ether compounds, spiro orthoester compounds, vinyl ether compounds, and the like. In the present invention, one or more of the above cationic polymerizable organic compounds may be used.

As the cationic polymerizable monomer (M _A2 ), the number of cationic polymerizable groups in one molecule is preferably 2 to 10, particularly preferably 2 to 5. The molecular weight of the compound is preferably 3000 or less, more preferably in the range of 200 to 2000, particularly preferably in the range of 400 to 1500. If it is this range, volatilization in a film formation process will not be a problem, and the compatibility with a curable composition is also satisfactory, and it is preferable.

Examples of the epoxy compound that is one of the cationic polymerizable monomers (M _A2 ) include aliphatic epoxy compounds and aromatic epoxy compounds.

  Examples of the aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers and copolymers such as glycidyl (meth) acrylate, and the like. be able to. In addition to the above epoxy compounds, for example, monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, butyl epoxide stearate, octyl epoxide stearate, epoxidized linseed oil, epoxidized polybutadiene, etc. Can be mentioned. Examples of the alicyclic epoxy compound include polyglycidyl ether of polyhydric alcohol having at least one alicyclic ring, or unsaturated alicyclic ring (for example, cyclohexene, cyclopentene, dicyclooctene, tricyclodecene, etc. ) Cyclohexene oxide or cyclopentene oxide-containing compound obtained by epoxidizing the containing compound with a suitable oxidizing agent such as hydrogen peroxide or peracid.

  Examples of the aromatic epoxy compound include mono- or polyglycidyl ethers of mono- or polyhydric phenols having at least one aromatic nucleus or alkylene oxide adducts thereof. As these epoxy compounds, for example, compounds described in paragraphs [0084] to [0086] of JP-A No. 11-242101, paragraph numbers [0044] to [0046] of JP-A No. 10-158385, and the like. And the compounds described.

  Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable, and alicyclic epoxides are particularly preferable in consideration of rapid curability. In the present invention, one of the above epoxy compounds may be used alone, but two or more may be used in appropriate combination.

  Examples of the cyclic thioether compound include compounds in which the epoxy ring is a thioepoxy ring.

  Specific examples of the compound containing an oxetanyl group as a cyclic ether include compounds described in paragraph numbers [0024] to [0025] in JP-A No. 2000-239309. These compounds are preferably used in combination with an epoxy group-containing compound.

  Examples of the spiro orthoester compound include compounds described in JP 2000-506908 A.

Examples of the vinyl hydrocarbon compound include a styrene compound, a vinyl group-substituted alicyclic hydrocarbon compound (vinyl cyclohexane, vinyl bicycloheptene, etc.), a vinyloxy compound (same as described in the above radical polymerizable compound), a propenyl compound. {"J. Polymer Science: Part A: Polymer Chemistry", Vol. 32, page 2895 (1994), etc.}, alkoxyallene compounds {"J. Polymer Science: Part A: Polymer Chemistry", Vol. 1995), etc.}, vinyl compounds {"J. Polymer Science: Part A: Polymer Chemistry", 34, 1015 (1996), Japanese Patent Application Laid-Open No. 2002-29162 Etc. according}, isopropenyl compound { "J.Polymer Science: Part A: Polymer Chemistry", 34 vol, may be mentioned p. 2051 (1996) described the like} and the like.
You may use these in combination of 2 or more types as appropriate.

  As a combination of a compound having a hydroxyl group and a compound that reacts with the hydroxyl group, it is also preferable to use various amino compounds as a curing agent for the hydroxyl group-containing oligomer or polymer. The amino compound used as the crosslinkable compound is, for example, a compound containing one or both of a hydroxyalkylamino group and an alkoxyalkylamino group in total, specifically, for example, a melamine compound, Examples include urea compounds, benzoguanamine compounds, glycoluril compounds, and the like. For curing these compounds, an organic acid or a salt thereof is preferably used.

1-1-3. [Curable multi-branched polymer (RHB)]
The curable composition for a hard coat layer and / or overcoat layer of the present invention has a curable composition having a multi-branched polymer (HB) as a core and a photo-curing and / or thermosetting reactive group bonded to a branch branch end. It is preferable to contain a branched polymer (RHB). Furthermore, the photocurable and / or thermosetting reactive group contained in the curable multi-branched polymer (RHB) is selected from a radical polymerizable group, a cationic polymerizable group, and a hydrolyzable group-substituted silyl group. It is preferably a curable reactive group (hereinafter sometimes simply referred to as a curable group).

[Multi-branched polymer (HB) as core]
The photocurable and / or thermosetting multibranched polymer (RHB) of the present invention has a multibranched polymer (HB) as a core (core), and a photocurable and / or thermosetting reactive group at the end of the branched branch. Highly “branched (dendritic)” macromolecules that are bound together. For example, it is the compound shown in FIG. 1 or FIG.

  As shown in FIG. 1, the compound includes a portion having branches extending from a central portion in a three-dimensional radial manner and further having a branch from its end. In addition, as shown in FIG. 2, the dendritic compound can be used in the present invention as long as the branching portion is radially expanded even if it does not grow uniformly in all directions. Specifically, the multi-branched polymer (HB) serving as the core is preferably composed of at least one selected from the group consisting of dendrimers, hyperbranched polymers, and starburst polymers.

  A multi-branched polymer (HB) serving as a nucleus is a compound that is bonded to a branched chain extension unit that is two or more regular dendritic branches with a polyvalent base nucleus as a center. The polyvalent group nucleus is a compound having at least two reactive groups (a) that form a linking group, and the linking group is chemically bonded to the reactive group (a) of the compound serving as the group nucleus. A hyperbranched polymer having a structure extended by repeating a chemical reaction between one reactive group (b) that forms a compound and a compound having at least two reactive groups (a) (branched chain extension compound) Preferably there is.

  Specific examples of the multi-branched polymer (HB) include multi-branched polyurea, multi-branched polyurethane, multi-branched polyamide amine, multi-branched polyamide, multi-branched polyester, multi-branched polycarbonate, multi-branched polycarbosilane, multi-branched polycarbosiloxane, Examples include multi-branched polycarbosilazenes, multi-branched polyethers, multi-branched poly (ether ketones), multi-branched poly (propylene imines), multi-branched polyalkylamines, and copolymers thereof.

  Such multi-branched polymers are, for example, edited by Yasuhiko Okada, “Science and Function of Dendrimers” pp 29-31 (IPC Co., Ltd., 2000), ibid, Chapter 2, edited by Koji Ishizu, “ Nanotechnology "Chapter 6 (IPC Co., Ltd., 2000), COMPREHENSIVE SUPERMOLECULAR 10, Chapter 26 (PeramonPress, New York, 1995), and the like can be mentioned. Preferred examples include multi-branched polyamidoamines, multi-branched polyamides, multi-branched polyesters, multi-branched polycarbosilanes, multi-branched polycarbosiloxanes, multi-branched polyethers, multi-branched poly (ether ketones), and multi-branched polyalkylamines.

  The polyvalent group nucleus of the multi-branched polymer (HB) serving as the nucleus (core) is not particularly limited as long as it is a polyfunctional compound having an organic residue, nitrogen atom, silicon atom or phosphorus atom as a nucleus. The organic residue includes a single ring containing at least one heteroatom selected from carbon atoms, aromatic hydrocarbon rings (benzene ring, naphthalene ring, biphenyl ring, phenanthrene ring, triphenylene ring, etc.), oxygen, nitrogen, and sulfur. Heterocyclic rings having a cyclic or polycyclic ring structure (eg, pyrazine ring, hydropyrazine ring, piperazine ring, triazine ring, hydrotriazine ring, phenazine ring, xanthene ring, thioxanthene ring, etc.), calixarene structure, azacryptant structure , Crown ether structure, porphyrin structure and the like. These are also not particularly limited.

  The multi-branched polymer (HB) serving as the core of the present invention is preferably a molecule prepared by a polycondensation cycle. Each cycle involves reacting all of the reactive functional groups of the core with one equivalent of a branched chain extending compound. Depending on the number of cycles (n), it is referred to as the “nth generation” multi-branched molecule. In the present invention, the first to sixth generations are preferred. The second generation to the fourth generation are particularly preferable.

  In the multi-branched polymer (HB) serving as the core of the present invention, it is preferable that the branched chain extension unit contains a cyclic structure. Further, it preferably contains a cyclic structure (also referred to as a ring structure) and an alkylene chain structure.

  The cyclic structure is selected from an alicyclic ring structure and an aromatic ring structure. Examples of the alicyclic ring structure include monocyclic, polycyclic and bridged cyclic C5-C22 aliphatic cyclic hydrocarbons, and specific examples thereof include cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, Cyclohexene, cyclohexadiene, cycloheptane, cycloheptene, cycloheptadiene, cyclooctane, cyclooctene, cyclooctadiene, cyclooctatriene, cyclononane, cyclononene, cyclodecane, cyclodecene, cyclodecandiene, cyclodecatriene, Cycloundecane, cyclododecane, bicycloheptane, bicyclohexane, bicyclohexene, tricyclohexene, norcaran, norpinane, norbornane, norbornene, tricycloheptane, tricycloheptene, decali And ring structure hydrocarbons such as adamantane).

  As the aromatic ring, an aryl ring (for example, benzene, naphthalene, dihydronaphthalene, indene, fluorene, acenaphthylene, acenaphthene, biphenylene, etc.), a monocyclic ring containing at least one of an oxygen atom, a sulfur atom, and a nitrogen atom or Heterocyclic group having a polycyclic ring structure (for example, furanyl group, tetrahydrofuranyl group, pyranyl group, pyroyl group, chromenyl group, phenoxathiinyl group, indazoyl group, pyrazoyl group, pyridyl group , Pyrazinyl group, pyrimidinyl group, indoyl group, isoindoyl group, quinoniyl group, pyrrolidinyl group, pyrrolinyl group, imidazolinyl group, pyrazolidinyl group, piperidinyl group, piperazinyl group, morpholinyl group, thienyl group, benzothienyl group and the like. The aryl ring is preferably an aryl ring having 6 to 18 carbon atoms.

The alkylene chain contained in the branched chain extension unit is preferably an alkylene group having 1 to 22 carbon atoms, and more preferably an alkylene group having 1 to 12 carbon atoms. The cyclic structure and the alkylene chain may be directly bonded or may be bonded via another divalent linking group. Examples of the divalent linking group include —O—, —S—, —COO—, —OCO—, —NHCOO—, —NHCONH—, —SO ₂ —, —CO—, —CON (Q ¹ ) —, — SO ₂ N (Q ¹ ) — and the like can be mentioned. (Where Q ¹ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, 2-chloroethyl group) 2-bromoethyl group, 2-cyanoethyl group, 2-methoxyethyl group, etc.).

  The branched chain extending unit constituted by the reaction of the multi-branched polymer (HB) serving as the nucleus with the branched chain extending compound is preferably an aspect selected from a polyester structure, a polyamide structure, and a polyamine amide structure. A curable multi-branched polymer containing these branched chain extension units is preferable because the strength of the cured film to be formed is further improved. Furthermore, these multi-branched polymers (HB) are preferable because they can be easily synthesized by a sequential polymerization reaction and are supplied as inexpensive materials.

  As described above, the branched group of the multi-branched polymer (HB) serving as the nucleus has a terminal structure of the reactive group (a) having reactivity with the branched extension compound. Examples of the reactive group (a) at the branched branch end include a carboxy group, a hydroxy group, an amino group, and an epoxy group. Further, the multi-branched polymer serving as the core of the present invention preferably has 6 to 128 groups of reactive groups (a) at the ends of the branched branches, and more preferably has 8 to 64 groups.

  The weight average molecular weight is generally about 1,000 to about 50,000, preferably about 1500 to about 20,000. Within this range, the curing reaction proceeds sufficiently and the film strength of the obtained cured film can be maintained.

  The average degree of branching (DB) of the multi-branched polymer (HB) is the number average ratio of branching groups per molecule, ie, “end group + the total number of end groups, branching groups and linear groups”. It is defined in the literature as the proportion of “branched groups”. For ideal dendrons and dendrimers, the degree of branching is 1. For an ideal linear polymer, the degree of branching is close to zero. The degree of branching (DB) is calculated according to Hawker C.I. J. et al. Lee, R .; Frechet, J .; M.M. J. et al. , “J. Am. Chem. Soc.” (1991) 113, 4583, represented by the following formula (in the following formula, Nt represents the number of terminal groups, Nb represents Represents the number of branching groups, and NI represents the number of linear groups).

  The degree of branching (DB) of the multibranched molecule used in the present invention ranges from dendrimers (ideally having a degree of branching of 1) to 0.25. More typically, multi-branched polymers having a degree of branching of 0.25 to 0.80 can be easily produced and are relatively inexpensive compared to dendrimers. In short, it is preferable that the multibranched molecules form a radially expanded form. A more preferable degree of branching is 0.3 to 0.8.

[Crosslinking curing group of curable multi-branched polymer (RHB)]
The curable multi-branched polymer (RHB) of the present invention has a curable group that undergoes a crosslinking reaction by light and / or heat at least at a part of the branched end of the multi-branched polymer (HB).

  It is preferable that 5% or more of the branches in the total number of branches of the multi-branched polymer (HB) (hereinafter also simply referred to as “core molecule”) as a core contains a curable group. Thereby, sufficient film strength is exhibited. More preferably, it is 10% to 90%.

  The curable groups that undergo crosslinking reaction may be the same or different. The curable group that undergoes a crosslinking reaction is not particularly limited. For example, a group having an active hydrogen atom (for example, a hydroxyl group, a carboxyl group, an amino group, a carbamoyl group, a mercapto group, a β-ketoester group, a hydrosilyl group, and a silanol group), A group having an unsaturated double bond capable of radical polymerization, a group capable of cationic polymerization, an acid anhydride-containing group, a hydrolyzable silyl group (eg, alkoxysilyl group, acyloxysilyl group, etc.), a group that can be substituted by a nucleophile (Active halogen atoms, sulfonate esters, etc.), isocyanate groups (which are protected and may be block isocyanate groups which generate isocyanate groups upon heating), and the like. The curable group that undergoes a crosslinking reaction is preferably at least one selected from a radical polymerizable group, a cationic polymerizable group, and a hydrolyzable silyl group. Hereinafter, these groups will be described.

(Radical polymerizable group)
Examples of the radical polymerizable group include a curable group represented by the following general formula (1).

, - - -COO In the general formula (1), V ¹¹ is _{OCO -, - CH 2 OCO -} , - CH 2 COO -, - O -, - CONHCOO -, - CONHCO -, - SO 2 -, - CO- , —CON (Q ¹¹ ) —, —SO ₂ N (Q ¹¹ ) — or a phenylene group (hereinafter, the phenylene group may be represented by Ph.
However, Ph represents 1,2-, 1,3- and 1,4-phenylene groups). Here, Q ¹¹ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxyethyl group, benzyl group, fluorobenzyl group, methylbenzyl group, cyclohexylmethyl group, 2-ethoxyethyl group, 3-methoxypropyl group, etc.). In a preferred embodiment of the ^{V 11, -COO -, - OCO} -, - CONH -, - CH 2 OCO -, - CH 2 COO -, - O-, include a phenylene group. a ¹¹ and a ¹² may be the same or different, and may be a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group, etc.) or -CH ₂ COOR ¹¹ group (R ¹¹ represents an alkyl group. for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc.) representing the.

  These polymerizable groups may be directly bonded to the organic residue chemically reacted (described later) with the reactive group (a) at the end of the branched branch of the core molecule, or may be bonded via a linking group. Also good. Here, the linking group represents a linking group having 1 to 22 total atoms (the total number of atoms herein excludes a hydrogen atom bonded to a carbon atom, a nitrogen atom or a silicon atom). As the linking group, a carbon atom-carbon atom bond (single bond or double bond), a carbon atom-heteroatom bond (such as an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom), a heteroatom-hetero It is composed of any combination of atomic groups composed of atomic bonds. For example, the following are mentioned as atomic groups. A direct bond or a linking group having 1 to 12 total atoms is preferable.

Here, z ¹¹ and z ¹² are a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, and an alkyl group (for example, a methyl group, an ethyl group, and a propyl group). Etc.) z ¹³ and z ¹⁴ are each a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, benzyl group, phenethyl group). , Phenyl group, tolyl group, etc.). z ¹⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms (for example, the same as z ¹³ described above).

(Cationically polymerizable group)
Examples of the cationically polymerizable group in the present invention include a functional group containing a polymerizable group that causes a polymerization reaction and / or a crosslinking reaction when irradiated with an active energy ray in the presence of an active energy ray-sensitive cationic polymerization initiator. 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. More specifically, those having the chemical structure exemplified in the cationically polymerizable monomer (M _A2 ) described later can be mentioned. These cationic photopolymerizable groups may be bonded directly to the branched branch of the core molecule or may be bonded via a linking group.

(Hydrolyzable silyl group)
Examples of the hydrolyzable group-substituted silyl group having the performance as a curable reactive group include those having the structure of the following general formula (2). Such a hydrolyzable group-substituted silyl group may be directly bonded to the branched branch of the core molecule or may be bonded via a linking group. General formula (2)

(R ²¹ O) _3-a (R ²² ) _a Si-

In the general formula (2), the (R ²¹ O) group represents an alkoxy group (when R ²¹ is an aliphatic group) or an acyloxy group (when R ²¹ is —COR ²⁰ ), and is hydrolyzed to form a silanol group. [typically _{(HO) 3-a -Si (} R 22) a -] next polycondensation reaction proceeds. When R ²¹ is an aliphatic group, a linear or branched aliphatic group having 1 to 8 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, Trifluoroethyl group, methoxymethyl group, benzyl group, phenethyl group, cyclohexyl group, cyclohexylmethyl group, etc.). When R ²¹ is —COR ²⁰ , R ²⁰ represents a hydrocarbon group, preferably a linear or branched aliphatic group having 1 to 6 carbon atoms which may be substituted (specifically, the aliphatic group represented by R ²¹ above). Synonymous with group groups, and the same specific examples can be given), and optionally substituted phenyl groups (for example, phenyl group, methoxyphenyl group, fluorophenyl group, tolyl group, xylyl group, etc.). Among them, preferred (R ²¹ O) groups include hydrolysis reactivity of the (R ²¹ O) group, and drying properties of alcohols or carboxylic acids generated by elimination as a by-product in the coating drying process. To an alkoxy group having 1 to 4 carbon atoms or an acyloxy group having 1 to 3 carbon atoms. R ²² represents a hydrocarbon group, preferably an aliphatic group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. These hydrocarbon groups may be substituted. Specifically, those having the same contents as the substituent R ⁰¹ of the non-polymerizable linking group described later can be mentioned.

The curable multi-branched polymer (RHB) of the present invention has a structure in which a non-polymerizable hydrocarbon group is bonded to a part of all branched branches, that is, a structure chemically modified with another non-polymerizable linking group. There may be. Examples of such a terminal linking group include —OR ⁰¹ , —OCOR ⁰¹ , —COOR ⁰¹ , —CONHR ⁰¹ , —NHCOR ⁰¹ , —NHSO ₂ R ⁰¹ , —N (R ⁰¹ ) (R ⁰² ), —OOCNHR ⁰¹ , -NHCONHR ⁰¹ etc. are mentioned.

Here, R ⁰¹ and R ⁰² represent a hydrocarbon group having 1 to 32 carbon atoms. The hydrocarbon group represents an aliphatic group, an aryl group or a heterocyclic group. As the aliphatic group, a linear or branched alkyl group having 1 to 32 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group) Decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nanodecyl group, eicosanyl group, heneicosanyl group, docosanyl group, etc.), straight chain having 2 to 32 carbon atoms Or branched alkenyl groups (for example, vinyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, dodecenyl, tridecenyl, tetradecenyl, hexadecenyl, octadecenyl, eicosenyl, dococenyl, butadienyl Group, pentadienyl group, hexadienyl group Octadienyl group, etc.), linear or branched alkynyl group having 2 to 22 carbon atoms (for example, ethynyl group, propynyl group, butynyl group, hexynyl group, octanyl group, decanyl group, dodecanyl group, etc.); 22 alicyclic hydrocarbon groups (the alicyclic hydrocarbon groups include monocyclic, polycyclic, and bridged cyclic aliphatic hydrocarbon groups, and specific examples thereof include cyclopentane and cyclopentene. , Cyclopentadiene, cyclohexane, cyclohexene, cyclohexadiene, cycloheptane, cycloheptene, cycloheptadiene, cyclooctane, cyclooctene, cyclooctadiene, cyclooctatriene, cyclononane, cyclononene, cyclodecane, cyclodecene, cyclodecanediene, cyclodecanetriene, Cycloundecane, Cyclod Kang, bicycloheptane, bicyclohexane, bi- cyclohexene, tri-cyclohexene, norcarane, norpinane, norbornane, norbornene, norbornadiene, tricyclo heptane, tricyclo-heptene, decalin, cyclic structures hydrocarbons such adamantane, etc.).

  Among these, a linear aliphatic group having 1 to 18 carbon atoms, a branched chain having 3 to 18 carbon atoms, and a cyclic aliphatic group having 5 to 16 carbon atoms are more preferable.

The aliphatic group may have a substituent, and as the substituent that can be introduced, a monovalent nonmetallic atomic group excluding hydrogen is used. Specific examples of the nonmetallic atomic group include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, —OH group, —OR ⁰¹¹ , —SR ⁰¹¹ , —COR ⁰¹¹ , -COOR ⁰¹¹ , -OCOR ⁰¹¹ , -SO ₂ R ⁰¹¹ , -NHCONHR ⁰¹¹ , -N (R ⁰¹² ) COR ⁰¹¹ , -N (R ⁰¹² ) SO ₂ R ⁰¹¹ , -N (R ⁰¹³ ) (R ⁰¹⁴ ),- CON (R ⁰¹³ ) (R ⁰¹⁴ ), —SO ₂ N (R ⁰¹³ ) (R ⁰¹⁴ ), —P (═O) (R ⁰¹⁵ ) (R ⁰¹⁶ ), —OP (═O) (R ⁰¹⁵ ) (R ⁰¹⁶ ), ^-Si (R ⁰¹⁷ ) (R ⁰¹⁸ ) (R ⁰¹⁹ ), an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, and 5 to 10 carbon atoms An alicyclic hydrocarbon group, an aryl group having 6 to 18 carbon atoms (the aryl ring includes benzene, naphthalene, dihydro A heterocyclic group having a monocyclic or polycyclic ring structure containing at least one of phthalene, indene, fluorene, acenaphthylene, acenaphthene, biphenylene, etc.), oxygen atom, sulfur atom, nitrogen atom (heterocyclic group) As, for example, furanyl group, tetrahydrofuranyl group, pyranyl group, pyroyl group, chromenyl group, phenoxathiinyl group, indazoyl group, pyrazoyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, indoyl group, isoindoyl group, quinoniyl group Pyrrolidinyl group, pyrrolinyl group, imidazolinyl group, pyrazolidinyl group, piperidinyl group, piperazinyl group, morpholinyl group, thienyl group, benzothienyl group and the like.

  These alkenyl group, alkynyl group, alicyclic hydrocarbon group, aryl group, and heterocyclic group may further have a substituent, and the substituent may be a group that can be introduced into the aliphatic group. The thing similar to what was illustrated as is mentioned.

R ⁰¹¹ represents an aliphatic group having 1 to 22 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heterocyclic group. The aliphatic group for R ^{011 has the same meaning as} the aliphatic group represented by R ⁰¹ . As the aryl group for R ^011, the same aryl groups as those exemplified above as the substituent which can be introduced into the aliphatic group represented by R ⁰¹ can be mentioned. Such an aryl group may further have a substituent, and examples of the substituent include those exemplified as the substituents that can be introduced into the aliphatic group in R ⁰¹ . R ⁰¹² represents a hydrogen atom or the same as the R ⁰¹¹ group.

R ⁰¹³ and R ⁰¹⁴ each independently represents a hydrogen atom or the same as R ^011, and R ⁰¹³ and R ⁰¹⁴ are bonded to each other to form a 5-membered or 6-membered ring containing an N atom. It may be formed.

R ⁰¹⁵ and R ⁰¹⁶ each independently represents an aliphatic group having 1 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms, or —OR ⁰¹¹ . The aliphatic group for R ⁰¹⁵ and R ⁰¹⁶ has the same ^{meaning as} the aliphatic group represented by R ⁰¹ . Examples of the aryl group in R ⁰¹⁵ and R ⁰¹⁶ include the same aryl groups as those exemplified as the substituent that can be introduced into the aliphatic group in R ⁰¹ . Such an aryl group may further have a substituent, and examples of the substituent include those exemplified as the substituents that can be introduced into the aliphatic group in R ⁰¹ .

R ⁰¹⁷ , R ⁰¹⁸ and R ⁰¹⁹ each independently represents a hydrocarbon group having 1 to 22 carbon atoms or —OR ^020, and at least one of these substituents represents a hydrocarbon group. The hydrocarbon group represents the same aliphatic group and aryl group represented by R ⁰¹ , and —OR ⁰²⁰ represents the same content as —OR ⁰¹¹ .

Examples of the aryl group of R ⁰¹ and R ⁰² in the polar group include the same aryl groups as those exemplified as the substituent that can be introduced into the aliphatic group in R ⁰¹ . Such an aryl group may further have a substituent, and examples of the substituent that can be introduced include the same substituents as those exemplified as the substituent that can be introduced into the aliphatic group in R ⁰¹ . .

Examples of the heterocyclic group represented by R ⁰¹ and R ⁰² in the polar group include the same heterocyclic groups as those exemplified as the substituent that can be introduced into the aliphatic group in R ⁰¹ . The heterocyclic group may further have a substituent, and the substituent that can be introduced is the same as that exemplified as the substituent that can be introduced into the aliphatic group represented by R ⁰¹ . Things.

When the terminal linking group is [—N (R ⁰¹ ) (R ⁰² )], R ⁰² represents a hydrogen atom or the same content as R ⁰¹ described above.

  When the curable multi-branched polymer (RHB) in the present invention is used in the matrix of the low refractive index layer of the antireflection film, the above-mentioned non-polymerizable chemical modification group is used so as not to increase the refractive index of the matrix. It is preferable to select a fluorine-containing hydrocarbon group as. As a fluorine-containing hydrocarbon group, a C1-C20 fluorine-containing alkyl group is preferable. Particularly preferred are those having 2 to 12 carbon atoms. Specifically, the same thing as the fluoroalkyl group of the below-mentioned fluorine compound for low refractive index layers is mentioned.

  The proportion of the branched branches composed of these non-polymerizable terminal linking groups in the molecule is preferably 0 to 95%, more preferably 5 to 80%, and particularly preferably 10 to 50% of the total number of branched branches. %. Within this range, the strength and humidity stability of the cured film become better.

  The curable multi-branched polymer (RHB) of the present invention is obtained by synthesizing a multi-branched polymer as a core by a synthesis method such as a conventionally known stepwise synthesis method (Divergent method) or polycondensation reaction of an ABx type compound. The polar group at the end of the branched branch can be obtained by modifying with a specific substituent according to a conventionally known synthesis method.

  Examples of the multi-branched polymer (HB) serving as a core include D.I. A. Tomalia, et al., “Angew. Chem. Int. Ed. Engl.”, 29, 138 (1990); , “Advanceds in Polymer Science”, Volume 143, 1 (Springer, New York) (1999); C. Salamone, Ed. , “Polymeric Materials Encyclopedia,” Volume 30, page 4949 (CRC Press, published by New York (1996); Masaaki Enomoto, “Polymer”, Volume 47, page 804 (1998), and references cited in the above-mentioned books, etc. The contents described in.

  As a specific example of the core multi-branched polymer (HB), for example, as a polyamino-based multi-branched polymer, for example, a reaction in which butylene diamine and acrylonitrile are reacted and a terminal nitrile group is reduced to an amine is performed in one step. Propyleneimine multibranched polymer obtained by repeating (WO093 / 14147, US5,530,092 specification, Japanese Examined Patent Publication No.7-330631); Ring opening using amine as nucleophilic component and palladium catalyst Amine-based multibranched polymer {M. Suzuki, et al. , “Macromolecules”, Vol. 31, p. 1716 (1998)}; Michael addition of methyl acrylate to ammonia or ethylenediamine, and further introducing a secondary amino group at the terminal by ester amide exchange reaction as one step, if necessary And an amidoamine-based multibranched polymer obtained by repeated reaction (WO0884705, JP-B-6-70132); polyamide-based multibranched polymer {S. C. E. Backson, et al. , “Macromol. Symp.”, Vol. 77, p. 1 (1994), JP-A No. 2000-86758, JP-A No. 2000-256659, etc.}; polyphenylene ester-based multibranched polymer {K. L. Wooley, et al. , “Polymer Journal”, 26, 187 (1994)}; polyetherketone-based multibranched polymer {C. J. et al. Hawker, “Macromolecules”, 29, 4370 (1996)}; polyurethane or polyurea multibranched polymers {R. Spindler, “Macromolecules”, 26 4809 (1993), A.M. Kumar, “Chem. Commun.”, 1629 (1998), etc.}; polyether-based multibranched polymers {V. Percec et al. “Macromolecules”, 27, 4441 (1994), C.I. J. et al. Hawker, et al. “J. Am. Chem. Soc.”, 112, 7638 (1990), JP-A-2001-206886, JP-A-2002-37823, etc.}; polyester-based multibranched polymer terminated with a hydroxyl group (US5) 418,301 specification, WO096 / 12754, JP 2003-522266, etc.); polyester-based multibranched polymer terminated with a carboxyl group (SR Turner, et al. “Macromolecules”, Vol. 27) 1611 (1994), JP-A-11-60540, etc.); polyester-based multibranched polymers terminated with a group containing an epoxy group (US Pat. No. 5,663,247, WO096 / 13558, etc.) it can. The present invention is not limited to these.

  Examples of the core multi-branched polymer (HB) include aliphatic polyester-based multi-branched polymers “BOLTORN” (trade name, manufactured by Perstorp), polypropylamino-based multi-branched polymers (manufactured by DSM), poly ( Commercially available products such as “STARBURST” (manufactured by PAMAN), “Dendrimer” (trade name, manufactured by Aldrich), etc., of amidoamine) multi-branched polymers can be used.

The compound having a curable group as the curable multi-branched polymer (RHB) is a polar group at the end of the branched branch of the multi-branched polymer (HB) serving as a core, that is, the central group of the multi-branched polymer (HB) as described above. A branched chain extension unit extends from the nucleus by chemical bonding over several generations with the residue of the reactive group (b) in the direction of the nucleus and the residues of the plurality of reactive groups (a) on the outside. Polymer of a reactive group that reacts with an unreacted reactive group (a)-(— OH, —NH ₂ , —COOH, epoxy group, etc.) at the terminal and a compound having a curable group It can be easily synthesized by reaction. A combination of these reactions includes conventionally known combinations, and is not particularly limited. Specifically, for example, a modification change is added to a specific polar group by a combination of reactive groups described in the following table.

The curable multi-branched polymer (RHB) is described in detail in, for example, “New Experimental Chemistry Course 14, Synthesis and Reaction of Organic Compounds [II], [III]” edited by The Chemical Society of Japan, Maruzen Co., Ltd. (published in 1977). Can be synthesized using the method described in 1).
As a specific compound, an ethylenically unsaturated group-containing polyester type which is a reaction product of a polyester polyol dendrimer compound (a) described in JP-A-2005-76005 and an ethylenically unsaturated group-containing monocarboxylic acid (b) A dendrimer compound (Synthesis Example 1) can be used. A method for introducing a non-polymerizable terminal linking group into the terminal of the branched branch can also be performed in the same manner.

M _A polymerizable compound, the curable hyperbranched polymer (RHB) 100 parts by weight per preferably added amount of about 1 to 500 parts by weight, in particular, curable hyperbranched polymer (RHB) 100 parts by weight per 5 It is preferable to make it an addition amount of about ~ 100 parts by mass.
The radical polymerizable compound and the cationic polymerizable compound described above are preferably contained in a mass ratio of radical polymerizable compound: cation polymerizable compound in a ratio of 90:10 to 20:80, and 80:20 to More preferably, it is contained at a ratio of 30:70.

  Examples of the compound that can be used in the present invention include compounds (RHB-1) to (RHB-16) described in Synthesis Examples 1 to 16 of JP-A-2006-10829.

1-1-4. [Curable fluorinated polymer]
In the present invention, in order to lower the refractive index of the overcoat layer, a fluorine-containing polymerizable polymer can be added to the overcoat layer coating composition. Specific compounds are described in 2-4-1. (1) A polymer containing a crosslinkable or polymerizable functional group that can be used in the low refractive index layer can be mentioned. Even when a low refractive index material is used for the overcoat layer, the overcoat layer is nλ / 4 (n is the refractive index of the overcoat layer, λ is the observation wavelength, typically 550 nm) at the interface with the hard coat layer. It is not used in an embodiment having a film thickness that reduces the reflectance by using optical interference.

1-1-5. Method of using polymerizable compound for hard coat layer and overcoat layer In the present invention, the weight average molecular weight (MOC) of the polymerizable compound contained in the overcoat layer coating composition is contained in the hard coat layer coating composition. The weight average molecular weight (MHC) or more of the polymerizable compound to be used is preferable from the viewpoint of curling, improving scratch resistance, immobilizing an antifouling agent, and the like. The MOC / MHC ratio is preferably 1.0 or more and 100 or less, more preferably 1.0 or more and 15.0 or less, and further preferably 1.1 or more and 6.0 or less. By setting the MOC / MHC ratio within this range, the curling and / or scratch resistance can be kept good. When the MOC / MHC ratio is less than 1.0, when the curl is satisfied, the scratch resistance and antifouling property are insufficient, and when the scratch resistance is satisfied, the curl may be deteriorated.

  The effect of increasing the molecular weight of the polymerizable compound in improving curl and scratch resistance is most effective when the molecular weight is increased to about 1000 to 10,000, and the effect tends to be saturated at more than that. Further, when the molecular weight is higher than 100,000, the reaction rate of the polymerizable functional group is lowered and the process for synthesizing the compound is complicated, and the practicality is lowered.

  The values of MOC and MHC are not particularly limited as long as the MOC / MHC ratio satisfies 1.0 or more and 100 or less, but MHC is preferably a combination of 290 to 1000 and MOC of 290 to 100,000, and MHC is 290 to 600. The MOC is more preferably a combination of 290 to 50,000, the MHC is most preferably 300 to 600, and the MOC is most preferably a combination of 300 to 9000. A combination of 300 to 600 for MHC and 300 to 3600 for MOC is particularly preferable.

  In addition, the weight average molecular weight of each layer weights the mass ratio of these components when the compound having a plurality of polymerizable functional groups in one molecule contained in the layer is composed of a compound having a plurality of structures. Average molecular weight.

  In addition, the compound which has a some polymerizable functional group in 1 molecule contained in the said coating composition for overcoat layers may be used individually or in multiple. When a plurality of the polymerizable compounds are present, the weight average molecular weight of the polymerizable compound defines the average molecular weight as a mass weighted average thereof. The molecular weight of the polymerizable compound is calculated in terms of polystyrene using a solvent THF and differential refractometer detection using a GPC analyzer using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation). be able to.

1-2. Inorganic fine particles The hard coat layer and overcoat layer of the present invention may contain inorganic fine particles. In the present invention, it is not always necessary to contain fine particles in both layers, and the type and content of inorganic particles in both layers can be adjusted according to the purpose.

  From the viewpoint of pencil hardness and curl prevention, an embodiment in which the inorganic fine particle content of the hard coat layer is larger than the inorganic fine particle content of the overcoat layer is preferable. It is also possible to take an embodiment in which the overcoat layer does not contain inorganic fine particles. From the viewpoint of improving the scratch resistance, it is preferable to introduce inorganic fine particles into the overcoat layer.

As the inorganic particles, an oxide of at least one metal selected from silicon, zirconium, titanium, aluminum, indium, zinc, tin, and antimony, specific examples include SiO ₂ , ZrO ₂ , TiO ₂ , Al ₂ O. ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and the like. In addition, BaSO ₄ , CaCO ₃ , talc and kaolin are included. In addition, particles formed by combining these can also be used.

The particle size of the inorganic particles used in the present invention is preferably as fine as possible in the dispersion medium, and the average particle size is preferably 1 to 1000 nm. More preferably, it is 5-150 nm, Most preferably, it is 10-100 nm. A film that does not impair the transparency can be formed by refining the inorganic particles to 100 nm or less. The particle diameter of the inorganic particles can be measured by a light scattering method or an electron micrograph. The specific surface area of the inorganic particles is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.

  In the present invention, from the viewpoint of curl improvement, the inorganic particle content is 1 to 70%, preferably 2 to 50%, more preferably 5 to 40%.

  In a preferred embodiment of the present invention, low refractive index particles, conductive particles, or high refractive particles can be used as the inorganic fine particles. Each will be described below.

1-2-1. Low Refractive Index Inorganic Fine Particles In the overcoat layer, it is preferable to use low refractive index inorganic particles in order to reduce surface reflection. Examples of the particles of the low refractive index layer include magnesium fluoride and silica fine particles. In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost.

  The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.

[Inorganic fine particles (silica particles) having pores on the surface or inside]
For the purpose of further reducing the refractive index, it is preferable to use inorganic fine particles (preferably silica particles) having pores on and / or inside the particles. The silica particles having pores preferably have a refractive index of 1.10 to 1.40, more preferably 1.15 to 1.35, and most preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle. The porosity of the silica having pores is preferably 10 to 75%, more preferably 25 to 70%, and most preferably 35 to 65%. Within this range, the dispersibility of the particles themselves, the strength of the particles themselves, and the hardness of the coating film are good.

A method for producing silica having pores is described in, for example, JP-A-2001-233611 and JP-A-2002-79616. In particular, particles having cavities inside the shell and having fine pores in the shell are particularly preferred. The refractive index of these silica particles can be calculated by the method described in JP-A-2002-79616. The specific surface area of the pore-containing silica in the present invention is preferably from 20 to 300 m ² / g, more preferably 30~120m ² / g, most preferably 40~90m ² / g. The surface area can be obtained by the BET method using nitrogen.

The average particle diameter of the low refractive index fine particles is preferably 1 to 1000 nm. More preferably, it is 5-150 nm, Most preferably, it is 10-100 nm. It is also preferable to use particles having different average particle sizes in combination, and it is preferable from the viewpoint of scratch resistance to use particles of 10 nm to 40 nm and particles of 40 to 100 nm in combination. The coating amount of the low refractive index particles is ^{preferably 1mg / m 2 ~500mg / m 2} , more preferably ^{5mg / m 2 ~200mg / m 2} , more preferably from ^{10mg / m 2 ~100mg / m 2} . By setting it within this range, the balance of scratch resistance, curling and antifouling properties is improved.

The specific surface area of the hollow silica in the present invention is preferably from 20 to 300 m ² / g, more preferably 30~120m ² / g, most preferably 40~90m ² / g. The surface area can be obtained by the BET method using nitrogen.

1-2-2. Conductive Particles Various conductive particles can be used for imparting conductivity to the film of the present invention.
The conductive particles are preferably formed from a metal oxide or nitride. Examples of metal oxides or nitrides include tin oxide, indium oxide, zinc oxide and titanium nitride. Tin oxide and indium oxide are particularly preferred. The conductive inorganic particles are mainly composed of oxides or nitrides of these metals, and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, S, B, Nb, In, V and halogen atoms are included. In order to increase the conductivity of tin oxide and indium oxide, it is preferable to add Sb, P, B, Nb, In, V and a halogen atom. Particularly preferred are tin oxide containing Sb (ATO) and indium oxide containing Sn (ITO). The ratio of Sb in ATO is preferably 3 to 20% by mass. The ratio of Sn in ITO is preferably 5 to 20% by mass.

The average particle diameter of the primary particles of the conductive inorganic particles is preferably 1 to 150 nm, more preferably 5 to 100 nm, and most preferably 5 to 70 nm. The average particle diameter of the conductive inorganic particles in the antistatic layer to be formed is 1 to 200 nm, preferably 5 to 150 nm, more preferably 10 to 100 nm, and more preferably 10 to 80 nm. Most preferred. The average particle diameter of the conductive inorganic particles is an average diameter weighted by the mass of the particles and can be measured by a light scattering method or an electron micrograph.
The specific surface area of the conductive inorganic particles is preferably from 10 to 400 m ² / g, more preferably 20 to 200 m ² / g, further preferably 30 to 150 m ² / g.

<Conductive particles whose inside is porous or hollow>
Among the conductive particles that can be used in the present invention, the conductive particles in which the inside of the particles whose refractive index is lowered by introducing voids are porous or hollow will be described. The conductive fine particles of the invention may be fine particles having any composition and structure as long as the inside of the particles is porous or hollow and has conductivity. Preferred conductive fine particles of the present invention are core / shell type composite fine particles having a high porosity (high porosity) fine particle as a core and a shell layer of a conductive material provided on the outside thereof, and soluble in acids, alkalis or organic solvents. After forming a composite fine particle by providing a shell layer of a conductive material on the outside of the fine particle as a core and then treating with acid, alkali or organic solvent, the core particle is removed to form an internal void. And void-type hollow fine particles.
In any case, the core particle may be conductive or non-conductive.

In the case of the former, that is, the core / shell type composite fine particle, the core particle is not limited as long as it is a high-porosity fine particle and can be shelled. And porous titanium oxide. Silica gel is particularly preferable.
In the case of the latter, that is, in the case of internal enveloping hollow fine particles, the core particles used in the production process are not limited as long as they can be dissolved and washed away through the shell layer by treatment with an acid, alkali or organic solvent, but preferred core particles are Metal oxide fine particles of a metal selected from 2A, 2B, 3A and 5B group elements of the periodic table, and among them, ZnO, Y ₂ O ₃ and Sb ₂ O ₅ fine particles are preferable.

In the case of core / shell type composite fine particles, examples of the shell attaching method include a sol-gel conversion method using a metal alkoxide, a metal ultrafine particle addition method via a coupling agent or a hydrolyzate thereof, and a conductive material doping method. Can do.
For example, the inorganic fine particles may be directly formed on the surface of SiO ₂ particles produced by the methods described in JP-A-7-133105 and JP-A-2001-233611 using an alkoxide of these metals or the like by a sol-gel method.
Further, in the case of the inner void type hollow fine particles, as a combination of the core particles and the shell material, the surface of the fine particles such as ZnO, Y ₂ O ₃ , Sb ₂ O ₅ is made ultra fine particles such as ATO, ITO, SnO ₂ or these A method of forming hollow conductive inorganic fine particles by eluting the fine particles inside with an acid or alkaline aqueous solution after coating with the above thin film can be used. The particle | grains which coat | covered the surface of the silica particle with the antimony oxide are described in Unexamined-Japanese-Patent No. 2005-119909.
On the other hand, metals such as Au, Ag, Cu, Sn, Al, Ni, Fe, and Rh and alloys such as Al—Cu and Cu—Ni are colored, but have a relatively low refractive index of 1.7 or less. In addition, it is known to exhibit high conductivity. Therefore, even when these metal (alloy) ultrafine particles are used in a small amount as a shell of conductive fine particles, conductive fine particles having substantially high transparency and a low refractive index can be formed.

  The core / shell type composite fine particles by shelling with a coupling agent, which is a preferred form of the hollow conductive fine particles of the present invention, will be described.

The conductive fine particles have an average particle size of 1 to 20 nm on the surface of at least one coupling agent or a hydrolyzate thereof, with semiconductor fine particles or insulator fine particles having an average particle size of 2 to 100 nm as core particles. Composite fine particles obtained by bonding a metallic ultrafine particle filler. In the present invention, the core particle of the semiconductor fine particle or insulator fine particle is preferably a transparent compound having a refractive index of 1.70 or less. Examples of such compounds include Al ₂ O ₃ and SiO ₂ . The coupling agent has two or more reactive groups in the molecule, and at least one of them is bonded to the semiconductor or insulator fine particles, and at least one of the remaining is bonded to the metal ultrafine particles, whereby the semiconductor or insulator is bonded. It is a bridge between fine particles and ultrafine metal particles. The coupling agent may be one in which the hydrolyzate crosslinks the semiconductor or insulating fine particles and the metal ultrafine particles.

A preferred coupling agent is a compound represented by the following general formula [I].
Formula [I]: M- (R) _n
In the general formula [I], M represents Si or Al, and n represents an integer corresponding to the valence of M. R represents an organic group, and the n Rs may be the same or different, and at least two of the n Rs are groups reactive with semiconductor fine particles, insulator fine particles, or metal ultrafine particles.

Among the organic groups represented by R, examples of the group having reactivity with semiconductor fine particles, insulator fine particles or metal ultrafine particles include (1) vinyl group, allyloxy group, acryloxy group, methacryloxy group, isocyanato group, formyl. group, an epoxy group, a styryl group, a ureido group, a reactive group such as a halogen, or an alkyl group having them end, (2) _{-SH terminated, -CN, -NH 2, -SO 2} OH, -SOOH, An alkyl group having an adsorptive group such as —OPO (OH) ₂ or —COOH; (3) an alkoxy group such as a methoxy group, an ethoxy group, an isopropoxy group, an n-propoxy group, a t-butoxy group, or an n-butoxy group. And (4) a phenoxy group. As these alkyl group, alkoxy group and phenoxy group, those having 8 or less carbon atoms are desirable. Further, these alkyl group, alkoxy group and phenoxy group may further have a substituent. The remaining organic group represented by R may be any group, but preferably has 8 or less carbon atoms.

Specific examples of the coupling agent are listed below, but are not limited thereto.
N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminophenoxydimethylvinylsilane, aminophenyltrimethoxysilane, 3-amino Propyltriethoxysilane, bis (trimethoxysilylpropyl) amine, (p-chloromethyl) phenyltrimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, 3-mercaptopropyltrimethoxysilane, (3-glycid Xylpropyl) -3-mercaptopropyldimethoxysilane, vinyltrichlorosilane, tetraethoxysilane, aminophenylaluminum dimethoxide, aluminum isopropoxide and the like.

  The ultrafine metal particles are preferably made of a metal or alloy (composite metal) having a specific resistance at 20 ° C. of 20 μΩ · cm or less (preferably 10 μΩ · cm or less, more preferably 6 μΩ · cm or less). Generally, it is known that the physical property value of a metal or an alloy is different between the bulk and the particle, but the range of the specific resistance refers to the bulk value of the metal or the alloy. Therefore, such physical property values are described in documents such as “Chemical Handbook (Edited by the Chemical Society of Japan)”, “Analytical Chemical Handbook (Edited by the Chemical Society of Japan)”, and the like.

  Examples of the metal that satisfies the above conditions include Au, Ag, Cu, Zn, Cd, Al, In, Tl, Sn, Co, Ni, Fe, Pd, Ir, Mo, Pt, Ru, Rh, and W. . Among these, Au, Ag, Cu, Pt, Pd, Ni, Ru, and Sn are preferable because of their low specific resistance and resistance to oxidation. When the ultrafine metal particles are made of an alloy, it is preferable to use an alloy containing at least one of Au, Ag, Cu, Pt, Pd, Ni, Ru, and Sn. Such alloys include Cu-Zn, Cu-Sn, Al-Cu, Cu-Sn-P, Cu-Ni, Au-Ag-Cu, Au-Zn, Au-Ni, Ag-Cu-Zn, Ag-Cu. -Zn-Sn, Sn-Pb, Ag-In, Cu-Ag-Ni, Ag-Pd and the like can be mentioned, but are not limited thereto. There is no restriction | limiting in particular about the composition ratio of each metal in an alloy, It can select variously. The metal and alloy may contain an impurity element, but the amount is preferably less than 1%. Examples of the impurity element include metals such as Cr, Sb, Bi, and Rh, and non-metals such as P, B, C, N, and S, alkali metals such as Na and K, and Mg and Ca. Examples include alkaline earth metals. One or more of these impurity elements may be contained.

In the core / shell type composite fine particles, it is preferable that the ultrafine metal particles are bonded at least 1/10 times the mass and more preferably 1/5 times the mass bonded per mass of the core particles.
In the present invention, the conductive fine particles preferably have a refractive index of 1.20 to 2.00, more preferably 1.30 to 1.80, and particularly preferably 1.30 to 1.70. Preferably, it is 1.35 to 1.65.
The powder resistance of the conductive fine particles is preferably as low as possible, preferably 1 × 10 ⁵ Ω · cm or less, more preferably 1 × 10 ⁴ Ω · cm or less, further preferably 1 × 10 ³ Ω · cm or less, particularly preferably. 1 × 10 ² Ω · cm or less. The powder resistance can be obtained, for example, by molding a sample powder at a pressure of 9.8 MPa (100 kg / cm ² ) to form a green compact, and measuring the direct current resistance. For example, it is described in JP-A-6-92636.
The average particle diameter of the primary particles of the conductive fine particles is required to be not more than the visible light wavelength region (that is, not more than 400 nm), preferably 1 to 200 nm, more preferably 1 to 100 nm, and still more preferably 1. ~ 80 nm. In the case where the particles are internally enveloping particles, the thickness of the shell part forming the outer shell of the particles is preferably 1 to 100 nm, more preferably 1 to 50 nm, and most preferably 1 to 20 nm. The shape of the conductive fine particles may be any of a rice granular shape, a spherical shape, a cubic shape, a spindle shape, a rod shape, an indefinite shape, or a mixed shape thereof. The average particle diameter here is represented by the average value of the maximum diameters of the respective fine particles. For example, in the case of a spindle shape, the average value of the major axis diameters of the respective fine particles is defined as the average particle diameter. The particle diameter of the conductive fine particles is defined by an average particle diameter measured for at least 1000 particles by an electron micrograph.

1-2-3. High refractive index particles At least one metal selected from titanium, zirconium, indium, zinc, tin, and antimony to adjust the refractive index of the hard coat layer or overcoat layer and to reduce cure shrinkage The oxide can be contained. The average particle size of the highly refractive fine particles is preferably 1 to 150 nm. More preferably, it is 1-100 nm, Most preferably, it is 2-60 nm.

Specific examples of the high refractive index inorganic filler include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO, and the like. TiO ₂ and ZrO ₂ are particularly preferable in terms of increasing the refractive index.

The crystal structure of the particles containing TiO ₂ as a main component is preferably a rutile, rutile / anatase mixed crystal, anatase, or amorphous structure, and particularly preferably a rutile structure.

By containing at least one element selected from Co (cobalt), Al (aluminum), and Zr (zirconium) in particles containing TiO ₂ as a main component, the photocatalytic activity of TiO ₂ can be suppressed. The weather resistance of the inventive film can be improved.
A particularly preferable element is Co (cobalt). It is also preferable to use two or more types in combination.
The inorganic particles mainly composed of TiO ₂ of the present invention may have a core / shell structure by surface treatment as described in JP-A No. 2001-166104.

1-2-4. Surface Treatment of Inorganic Particles Inorganic particles used in the present invention may be subjected to plasma discharge treatment or the like in order to stabilize dispersion in a dispersion or coating solution, or to increase affinity and binding properties with a binder component. A physical surface treatment such as a corona discharge treatment, or a chemical surface treatment with a surfactant or a coupling agent may be performed.

The surface treatment can be performed using a surface treatment agent of an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include inorganic compounds containing cobalt (CoO ₂ , Co ₂ O ₃ , Co ₃ O _4, etc.) and inorganic compounds containing aluminum (Al ₂ O ₃ , Al (OH) ₃ Etc.), zirconium-containing inorganic compounds (such as ZrO ₂ and Zr (OH) ₄ ), silicon-containing inorganic compounds (such as SiO ₂ ), and iron-containing inorganic compounds (such as Fe ₂ O ₃ ). .
An inorganic compound containing cobalt, an inorganic compound containing aluminum, and an inorganic compound containing zirconium are particularly preferable, and an inorganic compound containing cobalt, Al (OH) ₃ , and Zr (OH) ₄ are most preferable.
Examples of organic compounds used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Silane coupling agents are most preferred. In particular, the surface treatment is preferably performed with at least one of a silane coupling agent (organosilane compound), a partial hydrolyzate thereof, and a condensate thereof.

Examples of titanate coupling agents include metal alkoxides such as tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, and preneact (KR-TTS, KR-46B, KR-55, KR-41B, etc .; manufactured by Ajinomoto Co., Inc.) ) And the like.
Examples of the organic compound used for the surface treatment include polyols, alkanolamines, and other organic compounds having an anionic group, and particularly preferable are organic compounds having a carboxyl group, a sulfonic acid group, or a phosphoric acid group. is there. Stearic acid, lauric acid, oleic acid, linoleic acid, linolenic acid and the like can be preferably used.
The organic compound used for the surface treatment preferably further has a crosslinked or polymerizable functional group. Crosslinkable or polymerizable functional groups include ethylenically unsaturated groups (for example, (meth) acrylic groups, allyl groups, styryl groups, vinyloxy groups, etc.) that can undergo addition reactions and polymerization reactions with radical species, cationic polymerizable groups (Epoxy group, oxetanyl group, vinyloxy group, etc.), polycondensation reactive group (hydrolyzable silyl group, N-methylol group, etc.) and the like, preferably a group having an ethylenically unsaturated group. .

  Two or more kinds of these surface treatments can be used in combination, and it is particularly preferable to use an inorganic compound containing aluminum and an inorganic compound containing zirconium.

When the inorganic particles are silica, the use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, silane coupling treatment is particularly effective.
The above-mentioned coupling agent is used as a surface treatment agent for the inorganic filler of the low refractive index layer in advance for surface treatment prior to the preparation of the layer coating solution. It is preferable to make it contain in a layer.
The silica fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.
Specific examples of the surface treatment agent and the surface treatment catalyst that can be preferably used in the present invention include organosilane compounds and catalysts described in WO 2004/017105.

1-3. Organosilane compound At least one of the layers constituting the film of the present invention contains at least one of an organosilane compound and / or a hydrolyzate thereof and / or a partial condensate thereof in the coating solution forming the layer. It is preferable in terms of scratch resistance to contain a component, a so-called sol component (hereinafter sometimes referred to as such).

The organosilane compound is preferably one represented by the following general formula 1.
General formula 1: (R < ¹ >) _m- Si (X) _4-m
In the general formula 1, R ¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. As an alkyl group, a C1-C30 alkyl group is preferable, More preferably, it is C1-C16, Most preferably, it is a C1-C6 thing. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, decyl, hexadecyl and the like. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.

X represents a hydroxyl group or a hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I or the like). ) And R ² COO (R ² is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples include CH ₃ COO, C ₂ H ₅ COO, etc.), preferably An alkoxy group, particularly preferably a methoxy group or an ethoxy group.

  m represents an integer of 1 to 3, and preferably 1 or 2.

  When there are a plurality of Xs, the plurality of Xs may be the same or different.

The substituent contained in R ¹ is not particularly limited, but a halogen atom (fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl etc.), aryl groups (phenyl, naphthyl etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy etc.), aryloxy (phenoxy etc.) ), Alkylthio groups (methylthio, ethylthio, etc.), arylthio groups (phenylthio, etc.), alkenyl groups (vinyl, 1-propenyl, etc.), acyloxy groups (acetoxy, acryloyloxy, methacryloyloxy, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxy) Carbonyl, etc.), aryloxy Carbonyl groups (such as phenoxycarbonyl), carbamoyl groups (such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl), acylamino groups (acetylamino, benzoylamino, acrylicamino, methacrylamino) Etc.), and these substituents may be further substituted.
R ¹ is preferably a substituted alkyl group or a substituted aryl group. Among these, an organosilane compound having a vinyl polymerizable substituent represented by the following general formula 2 is preferable.
General formula 2

In the above general formula 2, R ₂ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom and a chlorine atom are preferred, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom and a chlorine atom are more preferred, and a hydrogen atom and a methyl group Is particularly preferred.
Y represents a single bond or * -COO-**, * -CONH-** or * -O-**, preferably a single bond, * -COO-** or * -CONH-**, * -COO-** is more preferable, and * -COO-** is particularly preferable. * Represents a position bonded to ═C (R ₂ ) —, and ** represents a position bonded to L.

  L represents a divalent linking chain. Specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group having a linking group (for example, ether, ester, amide, etc.) inside, and a linking group inside. A substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, an alkylene group having a linking group therein is preferred, an unsubstituted alkylene group, an unsubstituted arylene group Further, an alkylene group having an ether or ester linking group inside is more preferable, an unsubstituted alkylene group, and an alkylene group having an ether or ester linking group inside is particularly preferable. Examples of the substituent include a halogen, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group, and these substituents may be further substituted.

l represents a number satisfying the mathematical formula of l = 100−m, and m represents a number from 0 to 50. As for m, the number of 0-40 is more preferable, and the number of 0-30 is especially preferable.
R _{3 to} R ₅ are preferably a halogen atom, a hydroxyl group, an unsubstituted alkoxy group, or an unsubstituted alkyl group. R _{3 to} R ₅ are more preferably a chlorine atom, a hydroxyl group, or an unsubstituted alkoxy group having 1 to 6 carbon atoms, more preferably a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, and particularly preferably a hydroxyl group or a methoxy group.
R ₆ represents a hydrogen atom or an alkyl group. The alkyl group is preferably a methyl group or an ethyl group. R ₇ has the same meaning as R ^{1 in} formula 1 above, more preferably a hydroxyl group or an unsubstituted alkyl group, still more preferably a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydroxyl group or a methyl group.

  Two or more compounds of the general formula 1 may be used in combination. In particular, the compound of general formula 2 is synthesized using two types of compounds of general formula 1 as starting materials. Specific examples of the starting materials of the compound represented by Formula 1 and the compound represented by Formula 2 are shown below, but are not limited thereto.

    M-48 Methyltrimethoxysilane

Among the above compounds, (M-1), (M-2), and (M-25) are particularly preferable as the organosilane containing a polymerizable group.
In order to obtain the effect of the present invention, the content of the organosilane containing the vinyl polymerizable group in the hydrolyzate of organosilane and / or its partial condensate is preferably 30% by mass to 100% by mass, The mass% is more preferably 100% by mass, and more preferably 70% by mass to 95% by mass. If the content of the organosilane containing the vinyl polymerizable group is less than 30% by mass, the solid content is generated, the liquid is turbid, the pot life is deteriorated, or the molecular weight is difficult to control (increase in the molecular weight). Or because the content of the polymerizable group is small, it is difficult to improve the performance (for example, the scratch resistance of the antireflection film) when the polymerization treatment is performed. When synthesizing the compound represented by the general formula 2, (M-1) and (M-2) as the organosilane containing the vinyl polymerizable group, (MM) as the organosilane having no vinyl polymerizable group. It is preferable to use one of each of −19) to (M-21) and (M-48) in combination with the above amounts.

The sol component used in the present invention is prepared by hydrolysis and / or partial condensation of the organosilane.
In the hydrolysis condensation reaction, 0.05 to 2.0 mol, preferably 0.1 to 1.0 mol of water is added to 1 mol of the hydrolyzable group (X), and the presence of the catalyst used in the present invention. Under stirring at 25-100 ° C.

  In at least one of the hydrolyzate of organosilane and its partial condensate of the present invention, the weight average molecular weight of either the hydrolyzate of organosilane containing a vinyl polymerizable group or its partial condensate is less than 300. When this component is removed, 450 to 20000 is preferable, 500 to 10,000 is more preferable, 550 to 5000 is still more preferable, and 600 to 3000 is still more preferable.

  Of the components having a molecular weight of 300 or more in the hydrolyzate of organosilane and / or its partial condensate, the component having a molecular weight of more than 20000 is preferably 10% by mass or less, more preferably 5% by mass or less. More preferably, it is 3 mass% or less. When it contains more than 10% by mass, the cured film obtained by curing such a curable composition containing a hydrolyzate of organosilane and / or a partial condensate thereof has transparency and adhesion to the substrate. May be inferior.

Here, the weight average molecular weight and the molecular weight are converted into polystyrene by GTH analyzer using a column of TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (both trade names manufactured by Tosoh Co., Ltd.) and detection by a solvent THF and a differential refractometer. The content is the area% of the peak in the molecular weight range when the peak area of the component having a molecular weight of 300 or more is defined as 100%.
The dispersity (weight average molecule / number average molecular weight) is preferably 3.0 to 1.1, more preferably 2.5 to 1.1, still more preferably 2.0 to 1.1, and 1.5 to 1. 1 is particularly preferred.

The ²⁹ Si-NMR analysis of the hydrolyzate and partial condensate of the organosilane of the present invention can confirm the state in which X in the general formula 1 is condensed in the form of -OSi. At this time, when three bonds of Si are condensed in the form of -OSi (T3), when two bonds of Si are condensed in the form of -OSi (T2), one bond of Si is- When the condensation is performed in the form of OSi (T1), and the case where Si is not condensed at all (T0), the condensation rate α:

α = (T3 × 3 + T2 × 2 + T1 × 1) / 3 / (T3 + T2 + T1 + T0)

The condensation rate is preferably 0.2 to 0.95, more preferably 0.3 to 0.93, and particularly preferably 0.4 to 0.9. If the condensation rate is less than 0.1, hydrolysis and condensation are not sufficient, and monomer components increase, so that curing is not sufficient. If it is greater than 0.95, hydrolysis and condensation proceed too much, and there is a hydrolyzable group. Since they are consumed, the interaction between the binder polymer, the resin substrate, the inorganic fine particles and the like is lowered, and even if these are used, it is difficult to obtain the effect.

The hydrolyzate and partial condensate of the organosilane compound used in the present invention will be described in detail.
The hydrolysis reaction of organosilane and the subsequent condensation reaction are generally carried out in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, butyric acid, maleic acid, citric acid, formic acid, methanesulfonic acid and toluenesulfonic acid; sodium hydroxide, potassium hydroxide and ammonia Inorganic bases such as triethylamine, organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum, tetrabutoxyzirconium, tetrabutyltitanate, dibutyltin dilaurate; and metals such as Zr, Ti or Al as the central metal Metal chelate compounds and the like; F-containing compounds such as KF and NH4F are listed. The said catalyst may be used independently or may use multiple types together.

  The content of the hydrolyzate and partial condensate of the organosilane compound is preferably small in the case of a relatively thin antireflection layer and large in the case of a thick hard coat layer or antiglare layer. The content is preferably 0.1 to 50% by mass, and preferably 0.5 to 30% by mass based on the total solid content of the containing layer (added layer), considering the effect, refractive index, film shape / surface shape, and the like. More preferred is 1 to 15% by mass.

1-4. Antifouling property improving material 1-4-1, reactive silicone or fluorine compound Known for the purpose of imparting properties such as antifouling property, water resistance, chemical resistance and slipping property to the overcoat layer of the present invention. Silicone or fluorine-based antifouling agents, slipping agents, and the like can be added as appropriate.
When these additives are added, it is preferably added in the range of 0.01 to 20% by mass, more preferably in the range of 0.05 to 10% by mass of the total solid content of the overcoat. Particularly preferred is 0.1 to 5% by mass.

1-4-2. [Silicone compounds]
Next, the silicone compound will be described.
In the present invention, a compound having a polysiloxane structure can be used for the purpose of improving scratch resistance by imparting slipperiness and imparting antifouling property. There is no restriction | limiting in particular in the structure of a compound, The thing which has a substituent in the terminal and / or side chain of a compound chain | strand which contains multiple dimethylsilyloxy units as a repeating unit is preferable. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy. Hereinafter referred to as a silicone compound.

  The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include groups including acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, oxetanyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group, epoxy group and the like. From the viewpoint of improving the fixing property and antifouling property of the silicone compound in the film, a compound containing two or more (meth) acryloyl groups or epoxy groups in the molecule is preferred, and more preferably containing four or more. A compound. Although there is no restriction | limiting in particular in molecular weight, It is preferable that it is 100,000 or less, It is more preferable that it is 50,000 or less, It is especially preferable that it is 3000-30000, It is most preferable that it is 5000-20000. Although there is no restriction | limiting in particular in silicone atom content of a silicone type compound, it is preferable that it is 18.0 mass% or more, it is especially preferable that it is 25.0-37.0 mass%, and 30.0-37.0. Most preferably, it is mass%.

Examples of preferable silicone compounds include X-22-160AS, X-22-162C, X-22-163C, X-22-164B, X22-164C, X-22-170DX, X, manufactured by Shin-Etsu Chemical Co., Ltd. -22-173DX, X-22-174DX, X-22-176D, X-22-176DX, X-22-176F, X-22-1821, X-22-2426, KF-105, KF-6001, KF -6002, KF-6003, (trade name) manufactured by Chisso Corporation, FM-0411, FM-0421, FM-0425, FM-0725, FM-1121, FM-4411, FM-4421, FM-4425 , FM-5511, FM-5521, FM-5525, FM-6611, FM-6621, FM-6625, FM-7725, FM-D 11, FM-DA21, FM-DA25 (trade name), Gelest, CMS-626, CMS-222, DMS-U22, RMS-033, RMS-083, UMS-182, DMS-H21, DMS-H31, Examples thereof include, but are not limited to, HMS-301, FMS121, FMS123, FMS131, FMS141, and FMS221 (above trade names).
When these additives are added, it is preferably added in the range of 0.01 to 20% by mass, more preferably in the range of 0.05 to 10% by mass of the total solid content of the overcoat. Particularly preferred is 0.1 to 5% by mass.

1-4-3. Fluorine-containing compound As the fluorine-based compound used as an antifouling agent, a compound having a fluoroalkyl group is preferred. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain (for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.), even branched structures (eg, CH (CF ₃ ) ₂ , CH ₂ CF (CF ₃ ) ₂ , CH (CH ₃ ) CF ₂ CF ₃ , CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.), alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl group, perfluorocyclopentyl, etc. may group, or even those with substituted alkyl group etc.) which may have an ether bond (e.g. _{CH2OCH 2 CF 2 CF 3, CH} 2 CH 2 OCH 2 C 4 F 8 H, CH 2 CH ₂ O _{CH 2 CH 2 C 8 F 17} , CH 2 CH 2 OCF 2 CF 2 OCF 2 CF 2 H , etc.). A plurality of the fluoroalkyl groups may be contained in the same molecule.

  It is preferable that the fluorine-based compound further has a substituent that contributes to bond formation or compatibility with the overcoat layer film. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like. The fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited. Although there is no restriction | limiting in particular in fluorine atom content of a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%. Examples of preferred fluorine-based compounds include Daikin Chemical Industries, Ltd., R-2020, M-2020, R-3833, M-3833 (named above), Dainippon Ink Co., Ltd., Megafac F-171. , F-172, F-179A, and defender MCF-300 (named above), but are not limited thereto.

  From the viewpoint of improving the antifouling property of the overcoat layer and improving the scratch resistance of the coating film, a fluorine-containing compound having a (meth) acrylate group is particularly preferred. A preferable structure will be described below.

[Telomer-type acrylate containing fluorine atoms]
Telomer-type acrylate containing fluorine atom, for example, a mixture of fluorine-containing (meth) acrylic acid ester having a polymerization degree n of k or more represented by the following general formula (T-1) (hereinafter referred to as “telomer-type acrylate containing fluorine atom”) Simply called "telomers"). This mixture has a degree of polymerization n of k, k + 1, k + 2,. . . Is a mixture of telomers. However, this mixture may inevitably contain telomers where n is smaller than k, depending on the conditions of telomerization and the separation conditions of the reaction mixture.

As specific examples of the curable resin as an antifouling agent, n of the group Rf (CF ₂ CF ₂ ) nR ² CH ₂ CH ₂ O— in the following general formula (T-1) is k, k + 1, respectively. k + 2,. . . Is a mixture containing a plurality of fluorine-containing (meth) acrylic acid esters.

Formula (T-1): Rf ( CF 2 CF 2) n CH 2 CH 2 R 2 OCOCR 1 = CH 2

In the formula, Rf represents any of a fluoroalkyl group having 1 to 10 carbon atoms, R ¹ represents a hydrogen atom or a methyl group, R ² represents a single bond or an alkylene group, and n represents a degree of polymerization. The degree of polymerization n is equal to or greater than k (k represents any integer of 3 or more). Examples of the telomer acrylate containing a fluorine atom in the general formula (T-1) include a (meth) acrylic acid moiety or a fully fluorinated alkyl ester derivative.

  Specific examples of the telomer acrylate containing a fluorine atom used in the present invention are shown below, but the present invention is not limited thereto.

[Acrylate having a C10 fluoroalkyl group]
In this invention, the compound represented by the following general formula (T-2) is mentioned as a preferable fluorine-containing antifouling agent.
General formula (T-2)

(In the formula, X and Y are either a (meth) acryloyloxy group or a hydroxyl group, and at least one is a (meth) acryloyloxy group.)

The fluorine-containing (meth) acrylic acid ester represented by the general formula (T-2) has a fluoroalkyl group having 10 carbon atoms having a trifluoromethyl group (CF _3- ) at its terminal. Even if a small amount of fluorine (meth) acrylate is used, the trifluoromethyl group is effectively oriented on the surface. If the fluoroalkyl has a small number of carbon atoms, the orientation on the surface of the overcoat layer tends to decrease. The fluorine-containing (meth) acrylic acid ester having a fluoroalkyl group having 11 or more carbon atoms is difficult to produce and obtain.

  Specific examples of the fluorine-containing (meth) acrylic acid ester represented by the general formula (T-2) include 1- (meth) acryloyloxy-2-hydroxy-4,4,5,5,6,6,7. , 7,8,8,9,9,10,10,11,11,12,12,13,13,13-heneicosafluorotridecane, 2- (meth) acryloyloxy-1-hydroxy-4, 4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-heneicosafluorotridecane and 1,2 -Bis (meth) acryloyloxy 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-hen Examples include eicosafluorotridecane.

[Acrylate having perfluoropolyether group]
In the present invention, a perfluoropolyether group-containing acrylate compound can be mentioned as a particularly useful material for improving the slipperiness of the surface in addition to the antifouling property. Of these, heptafluoropropylene oxide group-containing acrylate is preferable. Although the example of a compound is given below, it is not limited to these.

(FC-1): HFPO-C (O) N (H) CH ₂ CH ₂ 0C (O) CH = CH ₂
(FC-2): HFPO-C (O) N (H) CH ₂ CH ₂ 0CH ₂ CH ₂ 0C (O) CH = CH ₂
(FC-3): HFPO-C (O) N (H) CH ₂ CH ₂ CH ₂ N (H) CH ₃ and TMPTA equimolar Michael adduct (FC-4): HFPO-C (O) N (H) C (CH ₂ 0C (O) CH = CH ₂ ) ₂ CH ₂ CH ₃
(FC-5): HFPO-C (O) N (H) C (CH ₂ 0C (O) CH = CH ₂ ) ₂ H
Here, HFPO- _{is, F (CF (CF 3)} CF 2 0) aCF (CF 3) - represents the average value of s is 6-7 (e.g., 6.3). TMPTA represents trimethylolpropane triacrylate.

  A method for synthesizing these compounds is described in International Patent Publication WO2005 / 113690. In the case of adding these additives, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the overcoat, more preferably in the range of 0.05 to 15% by mass. Especially preferred is 0.1 to 10% by mass.

1-5. Translucent Particle Of the embodiments of the present invention, at least one of the hard coat layer or the overcoat layer is preferably a light diffusion layer. The light diffusion layer may be either of the two layers, but an embodiment in which the hard coat layer is a light diffusion layer is particularly preferable. As one preferred embodiment of the method for diffusing light, a light diffusion layer can be formed from translucent particles and a translucent resin. The scattered light profile and the haze value are adjusted by the translucent particles and the translucent resin. In the present invention, it is preferable to use translucent fine particles having two or more types and / or materials in addition to using one type of particles.

  The refractive index of the light-transmitting fine particles and the refractive index of the light-transmitting resin constituting the entire light diffusing layer (when inorganic fine particles are added to the light-transmitting resin for adjusting the refractive index of the aforementioned layer, The difference from the optical average refractive index is preferably 0.03 to 0.30. If the difference in refractive index is less than 0.03, the difference in refractive index between the two is too small, making it difficult to obtain a light diffusion effect. If the difference in refractive index is greater than 0.30, the light diffusibility is too large. The whole film turns white. The difference in refractive index is more preferably 0.06 to 0.25, and most preferably 0.09 to 0.20.

  In the present invention, the particle diameter of translucent fine particles (first translucent fine particles) for the purpose of imparting a diffusion effect (improving display quality (improving viewing angle characteristics)) is 0.5 to 3.5 μm. And more preferably 0.5 μm to 2.0 μm. By adjusting the particle diameter, an angular distribution of light scattering can be obtained.

  The light diffusing layer suitable for the present invention is adjusted by appropriately combining the refractive index difference between the translucent particles and the translucent resin constituting the entire light diffusing layer and the particle size of the translucent fine particles. However, it is particularly preferable in terms of achieving both viewing angle characteristics and whitening (blur).

  The greater the diffusion effect, the better the viewing angle characteristics. However, in order to maintain the front brightness in terms of display quality, it is also necessary to increase the transmittance as much as possible. When the particle size is 0.5 μm or less, the scattering effect is large and the viewing angle characteristics are improved, but the backscattering is large and the brightness is greatly reduced. On the other hand, when the thickness is 2.0 μm or more, the scattering effect is reduced, and the improvement in viewing angle characteristics is reduced. Accordingly, the particle diameter is preferably 0.6 μm to 1.8 μm, and most preferably 0.7 μm to 1.6 μm.

  Further, it is also preferable to further add translucent fine particles (second translucent fine particles) that are not intended to impart a diffusion effect. It is used for providing unevenness on the surface of the diffusion film and providing a reflection preventing function. The particle diameter of the second light transmissive fine particles is preferably larger than the particle diameter of the first light transmissive particles, and more preferably 2.5 μm to 10.0 μm. Thereby, suitable surface scattering can be provided and anti-glare property can be provided. In order to achieve good display quality, it is also necessary to prevent reflection of external light. The lower the haze value of the surface, the less the whiteness caused by external light and the clear display display can be obtained. However, if the surface haze value is too low, the reflection increases, so the light diffusion layer is the outermost layer. Therefore, it is necessary to provide a low refractive index layer having a refractive index lower than that of the refractive index to lower the reflectance. In order to control the surface haze value, it is preferable to provide appropriate irregularities on the surface of the resin layer with the second light-transmitting fine particles, but this is not restrictive. When the particle diameter is 2.5 μm or less, when providing desired surface irregularities, the thickness of the layer has to be reduced, which is not preferable in terms of film hardness, whereas when it is 10 μm or more, one particle Since the weight of one is large, it is not always preferable from the viewpoint of particle sedimentation stability in the coating solution. Therefore, the particle diameter of the second light transmitting fine particles is preferably 2.7 to 9 μm, and most preferably 3 to 8 μm.

  In order to form irregularities on the surface, the first and / or second particles may be aggregated. Compared to the case where the fine particles are uniformly dispersed, various surface structures can be formed. The number of aggregated particles is preferably 2 to 100, more preferably 5 to 50. These particles may exist in the same plane parallel to the support in the optical film, but it is effective for forming unevenness to have a three-dimensional structure. Aggregates of these particles can be present in the film at regular intervals or randomly.

  The difference between the refractive index of the second light-transmitting particles and the refractive index of the light-transmitting resin constituting the entire light diffusion layer is preferably smaller than that of the first light-transmitting particles. The refractive index difference between the refractive index of the second light transmissive particles and the refractive index of the light transmissive resin constituting the light diffusion layer is preferably 0.00 to 0.20, more preferably 0.00 to 0.09.

  The surface roughness is preferably 0.5 μm or less, more preferably 0.3 μm or less, and most preferably 0.2 μm or less. The surface roughness Ra (centerline average roughness) can be measured according to JIS-B0601.

  The haze value of the light diffusion layer, particularly the internal scattering haze (internal haze) that greatly contributes to the diffusion of transmitted light has a strong correlation with the effect of improving the viewing angle characteristics. The light emitted from the backlight is diffused by the light diffusion layer provided on the surface of the polarizing plate on the viewing side, whereby the viewing angle characteristics are improved. However, since the front luminance is reduced if it is excessively diffused, the internal haze of the light diffusion layer is preferably 45% or more and 80% or less, more preferably 45% or more and 70% or less, and particularly preferably 45% or more and 60% or less. As a method to increase the noise to internal scattering, increase the particle concentration of translucent fine particles for the purpose of imparting diffusibility, increase the coating film thickness, and further increase the refractive index difference between the particles and the resin. There is a way.

  In order to improve display quality (improve viewing angle characteristics) in the present invention, it is particularly preferable that the scattered light intensity of 30 ° with respect to the light intensity of the output angle 0 ° of the scattered light profile of the goniophotometer is within a specific range. . The scattered light intensity of 30 ° with respect to the light intensity of the goniophotometer scattered light profile with an emission angle of 0 ° is preferably 0.05% or more from the viewpoint of visual characteristics, and 0.3% from the viewpoint of not greatly reducing the front luminance. The following is preferred. Accordingly, the light scattering layer of the present invention is preferably 0.05 to 0.3%, more preferably 0.05 to 0.2%, and 0.05 to 0.15%. Particularly preferred. It is more preferable to satisfy the above preferable range of the internal haze.

  The haze due to surface scattering (surface haze) of the polarizing plate of the present invention is preferably 0.1 to 30%, more preferably 10% or less, and more preferably 5% or less, from the viewpoint of achieving both reduction in reflection and reduction in white-brown feeling. Is particularly preferred. If importance is attached to the reduction of white-brown feeling due to external light, it is preferably 4% or less, and more preferably 2% or less. Since reflection increases when surface haze is reduced, a low refractive index layer is provided, and it is preferable that the average value in the wavelength region from 450 nm to 650 nm of the integrated reflectance at 5 ° incidence be 3.0% or less, It is more preferably 2.0% or less, and most preferably 1.0% or less. In order to improve display quality (improve viewing angle characteristics) in the present invention, it is necessary to adjust the internal scattering property as described above. At the same time, by setting the surface haze and / or reflectivity within a suitable range, The contrast is improved and the most preferable effect can be exhibited.

  The translucent fine particles may be monodispersed organic fine particles or inorganic fine particles. As the particle size is not more varied, the scattering characteristics are less varied, and the haze value can be easily designed. As the translucent fine particles, plastic beads are preferred, and those having particularly high transparency and a difference in refractive index from the translucent resin are preferred. As organic fine particles, polymethyl methacrylate beads (refractive index 1.49), acrylic-styrene copolymer beads (refractive index 1.54), melamine beads (refractive index 1.57), polycarbonate beads (refractive index 1.57). ), Styrene beads (refractive index 1.60), cross-linked polystyrene beads (refractive index 1.61), polyvinyl chloride beads (refractive index 1.60), benzoguanamine-melamine formaldehyde beads (refractive index 1.68), etc. It is done. As the inorganic fine particles, silica beads (refractive index 1.44 to 1.46), alumina beads (refractive index 1.63), and the like are used. The translucent fine particles may be contained in an amount of 5 to 30 parts by mass with respect to 100 parts by mass of the translucent resin.

  In the case of the above translucent fine particles, since the translucent fine particles are likely to settle in the resin composition (translucent resin), an inorganic filler such as silica may be added to prevent sedimentation. . As the amount of the inorganic filler added increases, it is more effective in preventing the sedimentation of the translucent fine particles, but adversely affects the transparency of the coating film. Therefore, it is preferable that an inorganic filler having a particle size of 0.5 μm or less is contained in an amount of less than 0.1% by mass so as not to impair the transparency of the coating film with respect to the translucent resin.

  As the translucent resin, there are three types of resins that are mainly cured by ultraviolet rays and electron beams, that is, an ionizing radiation curable resin, a mixture of an ionizing radiation curable resin and a thermoplastic resin and a solvent, and a thermosetting resin. Is done. In order to impart hard coat properties, an ionizing radiation curable resin is preferably the main component. The thickness of the light diffusion layer is usually 1.5 μm to 30 μm, preferably 3 μm to 20 μm. In general, the light diffusing layer also functions as a hard coat layer. However, when the thickness of the light diffusing layer becomes thinner than 1.5 μm, the hard coat property is not sufficient, whereas from 30 μm If the thickness is too thick, this is an undesirable direction in terms of curling and brittleness. When providing the low refractive index layer, the refractive index of the translucent resin is preferably 1.46 to 2.00, more preferably 1.48 to 1.90, and further preferably 1.50. 1.80. The refractive index of the translucent resin is an average value of the light diffusion layer measured without including the translucent fine particles. When the refractive index of the light diffusing layer is too small, the antireflection property is lowered. If it is too large, the color of the reflected light becomes strong, which is not preferable. From this point, the above range is preferable. The refractive index of the light diffusing layer is set to a desired value in terms of antireflection properties and reflected light color.

1-6. Polymerization initiator
[Photoinitiator]
Examples of photo radical polymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (JP-A No. 2001-139663, etc.), 2, 3 -Dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like.
Examples of acetophenones include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxy-dimethylphenylketone, 1-hydroxy-dimethyl-p-isopropylphenylketone, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4-phenoxydichloroacetophenone, 4-t- Butyl-dichloroacetophenone is included.

  Specific examples of the active halogens include Wakabayashi et al., “Bull Chem. Soc Japan”, 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-5-27830, M.M. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry”, Vol. 1 (No. 3), (1970), and in particular, oxazole compounds substituted with a trihalomethyl group: s-triazine compounds. More preferred are s-triazine derivatives in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-triazine ring. Specific examples include S-triazine and oxathiazole compounds, such as 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-styrylphenyl). -4,6-bis (trichloromethyl) -s-triazine, 2- (3-Br-4-di (ethyl acetate) aminophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- Trihalomethyl-5- (p-methoxyphenyl) -1,3,4-oxadiazole is included. Specifically, p.14 to p30 in JP-A-58-15503, p6-p10 in JP-A-55-77742, and p287 in JP-B-60-27673. 1-No. 8, No. pp. 443 to p444 of JP-A-60-239736. 1-No. 17, No. 4,701,399. Compounds such as 1-19 are particularly preferred.

  Specific examples of the active halogens are as follows.

  These initiators may be used alone or in combination. “Latest UV Curing Technology”, Technical Information Association, 1991, p. 159, and “UV curing system” written by Kayo Kiyomi, 1989, General Technology Center, p. Various examples are also described in 65-148 and are useful in the present invention.

  Commercially available radical photopolymerization initiators include KAYACURE (DETX-S, BP-100, BDKM, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, manufactured by Nippon Kayaku Co., Ltd. MCA, etc.), Irgacure (651, 184, 500, 819, 907, 369, 1173, 1870, 2959, 4265, 4263, etc.) manufactured by Ciba Specialty Chemicals Co., Ltd., Esacure (KIP100F, KB1, manufactured by Sartomer) EB3, BP, X33, KT046, KT37, KIP150, TZT) and the like and combinations thereof are preferred examples.

  It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.

<Photosensitizer>
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.
Further, one or more auxiliary agents such as an azide compound, a thiourea compound, and a mercapto compound may be used in combination.
Examples of commercially available photosensitizers include KAYACURE (DMBI, EPA) manufactured by Nippon Kayaku Co., Ltd.

<Thermal initiator>
As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Diazo compounds such as 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanecarbonitrile) as azo compounds such as ammonium sulfate and potassium persulfate And diazoaminobenzene, p-nitrobenzenediazonium and the like.

  In the present invention, in addition to the thermal acid generator described above, a compound that generates an acid upon irradiation with light, that is, a photosensitive acid generator may be further added. The photosensitive acid generator is a substance that imparts photosensitivity to the coating film of the curable resin composition and enables the coating film to be photocured by, for example, irradiation with radiation such as light. Examples of the photosensitive acid generator include (1) various onium salts such as iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, ammonium salt, pyridinium salt; (2) β-ketoester, β-sulfonylsulfone and these Sulfone compounds such as α-diazo compounds; (3) sulfonic acid esters such as alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters and imino sulfonates; (4) sulfonimide compounds; (5) diazomethane compounds Others can be mentioned and can be used as appropriate.

  The photosensitive acid generator can be used alone or in combination of two or more, and can also be used in combination with the thermal acid generator. The use ratio of the photosensitive acid generator is preferably 0 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the fluoropolymer in the curable resin composition. If the ratio of the photosensitive acid generator is less than or equal to the upper limit, it is preferable because the resulting cured film has excellent strength and good transparency.

The use ratio of the photosensitive acid generator is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the curable resin composition.
In addition, as specific compounds and usage, for example, the contents described in JP-A-2005-43876 can be used.

1-7. Surfactant In the film of the present invention, in order to ensure surface uniformity such as coating unevenness, drying unevenness, point defect, etc., light diffusion of either a fluorine-based surfactant or a silicone-based surfactant or both of them is performed. It is preferable to contain in the coating composition for layer formation. In particular, a fluorine-based surfactant can be preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects appears at a smaller addition amount. Productivity can be improved by giving high-speed coating suitability while improving surface uniformity.

  Preferable examples of the fluorosurfactant include a fluoroaliphatic group-containing copolymer (sometimes abbreviated as “fluorine polymer”), and the fluoropolymer includes the following monomer (i): An acrylic resin, a methacrylic resin, and a copolymer with a vinyl monomer copolymerizable therewith, containing the corresponding repeating unit or containing the repeating unit corresponding to the monomer (ii) below are useful.

(I) Fluoroaliphatic group-containing monomer represented by the following general formula A

In the general formula A, R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —, m is an integer of 1 to 6 and n is an integer of 2 to 4 Represents. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group. X is preferably an oxygen atom.

(Ii) Monomer represented by the following general formula (b) copolymerizable with the above (i)

In the general formula (b), R ¹³ represents a hydrogen atom or a methyl group, Y represents an oxygen atom, a sulfur atom or —N (R ¹⁵ ) —, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically Specifically, it represents a methyl group, an ethyl group, a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group. Y is an oxygen atom, -N (H) -, and -N (CH ₃₎ - are preferred.
R ¹⁴ represents a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms which may have a substituent. Examples of the substituent for the alkyl group represented by R ¹⁴ include a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, a carboxyl group, an alkyl ether group, an aryl ether group, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a nitro group, and a cyano group. , Amino groups and the like, but not limited thereto. Examples of the linear, branched or cyclic alkyl group having 4 to 20 carbon atoms include a butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and undecyl group which may be linear or branched. , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, eicosanyl group, etc., and monocyclic cycloalkyl groups such as cyclohexyl group, cycloheptyl group and bicycloheptyl group, bicyclodecyl group, tricycloundecyl group, A polycyclic cycloalkyl group such as a tetracyclododecyl group, an adamantyl group, a norbornyl group, a tetracyclodecyl group, or the like is preferably used.

  The amount of the fluoroaliphatic group-containing monomer represented by the general formula (a) used in the fluoropolymer used in the present invention is 10 mol% or more based on each monomer of the fluoropolymer, preferably Is 15 to 70 mol%, more preferably in the range of 20 to 60 mol%.

  The preferred weight average molecular weight of the fluoropolymer used in the present invention is preferably 3000 to 100,000, more preferably 5,000 to 80,000.

  The preferred addition amount of the fluoropolymer used in the present invention is in the range of 0.001 to 5% by mass, preferably in the range of 0.005 to 3% by mass, and more preferably in the range of 0.005 to 3% by mass. It is the range of 01-1 mass%. If the addition amount of the fluorine-based polymer is less than 0.001% by mass, the effect is insufficient, and if it exceeds 5% by mass, the coating film may not be sufficiently dried or the performance as a coating film (for example, reflectance) Adversely affect the scratch resistance). In the invention, both the hard coat layer and the overcoat layer can contain a surfactant, but the absolute content in the hard coat layer is less than the absolute content in the overcoat layer. This is preferable in terms of planar stability when stacked. Moreover, when coating two layers simultaneously as mentioned later, it is preferable that the amount of the surfactant in the hard coat layer is small, and an embodiment in which no surfactant is added can be taken.

1-8. Thickener The film of the present invention may use a thickener to adjust the viscosity of the coating solution. The term “thickener” as used herein means that the viscosity of the liquid is increased by adding it, and preferably 0.05 to 50 cP (0. 05 to 50 mPa.s), more preferably 0.10 to 20 cP (0.1 to 20 mPa.s), and most preferably 0.10 to 10 cP (0.10 to 10 mPa.s).

Examples of such thickeners include, but are not limited to:
Poly-ε-caprolactone, poly-ε-caprolactone diol, poly-ε-caprolactone triol, polyvinyl acetate, poly (ethylene adipate), poly (1,4-butylene adipate), poly (1,4-butylene glutarate), poly (1,4-butylene succinate), poly (1,4-butylene terephthalate), poly (ethylene terephthalate), poly (2-methyl-1,3-propylene adipate), poly (2-methyl-1,3-propylene) Glutarate), poly (neopentyl glycol adipate), poly (neopentyl glycol sebacate), poly (1,3-propylene adipate), poly (1,3-propylene glutarate), polyvinyl butyral, polyvinyl formal, polyvinyl acetal, poly Livinyl propanal, polyvinyl hexanal, polyvinyl pyrrolidone, polyacrylate, polymethacrylate, cellulose acetate, cellulose propionate, cellulose acetate butyrate.

  In addition to this, known viscosity adjustments such as smectite, tetrasilica mica, bentonite, silica, montmorillonite and sodium polyacrylate, JP-A-10-219136 ethyl cellulose, polyacrylic acid, organic clay described in JP-A-8-325491 An agent or a thixotropic agent can be used.

1-9. Coating solvent As a solvent used in the coating composition for forming each layer of the present invention, it is possible to dissolve or disperse each component, to easily form a uniform surface in the coating process and the drying process, and to maintain liquid stability. Various solvents selected from the viewpoints of being able to be secured, having an appropriate saturated vapor pressure, and the like can be used.
Two or more kinds of solvents can be mixed and used. In particular, from the viewpoint of drying load, it is preferable that a solvent having a boiling point of 100 ° C. or lower at normal pressure and room temperature as a main component and a small amount of solvent having a boiling point of 100 ° C. or higher for adjusting the drying speed.

  Examples of the solvent having a boiling point of 100 ° C. or lower include hydrocarbons such as hexane (boiling point 68.7 ° C.), heptane (98.4 ° C.), cyclohexane (80.7 ° C.), benzene (80.1 ° C.), Halogenated carbonization such as dichloromethane (39.8 ° C), chloroform (61.2 ° C), carbon tetrachloride (76.8 ° C), 1,2-dichloroethane (83.5 ° C), trichloroethylene (87.2 ° C) Hydrogens, diethyl ether (34.6 ° C), diisopropyl ether (68.5 ° C), dipropyl ether (90.5 ° C), tetrahydrofuran (66 ° C) and other ethers, ethyl formate (54.2 ° C), Esters such as methyl acetate (57.8 ° C.), ethyl acetate (77.1 ° C.), isopropyl acetate (89 ° C.), acetone (56.1 ° C.), 2-butanone (methyl ethyl) Ketones such as 79.6 ° C, the same as ketone, methanol (64.5 ° C), ethanol (78.3 ° C), 2-propanol (82.4 ° C), 1-propanol (97.2 ° C), etc. Alcohols, cyano compounds such as acetonitrile (81.6 ° C.), propionitrile (97.4 ° C.), carbon disulfide (46.2 ° C.), and the like. Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.

  Examples of the solvent having a boiling point of 100 ° C or higher include, for example, octane (125.7 ° C), toluene (110.6 ° C), xylene (138 ° C), tetrachloroethylene (121.2 ° C), chlorobenzene (131.7 ° C), Dioxane (101.3 ° C.), dibutyl ether (142.4 ° C.), isobutyl acetate (118 ° C.), cyclohexanone (155.7 ° C.), 2-methyl-4-pentanone (same as MIBK, 115.9 ° C.), Examples thereof include 1-butanol (117.7 ° C.), N, N-dimethylformamide (153 ° C.), N, N-dimethylacetamide (166 ° C.), dimethyl sulfoxide (189 ° C.) and the like. Cyclohexanone and 2-methyl-4-pentanone are preferable.

1-10. Other In the film of the present invention, in addition to the above components, resin, coupling agent, anti-coloring agent, coloring agent (pigment, dye), antifoaming agent, leveling agent, flame retardant, ultraviolet absorber, infrared absorber, Adhesion imparting agents, polymerization inhibitors, antioxidants, surface modifiers and the like can also be added.

1-11. Support The support of the film of the present invention is not particularly limited, such as a transparent resin film, a transparent resin plate, a transparent resin sheet, and transparent glass. Transparent resin films include cellulose acylate films (for example, cellulose triacetate film (refractive index 1.48), cellulose diacetate film, cellulose acetate butyrate film, cellulose acetate propionate film), polyethylene terephthalate film, polyethersulfone. Films, polyacrylic resin films, polyurethane resin films, polyester films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyetherketone films, (meth) acrylonitrile films, and the like can be used.

<Cellulose acylate film>
Among them, a cellulose acylate film having high transparency, optically low birefringence, easy production, and generally used as a protective film for a polarizing plate is preferable, and a cellulose triacetate film is particularly preferable. Further, the thickness of the transparent support is generally about 20 μm to 1000 μm. For the display surface, it is preferably 20 μm to 500 μm, more preferably 30 μm to 150 μm, and most preferably 15 μm to 60 μm.

In the present invention, it is preferable to use cellulose acetate having an acetylation degree of 59.0 to 61.5% for the cellulose acylate film.
The degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation follows the measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like).
The viscosity average degree of polymerization (DP) of cellulose acylate is preferably 250 or more, and more preferably 290 or more.
The cellulose acylate used in the present invention has a Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) value by gel permeation chromatography close to 1.0, in other words, a molecular weight distribution. Narrow is preferred. The specific value of Mw / Mn is preferably 1.0 to 1.7, more preferably 1.3 to 1.65, and most preferably 1.4 to 1.6. preferable.

In general, the hydroxyl groups at 2, 3, and 6 positions of cellulose acylate are not evenly distributed by 1/3 of the total substitution degree, and the substitution degree of the 6-position hydroxyl group tends to be small. In the present invention, it is preferable that the substitution degree of the 6-position hydroxyl group of cellulose acylate is larger than that of the 2- and 3-positions.
The hydroxyl group at the 6-position with respect to the total substitution degree is preferably substituted with 32% or more of an acyl group, more preferably 33% or more, and particularly preferably 34% or more. Furthermore, the substitution degree of the 6-position acyl group of cellulose acylate is preferably 0.88 or more. The 6-position hydroxyl group may be substituted with a propionyl group, butyroyl group, valeroyl group, benzoyl group, acryloyl group or the like, which is an acyl group having 3 or more carbon atoms, in addition to the acetyl group. The degree of substitution at each position can be determined by NMR.
In the present invention, as cellulose acylate, paragraphs “0043” to “0044” [Example] [Synthesis Example 1], paragraphs “0048” to “0049” [Synthesis Example 2], and paragraph “ Cellulose acetate obtained by the method described in “0051” to “0052” [Synthesis Example 3] can be used.

<Polyethylene terephthalate film>
In the present invention, a polyethylene terephthalate film is also preferably used because it is excellent in transparency, mechanical strength, flatness, chemical resistance and moisture resistance, and is inexpensive.
In order to further improve the adhesion strength between the transparent plastic film and the hard coat layer provided thereon, the transparent plastic film is more preferably subjected to an easy adhesion treatment.
Examples of commercially available PET films with an easily adhesive layer for optics include Cosmo Shine A4100 and A4300 manufactured by Toyobo Co., Ltd.

2. Configuration of optical film of the present invention In an optical film in which a hard coat layer is formed on a flexible support, the hardness after curing of the polymerizable compound forming the hard coat layer and the curl of the optical film are determined by the polymerization reaction being cured and contracted. As long as the reaction involving is utilized, it is largely contradictory. Attempts have been made to solve the problem with the structure of the polymerizable compound. However, there is a demand for further improvement in hardness and thinning of the support, and further improvement is required.

  There is a limit to satisfying this requirement with only one hard coat layer formed from a spatially uniform composition. The gist of the present invention is to solve these problems by changing the composition distribution of the polymerizable compound in the vertical direction (stacking direction) of the optical film. That is, the above object is achieved by setting the MOC / MHC ratio in a specific range. There is a large correlation between the hardness of the cured film and the molecular weight of the polymerizable compound. In the molecular weight region of about 300 to 100,000, when the molecular weight is high, the hardness tends to be high.

  In order to achieve both high hardness, high scratch resistance and low curl, it is more effective to selectively form a high-hardness coating film with a high molecular weight on the surface side of the optical film compared to a uniform composition. is there. That is, the hardness represented by pencil hardness is governed by the hardness of the entire coating film, and the scratch resistance represented by steel wool rubbing is largely governed by the hardness of the surface layer of about 0.1 to 1.0 μm. .

  In addition, the curl has found that it is effective that the layer having a large cure shrinkage is thin and the interface of layers having different cure shrinkage is not clear.

  In addition to the above, the optical film of the present invention is required to have antifouling properties and low reflectivity as the surface film of the display. There is an advantage as shown below by taking the configuration of the present application for improving the antifouling property.

  An unnecessary antifouling agent at the bottom of the hard coat layer is added to the upper overcoat layer having a two-layer structure instead of simply adding silicone or a fluorine compound to the single-layer hard coat layer. Therefore, the hardness of the optical film can be increased. In addition, the anti-fouling agent is more strongly fixed by curing together with a compound having a high molecular weight and a large number of functional groups per molecule in the overcoat layer, thereby improving the anti-fouling property and durability.

  Taking the configuration of the present invention with respect to low reflectivity has the following advantages. In the conventional method using optical interference, it is important to control the coating thickness of the interference layer. If the film thickness unevenness occurs, the interference unevenness occurs and the change in color becomes large. On the other hand, since the overcoat layer of the present invention does not actively use optical interference, it is possible to form an optical film that is insensitive to fluctuations in coating thickness. Reducing the refractive index of the surface of the overcoat layer by containing a low refractive index polymerizable compound and low refractive index inorganic fine particles, thereby reducing the surface reflection, preferably the refractive index interface between the overcoat layer and the hard coat layer As a result, it is possible to obtain an optical film in which unevenness is suppressed. As a means for making the refractive index interface indistinct, an overcoat layer can be provided on the hard coat layer without being cured, or simultaneous multilayering can be performed.

2-1. Hard coat layer and thickness of overcoat layer In the optical film of the present invention, it is essential to provide a hard coat layer, and the pencil hardness in a state of being applied and finally cured including the overcoat layer is 2H or more. Preferably there is. The hard coat layer is preferably 1.5 μm to 30 μm, more preferably 3 μm to 20 μm. The overcoat layer is preferably 0.15 μm to 10 μm, more preferably 0.25 μm to 6 μm. When the overcoat layer contains a curable multi-branched polymer (RHB), the effect of improving the scratch resistance is great, and the overcoat layer can be thinned, preferably 0.15 μm to 6 μm, more preferably 0.25 μm to 2 μm. The total thickness of the hard coat layer and the overcoat layer is preferably 1.6 μm to 30 μm, more preferably 3.0 μm to 20 μm.

  The thickness of the overcoat layer after curing with respect to the hard coat layer is preferably 0.5% to 70%, more preferably 3.0 to 40%, and most preferably 5.0 to 25%. By using this ratio, it is possible to achieve both hardness, scratch resistance and curl.

  Further, as will be described later, it is possible to adopt an embodiment in which the interface between the hard coat layer and the overcoat layer is not clear. Also, two or more overcoat layers with different compositions can be provided for the hard coat layer. In particular, when it is necessary to gradually change the composition of each layer, it is preferable to use a multilayer overcoat layer. Since the interface between the hard coat layer and the overcoat layer is not clear, curing shrinkage and rapid changes in hardness are suppressed, which is effective in reducing curl and improving scratch resistance (peeling at the interface).

2-2. Physical properties of each layer
[Refractive index]
The refractive index of the hard coat layer of the present invention is not particularly limited, but is preferably 1.46 to 2.00, more preferably 1.49 to 1.65. When providing a hard-coat layer adjacent to a support body, since a nonuniformity of interference can be reduced by making a refractive index difference with a support body 0.02 or less, it is preferable. Although there is no restriction | limiting in particular also in the refractive index of an overcoat layer, 1.25-2.00 are preferable, More preferably, it is 1.25-1.90. When used for the uppermost layer of the optical film used for the outermost surface of the display material, 1.25 to 1.49 is preferable, and more preferably 1.30 to 1.47. In addition, when the interface between the overcoat layer and the hard coat layer is not clear as described later, the average refractive index from the surface of the overcoat layer to the depth of 100 nm is preferably 1.25 to 1.49, more preferably 1.30 to 1.47.

  In particular, in order to make the fingerprint adhering mark inconspicuous, by making it 1.45 to 1.48, it is effective because the fat and oil of the fingerprint becomes close to the refractive index. Moreover, when the antiglare property is imparted to the optical film, the fingerprint marks are more difficult to be visually recognized, which is particularly effective.

  On the other hand, when a low refractive index layer is further provided as an optical interference layer on the overcoat layer, the refractive index of the overcoat layer is preferably 1.46 to 2.00, more preferably 1.49 to 2.00. 1.58 to 1.70 is most preferable. In order to increase the refractive index, it is preferable to use an inorganic fine particle having a high refractive index for the overcoat layer.

  When the interface between the overcoat layer and the hard coat layer is not clear as will be described later, the average refractive index from the surface of the overcoat layer to the depth of 100 nm is preferably from 1.46 to 2.00, and from 1.49 to 2. 00 is more preferable.

[Curing shrinkage]
From the viewpoint of improving the hardness and scratch resistance of the optical film and reducing the occurrence of curling, when using a general polyfunctional (meth) acrylate monomer, the thickness of the overcoat layer is the thickness of the hard coat layer. It is preferable that the curing shrinkage rate of the binder of the hard coat layer is made smaller than the cure shrinkage rate of the binder of the overcoat layer. On the other hand, when the overcoat layer contains a curable multi-branched polymer (RHB), it is not necessary to increase the cure shrinkage of the overcoat layer compared to the hard coat layer, and both hardness / abrasion resistance and curl reduction can be achieved. Cheap. Curing shrinkage was calculated by the following method.

Volumetric shrinkage: D = (S−S ′) / S × 100
(S: specific gravity before curing, S ′: specific gravity after curing, specific gravity is measured by B method pycnometer method of JIS K-7112)

[Surface properties]
The optical film of the present invention is one of the preferred embodiments in which the overcoat layer is the uppermost layer. In this embodiment, the method for measuring the surface properties of the overcoat layer and the preferred range will be described below.
(Contact angle)
The contact angle of the surface of the optical film of the present invention is preferably 94 degrees or more with respect to pure water. It is more preferably 97 degrees or more, and most preferably 101 degrees or more. The contact angle can be measured by the following method.

  Using a contact angle meter [“CA-X” type contact angle meter, manufactured by Kyowa Interface Science Co., Ltd.], using a pure water as a liquid in a dry state (20 ° C./65% RH), a diameter of 1.0 mm A droplet was made on the needle tip and brought into contact with the surface of the film to form a droplet on the film. The angle formed between the tangent to the liquid surface and the film surface at the point where the film and the liquid are in contact with each other is defined as the contact angle.

(Surface free energy)
The surface free energy of the optical film of the present invention is preferably 30 mN / m or less, and more preferably 20 mN / m or less. The surface free energy (γs ^v : unit, mN / m) of the film of the present invention is D.E. K. Owens: J.M. Appl. Polym. Sci. , 13, 1741 (1969), and can be obtained from the contact angles of pure water and methylene iodide CH ₂ I ₂ experimentally obtained on the antireflection film.

(Dynamic friction coefficient)
A dynamic friction coefficient can be used as an index of surface slipperiness. The optical film of the present invention is preferably 0.02 or more and 0.30 or less, more preferably 0.02 or more and 0.25 or less, and most preferably 0.05 or more and 0.20 or less. By setting it within the above range, the antifouling property and scratch resistance can be kept good. As the dynamic friction coefficient, the sample was conditioned at 25 ° C. and 60% for 24 hours, and then a value measured with a HEIDON-14 dynamic friction measuring machine at a 5 mmφ stainless steel ball, a load of 100 g, and a speed of 60 cm / min was used.

2-3. Interface of hard coat layer and overcoat layer In the present invention, the boundary between the hard coat layer and the overcoat layer may be clear, but the interface is not clear from the viewpoint of interfacial adhesion, scratch resistance, and interference unevenness prevention. A configuration is also preferable.

As a preferable first aspect, an aspect in which the composition of both layers is gradually changed can be mentioned. In the present invention, the composition refers to the constituent ratio of the polymerizable compound and / or fine particles in the cured film.
In this embodiment, the thickness of the composition change layer is preferably 0.05 μm to 5 μm, more preferably 0.1 μm to 2 μm. When the refractive index of the overcoat layer component alone and the hard coat layer component alone is different by 0.02 or more, the thickness of the composition change layer is particularly preferably 0.05 μm to 1 μm. The composition change layer is a layer in which the composition gradually changes from the composition of the bulk overcoat layer to the composition of the bulk hard coat layer between the upper end and the lower end.

In a preferred second embodiment, the hard coat layer and the overcoat layer form a further interfacial mixed layer at the interface. In this embodiment, the thickness of the interface mixed layer is preferably 0.05 μm to 1 μm, more preferably 0.05 μm to 0.5 μm.
In a preferred third aspect, the components of the hard coat layer and the overcoat layer form a sea-island structure or a co-continuous phase that is phase-separated at the interface. In this embodiment, the equivalent sphere diameter of the phase-separated island structure portion is preferably 0.01 μm to 1 μm, more preferably 0.02 to 0.3 μm, and most preferably 0.02 to 0.15 μm. Of these embodiments where the interface is not clear, the first embodiment is particularly preferable.

  These interfacial states should be controlled by the manufacturing method described later in addition to using components of the overcoat layer that easily penetrate into the hard coat layer, and including components that are easily extracted into the overcoat layer in the hard coat. Is possible.

2-4. Other optical functional layers In addition to the hard coat layer and the overcoat layer adjacent thereto, the optical film of the present invention is provided with another optical functional layer between the support and the hard coat layer or in the upper layer of the overcoat layer. be able to. For example, interference non-uniformity (rainbow non-uniformity) prevention layer, anti-static layer (when there is a request such as lowering the surface resistance from the display side, when dust on the surface becomes a problem), gas barrier layer, water absorption Examples thereof include a layer (moisture proof layer), an adhesion improving layer, an antifouling layer (contamination preventing layer), a medium refractive index layer, a high refractive index layer, and a low refractive index layer. As a particularly preferred embodiment, a low refractive index layer is provided on the overcoat layer.

  When an antireflective film is prepared by coating a medium refractive index layer, a high refractive index layer, and a low refractive index layer in order from the support, the refractive index of the high refractive index layer is 1.65 to 2.40. Preferably, it is 1.70 to 2.20. The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55 to 1.80.

2-4-1. Low refractive index layer By coating a layer having a refractive index lower than the refractive index of the overcoat layer on the overcoat layer of the present invention with an appropriate film thickness, antireflection performance can be obtained and external light reflected. Therefore, the contrast in a bright room environment can be increased, so that the image display apparatus is more preferable.

  The material for forming the low refractive index layer will be described below. The low refractive index layer of the present invention is formed by applying and curing a curable composition containing a fluorine-containing compound as a main component or a monomer having a plurality of bonding groups in the molecule and low refractive index particles. Thus, the refractive index is adjusted in the range of 1.20 to 1.50. 1.25 to 1.45 are preferred. More preferably 1.30 to 1.40.

  Preferred embodiments of the cured product composition include (1) a composition containing a fluorine-containing polymer having a crosslinkable or polymerizable functional group, and (2) a hydrolysis condensate of a fluorine-containing organosilane material as a main component. At least one of a composition and (3) a composition containing a monomer having two or more ethylenically unsaturated groups and inorganic fine particles having a hollow structure can be used. Thereby, compared with the low refractive index layer using magnesium fluoride or calcium fluoride, an optical film excellent in scratch resistance can be obtained even when used as the outermost layer. The dynamic friction coefficient of the cured low refractive index layer surface is preferably 0.03 to 0.15, and the contact angle with water is preferably 90 to 120 degrees.

(1) Fluorine-containing compound having a crosslinkable or polymerizable functional group As the fluorine-containing compound having a crosslinkable or polymerizable functional group, co-polymerization of a fluorine-containing monomer and a monomer having a crosslinkable or polymerizable functional group Coalescence can be mentioned. Examples of the fluorine-containing monomer include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.) (meta ) Acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, and the like.

  As an example of the monomer for imparting a crosslinkable group, a (meth) acrylate monomer having a crosslinkable functional group in the molecule in advance such as glycidyl methacrylate can be exemplified. In another embodiment, after synthesizing a fluorinated copolymer using a monomer having a functional group such as a hydroxyl group, the monomer is further modified to introduce a crosslinkable or polymerizable functional group by modifying the substituent. It is. These monomers include (meth) acrylate monomers having a carboxyl group, hydroxyl group, amino group, sulfonic acid group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.) Is mentioned. The latter embodiment is disclosed in Japanese Patent Laid-Open Nos. 10-25388 and 10-147739.

From the viewpoints of solubility, dispersibility, coatability, antifouling property, antistatic property and the like, the fluorine-containing copolymer can contain a copolymerizable component as appropriate. In particular, for imparting antifouling properties and slipperiness, it is preferable to introduce silicone, and it can be introduced into both the main chain and the side chain.
The polysiloxane partial structure introduction method to the main chain is, for example, an azo group-containing polysiloxane amide described in JP-A-6-93100 (VPS-0501, 1001 (trade name; Wako Pure Chemical Industries, Ltd. And a method using a polymer-type initiator such as a company)). Further, the method of introducing into the side chain is, for example, as described in J. Appl. Polym. Sci. 2000, 78, 1955, JP-A-56-28219, etc. For example, a silaplane series (manufactured by Chisso Corporation) can be synthesized by a method of polymer reaction or a method of polymerizing a polysiloxane-containing silicon macromer, and both methods can be preferably used.

  You may use together suitably the hardening | curing agent which has a polymerizable unsaturated group with respect to said polymer as Unexamined-Japanese-Patent No. 2000-17028. Moreover, combined use with the compound which has a fluorine-containing polyfunctional polymerizable unsaturated group as described in Unexamined-Japanese-Patent No. 2002-145952 is also preferable. Examples of the compound having a polyfunctional polymerizable unsaturated group include the above-described monomers having two or more ethylenically unsaturated groups. Moreover, the hydrolysis-condensation product of the organolane described in Unexamined-Japanese-Patent No. 2004-170901 is also preferable, and the hydrolysis-condensation product of the organosilane containing a (meth) acryloyl group is especially preferable. These compounds are particularly preferred because they have a large combined effect for improving scratch resistance, particularly when a compound having a polymerizable unsaturated group is used in the polymer body.

  When the polymer itself does not have sufficient curability, necessary curability can be imparted by blending a crosslinkable compound. For example, when the polymer body contains a hydroxyl group, various amino compounds are preferably used as the curing agent. The amino compound used as the crosslinkable compound is, for example, a compound containing one or both of a hydroxyalkylamino group and an alkoxyalkylamino group in total, specifically, for example, a melamine compound, Examples include urea compounds, benzoguanamine compounds, glycoluril compounds, and the like. For curing these compounds, an organic acid or a salt thereof is preferably used.

  Specific examples of these fluoropolymers are described in JP2003-222702A, JP2003-183322A, and the like.

(2) Hydrolyzed condensate of fluorine-containing organosilane material A composition containing a hydrolyzed condensate of a fluorine-containing organosilane compound as a main component is also preferable because of its low refractive index and high hardness on the coating film surface. A condensate of a tetraalkoxysilane with a hydrolyzable silanol-containing compound at one or both ends with respect to the fluorinated alkyl group is preferred. Specific compositions are described in JP-A Nos. 2002-265866 and 2002-317152.

(3) A composition containing a monomer having two or more ethylenically unsaturated groups and inorganic fine particles having a hollow structure As yet another preferred embodiment, a low refractive index layer comprising low refractive index particles and a binder can be mentioned. . The low refractive index particles may be organic or inorganic, but particles having pores inside are preferable. Specific examples of the hollow particles are described in the silica-based particles described in JP-A-2002-79616. The particle refractive index is preferably 1.15 to 1.40, more preferably 1.20 to 1.30. Examples of the binder include monomers having two or more ethylenically unsaturated groups described in the pages of the hard coat layer and the overcoat layer.

  In the low refractive index layer of the present invention, the above 1-6. It is preferable to add the polymerization initiator described in the polymerization initiator. When a radically polymerizable compound is contained, 1 to 10 parts by mass, preferably 1 to 5 parts by mass of a polymerization initiator can be used with respect to the compound.

  In the low refractive layer of the present invention, inorganic particles can be used in combination. In order to impart scratch resistance, fine particles having a particle size of 15% to 150%, preferably 30% to 100%, more preferably 45% to 60% of the thickness of the low refractive index layer can be used. .

  In the low refractive index layer of the present invention, for the purpose of imparting properties such as antifouling property, water resistance, chemical resistance, and slipping property, a known polysiloxane-based or fluorine-based antifouling agent, slipping agent, etc. are appropriately used. Can be added.

3. 3. Production method of optical film of the present invention 3-1. Coating liquid physical properties Since the coating speed of the present invention is greatly affected by the liquid physical properties, it is necessary to control the liquid physical properties, particularly the viscosity and surface tension at the moment of coating. The viscosity is preferably 2.0 [mPa · sec] or less, more preferably 1.5 [mPa · sec] or less, and most preferably 1.0 [mPa · sec] or less. Since there are some coating solutions whose viscosity changes depending on the shear rate, the above value indicates the viscosity at the shear rate at the moment of coating. When a thixotropic agent is added to the coating solution and the coating solution is subjected to high shear, the viscosity is low, and when the coating solution is hardly sheared, if the viscosity is high, unevenness during drying is less likely to occur.

Although it is not a liquid physical property, the amount of the coating liquid applied to the transparent support also affects the upper limit of the coating speed. The amount of the coating solution applied to the transparent support is preferably 2.0 to 5.0 [cc / m ² ]. Increasing the amount of the coating liquid applied to the transparent support is preferable because the upper limit of the application rate can be increased, but if the amount of the coating liquid applied to the transparent support is increased too much, the load on drying increases. It is preferable to determine the optimal amount of coating liquid to be applied to the transparent support depending on the liquid formulation and process conditions.

  The surface tension of the coating solution is preferably in the range of 15 to 36 [mN / m]. It is preferable to reduce the surface tension by adding a leveling agent or the like because unevenness during drying is suppressed. On the other hand, if the surface tension is too low, the upper limit speed at which coating can be performed is reduced. Therefore, a range of 17 [mN / m] to 32 [mN / m] is more preferable, and 19 [mN / m] to 26 [mN / m]. mN / m] is more preferable. In the layer containing translucent particles, the viscosity is preferably adjusted to 4 cp or more, more preferably 6 cp or more from the viewpoint of preventing sedimentation of the particles.

3-2. Coating Each layer of the film of the present invention can be formed by the following coating method, but is not limited to this method. Dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method or extrusion coating method (die coating method) (see US Pat. No. 2,681,294), micro gravure coating method, etc. Known methods are used, and among them, the micro gravure coating method and the die coating method are preferable.

  In particular, when two or more layers such as an overcoat layer and a low refractive index layer are coated on the hard coat layer, a method of simultaneously coating two or more layers with one coating apparatus (Japanese Patent Application Laid-Open No. 2002-86050). , JP 2003-260400 A, JP 7-108213 A) and a method of applying two or more layers in one winding by arranging the coating / drying / curing apparatus in multiple stages (JP 2003-26015 A). -205264) is preferred. In particular, as in the present invention, when the structures and compositions of the polymerizable compounds of the hard coat layer and the overcoat layer are different, or when the particles contained in both layers are different, interfacial adhesion, interference unevenness prevention, curl improvement, etc. From this point of view, it is preferable to apply two or more layers simultaneously, or to apply an overcoat layer with a low polymerization rate after applying a hard coat layer by the method described below.

3-3. Curing 3-3-1. Curing conditions After drying the solvent, the film of the present invention can pass through a zone where the coating film is cured by ionizing radiation and / or heat on the web to cure the coating film.

  The ionizing radiation species in the present invention is not particularly limited, and is appropriately selected from ultraviolet rays, electron beams, near ultraviolet rays, visible light, near infrared rays, infrared rays, X-rays and the like according to the type of curable composition forming the film. Although it can be selected, ultraviolet rays and electron beams are preferred, and ultraviolet rays are particularly preferred because they are easy to handle and high energy can be easily obtained.

  Moreover, an electron beam can be used similarly. As an electron beam, 50 to 1000 keV, preferably 100 to 100, emitted from various electron beam accelerators such as a cockroft Walton type, a bandegraph type, a resonance transformation type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. An electron beam having an energy of 300 keV can be given.

Irradiation conditions vary depending on each lamp, but the amount of irradiation light is preferably 10 mJ / cm ² or more, more preferably 50 mJ / cm ^{2 to} 10000 mJ / cm ² , and particularly preferably 50 mJ / cm ^{2 to} 2000 mJ / cm ^2. It is.

  The time for irradiating with ionizing radiation is preferably 0.7 seconds or longer and 60 seconds or shorter, and more preferably 0.7 seconds or longer and 10 seconds or shorter. If it is 0.5 seconds or less, the curing reaction cannot be completed, and sufficient curing cannot be performed. Also, maintaining low oxygen conditions for a long time is not preferable because the equipment becomes large and a large amount of inert gas is required.

  The oxygen concentration is preferably cured by a crosslinking reaction or polymerization reaction of an ionizing radiation curable compound in an atmosphere of 6% by volume or less, more preferably an oxygen concentration of 4% by volume or less, and particularly preferably an oxygen concentration of 2% by volume. Hereinafter, it is most preferably 1% by volume or less. In order to reduce the oxygen concentration more than necessary, a large amount of inert gas such as nitrogen is required, which is not preferable from the viewpoint of production cost.

  As a method of reducing the oxygen concentration to 10% by volume or less, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another gas, particularly preferably replacement with nitrogen (nitrogen purge). It is to be.

  During curing, the film surface is preferably heated at 40 ° C. or higher and 170 ° C. or lower. Below 40 ° C, the effect of heating is small, and above 170 ° C, problems such as deformation of the substrate occur. A more preferable temperature is 60 ° C to 100 ° C. The film surface temperature refers to the film surface temperature of the layer to be cured. The time for the film to reach the temperature is preferably 0.1 second or more and 300 seconds or less from the start of UV irradiation, and more preferably 10 seconds or less. If the time for maintaining the temperature of the film surface in the above temperature range is too short, the reaction of the curable composition that forms the film cannot be accelerated, and conversely, if it is too long, the optical performance of the film deteriorates and the equipment is large. Manufacturing problems such as

  There is no particular limitation on the heating method, but a method of heating a roll to contact the film, a method of spraying heated nitrogen, irradiation with far infrared rays or infrared rays is preferable. A method of heating a rotating metal roll described in Japanese Patent No. 2523574 by flowing a medium such as hot water, steam or oil can also be used. As a heating means, a dielectric heating roll or the like may be used.

  In the present invention, at least one layer laminated on the support can be cured by multiple times of ionizing radiation. In this case, it is preferable that at least two ionizing radiations are performed in a continuous reaction chamber in which the oxygen concentration does not exceed 3% by volume. By performing multiple times of ionizing radiation irradiation in the same low oxygen concentration reaction chamber, the reaction time required for curing can be effectively ensured. In particular, when the production rate is increased for high productivity, ionizing radiation irradiation is required multiple times to ensure the energy of ionizing radiation necessary for the curing reaction. Thereby, the uniformity of the progress of curing in the coating film surface is maintained, and it is effective in reducing surface failure.

  The ultraviolet irradiation may be performed every time one layer is provided for each of a plurality of constituent layers, or may be performed after lamination. Or you may irradiate combining these. From the viewpoint of productivity, it is preferable to irradiate ultraviolet rays after laminating multiple layers.

In the present invention, it is preferable that the overcoat layer is applied while the hard coat layer contains the unreacted polymerizable compound, and then the curing is further advanced. The polymerization rate of the polymerizable compound in the hard coat layer before coating the overcoat layer is preferably 0 to 70%, more preferably 0 to 50%, and most preferably 10 to 30%. By adjusting the polymerization rate within the above range, interfacial mixing can be controlled, and unevenness prevention and interfacial adhesion reinforcement can be achieved. For the polymerization rate, the method described in the Polymer Analysis Handbook (edited by the Japan Society for Analytical Chemistry) can be used. Specifically, for example, in the case of a polymerization reaction with a (meth) acryloyloxy group, the carbon-carbon double bond (C = C) of the (meth) acryloyloxy group of the binder in the coated hard coat layer infrared absorption peak area a and acyl groups vicinity of 810 cm ^-1 in the (C = O) was measured before and after the polymerization reaction an infrared absorption peak area B in the vicinity of 1720 cm ^-1 of the resulting, [(a / B after polymerization) / (A / B before polymerization)] * 100, the disappearance of the double bond is calculated, and this is defined as the polymerization rate (%).

3-3-2. Method of using polymerization initiators having different photosensitive wavelengths In the present invention, as a method for controlling the reaction rate of the polymerizable compound of the hard coat layer, the following two or more types of polymerization initiators having different photosensitive wavelengths are used. be able to. In the method for producing an optical film of the present invention, “a hard coat layer comprising two or more kinds of polymerization initiators having different absorption ends on the long wavelength side in the photosensitive wavelength region is used as at least one kind of the polymerization initiator ( a) is substantially unphotosensitized and is cured by irradiation with ionizing radiation having a wavelength at which at least one of the polymerization initiators (b) is sensitive (step 1), and then at least 1 on the hard coat layer. A coating liquid for an overcoat layer containing a seed polymerization initiator (c) is applied, and ionizing radiation is irradiated at a wavelength at which the polymerization initiators (a) and (c) are sensitive (step 2). The “coating / manufacturing method for curing the overcoat layer” is preferred.

  “Not substantially photosensitive” means that the ratio of the double bond reduced by the ionizing radiation used in step 1 to the double bond reduced by the ionizing radiation used in steps 1 and 2 is 30% or less. Means. This ratio is preferably 10% or less, and more preferably 3% or less. The amount of double bonds is measured by the above infrared absorption peak area ratio. It can be calculated.

When the overcoat layer is cured, the hard coat layer initiator is also exposed to light, making it less susceptible to oxygen-induced curing inhibition, allowing the layer to be fully cured, increasing hardness, and providing scratch resistance. improves.
As an actual preferred embodiment, for example, in Step 1, the hard coat layer is combined with a polymerization initiator (a) having a photosensitive region in the near ultraviolet and a polymerization initiator (b) having a photosensitive region only in the ultraviolet. Next, as a step 2, there is a method of applying an overcoat layer containing a polymerization initiator (c) having a photosensitive region only to ultraviolet rays, irradiating with ultraviolet rays, and curing by these two steps. .
In another preferred embodiment, in Step 1, the hard coat layer is used in combination with a polymerization initiator (a) having a photosensitive region in the near ultraviolet ray and a polymerization initiator (b) having a photosensitive region only in the ultraviolet ray, ( a) and (b) are irradiated with an amount of ultraviolet rays that only a part of the polymerization starts, and then, as step 2, an overcoat layer containing a polymerization initiator (c) having a photosensitive region only in the ultraviolet rays is applied, There is a method of irradiating near ultraviolet rays and ultraviolet rays and curing them by these two steps. In this method, near-ultraviolet light can easily reach the lower part of the lower hard coat layer, which is advantageous in improving pencil hardness.
By adjusting the absolute amount and ratio of the polymerization initiators (a) and (b) in the hard coat layer, the polymerization rate of the hard coat layer in step 1 and the polymerization rate after completion of step 2 can be controlled. Easy.

  The polymerization initiator having a different photosensitive wavelength is preferably selected from the following.

  As a polymerization initiator having a photosensitive wavelength in the near ultraviolet region, 2,4,6-trimethylbenzoyldiphenylphosphine oxide {"DAROCUR TPO" (trade name); manufactured by Ciba Specialty Chemicals Co., Ltd.}, phenylenebis (2 , 4,6-trimethylbenzoyl) -phosphine oxide {"IRGACURE 819" (trade name); manufactured by Ciba Specialty Chemicals Co., Ltd.}; bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl- Phosphine oxides such as pentylphosphine oxide, thioxanthone such as 2,4-diethylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, N-methylacridone, bis (dimethylaminophenyl) ketone, 2-benzyl -2-dimethyl Ketones such as amino-1- (4-morpholinophenyl) -butan-1-one {“IRGACURE 369” (trade name); manufactured by Ciba Specialty Chemicals Co., Ltd.}, 1,2-octanedione-1- Compounds having an absorption terminal up to around 400 nm, such as oximes such as [4- (phenylthio) -2,2- (O-benzoyloxime)] are preferred. Phosphine oxides are particularly preferable because the produced film is less colored and the decolorization after irradiation is large.

  As a polymerization initiator that has a photosensitive wavelength region different from that of the above polymerization initiator and can be used in combination, an initiator mainly absorbing in the ultraviolet region is 2,2-dimethoxy-1,2-diphenylethane. -1-one {"IRGACURE 651" (trade name); manufactured by Ciba Specialty Chemicals Co., Ltd.}, 1-hydroxycyclohexyl-phenyl ketone {"IRGACURE 184" (trade name); Ciba Specialty Chemicals Co., Ltd. Made}, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one {“IRGACURE 907” (Product name); Acetophenones and benzoins such as Ciba Specialty Chemicals Co., Ltd.} Benzophenones, ketals, can be mentioned publicly known initiator such as anthraquinones.

  The amount of the polymerization initiator with respect to the curable composition is preferably 1% by mass or more and 10% by mass or less. If the amount of the polymerization initiator is not less than the lower limit, the reaction can proceed sufficiently to obtain a desired hardness, and if it is not more than the upper limit, the resulting cured layer (hereinafter also referred to as a film). It is preferable to use in this range, since it is difficult to cause problems such as coloring or hardness changing in the depth direction.

  When a polymerization initiator having absorption in the near ultraviolet region and a polymerization initiator having absorption in the ultraviolet region are used in combination, the ratio of the amounts used (near ultraviolet: ultraviolet) should be within the range of the above addition amount. There is no particular limitation. The amount of the hard coat layer-containing polymerization initiator (a) that absorbs ultraviolet rays (ionizing radiation) having a wavelength for curing the overcoat layer is preferably large within a range where there is no problem in coloring, hardness, and the like.

The ionizing radiation used in the hard coat layer curing step 1 can be appropriately selected according to the type of polymerization initiator and curable composition used. For example, when irradiating light in the near ultraviolet region, a lamp that mainly emits light in the wavelength region of 400 to 480 nm {a lamp having an emission peak in the range of 400 to 480 nm, such as 400 to 480 nm (preferably 420 nm ± 20 nm) ) The light emitted from the hot cathode fluorescent lamp provided with a phosphor so as to have a radiation peak} or the light of a metal halide lamp having a wide distribution of radiation wavelengths, etc., is short wavelength side (for example, 380 nm or less) Can be used. The irradiation of the near ultraviolet, preferably 30~1000mJ / cm ^2, more preferably 50~700mJ / cm ^2.

After applying the overcoat layer-forming coating solution containing the curable composition in Step 2, the ionizing radiation used for curing can be appropriately selected according to the type of polymerization initiator used and the curable composition. . There is no particular limitation as long as the polymerization initiators (a) and (c) have a wavelength to be sensitized, but irradiation with ultraviolet rays is preferable. Ultraviolet curing is preferred because the polymerization rate is fast, the equipment can be made compact, the types of compounds that can be selected are abundant, and the price is low. In the case of ultraviolet rays, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, etc. can be used. The irradiation dose of ultraviolet rays is preferably 30~1000mJ / cm ^2, more preferably 50~700mJ / cm ^2.

3-4. Saponification treatment When producing a polarizing plate using the film of the present invention as one of the surface protective films of two polarizing films, the surface on the side to be bonded to the polarizing film is made hydrophilic so that It is preferred to improve adhesion. Any of the following methods can be taken.
a. Method of immersing in alkaline solution b. Method of applying alkaline solution c. Method of saponification by protecting with a laminate film d. Method of immersing in alkaline solution after forming up to mid layer e. Method for forming a coating layer on a previously saponified triacetyl cellulose film

4). Form of use of the present invention The film of the present invention is used in image display devices such as liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD) and cathode ray tube display devices (CRT). The optical filter according to the present invention can be used on a known image display device such as a plasma display panel (PDP) or a cathode ray tube display (CRT).

<Liquid crystal display device>
The film and polarizing plate of the present invention can be advantageously used for an image display device such as a liquid crystal display device, and is preferably used for the outermost layer of the display. The liquid crystal display device has a liquid crystal cell and two polarizing plates arranged on both sides thereof, and the liquid crystal cell carries a liquid crystal between two electrode substrates. Furthermore, one optically anisotropic layer may be disposed between the liquid crystal cell and one polarizing plate, or two optically anisotropic layers may be disposed between the liquid crystal cell and both polarizing plates.

  The liquid crystal cell is preferably in TN mode, VA mode, OCB mode, IPS mode or ECB mode.

<Touch panel>
The film of the present invention can be applied to touch panels described in JP-A-5-127822 and JP-A-2002-48913.

<Organic EL device>
The film of the present invention can be used as a substrate (base film) such as an organic EL element or a protective film.
When the film of the present invention is used for an organic EL device or the like, JP-A-11-335661, JP-A-11-335368, JP-A-2001-192651, JP-A-2001-192652, JP-A-2001-192653, JP-A-2001-335776, JP-A-2001-247859, JP-A-2001-181616, JP-A-2001-181617, JP-A-2002-181816, JP-A-2002-181617, JP-A-2002-056776, etc. The contents described in each publication can be applied. Moreover, it is preferable to use together with the content of each gazette of Unexamined-Japanese-Patent No. 2001-148291, Unexamined-Japanese-Patent No. 2001-221916, and Unexamined-Japanese-Patent No. 2001-231443.

In order to describe the present invention in detail, examples will be described below, but the present invention is not limited thereto. Unless otherwise specified, “part” and “%” are based on mass.
Hereinafter, Examples 1, 2, 4, 5, 6, and 7 shall be read as Reference Examples 1, 2, 4, 5, 6, and 7, respectively.

Example of production of optical film (Example 1)
Hard coat layer coating solutions (HCL-1) to (HCL-7) and overcoat layer coating solutions (OCL-1) to (OCL-12) shown in the following table were prepared.

The constituents in the table are expressed as mass percentages of solids. Details of the compounds used are shown below.
MANDA:
(Bifunctional acrylate, KAYARAD MANDA, Nippon Kayaku Co., Ltd., molecular weight 312)
PETA:
(A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, Nippon Kayaku Co., Ltd., average molecular weight of about 300)
DPHA:
(Dipentaerythritol hexaacrylate, mixture of dipentaerythritol pentaacrylate, Nippon Kayaku Co., Ltd., average molecular weight 540)
M-215:
(Isocyanuric acid EO-modified diacrylate, manufactured by Toa Gosei Co., Ltd., molecular weight 369)
Urethane hexaacrylate:
(Hexafunctional acrylate having two urethane bonds in the molecule, compound PETA-IPDI-PETA of JP 2005-272702, molecular weight 488)
RHB-10:
(Dendrimer type 12-functional acrylate, Exemplified compound RHB-10 of JP-A-2006-10829, molecular weight 3324)
RHB-17:
(Dendrimer type 14-functional acrylate, compound of Synthesis Example 1 below, molecular weight 2280)
IRG184:
(Photopolymerization initiator, Irgacure 184, manufactured by Ciba Geigy Japan Ltd.)
IRG369:
(Photopolymerization initiator, Irgacure 369, manufactured by Nippon Ciba Geigy Co., Ltd.)
MIBK-ST:
(Colloidal silica, average particle size of about 12 nm, solid content of 30%, manufactured by Nissan Chemical Co., Ltd.)
IPA-ST-L:
(Colloidal silica, average particle size of about 50 nm, solid content of 30%, manufactured by Nissan Chemical Co., Ltd.)
IPA-ST-ZL:
(Colloidal silica, average particle size of about 90 nm, solid content of 30%, manufactured by Nissan Chemical Co., Ltd.)
Low refractive index silica:
(Silica with a diameter of about 60 nm, voids inside, refractive index 1.25, 3% trimethylmethoxysilane and 7% acryloyloxypropyltrimethoxysilane as a surface treatment agent, solid content concentration 33%, MIBK dispersion, (Made by changing the size according to Example 4 of JP-A-2002-79616)
MEK: (Methyl ethyl ketone)
MIBK: (Methyl isobutyl ketone)
IPA: (Isopropyl alcohol)

(Synthesis of RHB-17)
In accordance with the description in Japanese Patent No. 2574201, a reactor equipped with a reflux cooler, a stirrer, a thermometer, a temperature control device, and a water separator is used as a multi-branched polymer (HB-1) as a BOLTORN manufactured by Pelstor Poor Bae H20 (OH value: 510 mg KOH / g), 59.6 g of acrylic acid, 39.6 g (0.55 mol) of acrylic acid, 63.4 g of toluene as a reaction solvent, 0.143 g of hydroquinone as a polymerization inhibitor, 0 methanesulfonic acid as an acid catalyst .953 g was charged, and the reaction was performed while removing the produced water azeotropically with the solvent at a reaction temperature of 100 to 115 ° C., and the reaction was terminated when the produced water reached 7.8 ml. The reaction mixture was dissolved in 40 g of toluene, neutralized with 25% aqueous sodium hydroxide solution, and then washed 3 times with 20 g of 15% brine. The solvent was distilled off under reduced pressure to obtain a curable multi-branched polymer (RHB-17). The OH value of the curable multibranched polymer (RHB-17) was 68 mgKOH / g, and the conversion rate from the reactive hydroxyl group to the curable reactive group was 87 mol%.

(Preparation of optical film (101))
On the triacetyl cellulose film “TAC-TD80U” {manufactured by FUJIFILM Corporation) with a film thickness of 80 μm and a width of 1340 mm, the hard coat layer coating material (HCL-1) is applied by a microgravure coating method at a conveyance speed of 30 m / After applying for 150 minutes and drying at 60 ° C. for 150 seconds, using a 160 W / cm air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen (oxygen concentration 0.05% or less), The coating layer was cured by irradiating ultraviolet rays having an irradiance of 400 mW / cm ² and an irradiation energy amount of 20 mJ / cm ² to prepare a hard coat layer having a thickness of 5.0 μm.

On the obtained hard coat layer, the coating speed for the overcoat layer (OCL-1) is adjusted by a die coater coating method so that the film thickness after curing is 3.0 μm, while the conveyance speed is 30 m / After applying for 150 minutes and drying at 60 ° C. for 150 seconds, using a 160 W / cm air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen (oxygen concentration 0.05% or less), Sample 101 was obtained by irradiating ultraviolet rays with an irradiance of 400 mW / cm ² and an irradiation energy amount of 240 mJ / cm ² to cure the coating layer.

  Samples 102 to 117 were prepared by changing the composition of the hard coat layer and the overcoat layer as shown in the following table with respect to the obtained sample 101.

(Evaluation of optical film)
About the obtained film, the following items were evaluated.
(Evaluation 1) Curling degree The optical film sample was cut into a size of 20 cm × 20 cm, and placed on a horizontal desk in an environment of 25 ° C. and 60% RH with the surfaces where the four corners were raised facing upward. After 24 hours, the lifting distance from the desk surface at each of the four corners was measured with a ruler, and the average of the four corners was taken. The average values were classified and evaluated according to the following criteria.
◎: Less than 5 mm ○: Less than 5-10 mm ○ △: Less than 10-20 mm △: Less than 20-40 mm ×: 40 mm or more

(Evaluation 2) Steel wool scratch resistance evaluation (SW)
A rubbing test was conducted using a rubbing tester under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH
Rub material: Steel wool (No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) was wound around the rubbing tip (1 cm × 1 cm) of a tester in contact with the sample, and the band was fixed so as not to move. Then, the reciprocating rubbing motion under the following conditions was given.
Moving distance (one way): 13 cm, rubbing speed: 13 cm / second,
Load: 500 g / cm ³ , tip contact area: 1 cm × 1 cm,
Number of rubs: 10 round trips.
An oil-based black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
○: Even when viewed very carefully, no scratches are visible.
○ △: Slightly weak scratches are visible when viewed very carefully.
Δ: A weak scratch is visible.
Δ ×: moderate scratches are visible.
X: There are scratches that can be seen at first glance.
◎: Even if an additional rubbing test is performed on the above-obtained conditions for those obtained with ○ evaluation
I can't see any scratches.

(Evaluation 3) Pencil Hardness Evaluation Pencil hardness evaluation described in JIS K 5400 was performed as an index of scratch resistance. The antireflection film was conditioned at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours, and then evaluated using a test pencil specified in JIS S 6006 with a load of 1 kg.
The evaluation results are shown in the following table.
The present invention in the remarks column in Table 4 below shall be read as a reference example.

  According to the above table, it can be seen that the optical film containing the compound in which the overcoat layer contains three or more polymerizable functional groups in one molecule according to the present invention is excellent in curl, scratch resistance and hardness. In particular, it can be seen that the scratch resistance is significantly improved when a curable multi-branched polymer (RHB) or inorganic particles are used.

(Example 2)
Overcoat layer coating solutions (OCL-13) to (OCL-24) shown in Table 5 were prepared.

The constituents in the above table are expressed as mass percentages of solids. Details of the compounds used are shown below.
FM-0421:
(Hydroxyl-modified dimethylsiloxane, average molecular weight of about 5000, manufactured by Chisso Corporation)
X22-164C:
(Both-end methacryl-modified dimethylsiloxane, average molecular weight of about 5000, manufactured by Shin-Etsu Chemical Co., Ltd.)
RMS-033:
(Acrylic modified dimethylsiloxane, average molecular weight of about 25000, manufactured by Gelest)
Exemplary compound (a-10):
(Fluorine-containing telomer acrylate, exemplified compound in the text)
FAA:
(Fluorine-containing compound of general formula (T-2) in the main text, 1-acryloyloxy-2-hydroxy-4,4,5,5,6,6,7,7,8,8,9,9,10, 10, 11, 11, 12, 12, 13, 13, 13-heneicosafluorotridecane)
FC-1:
(Acrylate with perfluoropolyether group in the text)
FC-3:
(Acrylate with perfluoropolyether group in the text)
Conductive particles:
(Antimony oxide-coated silica fine particles prepared according to Example 1 of JP-A-2005-119909, 20% isopropyl alcohol dispersion, average particle size 60 nm, refractive index 1.41, volume resistance 1500 Ω · cm, per inorganic particle solid content 4% methacrylic silane coupling agent (Shin-Etsu Chemical Co., Ltd .: KBM-503) surface treatment)

  The following optical films were produced using the obtained coating liquid for hard coat layer and overcoat layer.

(Preparation of optical film (201))
On the triacetyl cellulose film “TAC-TD80U” {manufactured by FUJIFILM Corporation) with a film thickness of 80 μm and a width of 1340 mm, a hard coat layer coating (HCL-5) is transported by a micro gravure coating method at a conveyance speed of 30 m / min. After applying for 150 seconds and drying at 60 ° C. for 150 seconds, using a 160 W / cm air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen (oxygen concentration 0.05% or less), radiation The coating layer was cured by irradiating ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation energy amount of 20 mJ / cm ² to prepare a hard coat layer having a thickness of 4.6 μm.

On the obtained hard coat layer, the coating speed for the overcoat layer (OCL-4) is adjusted by a die coater coating method so that the film thickness after curing is 0.4 μm, while the conveyance speed is 30 m / After applying for 150 minutes and drying at 60 ° C. for 150 seconds, using a 160 W / cm air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen (oxygen concentration 0.05% or less), Sample 201 was obtained by irradiating ultraviolet rays with an irradiance of 400 mW / cm ² and an irradiation energy amount of 240 mJ / cm ² to cure the coating layer.

  Samples 202 to 213 in which the compositions of the hard coat layer and the overcoat layer were changed as shown in the following table were prepared for the obtained sample 201.

(Evaluation of optical film)
About the obtained film, in addition to the evaluation of Example 1, the following items were evaluated.
(Evaluation 4) Antifouling Durability An optical film is fixed on a glass surface with an adhesive, and a black magic “Mackey Extra Fine (trade name: made by ZEBRA)” nib (fine) under the condition of 25 ° C. and 60 RH%. A circle of 5 mm in diameter is written three times and wiped back and forth 20 times with a load that causes the bundle of Bencot to be dented with Bencot (trade name, Asahi Kasei Co., Ltd.) folded in 10 sheets after 5 seconds. The writing and wiping were repeated under the above conditions until the magic traces were not erased by wiping, and the antifouling property was evaluated by the number of times that the wiping was completed. The number of times until disappearance is preferably 10 times or more, and more preferably 30 times or more.
(Evaluation 5) Surface Free Energy Under the condition of 25 ° C. and 60 RH%, the contact angle was measured with pure water and methylene iodide, and the surface free energy was calculated by the method described in the text.
The evaluation results are shown in the following table.
The present invention in the remarks column in Table 7 below should be read as a reference example.

  According to the above table, according to the present invention, the overcoat layer contains a compound containing three or more polymerizable functional groups in one molecule, and further contains an antifouling agent. The optical film contains curl, scratch resistance, hardness It can be seen that it is excellent in terms of antifouling properties. In particular, it can be seen that the antifouling property, scratch resistance and pencil hardness are improved when the antifouling agent has a group polymerizable with the overcoat constituent binder. Moreover, it turns out that antifouling durability is improved when curable multi-branched polymer (RHB) is used together. Moreover, as a result of evaluating the following dust removability with respect to the sample 213 containing conductive particles in the overcoat layer, the dust could be removed within 3 times, and the dust removability was excellent.

(Evaluation 6) Dust removability The film of the present invention was attached to a monitor, dust (futon, clothes fiber waste) was sprinkled on the monitor surface, the dust was wiped off with a cleaning cloth, and the dust removability was evaluated. It is preferable to remove completely by wiping 6 times, and it is more preferable to remove dust completely by wiping within 3 times.

(Example 3)
Overcoat layer coating solutions (OCL-25) to (OCL-32) shown in the following table were prepared.

The constituents in the above table are expressed as mass percentages of solids. Details of the compounds used are shown below.
Organosilane:
(6-9-mer hydrolysis condensate of 3-acryloyloxypropyltrimethoxysilane (KBM-5103, Shin-Etsu Chemical Co., Ltd.))
IRG651:
(Photopolymerization initiator, Irgacure 651, manufactured by Ciba Geigy Japan Ltd.)
F-containing polymerizable polymer:
(Fluorine-containing silicone-containing methacryloyloxy group-containing polymer, synthesized according to compound A-3 of Example 3 of JP-A-2003-183322, molecular weight of about 32000)

  The following optical films (301 to 308) were produced using the obtained coating liquid for hard coat layer and overcoat layer.

(Preparation of optical film (301A))
A hard coat layer coating (HCL-5) is coated on a triacetyl cellulose film “TAC-TD80U” (manufactured by Fuji Film Co., Ltd.) having a thickness of 80 μm and a width of 1340 mm with a die coater under a condition of a conveyance speed of 30 m / min. After applying and drying at 60 ° C. for 150 seconds, using a 160 W / cm air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen (oxygen concentration 0.05% or less), an irradiance of 400 mW / The coating layer was cured by irradiating ultraviolet rays having a cm ² and an irradiation energy amount of 80 mJ / cm ² to prepare a hard coat layer having a thickness of 5.5 μm. The polymerization rate of the hard coat layer was measured by the method described in the text, and it was 75%.

On the obtained hard coat layer, the above coating liquid for overcoat layer (OCL-25) is adjusted by a die coater coating method so that the film thickness after curing is 0.5 μm, while the conveyance speed is 30 m. After applying at 60 ° C. for 150 seconds, using a 160 W / cm air-cooled metal halide lamp {made by Eye Graphics Co., Ltd.] while purging with nitrogen (oxygen concentration 0.05% or less). The coating layer was cured by irradiating with ultraviolet rays having an irradiance of 400 mW / cm ² and an irradiation energy amount of 240 mJ / cm ² to obtain a sample 301A. The coating / curing manufacturing conditions for this sample are referred to as manufacturing process A.

(Preparation of optical film (301B))
In the production of the hard coat layer of the optical film (301A), the hard coat layer was hardened in the same manner as the production of the hard coat layer of the optical film (301A), except that the irradiation energy amount during photopolymerization of the hard coat layer was changed to 20 mJ / cm ^2. A coat layer was prepared. The polymerization rate of the hard coat layer was measured by the method described in the text, and found to be 45%.

  On the obtained hard coat layer, the overcoat layer coating solution (OCL-25) was applied and cured in the same manner as the optical film (301A). The optical film thus obtained is designated as Sample 301B. The coating / curing manufacturing conditions for this sample are referred to as manufacturing process B.

(Preparation of optical film (301C))
In the production of the hard coat layer of the optical film (301A), only the drying was performed without irradiating the hard coat layer with light. On the obtained hard coat layer, the overcoat layer coating solution (OCL-25) was applied and cured in the same manner as the optical film (301A). The optical film thus obtained is designated as Sample 301C. The coating / curing manufacturing conditions for this sample are referred to as manufacturing process C.

(Preparation of optical film (301D))
A triacetyl cellulose film “TAC-TD80U” {manufactured by FUJIFILM Corporation} having a film thickness of 80 μm and a width of 1340 mm is unrolled in a roll form, and is applied to a hard coat layer coating solution (HCL-5) using a simultaneous multilayer coating machine. ) And an overcoat layer coating solution (OCL-25) are coated at the same time, coated at a conveyance speed of 30 m / min, dried at 60 ° C. for 150 seconds, and then air-cooled at 160 W / cm under a nitrogen purge. Using a metal halide lamp (manufactured by Eye Graphics Co., Ltd.), ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 240 mJ / cm ² were irradiated to cure the coating layer, and a functional layer was formed and wound. The sample thus obtained is designated as 301D. The coating / curing manufacturing condition of this sample is referred to as manufacturing process D.

  With respect to the obtained samples 301A to 301D, the compositions of the hard coat layer and the overcoat layer were changed as shown in the following table, and the samples were manufactured under the corresponding manufacturing process conditions B to D to prepare samples 302B to 308D.

(Evaluation of optical film)
In addition to the evaluation performed in Example 2, the following evaluation was performed on the obtained film.
(Evaluation 7) Observation of interface between hard coat layer and overcoat layer In the above table, the layer interface represents the state of mixing at the interface. As for the layer interface, each optical film was taken as a section having a thickness of 50 nm, and the cross section was photographed 150,000 times using a transmission electron microscope, and the mixing state of the interface was observed.

  According to the above table, it can be seen that the sample of the present invention is excellent in curl, scratch resistance, hardness and antifouling properties. In particular, a sample in which the polymerization rate of the hard coat layer was lowered and an overcoat layer was coated thereon had a tendency to improve curl. Moreover, the sample produced by the manufacturing method C and the manufacturing method D had a layer interface having a gradient, the composition was changed, or a mixed layer was formed, and curling was reduced. In production methods C and D, since the overcoat layer was applied while the polymerizable compound of the hard coat layer was uncured, the components of the overcoat layer partially diffused into the uncured hard coat layer, It is presumed that a particle density gradient or a mixed layer was formed.

  Samples 305C, 305D, 306C, 306D, 307C, 307D, 308C, and 308D have no interference unevenness and reflectivity in the range of 3.0 to 3.3%, which is 4.3% of sample 301A. The 1% strong reflectance was lowered and the antireflection performance was excellent. In addition, the fingerprints of these samples were not particularly noticeable, and the fingerprints were excellent in wiping. This is because the overcoat layer of these samples has an antifouling agent, and in addition to being easy to repel the fingerprint oil, the refractive index of the fingerprint oil is low (1.45-1). This is because the fingerprint trace is not conspicuous. Furthermore, the antifouling agent facilitates fingerprint removal. Samples 307B to 308D containing conductive particles were also excellent in dust removability. (The reflectance was measured as follows. After the back surface of the optical film was roughened, it was light-absorbed with black ink (transmittance at 380 to 780 nm was less than 10%). Spectral reflectance at an incident angle of 5 ° was measured in a wavelength range of 380 to 780 nm using a meter {manufactured by JASCO Corp.} (average reflectance of 450 to 650 nm was used for the result).

Example 4
Hard coat layer coating solutions (HCL-8) to (HCL-10) shown in Table 11 were prepared.

The compounds used are shown below.
Cross-linked styrene particles:
(SX-350, average particle size 3.5 μm crosslinked polystyrene particles {refractive index 1.60, manufactured by Soken Chemicals Co., Ltd.})
Cross-linked acrylic-styrene particles:
(Average particle size 3.5 μm {refractive index 1.55, manufactured by Soken Chemical Co., Ltd.})
Cross-linked acrylic particles:
(MX-300, average particle size 3.0 μm crosslinked acrylic particles {refractive index 1.49, manufactured by Soken Chemicals Co., Ltd.})
Silica particles:
(Cycilia 430, silica particles having an average particle diameter of 2.5 μm, manufactured by Fuji Silysia Ltd.)
PMMA:
(Polymethyl methacrylate, molecular weight 80000)

(Preparation of optical film (401))
A hard coat layer coating (HCL-8) is coated on a triacetyl cellulose film “TAC-TD80U” (manufactured by Fujifilm Corporation) with a thickness of 80 μm and a width of 1340 mm on a die coater at a conveying speed of 30 m / min. After applying and drying at 60 ° C. for 150 seconds, using a 160 W / cm air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen (oxygen concentration 0.05% or less), an irradiance of 400 mW / The coating layer was cured by irradiating ultraviolet rays having a cm ² and an irradiation energy amount of 20 mJ / cm ² to prepare a hard coat layer having a thickness of 7.2 μm.

On the obtained hard coat layer, the coating for overcoat layer (OCL-5) used in Example 1 was adjusted by a die coater coating method so that the film thickness after curing was 0.4 μm. However, it was applied at a transfer speed of 30 m / min, dried at 60 ° C. for 150 seconds, and then purged with nitrogen (oxygen concentration 0.05% or less), and then an air-cooled metal halide lamp of 160 W / cm {eye graphics Co., Ltd. The coating layer was cured by irradiating with ultraviolet rays having an irradiance of 400 mW / cm ² and an irradiation energy amount of 240 mJ / cm ² .

Samples 402 to 436 were prepared by changing the composition of the hard coat layer and the overcoat layer as shown in Table 12 with respect to the obtained sample 401.
The present invention in the remarks column in Table 12 below should be read as a reference example.

(Evaluation of optical film)
The obtained film was evaluated according to Example 2. As a result, it was found that according to the present invention, a sample having excellent curling and scratch resistance can be obtained. Moreover, it turned out that the sample which contains antifouling agent in the coating liquid for overcoat layers is excellent in antifouling property, especially durability. In particular, an optical film having an antiglare property with black spots in a sample using the coating liquid for overcoat layer (OCL-15), (OCL-18), (OCL-20) and (OCL-21). was gotten.
In addition, the samples using the overcoat layer coating liquids (OCL-30) and (OCL-31) have antiglare properties, so that the fingerprint marks are particularly less noticeable than the sample of Example 3. Also, the fingerprint wiping property was excellent.

(Example 5)
In the production process B of Example 3, when the hard coat layer was polymerized, when light was irradiated through a sharp cut filter of 390 nm or less, the photopolymerization initiator IRG369 having long wave absorption mainly reacted, and the hard coat layer was reacted. It was easy to control the polymerization rate of the layer to a specific value of 50% or less.

(Example 6)
The following coating liquids for overcoat layer (OCL-33) to (OCL-34) and coating liquids for low refractive index layer (LnL-1) to (LnL-4) were prepared.

(Preparation of overcoat layer coating solution (OCL-33))
DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 38.0 g, PETA (mixture of pentaerythritol triacrylate, pentaerythritol tetraacrylate, manufactured by Nippon Kayaku Co., Ltd.) ) 10.0 g, 2.0 g of a photopolymerization initiator (Irgacure 369 (trade name), manufactured by Ciba Specialty Chemicals, Inc., molecular weight 367) was dissolved in 110 g of methyl isobutyl ketone and 7.0 g of cyclohexanone. Thereafter, 250.0 g of ZrO2 dispersion (average particle size 5 to 20 nm, methyl isobutyl ketone dispersion 20%, manufactured by Sumitomo Osaka Cement Co., Ltd.) was added and stirred to prepare an overcoat layer coating solution (OCL-33). . The MOC of this overcoat layer coating solution was 492, and the refractive index of the cured product was 1.62.

(Preparation of overcoat layer coating solution (OCL-34))
DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 18.0 g, PETA (mixture of pentaerythritol triacrylate, pentaerythritol tetraacrylate, manufactured by Nippon Kayaku Co., Ltd.) ) 10.0 g, RHB-17 (dendrimer type 14 functional acrylate, compound of Example 1) 20.0 g, photopolymerization initiator (Irgacure 369 (trade name), manufactured by Ciba Specialty Chemicals, Inc., molecular weight 367) 2.0 g was dissolved in 110 g of methyl isobutyl ketone and 7.0 g of cyclohexanone. Thereafter, 250.0 g of ZrO ₂ dispersion (average particle size 5 to 20 nm, methyl isobutyl ketone dispersion 20%, manufactured by Sumitomo Osaka Cement Co., Ltd.) was added and stirred to prepare an overcoat layer coating solution (OCL-34). did. The MOC of this overcoat layer coating solution was 1215, and the refractive index of the cured product was 1.62.

(Preparation of coating solution for low refractive index layer (LnL-1))
Heat-crosslinkable fluorine-containing polymer (fluorine-containing silicone thermosetting polymer described in Example 1 of JP-A-11-189621) 4.52 g, curing agent (Cymel 303; trade name, manufactured by Nippon Cytec Industries Co., Ltd.) 13 g, curing catalyst (Catalyst 4050; trade name, manufactured by Nippon Cytec Industries Co., Ltd.) 0.11 g, colloidal silica dispersion (MEK-ST-L; trade name, Nissan Chemical Co., Ltd., solid content concentration 30%, 1.5 g of an average particle size of about 50 nm, 15.0 g of silica dispersion B (cyclohexanone dispersion of hollow silica, 15% polymerizable functional group-containing surface treatment agent relative to silica, 23% solid content), sol solution a2.5 g, photopolymerization initiator (PM980M, molecular weight 527, manufactured by Wako Pure Chemical Industries) 0.60 g, and methyl ethyl ketone 114 g Pressurizing, after stirring, the mixture was filtered through a polypropylene filter having a pore size of 1 [mu] m, to prepare a coating solution for low refractive index layer (LnL-1).

(Preparation of coating solution for low refractive index layer (LnL-2))
2.65 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), silica dispersion B (hollow silica dispersion, surface treatment agent containing a polymerizable functional group with respect to silica) 15% used, solid content concentration 23%) 30.0 g, sol liquid 2.93 g, reactive silicone X-22-164C (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.) 0.15 g, fluorine-containing compound F3035 (trade name; Nippon Oil & Fat Co., Ltd., solid content concentration 30%) 0.15 g, photopolymerization initiator (Irgacure 369 (trade name), Ciba Specialty Chemicals Co., Ltd., molecular weight 367) 0.20 g and methyl ethyl ketone 103 g, cyclohexanone 3 .5g was added, stirred, and filtered through a polypropylene filter with a pore size of 1μm. Rate layer coating solution (LnL-2) was prepared.

(Preparation of coating solution for low refractive index layer (LnL-3))
Radical polymerizable fluorine-containing polymer (fluorinated silicone-containing radical polymerizable polymer P9 described in JP-A-2003-222702) 5.22 g, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku) 0.50 g, silica dispersion B (hollow silica dispersion, solid content concentration 23%) 15.0 g, sol liquid a 4.4 g, reactive silicone RMS-033 (trade name; manufactured by Gelest) 0 .15 g, 0.17 g of photopolymerization initiator Irgacure 369 (manufactured by Ciba Specialty Chemicals Co., Ltd., molecular weight 367), 114 g of methyl ethyl ketone, and 3.5 g of cyclohexanone were added, stirred, and then filtered through a polypropylene filter having a pore size of 1 μm. The coating liquid for the low refractive index layer (LnL 3) was prepared.

(Preparation of coating solution for low refractive index layer (LnL-4))
Colcoat N103 (organoorganosiloxane oligomer (average molecular weight 950, manufactured by Colcoat Co.) (245%), Opstar JTA105 (fluorinated organosiloxane oligomer (5%), polyethylene glycol, hexamethylolmelamine, containing acid generator, 100 parts by mass of JSR), 1 part by mass of OPSTA-JTA105A (curing agent (5%), made by JSR), 23 parts by mass of hollow silica dispersion A (30%), 365 parts by mass of butyl acetate, and low A coating solution for refractive index layer (LnL-4) was prepared.

The dispersion used is shown below.
Hollow silica dispersion A: (hollow silica fine particle sol, average particle diameter 65 nm, shell thickness 8 nm, silica particle refractive index 1.28, prepared by changing the size according to Preparation Example 4 of JP-A-2002-79616, IPA dispersion Liquid, solid content 30%),
Hollow silica dispersion B: The silica in the hollow silica dispersion A is surface-modified with 15 parts by mass of 3-acryloyloxypropyltrimethoxysilane as a surface treatment agent, and after modification, the solvent is substituted with cyclohexanone to obtain a solid content concentration of 23. %. )

(Sol solution a)
A stirrer, a reactor equipped with a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed. After that, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain a sol solution. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all. Sol solution a was adjusted with methyl ethyl ketone so that the solid content was 29%.

Subsequently, in the configuration shown in Table 13, a hard coat layer, an overcoat layer, and a low refractive index layer were applied. The hard coat layer was cured under an ultraviolet irradiation energy amount of 20 mJ / cm ² , the overcoat layer was cured under an ultraviolet irradiation energy amount of 20 mJ / cm ² , and the low refractive index layer was cured under the following conditions.

(Curing conditions for optical film using LnL-1 and LnL-4)
After drying at 90 ° C. for 150 seconds, thermosetting was performed at 110 ° C. for 10 minutes. Thereafter, using a 160 W / cm air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen (oxygen concentration 0.05% or less), the irradiance is 400 mW / cm ² and the irradiation energy amount is 240 mJ / cm ^2. The ultraviolet ray was irradiated to cure the coating layer.

(Curing conditions for optical films using LnL-2 and LnL-3)
After drying at 90 ° C. for 150 seconds, using a 160 W / cm air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen (oxygen concentration 0.05% or less), an irradiance of 400 mW / cm ² , The coating layer was cured by irradiating with an ultraviolet ray having an irradiation energy amount of 240 mJ / cm ² .
The present invention in the remarks column in Table 13 below shall be read as a reference example.

  As a result of evaluating the obtained sample according to Example 2, it was confirmed that the sample of the present invention was low curl and excellent in scratch resistance, and the sample coated with a low refractive index layer was a reflectance. Was confirmed to be low.

(Example 7)
In Example 1, a sample in which the thickness of the support was changed to 40 μm was prepared. The results of the same evaluation as in Example 1 are shown in the following table.
The present invention in the remarks column in Table 14 below shall be read as a reference example.

According to the above table, it was confirmed that by combining the hard coat layer and the overcoat layer of the present invention, an optical film with less curling and excellent scratch resistance and antifouling properties can be obtained. Although the degree of curling tends to deteriorate by lowering the film thickness of the support relative to Example 1, when the overcoat layer using the dendrimer or inorganic particles of the present invention is used, the curling deteriorates. You can see that it is suppressed.
Moreover, it was the same result as a result of having evaluated the combination of the layer structure of Example 1 using Toyobo Co., Ltd. Cosmo Shine A4100 and A4300 which are commercially available PET films with an easily bonding layer for optics.

(Example 8)
[Saponification of optical film]
The back surface of the samples of Examples 1 to 7 was saponified under the conditions shown below.
Alkaline bath: 1.5 mol / dm ³ sodium hydroxide aqueous solution, 55 ° C.-120 seconds.
First washing bath: tap water, 60 seconds.
Neutralization bath: 0.05 mol / dm ³ sulfuric acid, 30 ° C. for 20 seconds.
Second washing bath: tap water, 60 seconds.
Drying: 120 ° C, 60 seconds

[Production of polarizing plate with optical film]
A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. A saponified antireflection film of Example 1 was attached to one side of the polarizing film using a polyvinyl alcohol adhesive so that the support (triacetylcellulose) side of the antireflection film was the polarizing film side. . A viewing angle widening film “Wide View Film SA12B” (manufactured by Fuji Film Co., Ltd.) having an optical compensation layer was saponified and attached to the other side of the polarizing film using a polyvinyl alcohol-based adhesive. In this way, a polarizing plate was produced.
As a result of evaluating the TN mode transmissive liquid crystal display device equipped with the produced polarizing plate of the present invention, it was confirmed that a display device excellent in visibility, dust resistance and scratch resistance could be produced.

Example 9
When the optical film of Example 3 (samples 305C, 305D, 306C, 306D, 307C, 307D, 308C, and 308D) was bonded to the glass plate on the surface of the organic EL display device via an adhesive, Reflection was suppressed, and a display device with high visibility was obtained.

(Example 10)
In the optical film of Example 3 (samples 305C, 305D, 306C, 306D, 307C, 307D, 308C, and 308D), PET with an easily adhesive layer (Cosmo Shine A4100 manufactured by Toyobo Co., Ltd., film thickness 188 μm) was used as the transparent support. Produced an optical film in the same manner. When the surface film of a 42-inch plasma display (pioneer direct color filter type PDU-42H6A1) without a front plate is peeled off and the optical film of the present invention is attached with an adhesive, it has excellent low reflection, scratch resistance and antifouling properties. Was confirmed.

(Example 11)
When the optical film of Example 3 (samples 305C, 305D, 306C, 306D, 307C, 307D, 308C, and 308D) was attached to the surface of the organic EL display with an adhesive so that the low refractive index layer was on the outside, the low It was confirmed to be excellent in reflection, scratch resistance and antifouling properties.

(Example 12)
When the optical film of Example 3 was used as a protective film on the surface of the reflective liquid crystal display and the transflective liquid crystal display so that the low refractive index layer was on the outside, it was excellent in low reflection, scratch resistance and antifouling properties. Was confirmed.

This is an example of a compound that can be used in the present invention and includes a portion having branches extending from a central portion in a three-dimensional radial shape and further having a branch from its end. This is an example of a dendritic compound that can be used in the present invention, in which branch portions are radially expanded even if they do not grow uniformly in all directions.

Claims (15)

A coating composition for a hard coat layer containing a compound having a plurality of polymerizable functional groups in one molecule and a coating composition for an overcoat layer containing a compound having at least three polymerizable functional groups on a support. A method for producing an optical film to be applied simultaneously,
Wherein the optical film is, on the supporting lifting member, and the hard coat layer obtained by curing the hard Dokoto layer coating composition, obtained by curing the O Bakoto layer coating composition, film thickness 0.15μm and an overcoat layer is 10μm inclusive possess in this order,
Weight average molecular weight (MOC) of a compound having a plurality of polymerizable functional groups in one molecule contained in the overcoat layer coating composition and polymerization in one molecule contained in the hardcoat layer coating composition The ratio (MOC / MHC) to the weight average molecular weight (MHC) of the compound having a plurality of functional functional groups is 1.1 or more and 6.0 or less,
At least one of the hard coat layer coating composition and the overcoat layer coating composition contains inorganic fine particles,
The method for producing an optical film, wherein the overcoat layer contains inorganic fine particles mainly composed of silica having an average particle diameter of 1 nm or more and 1 μm or less. The method for producing an optical film according to claim 1, wherein the MOC is 300 to 3600, and the MHC is 300 to 600. The manufacturing method of the optical film of Claim 1 or 2 whose film thickness of the said hard-coat layer is 1.5-30 micrometers. The compound having a plurality of polymerizable functional groups in one molecule, the manufacturing method of the optical film arm according to claim 1 is a monomer having a hydrogen bonding group. The compound having a plurality of polymerizable functional groups in one molecule, the manufacturing method of the optical film arm according to any one of claims 1-4 is isocyanuric acid ethoxy-modified diacrylate. The compound having a plurality of polymerizable functional groups in one molecule is a curable multi-branch having a multi-branched polymer (HB) as a nucleus and a photo-curing and / or thermo-setting reactive group bonded to the end of the branch. the method for manufacturing an optical fill beam according to any one of claims 1-5 is a polymer (RHB). The inorganic fine particles contained in the overcoat layer coating composition, a manufacturing method of the optical film arm according to any one of claims 1 to 6, having a surface and / or inside the pores of the particles. Wherein the inorganic fine particles, method for producing optical film arm according to any one of claims 1 to 7 is electrically conductive particles. The said coating composition for hard-coat layers or the coating composition for overcoat layers contains an organosilane compound and / or its hydrolyzate, and / or its condensate of any one of Claims 1-8 . the method for manufacturing an optical fill-time. The overcoat layer coating composition, a manufacturing method of the optical film arm according to any one of claims 1-9 containing at least one reactive silicone and reactive fluorine compound. The method for manufacturing an optical fill beam according to any one of claims 1 to 10, the hard coat layer contains a light-diffusing particles. The thickness of the support, a manufacturing method of the optical film arm according to any one of claims 1 to 11 at 15μm or 60μm or less.   The optical film manufactured with the manufacturing method of any one of Claims 1-12. A polarizing plate comprising a polarizing film and protective films provided on both sides of the polarizing film, wherein at least one of the protective films is the optical film according to claim 13 . An image display device comprising the optical film according to claim 13 or the polarizing plate according to claim 14 .

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