Composition for forming hard coat layer, film, laminate, polarizing plate, and image display device

Abstract

Provided is a composition for forming a hard coat layer, capable of forming a hard coat layer having excellent smoothness.　The composition for forming a hard coat layer contains an active energy ray-curable compound and a silicone-containing polymer. The silicone-containing polymer is a random copolymer containing, as polymerization components, at least a polymerizable monomer (a1) having a group represented by general formula (a) and having a weight average molecular weight that is within the range from 100 to 4,000, and a polymerizable monomer (a2) having one or more selected from the group consisting of an alkyl group having 1-18 carbon atoms, an aromatic group having 6-18 carbon atoms, a group including a polyoxyalkylene chain, and a group including a polyester chain.

Description

Hard coat layer-forming composition, film, laminate, polarizing plate and image display device

[0001] The present invention relates to a composition for forming a hard coat layer, a film, a laminate, a polarizing plate, and an image display device.

[0002] BACKGROUND ART Image display devices such as liquid crystal display devices and organic EL display devices usually include an optical control film such as a polarizing plate to eliminate problems such as external light reflection and background glare and to improve image visibility.

[0003] Since the visibility of the optical control film such as the polarizing plate is significantly reduced if the outermost surface thereof is scratched, a hard coat layer is provided to impart scratch resistance to the optical control film. The hard coat layer is generally formed by applying and curing a curable resin composition, but there have been problems in that the function of the optical control film is significantly reduced if there are coating irregularities and repelling, or if the leveling property of the cured film surface is insufficient and the film thickness is uneven.

[0004] In order to solve the above problems, a fluorine-based additive is generally added to a curable resin composition that forms a hard coat layer (for example, Patent Document 1), and the fluorine-based additive ensures the leveling properties of the surface of the obtained cured film.

[0005] JP 2012-73377 A

[0006] The fluorine-based additives that ensure the smoothness of the hard coat layer are PFAS (perfluoroalkyl compounds and polyfluoroalkyl compounds), and in recent years, PFAS has become a substance that has been of great concern due to its persistence and toxicity to the human body. Due to changes in social conditions, there is a demand for additives for hard coat layers that do not contain PFAS.

[0007] The problem to be solved by the present invention is to provide a composition for forming a hard coat layer that can form a hard coat layer having excellent smoothness. Another problem to be solved by the present invention is to provide a laminate and a polarizing plate that include a hard coat layer having excellent smoothness.

[0008] As a result of extensive research to solve the above problems, the present inventors discovered that smoothness can be imparted to a hard coat layer by using a random copolymer of specific silicone monomers, and thus completed the present invention.

[0009] That is, the present invention relates to a composition for forming a hard coat layer, etc. 1. A composition for forming a hard coat layer containing an active energy ray-curable compound and a silicone-containing polymer, wherein the silicone-containing polymer is a random copolymer having as polymerization components at least a polymerizable monomer (a1) having a group represented by the following general formula (a) and a weight average molecular weight in the range of 100 to 4,000, and a polymerizable monomer (a2) having one or more selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, a group containing a polyoxyalkylene chain, and a group containing a polyester chain: (In the general formula (a), R １１ are each independently an alkyl group having 1 to 6 carbon atoms or —OSi(R １４ ) ３ A group represented by R １４ are each independently an alkyl group having 1 to 3 carbon atoms, １２ are each independently an alkyl group having 1 to 6 carbon atoms; R １３ represents an alkyl group having 1 to 12 carbon atoms, and x represents the number of repetitions.) 2. The composition for forming a hard coat layer according to 1, wherein the polymerizable monomer (a1) is a compound represented by the following general formula (a1-1) and / or a compound represented by the following general formula (a1-2): (In the general formulae (a1-1) and (a1-2), R １１ , R １２ , R １３ and x are each R in the general formula (a). １１ , R １２ , R １３ and x, R １５ is a hydrogen atom or a methyl group, and L １is a divalent organic group.) 3. The composition for forming a hard coat layer according to 1 or 2, wherein the polymerizable monomer (a2) is one or more selected from the group consisting of compounds represented by the following general formula (a2-1), compounds represented by the following general formula (a2-2), compounds represented by the following general formula (a2-3), and compounds represented by the following general formula (a2-4): (In the general formulae (a2-1), (a2-2), (a2-3) and (a2-4), R ２１ is a hydrogen atom or a methyl group, R ２２ is an alkyl group having 1 to 18 carbon atoms; R ２３ is a hydrogen atom or a methyl group, R ２４ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms; R ２５ is a hydrogen atom or a methyl group, R ２６ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms and an ether bond, and R ２７ is a hydrogen atom or a methyl group, R ２８ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms and an ether bond; L ２represents a divalent organic group or a single bond, n is an integer ranging from 1 to 4, m represents the number of repetitions, the number average value of m being in the range of 1 to 200, p is an integer ranging from 1 to 10, q represents the number of repetitions, the number average value of q being in the range of 1 to 100. 4. The hard coat layer forming composition according to 3, wherein the polymerizable monomer (a2) comprises a compound represented by general formula (a2-2). 5. The hard coat layer forming composition according to any one of 1 to 4, wherein the content of the polymerizable monomer (a1) in the polymerization components is in the range of 10 to 60 mass%. 6. The hard coat layer forming composition according to any one of 1 to 5, wherein the silicone-containing polymer does not contain a fluorine atom. 7. The hard coat layer forming composition according to any one of 1 to 6, wherein the silicone-containing polymer is contained in an amount of 0.01 to 5 parts by mass per 100 parts by mass of the active energy ray-curable compound. 8. A film obtained by curing the hard coat layer forming composition according to any one of 1 to 7. A laminate comprising, on a substrate, the film according to 8. 10. A polarizing plate having a polarizer and a hard coat layer, wherein the hard coat layer contains a silicone-containing polymer, and the silicone-containing polymer is a random copolymer having, as polymerization components, at least a polymerizable monomer (a1) having a group represented by the following general formula (a) and a weight average molecular weight in the range of 100 to 4,000, and a polymerizable monomer (a2) having one or more selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, a group containing a polyoxyalkylene chain, and a group containing a polyester chain: (In the general formula (a), R １１ are each independently an alkyl group having 1 to 6 carbon atoms or —OSi(R １４ ) ３ A group represented by R １４ are each independently an alkyl group having 1 to 3 carbon atoms, １２ are each independently an alkyl group having 1 to 6 carbon atoms; R １３ represents an alkyl group having 1 to 6 carbon atoms, and x represents the number of repetitions.) 11. The polarizing plate according to 10, wherein the polymerizable monomer (a1) is a compound represented by the following general formula (a1-1) and / or a compound represented by the following general formula (a1-2): (In the general formulae (a1-1) and (a1-2), R １１ , R １２ , R １３ and x are each R in the general formula (a). １１ , R １２ , R １３ and x, R １５ is a hydrogen atom or a methyl group, and L １ represents a divalent organic group. 12. An image display device comprising the polarizing plate according to 10 or 11.

[0010] According to the present invention, there is provided a composition for forming a hard coat layer capable of forming a hard coat layer having excellent smoothness, and a laminate and a polarizing plate provided with a hard coat layer having excellent smoothness.

[0011] An embodiment of the present invention will be described below. The present invention is not limited to the following embodiment, and can be carried out by making appropriate modifications within the scope that does not impair the effects of the present invention. In this specification, "(meth)acrylate" refers to either or both of acrylate and methacrylate.

[0012] [Hard Coat Layer-Forming Composition] The hard coat layer-forming composition of the present invention is a composition containing an active energy ray-curable compound and a silicone-containing polymer. Hereinafter, each component contained in the hard coat layer-forming composition of the present invention will be described.

[0013] (Silicone-Containing Polymer) The silicone-containing polymer contained in the composition for forming a hard coat layer of the present invention (hereinafter, may be simply referred to as the "silicone-containing polymer of the present invention") is a random copolymer having as at least polymerization components: a polymerizable monomer (a1) having a group represented by the following general formula (a) and having a weight-average molecular weight in the range of 100 to 4,000; and a polymerizable monomer (a2) having one or more selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, a group containing a polyoxyalkylene chain, and a group containing a polyester chain.

[0014] (In the general formula (a), R１１ are each independently an alkyl group having 1 to 6 carbon atoms or —OSi(R １４ ) ３ A group represented by R １４ are each independently an alkyl group having 1 to 3 carbon atoms, １２ are each independently an alkyl group having 1 to 6 carbon atoms; R １３ is an alkyl group having 1 to 12 carbon atoms, and x indicates the number of repetitions.

[0015] The silicone-containing polymer of the present invention can function as a leveling agent, and by forming it into a random copolymer having at least the polymerizable monomer (a1) and the polymerizable monomer (a2) as polymerization components, the silicone moieties do not cause cissing of the coating film, and the occurrence of coating film defects can be prevented.

[0016] In the present invention, the term "polymerizable monomer" refers to a compound having a polymerizable unsaturated group, and examples of the polymerizable unsaturated group possessed by the polymerizable monomer (a1) and the polymerizable monomer (a2) include C=C-containing groups such as (meth)acryloyl, (meth)acryloyloxy, (meth)acryloylamino, vinyl ether, allyl, styryl, and maleimide groups. Among these, (meth)acryloyl and (meth)acryloyloxy groups are preferred because of their easy availability as raw materials and good polymerization reactivity. The number of polymerizable unsaturated groups possessed by the polymerizable monomer may be one or two or more.

[0017] In the present invention, the term "polymerization component" means a component that constitutes a polymer, and does not include solvents, polymerization initiators, and the like that do not constitute a polymer.

[0018] In the general formula (a), R １１ is preferably a methyl group or a trimethylsiloxy group, and R １２ is preferably a methyl group.

[0019] In the general formula (a), R １３ The alkyl group having 1 to 12 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

[0020] In the general formula (a), x represents the number of repetitions, and may be, for example, an integer of 1 or greater. The number average of x is, for example, in the range of 1 to 50, preferably in the range of 2 to 45, more preferably in the range of 3 to 35, even more preferably in the range of 4 to 25, and particularly preferably in the range of 5 to 15. The number average of x can be confirmed by measuring the number average molecular weight of the polymerizable monomer (a1) by the method described in the Examples.

[0021] In the general formula (a), a plurality of R １１ may be the same or different. １２ may be the same or different from each other.

[0022] The polymerizable monomer (a1) is preferably a compound represented by the following general formula (a1-1) and / or a compound represented by the following general formula (a1-2). (In the general formulae (a1-1) and (a1-2), R １１ , R １２ , R １３ and x are each R in the general formula (a). １１ , R １２ , R １３ and x, R １５ is a hydrogen atom or a methyl group, and L １ is a divalent organic group.

[0023] L １ The divalent organic group is preferably a single bond, an alkylene group having 1 to 50 carbon atoms, or an alkyleneoxy group having 1 to 50 carbon atoms.

[0024] L １ Examples of the alkylene group having 1 to 50 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, an n-decylene group, an n-dodecylene group, an isopropylene group, a 2-methylpropylene group, a 2-methylhexylene group, and a tetramethylethylene group.

[0025] L １The alkylene group having 1 to 50 carbon atoms is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group, an ethylene group, an n-propylene group, or an isopropylene group.

[0026] L １ The alkyleneoxy group having 1 to 50 carbon atoms is, for example, one of the alkylene groups -CH ２ - is a group in which - is substituted with -O-. １ The alkyleneoxy group having 1 to 50 carbon atoms is preferably an alkyleneoxy group having 1 to 15 carbon atoms, more preferably an alkyleneoxy group having 1 to 8 carbon atoms, and even more preferably a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, an oxytrimethylene group, a butyleneoxy group, an oxytetramethylene group, a pentyleneoxy group, a heptyleneoxy group, or an octyleneoxy group.

[0027] L １ When the divalent organic group is an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms, these divalent organic groups are -CH ２ A part of the - may be replaced by a carbonyl group (-C(=O)-), a phenylene group, an amide bond or a urethane bond, and furthermore, a hydroxyl group or the like may be substituted on the carbon atom.

[0028] The polymerizable monomer (a1) can be produced by a known method, or a commercially available product may be used. Specific examples of the polymerizable monomer (a1) include α-(3-methacryloyloxy)propylpolydimethylsiloxane, 3-(methacryloyloxy)propyltris(trimethylsiloxy)silane, and 3-acryloyloxypropyltris(trimethylsiloxy)silane.

[0029] The polymerizable monomer (a1) constituting the silicone-containing polymer of the present invention may be one type alone or two or more types.

[0030] The weight-average molecular weight of the polymerizable monomer (a1) constituting the silicone-containing polymer of the present invention is in the range of 100 to 4,000. If the weight-average molecular weight of the polymerizable monomer (a1) exceeds 4,000, the compatibility of the silicone-containing polymer may decrease. Here, the "weight-average molecular weight" is a value measured by the method described in the examples.

[0031] In the silicone-containing polymer of the present invention, the lower limit of the content of polymerizable monomer (a1) in the polymerization components (hereinafter simply referred to as the "content of polymerizable monomer (a1)") is, for example, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 30% by mass or more, or 40% by mass or more. There are no particular restrictions on the upper limit of the content of polymerizable monomer (a1), but it is, for example, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or less than 50% by mass. A preferred combination of the content of polymerizable monomer (a1) in the polymerization components is in the range of 10 to 90% by mass. The content of polymerizable monomer (a1) can be adjusted by the raw material charging ratio of polymerizable monomer (a1) when producing the silicone-containing polymer.

[0032] The polymerizable monomer (a2) is a polymerizable monomer having one or more selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, a group containing a polyoxyalkylene chain, and a group containing a polyester chain.

[0033] The alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (a2) may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, a hexadecyl group, etc. The alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (a2) is preferably an alkyl group having 1 to 6 carbon atoms.

[0034] Examples of the aromatic group having 6 to 18 carbon atoms contained in the polymerizable monomer (a2) include a phenyl group, a naphthyl group, an anthracen-1-yl group, and a phenanthrene-1-yl group.

[0035] The group containing a (poly)oxyalkylene chain contained in the polymerizable monomer (a2) is a monovalent group containing a repeating oxyalkylene moiety or a divalent linking group containing a repeating oxyalkylene moiety.

[0036] The group containing a polyester chain contained in the polymerizable monomer (a2) is a monovalent group containing a repeating ester bond moiety or a divalent linking group containing a repeating ester bond moiety.

[0037] Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloyl group include methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate, s-butyl(meth)acrylate, isobutyl(meth)acrylate, t-butyl(meth)acrylate, n-pentyl(meth)acrylate, n-hexyl(meth)acrylate, n-heptyl(meth)acrylate, n-octyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, decyl(meth)acrylate, and methyl(meth)acrylate. (meth)acrylic acid alkyl esters having 1 to 18 carbon atoms, such as dicyclopentanyloxylethyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate; and (meth)acrylic acid bridged cyclic alkyl esters having 1 to 18 carbon atoms, such as dicyclopentanyloxylethyl (meth)acrylate, isobornyloxylethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyl (meth)acrylate.

[0038] Examples of the polymerizable monomer (a2) having a phenylalkyl group having 7 to 18 carbon atoms or a phenoxyalkyl group having 7 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloyl group include benzyl (meth)acrylate, phenoxymethyl (meth)acrylate, and 2-phenoxyethyl (meth)acrylate.

[0039] Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a vinyl ether group include alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether; and cycloalkyl vinyl ethers.

[0040] Examples of the polymerizable monomer (a2) having an aromatic group having 6 to 18 carbon atoms include styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene.

[0041] Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloylamino group include N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, diacetoneacrylamide, and acroylmorpholine.

[0042] Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a maleimide group include methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide.

[0043] Examples of the polymerizable monomer (a2) having a group containing a polyoxyalkylene chain and in which the polymerizable unsaturated group is a (meth)acryloyl group include polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polytrimethylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, poly(ethylene glycol.propylene glycol) mono(meth)acrylate, polyethylene glycol.polypropylene glycol mono(meth)acrylate, poly(ethylene glycol.tetramethylene glycol) mono(meth)acrylate, polyethylene glycol.polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol.tetramethylene glycol) mono(meth)acrylate, polypropylene glycol.polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol.1,2-butylene glycol) mono(meth)acrylate, polypropylene glycol.poly1,2-butylene glycol mono(meth)acrylate, Poly(ethylene glycol·1,2-butylene glycol) mono(meth)acrylate, polyethylene glycol·poly 1,2-butylene glycol mono(meth)acrylate, poly(tetraethylene glycol·1,2-butylene glycol) mono(meth)acrylate, polytetraethylene glycol·poly 1,2-butylene glycol mono(meth)acrylate, poly 1,2-butylene glycol mono(meth)acrylate, poly(ethylene glycol·trimethylene glycol) mono(meth)acrylate, polyethylene Glycol / polytrimethylene glycol mono(meth)acrylate, poly(propylene glycol / trimethylene glycol) mono(meth)acrylate, polypropylene glycol / polytrimethylene glycol mono(meth)acrylate, poly(trimethylene glycol / tetramethylene glycol) mono(meth)acrylate, polytrimethylene glycol / polytetramethylene glycol mono(meth)acrylate, poly(1,2-butylene glycol / trimethylene glycol) mono(meth)acrylate, poly 1,Examples include 2-butylene glycol-polytrimethylene glycol mono(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, poly(1,2-butylene glycol-tetramethylene glycol) mono(meth)acrylate, and poly(1,2-butylene glycol-polytetramethylene glycol mono(meth)acrylate). The above "poly(ethylene glycol-propylene glycol)" refers to a random copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol-polypropylene glycol" refers to a block copolymer of ethylene glycol and propylene glycol.

[0044] The polymerizable monomer (a2) is preferably at least one selected from the group consisting of compounds represented by the following general formula (a2-1), compounds represented by the following general formula (a2-2), compounds represented by the following general formula (a2-3), compounds represented by the following general formula (a2-4), and compounds represented by the following general formula (a2-5), and is more preferably at least one selected from the group consisting of compounds represented by the following general formula (a2-1), compounds represented by the following general formula (a2-2), compounds represented by the following general formula (a2-3), and compounds represented by the following general formula (a2-4). These compounds can exhibit high compatibility when the silicone-containing polymer of the present invention is used as a leveling agent.

[0045] (In the general formulas (a2-1), (a2-2), (a2-3), (a2-4) and (a2-5), R ２１ is a hydrogen atom or a methyl group, R ２２ is an alkyl group having 1 to 18 carbon atoms; R ２３ is a hydrogen atom or a methyl group, R ２４ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms; R ２５ is a hydrogen atom or a methyl group, R ２６is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms and an ether bond, and R ２７ is a hydrogen atom or a methyl group, R ２８ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms and an ether bond; L ２ is a divalent organic group or a single bond, R ２９ is a hydrogen atom or a methyl group, R ３０ are each independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, n is an integer ranging from 1 to 4, m is the number of repetitions, the number average value of m being in the range of 1 to 200, p is an integer ranging from 1 to 10, q is the number of repetitions, the number average value of q being in the range of 1 to 100, and 1 is an integer ranging from 0 to 5.

[0046] In the general formula (a2-2), the m n's in the parentheses may be the same or different from each other. In the general formula (a2-3), the q p's in the parentheses may be the same or different from each other. In the general formula (a2-4), the q p's in the parentheses may be the same or different from each other.

[0047] L in the general formulae (a2-3) and (a2-4) ２ The divalent organic group is L １ The divalent organic groups are the same as those mentioned above.

[0048] The polymerizable monomer (a2) preferably contains one or more selected from the group consisting of the compound represented by the general formula (a2-2), the compound represented by the general formula (a2-3), and the compound represented by the general formula (a2-4). When the polymerizable monomer (a2) contains one or more selected from the group consisting of the compound represented by the general formula (a2-2), the compound represented by the general formula (a2-3), and the compound represented by the general formula (a2-4), it is preferable that the total amount of the compound represented by the general formula (a2-2), the compound represented by the general formula (a2-3), and the compound represented by the general formula (a2-4) is 50 mass% or more relative to the total amount of the polymerizable monomer (a2).

[0049] The polymerizable monomer (a2) can be produced by a known method. Alternatively, a commercially available product may be used as the polymerizable monomer (a2). For example, commercially available products of the polymerizable monomer (a2) having a group containing a polyoxyalkylene chain and in which the polymerizable unsaturated group is a (meth)acryloyl group include "NK ESTER M-20G", "NK ESTER M-40G", "NK ESTER M-90G", "NK ESTER M-230G", "NK ESTER AM-90G", "NK ESTER AMP-10G", "NK ESTER AMP-20G", and "NK ESTER AMP-60G" manufactured by Shin-Nakamura Chemical Co., Ltd., and "BLEMMER PE-90", "BLEMMER PE-200", "BLEMMER PE-350", and "BLEMMER PME-100" manufactured by NOF Corporation. Examples of such polymers include "Blenmer PME-200," "Blenmer PME-400," "Blenmer PME-4000," "Blenmer PP-1000," "Blenmer PP-500," "Blenmer PP-800," "Blenmer 70PEP-350B," "Blenmer 55PET-800," "Blenmer 50POEP-800B," "Blenmer 10PPB-500B," "Blenmer NKH-5050," "Blenmer AP-400," "Blenmer AE-350," the Plaxel F series manufactured by Daicel Corporation, and the Viscoat series manufactured by Osaka Organic Chemical Industry Ltd.

[0050] The polymerizable monomer (a2) constituting the silicone-containing polymer of the present invention may be one type alone or two or more types.

[0051] The silicone-containing polymer of the present invention is a random copolymer having at least polymerizable monomer (a1) and polymerizable monomer (a2) as polymerization components. That is, the silicone-containing polymer of the present invention is a copolymer in which structures derived from polymerizable monomer (a1) and structures derived from polymerizable monomer (a2) are randomly arranged. The silicone-containing polymer of the present invention can be produced by the method described below.

[0052] The silicone-containing polymer of the present invention preferably does not contain a block copolymer in which a block having a structure derived from polymerizable monomer (a1) and a block having a structure derived from polymerizable monomer (a2) are linked together, and more preferably does not contain a block having a structure derived from polymerizable monomer (a1) and / or a block having a structure derived from polymerizable monomer (a2). The production of block polymers generally requires a metal catalyst, and the resulting block polymer contains unavoidable metal impurities. The silicone-containing polymer of the present invention is preferably a free-radical random copolymer that can be produced without the use of a metal catalyst. Furthermore, the production of block copolymers generally requires complicated control. Specifically, adding a monomer that will form the second block when the polymerization rate of the first block is low can result in insufficient blocking. On the other hand, adding a monomer that will form the second block when the polymerization rate of the first block is high can result in deactivation of the active terminals, preventing the polymerization reaction from proceeding sufficiently. Additionally, measures must be taken to prevent the inclusion of substances that cause polymerization deactivation, such as oxygen, which inhibits blocking. The silicone-containing polymer of the present invention is also advantageous in that production control is not complicated.

[0053] The mass ratio of the polymerizable monomer (a1) to the polymerizable monomer (a2) in the silicone-containing polymer of the present invention satisfies, for example, polymerizable monomer (a1):polymerizable monomer (a2)=5:95 to 95:5, preferably polymerizable monomer (a1):polymerizable monomer (a2)=20:80 to 80:20, more preferably polymerizable monomer (a1):polymerizable monomer (a2)=30:70 to 80:20, and even more preferably polymerizable monomer (a1):polymerizable monomer (a2)=40:60 to 80:20.

[0054] The proportion of silicone chains (proportion of groups represented by general formula (a)) in the silicone-containing polymer of the present invention is, for example, in the range of 5 to 70 mass%, preferably in the range of 10 to 60 mass%, more preferably in the range of 15 to 55 mass%, and even more preferably in the range of 20 to 50 mass%. The proportion of silicone chains can be calculated from the amount of polymerizable monomer (a1) used.

[0055] The silicone-containing polymer of the present invention may contain at least the polymerizable monomer (a1) and the polymerizable monomer (a2) as polymerization components, and may contain other polymerizable monomers as polymerization components other than the polymerizable monomer (a1) and the polymerizable monomer (a2) as long as the effects of the present invention are not impaired. The silicone-containing polymer of the present invention is preferably a copolymer essentially consisting of the polymerizable monomer (a1) and the polymerizable monomer (a2), and more preferably a copolymer consisting only of the polymerizable monomer (a1) and the polymerizable monomer (a2). Here, "consisting essentially of" refers to a case where the total content of the polymerizable monomer (a1) and the polymerizable monomer (a2) in the polymerization components is 75% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, or 99% by mass or more.

[0056] The silicone-containing polymer of the present invention preferably does not contain fluorine atoms. When the silicone-containing polymer of the present invention is composed of, for example, the polymerizable monomer (a1) and the polymerizable monomer (a2), the copolymer of the present invention can be a copolymer that does not contain fluorine atoms.

[0057] The number average molecular weight (Mn) of the silicone-containing polymer of the present invention is preferably in the range of 1,000 to 100,000, more preferably in the range of 2,000 to 50,000, and even more preferably in the range of 2,000 to 20,000. The weight average molecular weight (Mw) of the silicone-containing polymer of the present invention is preferably in the range of 2,000 to 500,000, more preferably in the range of 3,000 to 100,000, and even more preferably in the range of 5,000 to 50,000. The upper limit of the weight average molecular weight (Mw) of the silicone-containing polymer of the present invention is preferably less than 10,000.

[0058] In the present invention, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured by gel permeation chromatography (GPC) and converted into polystyrene equivalents. The number average molecular weight (Mn) and weight average molecular weight (Mw) values ​​of the silicone-containing polymer of the present invention are measured by the method described in the examples.

[0059] The content of the silicone-containing polymer in the composition for forming a hard coat layer of the present invention may be set as appropriate, and is, for example, in the range of 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass, more preferably 0.02 to 2 parts by mass, and even more preferably 0.02 to 1 part by mass, relative to 100 parts by mass of the active energy ray-curable compound. Even a small amount of the silicone-containing polymer of the present invention can exert a leveling effect, and can suppress the occurrence of problems such as foaming during coating.

[0060] (Method for producing silicone-containing polymer) The method for producing the silicone-containing polymer of the present invention is not particularly limited, and the polymer can be produced by known methods. The silicone-containing polymer of the present invention can be produced by solution polymerization, bulk polymerization, emulsion polymerization, etc., based on a polymerization mechanism such as radical polymerization, cationic polymerization, or anionic polymerization. For example, in the case of radical polymerization, the silicone-containing polymer of the present invention can be produced by charging a polymerizable monomer mixture into an organic solvent and adding a general-purpose radical polymerization initiator.

[0061] As the polymerization initiator, various types can be used, for example, peroxides such as t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, and diacyl peroxide, azo compounds such as azobisisobutyronitrile, dimethyl azobisisobutyrate, and phenylazotriphenylmethane, Mn(acac) ３ If necessary, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, ethyl thioglycolic acid, or octyl thioglycolic acid, or a thiol compound having a coupling group such as γ-mercaptopropyltrimethoxysilane may be used as an additive such as a chain transfer agent.

[0062] Examples of the organic solvent include alcohol solvents such as ethanol, isopropyl alcohol, n-butanol, iso-butanol, and tert-butanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and butyl lactate; monocarboxylic acid ester solvents such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, and butyl 2-methoxypropionate; dimethylformamide, dimethyl sulfoxide, N Examples of suitable solvents include polar solvents such as methyl-methylpyrrolidone; ether solvents such as methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, and ethyl cellosolve acetate; propylene glycol and ester solvents such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate; halogenated solvents such as 1,1,1-trichloroethane and chloroform; cyclic ether solvents such as tetrahydrofuran and dioxane; aromatic solvents such as benzene, toluene, and xylene; and fluorinated solvents such as perfluorooctane and perfluorotri-n-butylamine. These solvents can be used alone or in combination of two or more.

[0063] The silicone-containing polymer of the present invention can also be produced by living polymerization such as living radical polymerization or living anionic polymerization using at least the polymerizable monomer (a1) and the polymerizable monomer (a2) as polymerization components.

[0064] In living radical polymerization, a dormant species, whose active polymerization terminal is protected by an atom or atomic group, reversibly generates radicals and reacts with a monomer, thereby causing a propagation reaction. Even when a first monomer is consumed, the propagating terminal does not lose its activity and reacts with a second monomer that is successively added to produce a block polymer. Examples of such living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-fragmentation radical polymerization (RAFT), nitroxide-mediated radical polymerization (NMP), and organotellurium radical polymerization (TERP). While there are no particular restrictions on which of these methods is used, ATRP is preferred due to its ease of control. ATRP uses an organic halide or a sulfonyl halide compound as a polymerization initiator and a metal complex composed of a transition metal compound and a ligand as a catalyst.

[0065] Specific examples of polymerization initiators that can be used in ATRP include 1-phenylethyl chloride, 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, α,α'-dichloroxylene, α,α'-dibromoxylene, hexakis(α-bromomethyl)benzene, and C1-6 alkyl esters of C2-halogenated carboxylic acids (e.g., 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, etc.). More specific examples of C1-6 alkyl esters of C2-halogenated carboxylic acids include, for example, methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate, and ethyl 2-bromoisobutyrate.

[0066] The transition metal compounds that can be used in ATRP are M ｎ＋ X ｎ It is expressed as follows: M ｎ＋ X ｎ The transition metal M of the transition metal compound represented by ｎ＋ As the ＋ , Cu ２＋ , Fe ２＋ , Fe ３＋ , Ru ２＋ , Ru ３＋, Cr ２＋ , Cr ３＋ , Mo ０ , Mo ＋ , Mo ２＋ , Mo ３＋ , W ２＋ , W ３＋ , Rh ３＋ , Rh ４＋ , Co ＋ , Co ２＋ , Re ２＋ , Re ３＋ , Ni ０ , Ni ＋ , Mn ３＋ , Mn ４＋ , V ２＋ , V ３＋ , Zn ＋ , Zn ２＋ , Au ＋ , Au ２＋ , Ag ＋ and Ag ２＋ M ｎ＋ X ｎ X in the transition metal compound represented by the formula (I) is a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, (SO ４ ) １／２ , (PO ４ ) １／３ , (HPO ４ ) １／２ , (H ２ P.O. ４ ), triflate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate), SeR １１ , C.N. and R. １２ COO, where R １１ represents an aryl group or a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), R １２ represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms (preferably a methyl group) which may be substituted 1 to 5 times with halogen (preferably 1 to 3 times with fluorine or chlorine). ｎ＋ X ｎ In the transition metal compound represented by the formula (I), n represents the formal charge on the metal and is an integer of 0 to 7.

[0067] Examples of the ligand compound capable of forming a coordinate bond to the transition metal of the transition metal compound include a compound having a ligand containing one or more nitrogen atoms, oxygen atoms, phosphorus atoms, or sulfur atoms that can be coordinated to the transition metal via a σ bond, a compound having a ligand containing two or more carbon atoms that can be coordinated to the transition metal via a π bond, and a compound having a ligand that can be coordinated to the transition metal via a μ bond or an η bond.

[0068] The transition metal complex is not particularly limited, but preferred examples include complexes of transition metals of Groups 7, 8, 9, 10, and 11, and more preferred examples include complexes of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel.

[0069] Specific examples of catalysts that can be used in ATRP include complexes with ligands such as 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, and polyamines such as tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexamethyltris(2-aminoethyl)amine when the central metal is copper. Examples of divalent ruthenium complexes include dichlorotris(triphenylphosphine)ruthenium, dichlorotris(tributylphosphine)ruthenium, dichloro(cyclooctadiene)ruthenium, dichlorobenzeneruthenium, dichloro-p-cymeneruthenium, dichloro(norbornadiene)ruthenium, cis-dichlorobis(2,2'-bipyridine)ruthenium, dichlorotris(1,10-phenanthroline)ruthenium, and carbonylchlorohydridotris(triphenylphosphine)ruthenium. Examples of divalent iron complexes include bistriphenylphosphine complexes and triazacyclononane complexes.

[0070] In living radical polymerization, it is preferable to use a solvent. Examples of solvents used in living radical polymerization include ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ether solvents such as diisopropyl ether, dimethoxyethane, and diethylene glycol dimethyl ether; halogenated solvents such as dichloromethane and dichloroethane; aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, and isopropanol; and aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide. The above solvents may be used alone or in combination of two or more.

[0071] The polymerization temperature during the living radical polymerization is preferably in the range of room temperature to 120°C.

[0072] (Active energy ray-curable compound) In the present invention, the "active energy ray-curable compound" refers to a compound that has the property of being cured by exposure to active energy rays such as electron beams, ultraviolet rays, and visible light. Here, the active energy ray-curable compound may be in the form of a monomer, oligomer, or polymer. The ultraviolet rays refer to active energy rays having a wavelength in the range of 10 nm or more and less than 380 nm, and the visible light refers to active energy rays having a wavelength of 380 nm or more and 800 nm or less.

[0073] When the active energy ray-curable compound is a resin (polymer), examples of the active energy ray-curable resin include polyester resins, (meth)acrylic resins, urethane resins, (meth)acrylic urethane resins, amide resins, silicone resins, silicate resins, epoxy resins, melamine resins, oxetane resins, etc. Among the above, (meth)acrylic resins, (meth)acrylic urethane resins, and epoxy resins are preferred, and (meth)acrylic resins and (meth)acrylic urethane resins are more preferred, because they have high hardness, are UV-curable, and are excellent in productivity.

[0074] When the active energy ray-curable compound is a monomer, the active energy ray-curable monomer may be an acrylic monomer having two or more acryloyl groups, which are ultraviolet-polymerizable functional groups, and preferably an acrylic monomer having 3 to 6 acryloyl groups.

[0075] Examples of the active energy ray-curable acrylic monomer include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, EO-modified pentaerythritol tetra(meth)acrylate, PO-modified pentaerythritol tetra(meth)acrylate, and pentaerythritol tri(meth)acrylate. acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate.

[0076] The active energy ray-curable acrylic monomer is preferably pentaerythritol tetra(meth)acrylate, EO-modified pentaerythritol tetra(meth)acrylate, PO-modified pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, or tricyclodecane dimethanol di(meth)acrylate.

[0077] The active energy ray-curable compounds used may be used alone or in combination of two or more.

[0078] The content of the active energy ray-curable compound is, for example, in the range of 10 to 99 mass % of the solid content of the hard coat layer-forming composition, and preferably in the range of 50 to 99 mass %. Note that, when the hard coat layer-forming composition contains a solvent, the "solid content of the hard coat layer-forming composition" means the total amount of components excluding the solvent from the hard coat layer-forming composition.

[0079] (Fine Particles) When antiglare properties are also imparted to the hard coat layer, the composition for forming the hard coat layer preferably further contains fine particles, which are dispersed in the hard coat layer. Examples of the fine particles include metal oxide fine particles such as silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide; organic fine particles made of transparent polymers such as polymethyl methacrylate, polystyrene, polyurethane, acrylic-styrene copolymer, benzoguanamine, melamine, and polycarbonate; glass fine particles, silicone fine particles, and the like.

[0080] The lower limit of the average particle size of the fine particles is, for example, 0.001 μm or more. The upper limit of the average particle size of the fine particles is, for example, 10 μm or less, preferably 1 μm or less, and more preferably 0.5 μm or less. The average particle size of the fine particles can be measured using a coulometer.

[0081] The fine particles used may be of one type alone or in combination of two or more types.

[0082] The content of the fine particles is, for example, in the range of 6 to 20 parts by mass per 100 parts by mass of the active energy ray-curable compound.

[0083] (Photopolymerization initiator) When the hard coat layer-forming composition is radically curable, the hard coat layer-forming composition preferably further contains a photopolymerization initiator. Examples of the photopolymerization initiator include an α-hydroxyacetophenone-based photopolymerization initiator, an α-aminoacetophenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and an intramolecular hydrogen abstraction photopolymerization initiator, and the like, and the α-hydroxyacetophenone-based photopolymerization initiator and the α-aminoacetophenone-based photopolymerization initiator are preferred.

[0084] Examples of commercially available photopolymerization initiators include Omnirad 2959, Omnirad 184, Omnirad 127D, and Omnirad 1173 (IGM Resins), and examples of commercially available α-aminoacetophenone photopolymerization initiators include Omnirad 907 and Omnirad 369E (IGM Resins).

[0085] The content of the photopolymerization initiator is, for example, in the range of 0.1 to 15 parts by mass, preferably in the range of 1 to 10 parts by mass, more preferably in the range of 2 to 8 parts by mass, and even more preferably in the range of 3 to 6 parts by mass, relative to 100 parts by mass of the active energy ray-curable compound.

[0086] (UV absorber) The hard coat layer-forming composition preferably further contains an UV absorber. By including an UV absorber in the hard coat layer-forming composition, the obtained hard coat layer can be provided with UV absorbency. The UV absorber may be any compound that absorbs UV light (e.g., wavelength 355 nm), and examples thereof include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, triazine-based UV absorbers, salicylate-based UV absorbers, and cyanoacrylate-based UV absorbers. Triazine-based UV absorbers and benzotriazole-based UV absorbers are preferred. When a triazine-based UV absorber is used as the UV absorber, the triazine-based UV absorber is preferably a hydroxyphenyltriazine-based UV absorber.

[0087] The content of the ultraviolet absorber is, for example, in the range of 0.1 to 3 parts by mass, and preferably in the range of 0.5 to 2.5 parts by mass, relative to 100 parts by mass of the active energy ray-curable compound.

[0088] (Solvent) The composition for forming a hard coat layer may contain a solvent for the purpose of adjusting the viscosity and the like to provide coating suitability. Examples of the solvent include dibutyl ether, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole, phenetole, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, acetone, methyl ethyl ketone (MEK), diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, 2-methoxymethyl acetate, 2-ethoxymethyl acetate, 2-ethoxyethyl acetate, 2-ethoxymethyl ... Examples of suitable alcohols include methyl alcohols such as ethyl propionate, 2-methoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1,2-diacetoxyacetone, acetylacetone, diacetone alcohol, methyl acetoacetate, and ethyl acetoacetate, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, cyclohexyl alcohol, isobutyl acetate, methyl isobutyl ketone (MiBK), 2-octanone, 2-pentanone, 2-hexanone, ethylene glycol ethyl ether, ethylene glycol isopropyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, ethyl carbitol, butyl carbitol, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, benzene, toluene, and xylene.

[0089] The solvents used may be one type alone or two or more types in combination.

[0090] The content of the solvent may be appropriately determined so as to obtain a desired viscosity, and may be set, for example, so that the concentration of the solid content of the composition for forming a hard coat layer falls within the range of 5 to 90% by mass.

[0091] (Other Additives) In addition to the above-mentioned components, the composition for forming a hard coat layer may optionally contain other additives such as a plasticizer, an infrared absorber, a colorant (pigment, dye, etc.), a fluorescent brightener, a dispersant, a heat stabilizer, a light stabilizer, an antistatic agent, an antioxidant, etc. The content of these other additives may be appropriately determined depending on the purpose and application.

[0092] The method for producing the composition for forming a hard coat layer is not particularly limited, and the composition can be produced by a known method. For example, the above-mentioned components may be mixed all at once, or may be mixed in portions and in stages.

[0093] [Hard Coat Layer] The composition for forming a hard coat layer of the present invention is applied to a substrate, and the resulting coating film is cured by irradiating it with active energy rays such as electron beams, ultraviolet rays, or visible light, to form a hard coat layer (hereinafter sometimes referred to as the "hard coat layer of the present invention"). When the active energy rays are ultraviolet rays, the irradiation intensity of the ultraviolet rays is, for example, 10 to 5,000 mW / cm. ２ The irradiation dose is preferably in the range of 10 to 10,000 mJ / cm ２ It is recommended to set the range as follows.

[0094] The thickness of the hard coat layer is, for example, in the range of 1 μm to 30 μm, preferably in the range of 3 μm to 15 μm, and more preferably in the range of 5 μm to 12 μm.

[0095] The substrate is not particularly limited, and examples thereof include cellulose ester films, polycarbonate films, polyester films such as polyethylene terephthalate and polyethylene naphthalate, (meth)acrylic films such as polymethyl methacrylate, styrene copolymer films such as polystyrene and acrylonitrile-styrene copolymer, and cyclic polyolefin films.

[0096] The thickness of the substrate is preferably in the range of 20 μm to 1000 μm, and when the substrate is a cellulose ester film, the thickness of the cellulose ester film is preferably in the range of 20 μm to 70 μm.

[0097] [Polarizing Plate] The polarizing plate of the present invention has a polarizer and the hard coat layer of the present invention. Each of the components of the polarizing plate of the present invention will be described below.

[0098] (Polarizer) The polarizer may be a polarizer formed by adsorbing and aligning a dichroic dye in a layer containing a polyvinyl alcohol (hereinafter sometimes referred to as "PVA")-based resin.

[0099] Known polarizers can be used, and examples thereof include a film formed by dyeing a PVA-based resin film with a dichroic dye and uniaxially stretching the dye; and a film formed by applying a coating liquid containing a PVA-based resin to a substrate, dyeing a PVA-based resin layer of the laminate with a dichroic dye, and uniaxially stretching the laminate.

[0100] The polarizer is formed from, for example, a PVA-based resin obtained by saponifying a polyvinyl acetate-based resin. Examples of the polyvinyl acetate-based resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate with other copolymerizable monomers. Examples of the other copolymerizable monomers include unsaturated carboxylic acids, olefins such as ethylene, vinyl ethers, and unsaturated sulfonic acids.

[0101] The PVA resin may be modified, for example, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, etc., modified with aldehydes.

[0102] The saponification degree of the PVA-based resin is preferably 85 mol% or more, more preferably 90 mol% or more, and even more preferably 99 mol% to 100 mol%. The polymerization degree of the PVA-based resin is, for example, in the range of 1,000 to 10,000, and preferably in the range of 1,500 to 5,000.

[0103] The polarizer preferably exhibits absorptive dichroism at any wavelength between 380 nm and 780 nm. The single transmittance of the polarizer is, for example, 41.0% or more, preferably in the range of 43.0% to 46.0%, and more preferably in the range of 44.5% to 46.0%. The degree of polarization of the polarizer is preferably 97.0% or more, more preferably 99.0% or more, and even more preferably 99.9% or more.

[0104] The thickness of the polarizer is, for example, in the range of 5 μm to 50 μm, preferably in the range of 5 μm to 40 μm, and more preferably in the range of 8 μm to 30 μm.

[0105] The polarizing plate of the present invention may be a laminate having a polarizer and the hard coat layer of the present invention, and may have other layers. The layer structure of the polarizing plate may be, for example, a polarizer / adhesive layer / protective layer / hard coat layer, and a layer having an optical function, such as a retardation layer, may be further laminated on the hard coat layer.

[0106] (Protective Layer) The protective layer may be a known one, and examples thereof include transparent resin films such as cellulose-based resins such as triacetyl cellulose (TAC), polyester-based resins, polyvinyl alcohol-based resins, polycarbonate-based resins, polyamide-based resins, polyimide-based resins, polyethersulfone-based resins, polysulfone-based resins, polystyrene-based resins, polynorbornene-based resins, polyolefin-based resins, (meth)acrylic resins, and acetate-based resins.

[0107] The thickness of the protective layer is, for example, in the range of 1 to 300 μm, preferably in the range of 5 μm to 200 μm, more preferably in the range of 10 μm to 100 μm, and even more preferably in the range of 10 μm to 60 μm.

[0108] (Adhesive Layer) The adhesive constituting the adhesive layer may be any adhesive that can be used for optical purposes, and examples of such adhesives include water-based adhesives and photo-curable adhesives.

[0109] As the aqueous adhesive, an aqueous adhesive containing a PVA-based resin (PVA-based adhesive) is preferably used. The average degree of polymerization of the PVA-based resin contained in the aqueous adhesive is, from the viewpoint of adhesiveness, for example, in the range of 100 to 5,500, preferably in the range of 1,000 to 4,500. The average degree of saponification of the PVA-based resin contained in the aqueous adhesive is, from the viewpoint of adhesiveness, for example, in the range of 85 mol% to 100 mol%, preferably in the range of 90 mol% to 100 mol%.

[0110] The PVA-based resin contained in the aqueous adhesive is preferably a PVA-based resin containing an acetoacetyl group, and the degree of acetoacetyl group modification of the acetoacetyl-containing PVA-based resin is, for example, 0.1 mol % or more, preferably in the range of 0.1 mol % to 20 mol %. The concentration of the PVA-based resin contained in the aqueous adhesive is, for example, in the range of 0.1 mol % to 15 mol %, preferably in the range of 0.5 mol % to 10 mol %.

[0111] The aqueous adhesive containing a PVA-based resin may further contain a crosslinking agent. Examples of the crosslinking agent include a water-soluble epoxy compound, a dialdehyde, and an isocyanate. When the PVA-based resin is an acetoacetyl group-containing PVA-based resin, the crosslinking agent is preferably one or more selected from glyoxal, glyoxylate, and methylolmelamine.

[0112] The aqueous adhesive may contain an organic solvent. The organic solvent is preferably an alcohol because it is miscible with water, and among alcohols, methanol and / or ethanol are preferred. When the aqueous adhesive contains an alcohol, the concentration of the alcohol is, for example, in the range of 10% to 70% by mass, preferably in the range of 15% to 60% by mass, and more preferably in the range of 20% to 60% by mass.

[0113] Photocurable adhesives are adhesives that harden when irradiated with active energy rays including ultraviolet rays, and examples thereof include compositions containing photopolymerizable monomers such as photocurable epoxy monomers, photocurable acrylic monomers, and photocurable urethane monomers, and oligomers derived from these monomers, as well as substances that generate active species such as neutral radicals, anion radicals, and cation radicals when irradiated with active energy rays.

[0114] The thickness of the adhesive layer is, for example, in the range of 0.01 to 10 μm, preferably in the range of 0.01 to 5 μm, more preferably in the range of 0.01 to 2 μm, and even more preferably in the range of 0.01 to 1 μm.

[0115] (Optical Functional Layer) The optical functional layer is a layer that adds optical functions to the polarizing plate, and examples thereof include a retardation layer. Examples of the retardation layer include a layer that imparts a retardation of λ / 2, a layer that imparts a retardation of λ / 4 (positive A plate), and a positive C plate. When the polarizing plate has a layer that imparts a retardation of λ / 4 as an optical functional layer, the polarizing plate can be a circular polarizing plate.

[0116] The optical functional layer may include an alignment layer and a substrate, or may have two or more liquid crystal layers, alignment layers, and substrates. The protective layer may also serve as a retardation layer, or a retardation layer may be laminated separately from the protective layer. The retardation layer may be laminated on the polarizing plate via a pressure-sensitive adhesive layer described later.

[0117] Examples of the retardation layer include a birefringent film made of a stretched film of a light-transmitting thermoplastic resin, and a liquid crystal layer formed on a substrate film of a cellulose ester resin such as triacetyl cellulose.

[0118] Examples of the thermoplastic resin constituting the retardation layer include polycarbonate-based resins, polyester carbonate-based resins, polyester-based resins, polyvinyl acetal-based resins, polyarylate-based resins, cyclic olefin-based resins, cellulose-based resins, polyvinyl alcohol-based resins, polyamide-based resins, polyimide-based resins, polyether-based resins, polystyrene-based resins, and acrylic-based resins.

[0119] When the optical functional layer is a retardation layer, the thickness of the retardation layer may be appropriately determined depending on the required optical properties, and is, for example, in the range of 50 to 300 μm.

[0120] Examples of other optical functional layers include a light collecting plate, a brightness enhancing film, a reflective layer (reflective film), a semi-transmissive reflective layer (semi-transmissive reflective film), a light diffusing layer (light diffusing film), and an anti-reflection film.

[0121] (Adhesive Layer) An adhesive layer may be used for laminating the optical functional layer. The adhesive layer is a layer used for bonding the optical functional layer, and is made of an adhesive composition containing an adhesive resin such as a (meth)acrylic resin, a rubber resin, a urethane resin, an ester resin, a silicone resin, or a polyvinyl ether resin as a base polymer. The adhesive composition may be either a photocurable or a thermosetting type.

[0122] Examples of the (meth)acrylic resin used in the pressure-sensitive adhesive layer include polymers or copolymers containing (meth)acrylic acid esters as monomers, such as butyl (meth)acrylate, ethyl (meth)acrylate, isooctyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. The (meth)acrylic resins may be further copolymerized with polar monomers, and examples of the polar monomers include monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group, or the like, such as (meth)acrylic acid, 2-hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, and glycidyl (meth)acrylate.

[0123] The pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer preferably contains a crosslinking agent in addition to the pressure-sensitive adhesive resin. Examples of the crosslinking agent include metal compounds, polyamine compounds, polyepoxy compounds, polyols, and polyisocyanate compounds.

[0124] The thickness of the pressure-sensitive adhesive layer is, for example, in the range of 1 μm to 200 μm, preferably in the range of 2 μm to 100 μm, more preferably in the range of 2 μm to 80 μm, and even more preferably in the range of 3 μm to 50 μm.

[0125] The polarizing plate of the present invention can be produced by a known method, for example, by forming a hard coat layer on a protective layer and bonding the protective layer having the hard coat layer to a polarizer via an adhesive layer.

[0126] The polarizing plate of the present invention is suitably used in image display devices, such as liquid crystal displays, electroluminescence (EL) displays, plasma displays (PDs), and field emission displays (FEDs).

[0127] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0128] In the examples and comparative examples, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​calculated in terms of polystyrene based on gel permeation chromatography (GPC) measurements. The GPC measurement conditions are as follows:

[0129] [GPC measurement conditions] Measurement apparatus: High-speed GPC apparatus "HLC-8320GPC" manufactured by Tosoh Corporation Column: "TSKGUARDCOLUMNSuperHZ-L" manufactured by Tosoh Corporation + "TSKgelSuperHZM-N" manufactured by Tosoh Corporation + "TSKgelSuperHZM-N" manufactured by Tosoh Corporation + "TSKgelSuperHZM-N" manufactured by Tosoh Corporation + "TSKgelSuperHZM-N" manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: "EcoSEC DataAnalysis version 1.07" manufactured by Tosoh Corporation Column temperature: 40°C Developing solvent: tetrahydrofuran Flow rate: 0.35 mL / min Measurement sample: 7.5 mg of sample was dissolved in 10 mL of tetrahydrofuran, and the resulting solution was filtered through a microfilter to prepare a measurement sample. Sample injection volume: 20 μL Standard sample: The following monodisperse polystyrene with known molecular weight was used in accordance with the measurement manual for the "HLC-8320GPC" mentioned above.

[0130] (Monodisperse polystyrene) "A-300" manufactured by Tosoh Corporation "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation "F-128" manufactured by Tosoh Corporation "F-288" manufactured by Tosoh Corporation

[0131] Synthesis Example 1 Synthesis of Silicone-Containing Random Copolymer (1) A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 100.0 g of propylene glycol monomethyl ether acetate as a solvent, and the temperature was raised to 95°C while stirring under a nitrogen stream. Next, a monomer polymerization initiator solution prepared by dissolving 33.0 g of 3-methacryloyloxypropyltris(trimethylsiloxy)silane (molecular weight 423), 67.0 g of polypropylene glycol monomethacrylate (average propylene glycol repeat number 4 to 6), and 7.5 g of the polymerization initiator t-butylperoxy-2-ethylhexanoate in 112.5 g of propylene glycol monomethyl ether acetate was placed in the dropping device, and added dropwise over 2 hours while maintaining the temperature inside the flask at 95°C. After completion of the dropwise addition, the mixture was allowed to react at 95°C for 5 hours under a nitrogen stream, and then the temperature was raised to 110°C and the mixture was allowed to react for 1 hour. After the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain a silicone-containing random copolymer (1).

[0132] The molecular weight of the resulting silicone-containing random copolymer (1) was measured by GPC, and the weight average molecular weight (Mw) was found to be 8,000. Furthermore, based on the raw material charging ratio, the content of the silicone-containing polymerizable monomer in copolymer (1) was found to be 33 mass%.

[0133] Synthesis Example 2: Synthesis of Silicone-Containing Random Copolymer (2) A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 100.0 g of propylene glycol monomethyl ether acetate as a solvent, and the temperature was raised to 95°C while stirring under a nitrogen stream. Next, a monomer polymerization initiator solution prepared by dissolving 44.0 g of 3-methacryloyloxypropyltris(trimethylsiloxy)silane (molecular weight 423), 56.0 g of polypropylene glycol monomethacrylate (average propylene glycol repeat number 4 to 6), and 7.5 g of the polymerization initiator t-butylperoxy-2-ethylhexanoate in 112.5 g of propylene glycol monomethyl ether acetate was placed in the dropping device, and added dropwise over 2 hours while maintaining the temperature inside the flask at 95°C. After completion of the dropwise addition, the mixture was allowed to react at 95°C for 5 hours under a nitrogen stream, and then the temperature was raised to 110°C and the mixture was allowed to react for 1 hour. After the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain a silicone-containing random copolymer (2).

[0134] The molecular weight of the resulting silicone-containing random copolymer (1) was measured by GPC, and the weight average molecular weight (Mw) was found to be 10,000. Furthermore, based on the raw material charging ratio, the content of the silicone-containing polymerizable monomer in copolymer (2) was found to be 44 mass%.

[0135] Synthesis Example 3: Synthesis of Silicone-Containing Random Copolymer (3) A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 100.0 g of butyl acetate as a solvent, and the temperature was raised to 90°C while stirring under a nitrogen stream. Next, a monomer polymerization initiator solution prepared by dissolving 33.0 g of 3-methacryloyloxypropyltris(trimethylsiloxy)silane (molecular weight 423), 67.0 g of polypropylene glycol-polybutylene glycol monomethacrylate (average repeat number of propylene glycol: 1, average repeat number of butylene glycol: 6), and 3.0 g of the polymerization initiator t-butylperoxy-2-ethylhexanoate in 133.3 g of butyl acetate was placed in the dropping device, and added dropwise over 2 hours while maintaining the temperature inside the flask at 90°C. After completion of the dropwise addition, the mixture was allowed to react at 90°C for 5 hours under a nitrogen stream, and then the temperature was raised to 110°C and the mixture was allowed to react for 1 hour. After the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain a silicone-containing random copolymer (3).

[0136] The molecular weight of the resulting silicone-containing random copolymer (3) was measured by GPC, and the weight average molecular weight (Mw) was found to be 16,000. Furthermore, based on the raw material charging ratio, the content of the silicone-containing polymerizable monomer in copolymer (3) was found to be 33 mass%.

[0137] Synthesis Example 4: Synthesis of Silicone-Containing Random Copolymer (4) A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 100.0 g of butyl acetate as a solvent, and the temperature was raised to 95°C while stirring under a nitrogen stream. Next, a monomer and polymerization initiator solution prepared by dissolving 33.0 g of a silicone-containing polymerizable monomer (weight average molecular weight 1,000) represented by the following formula, 67.0 g of polypropylene glycol monomethacrylate, and 2.0 g of the polymerization initiator t-butylperoxy-2-ethylhexanoate in 110.0 g of butyl acetate was placed in the dropping device, and added dropwise over 2 hours while maintaining the temperature inside the flask at 95°C. After completion of the addition, the mixture was allowed to react for 3 hours at 95°C under a nitrogen stream. After completion of the reaction, the solvent was distilled off under reduced pressure, yielding a silicone-containing random copolymer (4).

[0138] (In the general formula (a1-1-1), the number average of x1 is 10.)

[0139] The molecular weight of the resulting silicone-containing random copolymer (4) was measured by GPC, and the weight average molecular weight (Mw) was found to be 26,000. Furthermore, based on the raw material charging ratio, the content of the silicone-containing polymerizable monomer in copolymer (4) was found to be 33 mass%.

[0140] (Examples 1-4 and Comparative Example 1: Formation and Evaluation of Coating Films) A coating composition for a hard coat layer was prepared by mixing and dissolving 5 parts by mass of an ultraviolet-curable urethane acrylate resin ("Luxidia 17-806" manufactured by DIC Corporation, a butyl acetate solution containing 80% by mass of ultraviolet-curable urethane acrylate resin), 0.2 parts by mass of Irgacure 184 (manufactured by Ciba Specialty Chemicals), 0.012 parts by mass of the copolymer shown in Table 1, 2 parts by mass of toluene, 1 part by mass of 2-propanol, 1 part by mass of ethyl acetate, and 1 part by mass of propylene glycol monomethyl ether. The obtained coating composition for a hard coat layer was applied to a 188 μm-thick PET film using a bar coater No. 13, and then placed in a dryer set at 60° C. for 5 minutes to volatilize the solvent. The coating film on the PET film was cured using an ultraviolet curing device (under a nitrogen atmosphere, using a high-pressure mercury lamp, ultraviolet irradiation dose 200 mJ / cm). ２ The coating was cured by irradiating it with ultraviolet light using a UV lamp, to prepare a hard coat film having a hard coat layer with a thickness of 8 μm on one side.

[0141] The smoothness of the hard coat layer of the produced hard coat film was evaluated by the following method. The results are shown in Table 1. (Smoothness) The hard coat layer of the obtained hard coat film was visually observed, and the smoothness of the hard coat layer was evaluated according to the following criteria: ◯: Almost no unevenness was observed on the surface of the hard coat layer. Δ: Unevenness was observed in some parts of the surface of the hard coat layer. ×: Unevenness was observed on the entire surface of the hard coat layer.

[0142]

[0143] The results of the examples show that the hard coat layer containing the copolymer of the present invention exhibits excellent smoothness.

Claims

1. A composition for forming a hard coat layer, comprising an active energy ray-curable compound and a silicone-containing polymer, The silicone-containing polymer is a random copolymer having as polymerization components at least a polymerizable monomer (a1) having a group represented by the following general formula (a) and a weight-average molecular weight in the range of 100 to 4,000, and a polymerizable monomer (a2) having one or more selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, and a group containing a polyoxyalkylene chain, wherein the weight-average molecular weight (Mw) of the silicone-containing polymer is 8,000 or more, and the content of the polymerizable monomer (a1) in the polymerization components of the silicone-containing polymer is 15 mass% or more: 【Chemistry 1】 (In the general formula (a), R １１ are each independently an alkyl group having 1 to 6 carbon atoms or —OSi(R １４ ) ３ A group represented by R １４ are each independently an alkyl group having 1 to 3 carbon atoms, R １２ are each independently an alkyl group having 1 to 6 carbon atoms, R １３ is an alkyl group having 1 to 12 carbon atoms, x represents the number of repetitions and is an integer from 1 to 15.

2. The composition for forming a hard coat layer according to claim 1, wherein the polymerizable monomer (a1) is a compound represented by the following general formula (a1-1) and / or a compound represented by the following general formula (a1-2): 【Chemistry 2】 (In the general formulae (a1-1) and (a1-2), R １１ , R １２ , R １３ and x are each R in the general formula (a). １１ , R １２ , R １３ and x, R １５ is a hydrogen atom or a methyl group, L １ is a divalent organic group.

3. The composition for forming a hard coat layer according to claim 1, wherein the polymerizable monomer (a2) is at least one selected from the group consisting of a compound represented by the following general formula (a2-1), a compound represented by the following general formula (a2-2), a compound represented by the following general formula (a2-3), and a compound represented by the following general formula (a2-4): 【Transformation 3】 (In the general formulae (a2-1), (a2-2), (a2-3) and (a2-4), R ２１ is a hydrogen atom or a methyl group, R ２２ is an alkyl group having 1 to 18 carbon atoms, R ２３ is a hydrogen atom or a methyl group, R ２４ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, R ２５ is a hydrogen atom or a methyl group, R ２６ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms and an ether bond, R ２７ is a hydrogen atom or a methyl group, R ２８ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms and an ether bond, L ２ is a divalent organic group or a single bond, n is an integer ranging from 1 to 4, m is the number of repetitions, the number average value of m is in the range of 1 to 200, p is an integer ranging from 1 to 10, q is the number of repetitions, the number average value of q is in the range of 1 to 100.

4. 4. The composition for forming a hard coat layer according to claim 3, wherein the polymerizable monomer (a2) includes a compound represented by the general formula (a2-2).

5. 3. The composition for forming a hard coat layer according to claim 1, wherein the silicone-containing polymer does not contain fluorine atoms.

6. 3. The composition for forming a hard coat layer according to claim 1, wherein the silicone-containing polymer is contained in an amount of 0.01 to 5 parts by mass per 100 parts by mass of the active energy ray-curable compound.

7. A film obtained by curing the composition for forming a hard coat layer according to claim 1 or 2.

8. A laminate comprising the film of claim 7 on a substrate.

9. A polarizing plate having a polarizer and a hard coat layer, the hard coat layer contains a silicone-containing polymer, a polymerizable monomer (a1) having a group represented by the following general formula (a) and a weight-average molecular weight in the range of 100 to 4,000; and a polymerizable monomer (a2) having one or more selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, and a group containing a polyoxyalkylene chain, the weight-average molecular weight (Mw) of the silicone-containing polymer being 8,000 or more, and the content of the polymerizable monomer (a1) in the polymerization components of the silicone-containing polymer being 15% by mass or more. 【Chemistry 4】 (In the general formula (a), R １１ are each independently an alkyl group having 1 to 6 carbon atoms or —OSi(R １４ ) ３ A group represented by R １４ are each independently an alkyl group having 1 to 3 carbon atoms, R １２ are each independently an alkyl group having 1 to 6 carbon atoms, R １３ is an alkyl group having 1 to 6 carbon atoms, x represents the number of repetitions and is an integer from 1 to 15.

10. 10. The polarizing plate according to claim 9, wherein the polymerizable monomer (a1) is a compound represented by the following general formula (a1-1) and / or a compound represented by the following general formula (a1-2): 【Transformation 5】 (In the general formulae (a1-1) and (a1-2), R １１ , R １２ , R １３ and x are each R in the general formula (a). １１ , R １２ , R １３ and x, R １５ is a hydrogen atom or a methyl group, L １ is a divalent organic group.

11. An image display device comprising the polarizing plate according to claim 9 or 10.

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