Compositions for forming hard coat layers, films, laminates, polarizing plates, and image display devices.

Abstract

The present invention provides a hard coat layer forming composition capable of forming a hard coat layer with excellent smoothness. [Solution] A hard coat layer forming composition containing an active energy ray curable compound and a silicone-containing polymer, wherein the silicone-containing polymer is a random copolymer comprising at least one 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 one or more polymerizable monomers (a2) selected from the group consisting of alkyl groups having 1 to 18 carbon atoms, aromatic groups having 6 to 18 carbon atoms, groups containing polyoxyalkylene chains, and groups containing polyester chains as polymerizable components. TIFF2026131665000017.tif2370

Description

[Technical Field]

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

[0002] In image display devices such as liquid crystal displays and organic EL displays, optical control films such as polarizing plates are usually placed to eliminate problems such as external light reflection and background glare, and to improve image visibility.

[0003] Since the outermost surface of optical control films such as the polarizing plates mentioned above can be significantly reduced in visibility if scratched, a hard coat layer is provided to the optical control film to provide scratch resistance. The hard coat layer is generally formed by applying and curing a curable resin composition. However, problems exist where the functionality as an optical control film is significantly reduced if there are uneven application or repelling issues, or if the leveling properties of the cured film surface are insufficient, resulting in uneven film thickness.

[0004] To solve the above problem, a fluorine-based additive is generally added to the curable resin composition that forms the hard coat layer (for example, Patent Document 1), and this fluorine-based additive ensures the leveling properties of the surface of the resulting cured film. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2012-73377 [Overview of the project] [Problems that the invention aims to solve]

[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 have become a substance of great concern due to their poor biodegradability and harmful effects on human health. Due to changing social circumstances, there is a demand for hard coat layer additives that do not contain PFAS.

[0007] The problem that the present invention aims to solve is to provide a hard coat layer forming composition that can form a hard coat layer having excellent smoothness. Another problem that the present invention aims to solve is to provide laminates and polarizing plates having a hard coat layer with excellent smoothness. [Means for solving the problem]

[0008] The inventors of the present invention conducted diligent research to solve the above problems and, as a result, discovered that smoothness can be imparted to the hard coat layer by using a random copolymer of specific silicone monomers, thereby completing the present invention.

[0009] In other words, the present invention relates to a composition for forming a hard coat layer, etc. 1. A hard coat layer forming composition containing an active energy ray curable compound and a silicone polymer, The aforementioned silicone-containing polymer is a random copolymer comprising at least one 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 one or more polymerizable monomers (a2) selected from the group consisting of alkyl groups having 1 to 18 carbon atoms, aromatic groups having 6 to 18 carbon atoms, groups containing polyoxyalkylene chains, and groups containing polyester chains, as polymerizable components, for forming a hard coat layer. [ka] (In the above general formula (a), R 11 Each is independently an alkyl group having 1 to 6 carbon atoms or -OSi(R 14 )3 is represented by the group (R14 is each independently an alkyl group having 1 to 3 carbon atoms), R 12 is 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.) 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).

Chemical formula

Chemical formula

[0010] The present invention provides a hard coat layer forming composition capable of forming a hard coat layer having excellent smoothness. The present invention provides laminates and polarizing plates having a hard coat layer with excellent smoothness. [Modes for carrying out the invention]

[0011] The following describes one embodiment of the present invention. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications without impairing the effects of the present invention. In this specification, "(meth)acrylate" means either acrylate or methacrylate, or both.

[0012] [Composition for forming a hard coat layer] The hard coat layer forming composition of the present invention is a composition containing an active energy ray curable compound and a silicone polymer. The components contained in the hard coat layer forming composition of the present invention will be described below.

[0013] (Contains silicone polymer) The silicone-containing polymer contained in the hard coat layer forming composition of the present invention (hereinafter sometimes simply referred to as "the silicone-containing polymer of the present invention") is a random copolymer comprising at least one 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 one or more polymerizable monomers (a2) selected from the group consisting of alkyl groups having 1 to 18 carbon atoms, aromatic groups having 6 to 18 carbon atoms, groups containing polyoxyalkylene chains, and groups containing polyester chains as polymerizable components.

[0014] [ka] (In the above general formula (a), R 11 Each is independently an alkyl group having 1 to 6 carbon atoms or -OSi(R 14 )3 is represented by the group (R 14Each of these is an alkyl group having 1 to 3 carbon atoms. R 12 Each of these is an alkyl group having 1 to 6 carbon atoms, R 13 These are alkyl groups having 1 to 12 carbon atoms. x indicates the number of repetitions.

[0015] The silicone-containing polymer of the present invention can function as a leveling agent, and by forming a random copolymer in which polymerizable monomer (a1) and polymerizable monomer (a2) are at least polymerizable components, the silicone portion does not cause the coating film to repel, and thus the occurrence of coating film defects can be prevented.

[0016] In the present invention, "polymerizable monomer" means a compound having a polymerizable unsaturated group. Examples of polymerizable unsaturated groups in polymerizable monomer (a1) and polymerizable monomer (a2) include C=C-containing groups such as (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamino group, vinyl ether group, allyl group, styryl group, and maleimide group. Among these, (meth)acryloyl group and (meth)acryloyloxy group are preferred due to the ease of obtaining raw materials and good polymerization reactivity. Furthermore, the polymerizable monomer may have one polymerizable unsaturated group or two or more groups.

[0017] In this invention, "polymerization component" means a component that constitutes a polymer, and does not include solvents, polymerization initiators, etc. that do not constitute a polymer.

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

[0019] In the above 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, and more preferably an alkyl group having 1 to 4 carbon atoms.

[0020] In the general formula (a) above, x represents the number of repetitions, and for example, x can be any integer greater than or equal to 1. The average of the numbers 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 value of x can be determined by measuring the number-average molecular weight of the polymerizable monomer (a1) using the method described in the examples.

[0021] In the above general formula (a), multiple R 11 These can be the same or different from one another. Similarly, multiple R's can be different. 12 They 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). [ka] (In the above general formulas (a1-1) and (a1-2), R 11 , R 12 , R 13 and x are R in the general formula (a) above, respectively. 11 , R 12 , R 13 and are the same as x, R 15 is a hydrogen atom or a methyl group, L 1 (This is a divalent organic group.)

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

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

[0025] L 1 The 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 alkylene oxy group having 1 to 50 carbon atoms is, for example, a group in which one of the alkylene groups has one -CH2- replaced by -O-. L 1 The alkylene oxy group having 1 to 50 carbon atoms is preferably an alkylene oxy group having 1 to 15 carbon atoms, more preferably an alkylene oxy group having 1 to 8 carbon atoms, and even more preferably a methylene oxy group, ethylene oxy group, propylene oxy group, oxytrimethylene group, butylene oxy group, oxytetramethylene group, pentylene oxy group, heptylene oxy group, or octylene oxy group.

[0027] L 1 If the divalent organic group is an alkylene group having 1 to 50 carbon atoms or an alkylene oxy group having 1 to 50 carbon atoms, then some of the -CH2- in these divalent organic groups may be replaced by a carbonyl group (-C(=O)-), a phenylene group, an amide bond, or a urethane bond, and furthermore, carbon atoms may be substituted with hydroxyl groups or the like.

[0028] Polymerizable monomer (a1) can be produced by known methods, or commercially available products may be used. Specific examples of polymerizable monomers (a1) include α-(3-methacryloyloxy)propyl polydimethylsiloxane, 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 a single type 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. However, if the weight-average molecular weight of the polymerizable monomer (a1) exceeds 4,000, the compatibility of the silicone-containing polymer may decrease. Here, "weight-average molecular weight" is the value measured by the method described in the Examples.

[0031] In the silicone polymer of the present invention, the lower limit of the content of polymerizable monomer (a1) in the polymerization component (hereinafter simply referred to as "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 is no particular upper limit to the content of polymerizable monomer (a1), but for example, it may be 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. The preferred combination of polymerizable monomer (a1) content in the polymerization component is in the range of 10 to 90% by mass. The content ratio of polymerizable monomer (a1) can be adjusted by the raw material charge ratio of polymerizable monomer (a1) when manufacturing the silicone-containing polymer.

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

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

[0034] Examples of aromatic groups with 6 to 18 carbon atoms that polymerizable monomer (a2) may possess include phenyl groups, naphthyl groups, anthracene-1-yl groups, and phenanthrene-1-yl groups.

[0035] The groups containing (poly)oxyalkylene chains in the polymerizable monomer (a2) are monovalent groups containing the repeating portion of oxyalkylene or divalent linking groups containing the repeating portion of oxyalkylene.

[0036] The polyester chain-containing groups of the polymerizable monomer (a2) are monovalent groups containing repeating ester bonds or divalent linking groups containing repeating ester bonds.

[0037] Examples of polymerizable monomers (a2) having an alkyl group with 1 to 18 carbon atoms and a polymerizable unsaturated group being 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. Examples include alkyl esters of (meth)acrylic acid having 1 to 18 carbon atoms, such as (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate; and bridged cyclic alkyl esters of (meth)acrylic acid having 1 to 18 carbon atoms, such as dicyclopentanyloxyethyl (meth)acrylate, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyl (meth)acrylate.

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

[0039] Examples of polymerizable monomers (a2) having an alkyl group with 1 to 18 carbon atoms and a polymerizable unsaturated group being 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 polymerizable monomers (a2) having aromatic groups with 6 to 18 carbon atoms include styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene.

[0041] Examples of polymerizable monomers (a2) having an alkyl group with 1 to 18 carbon atoms and a polymerizable unsaturated group being a (meth)acryloylamino group include N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, diacetoneacrylamide, and acroylmorpholin.

[0042] Examples of polymerizable monomers (a2) having an alkyl group with 1 to 18 carbon atoms and a maleimide group as the polymerizable unsaturated group include methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, and cyclohexyl maleimide.

[0043] Examples of polymerizable monomers (a2) having a group containing a polyoxyalkylene chain and whose 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-poly1,2-butylene glycol mono(meth)acrylate, poly(tetraethylene glycol-1,2-butylene glycol) mono(meth)acrylate, polytetraethylene glycol-poly1,2-butylene glycol mono(meth)acrylate, poly1,2-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, poly1,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 poly1,2-butylene glycol / polytetramethylene glycol mono(meth)acrylate. Furthermore, "poly(ethylene glycol / propylene glycol)" above refers to a random copolymer of ethylene glycol and propylene glycol, while "polyethylene glycol / polypropylene glycol" refers to a block copolymer of ethylene glycol and propylene glycol.

[0044] The polymerizable monomer (a2) is preferably one or more selected from the group consisting of the compound represented by the following general formula (a2-1), the compound represented by the following general formula (a2-2), the compound represented by the following general formula (a2-3), the compound represented by the following general formula (a2-4), and the compound represented by the following general formula (a2-5), and more preferably one or more selected from the group consisting of the compound represented by the following general formula (a2-1), the compound represented by the following general formula (a2-2), the compound represented by the following general formula (a2-3), and the compound 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] [ka] (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 These are alkyl groups with 1 to 18 carbon atoms. R 23 is a hydrogen atom or a methyl group, R24 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 This is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having an ether bond with 1 to 18 carbon atoms. R 27 is a hydrogen atom or a methyl group, R 28 This is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having an ether bond with 1 to 18 carbon atoms. L 2 is a divalent organic group or single bond, R 29 is a hydrogen atom or a methyl group, R 30 Each of these is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. n is an integer in the range of 1 to 4, m represents the number of repetitions, with the average value of m being in the range of 1 to 200, p is an integer in the range of 1 to 10, q represents the number of repetitions, with the average value of q being in the range of 1 to 100, and l is an integer in the range of 0 to 5.

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

[0047] L in the above general formulas (a2-3) and (a2-4) 2 The divalent organic group is L 1 Examples include the same divalent organic groups as shown above.

[0048] The polymerizable monomer (a2) preferably contains one or more compounds 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) includes one or more compounds 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 general formula (a2-4) is 50% by mass or more of the total amount of the polymerizable monomer (a2).

[0049] Polymerizable monomer (a2) can be produced by known methods. Furthermore, commercially available polymerizable monomers (a2) may also be used. For example, commercially available polymerizable monomers (a2) having a group containing a polyoxyalkylene chain and whose 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" from Shin Nakamura Chemical Industry Co., Ltd., and "Bremmer PE-90", "Bremmer PE-200", "Bremmer PE-350", and "Bremmer PME-100" from NOF Corporation. Examples include the "Bremmer PME-200", "Bremmer PME-400", "Bremmer PME-4000", "Bremmer PP-1000", "Bremmer PP-500", "Bremmer PP-800", "Bremmer 70PEP-350B", "Bremmer 55PET-800", "Bremmer 50POEP-800B", "Bremmer 10PPB-500B", "Bremmer NKH-5050", "Bremmer AP-400", "Bremmer AE-350", the Praxel F series from Daicel Corporation, and the Viscoat series from Osaka Organic Chemical Industry Co., Ltd.

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

[0051] The silicone-containing polymer of the present invention is a random copolymer comprising at least polymerizable monomer (a1) and polymerizable monomer (a2) as polymer 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 later.

[0052] The silicone-containing polymer of the present invention preferably does not contain a block copolymer in which a block of structure derived from polymerizable monomer (a1) and a block of structure derived from polymerizable monomer (a2) are linked, and more preferably does not contain a block of structure derived from polymerizable monomer (a1) and / or a block of structure derived from polymerizable monomer (a2). The production of block polymers generally requires a metal catalyst, and the resulting block polymers inevitably contain 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 is generally complicated to manage. Specifically, if the monomer for the second block is added when the polymerization rate of the first block is low, the blocking may be insufficient. On the other hand, if the monomer for the second block is added when the polymerization rate of the first block is high, the active ends may be deactivated, and the polymerization reaction may not proceed sufficiently. In addition, measures are needed to prevent contamination with substances that cause polymerization deactivation, such as oxygen, which hinders blocking. The silicone-containing polymer of the present invention is superior in that it does not require complicated production management.

[0053] In the silicone-containing polymer of the present invention, the mass ratio of polymerizable monomer (a1) to polymerizable monomer (a2) 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% by mass, preferably in the range of 10 to 60% by mass, more preferably in the range of 15 to 55% by mass, and even more preferably in the range of 20 to 50% by mass. Furthermore, the proportion of the above-mentioned 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 polymerizable monomer (a1) and polymerizable monomer (a2) as polymerization components, and may also contain other polymerizable monomers other than polymerizable monomer (a1) and polymerizable monomer (a2) as polymerization components, as long as the effects of the present invention are not impaired. The silicone-containing polymer of the present invention is preferably a copolymer substantially composed of a polymerizable monomer (a1) and a polymerizable monomer (a2), and more preferably a copolymer consisting only of a polymerizable monomer (a1) and a polymerizable monomer (a2). Here, "substantially composed" means that the total content ratio of polymerizable monomer (a1) and polymerizable monomer (a2) in the polymerization component 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 polymer of the present invention preferably does not contain fluorine atoms. If the silicone-containing polymer of the present invention consists of, for example, a polymerizable monomer (a1) and a 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 weight-average molecular weight (Mw) of the silicone-containing polymer of the present invention is preferably less than 10,000.

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

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

[0060] (Method for producing silicone polymers) The method for producing the silicone-containing polymer of the present invention is not particularly limited and 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 polymerization mechanisms such as radical polymerization, cationic polymerization, and 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] Various polymerization initiators can be used, including, for example, peroxides such as t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, and diacyl peroxide; azo compounds such as azobisisobutyronitrile, dimethyl azobisisobutyrate, and phenylazotriphenylmethane; and metal chelate compounds such as Mn(acac)3. If necessary, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, ethylthioglycolic acid, and octylthioglycolic acid, or thiol compounds having a coupling group such as γ-mercaptopropyltrimethoxysilane may be used as additives such as chain transfer agents.

[0062] Examples of the organic solvents 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 include polar solvents such as methylpyrrolidone; ether solvents such as methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, and ethyl cellosolve acetate; solvents for propylene glycol and its esters such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate; halogen 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 individually 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 polymerizable monomer (a1) and polymerizable monomer (a2) as polymerizable components.

[0064] In the aforementioned living radical polymerization, a dormant species, whose active polymerization end is protected by an atom or group of atoms, reversibly generates radicals and reacts with a monomer, allowing the growth reaction to proceed. Even after the first monomer is consumed, the growth end does not lose its activity and reacts with successively added second monomers to obtain a block polymer. Examples of such living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-cleavage radical polymerization (RAFT), nitroxide-mediated radical polymerization (NMP), and organotellurium-based radical polymerization (TERP). There are no particular restrictions on which of these methods to use, but ATRP is preferred due to its ease of control. ATRP is polymerized using an organic halide or sulfonyl halogenated compound as a polymerization initiator and a metal complex consisting of a transition metal compound and a ligand as a catalyst.

[0065] Specific examples of polymerization initiators that can be used with ATRP include 1-phenylethyl chloride, 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, α,α'-dichloroxylene, α,α'-dibromoxylen, hexakis(α-bromomethyl)benzene, and alkyl esters of 2-halogenated carboxylic acids with 1 to 6 carbon atoms (e.g., 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, etc.). More specific examples of alkyl esters of 2-halogenated carboxylic acids having 1 to 6 carbon atoms 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 those represented by M n+ X n . M n+ X n For the transition metal M of the transition metal compound represented by n+ Cu + , 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[[ID=7​​​​​​​​​​​​​​​​​​​​​​R represents an aryl group, a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), 12 This represents 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 a hydrogen atom or halogen (preferably 1 to 3 times with fluorine or chlorine). M n+ X n In the transition metal compounds represented by , n represents the formal charge on the metal and is an integer between 0 and 7.

[0067] Examples of ligand compounds capable of coordinating with the transition metal in the above-mentioned transition metal compounds include compounds having ligands containing one or more nitrogen, oxygen, phosphorus, or sulfur atoms that can coordinate with the transition metal via σ bonds, compounds having ligands containing two or more carbon atoms that can coordinate with the transition metal via π bonds, and compounds having ligands that can coordinate with the transition metal via μ bonds or η bonds.

[0068] The above transition metal complexes are not particularly limited, but preferred examples include transition metal complexes of groups 7, 8, 9, 10, and 11, and more preferred examples include complexes of 0-valent copper, 1-valent copper, 2-valent ruthenium, 2-valent iron, or 2-valent 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, tetramethylethylenediamine, pentamethyldiethylenetriamine, and polyamines such as hexamethyltris(2-aminoethyl)amine, when copper is the central metal. Examples of divalent ruthenium complexes include dichlorotris(triphenylphosphine)ruthenium, dichlorotris(tributylphosphine)ruthenium, dichloro(cyclooctadiene)ruthenium, dichlorobenzeneruthenium, dichlorop-cymenruthenium, 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; halogen 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 individually or in combination of two or more.

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

[0072] (Activated energy ray curable compound) In the present invention, "active energy ray curable compound" refers to a compound that has the property of hardening when exposed to active energy rays such as electron beams, ultraviolet rays, and visible light. Here, the active energy ray curable compound may take the form of a monomer, oligomer, or polymer. Furthermore, the above-mentioned ultraviolet rays refer to active energy rays with wavelengths between 10 nm and less than 380 nm, and the above-mentioned visible light rays refer to active energy rays with wavelengths between 380 nm and 800 nm.

[0073] When the active energy ray-curable compound is a resin (polymer), examples of such active energy ray-curable resins include polyester resins, (meth)acrylic resins, urethane resins, (meth)acrylic urethane resins, amide resins, silicone resins, silicate resins, epoxy resins, melamine resins, oxetane resins, and the like. Among the above, (meth)acrylic resin, (meth)acrylic urethane resin, and epoxy resin are preferred due to their high hardness, UV curing capability, and excellent productivity, with (meth)acrylic resin and (meth)acrylic urethane resin being more preferred.

[0074] When the active energy ray curable compound is a monomer, examples of such active energy ray curable monomers include acrylic monomers having two or more acryloyl groups, which are UV polymerizable functional groups, and preferably acrylic monomers having three to six acryloyl groups.

[0075] Examples of active energy ray curable acrylic monomers 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. Examples include 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 tricyclodecanedimethanol di(meth)acrylate.

[0076] The active energy ray curable acrylic monomers are 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, and tricyclodecanedimethanol di(meth)acrylate.

[0077] The active energy ray-curable compound used may be a single compound or two or more compounds may be used in combination.

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

[0079] (fine particles) When the hard coat layer also needs to have anti-glare properties, the hard coat layer forming composition preferably further contains fine particles, which are dispersed within the hard coat layer. Examples of the fine particles mentioned above 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; and glass fine particles and silicone fine particles.

[0080] The lower limit of the average particle diameter of the fine particles is, for example, 0.001 μm or more. The upper limit of the average particle diameter 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 diameter of the fine particles can be measured by a call counter.

[0081] The fine particles used may be a single type or two or more types may be used in combination.

[0082] The content of 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) If the hard coat layer forming composition is radical curable, the hard coat layer forming composition preferably further contains a photopolymerization initiator. Examples of the above-mentioned photopolymerization initiators include α-hydroxyacetophenone-based photopolymerization initiators, α-aminoacetophenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and intramolecular hydrogen abstraction type photopolymerization initiators, with α-hydroxyacetophenone-based photopolymerization initiators and α-aminoacetophenone-based photopolymerization initiators being preferred.

[0084] Examples of commercially available photopolymerization initiators include Omnirad2959, Omnirad184, Omnirad127D, and Omnirad1173 (IGMResins) as examples of α-hydroxyacetophenone-based photopolymerization initiators, and Omnirad907 and Omnirad369E (IGMResins) as examples of α-aminoacetophenone-based photopolymerization initiators.

[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, per 100 parts by mass of the active energy ray curable compound.

[0086] (UV absorber) The hard coat layer forming composition preferably further contains an ultraviolet absorber. The inclusion of an ultraviolet absorber in the hard coat layer forming composition can impart ultraviolet absorption properties to the resulting hard coat layer. The above-mentioned ultraviolet absorbers can be any compounds that absorb ultraviolet light (for example, with a wavelength of 355 nm), and examples include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, etc., with triazine-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers being preferred. When using a triazine-based UV absorber as the UV absorber, the triazine-based UV absorber is preferably a hydroxyphenyltriazine-based UV absorber.

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

[0088] (solvent) The hard coat layer forming composition may contain a solvent to adjust viscosity and other properties to provide suitable application. Examples of such solvents include dibutyl ether, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole, phenethole, 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-butylolactone, methyl 2-methoxyacetate, methyl 2-ethoxyacetate, ethyl 2-ethoxyacetate, ethyl 2-ethoxyacetate, ethyl 2-ethoxyacetate Examples include ethyl propionate, 2-methoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1,2-diacetoxyacetone, acetylacetone, diacetone alcohol, methyl acetoacetate, ethyl acetoacetate, methyl alcohol, 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, xylene, etc.

[0089] The solvent used may be a single type or two or more types may be used in combination.

[0090] The solvent content can be appropriately determined to achieve the desired viscosity; for example, it is preferable to set the concentration of the solids in the hard coat layer forming composition to be in the range of 5 to 90% by mass.

[0091] (Other additives) In addition to the components mentioned above, the hard coat layer forming composition may optionally contain other additives such as plasticizers, infrared absorbers, colorants (pigments, dyes, etc.), fluorescent whitening agents, dispersants, heat stabilizers, light stabilizers, antistatic agents, and antioxidants. The content of these other additives should be appropriately determined according to the purpose and application.

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

[0093] [Hard coat layer] A hard coat layer (hereinafter sometimes referred to as "the hard coat layer of the present invention") can be formed by applying the hard coat layer composition of the present invention onto a substrate and curing the resulting coating film by irradiating it with active energy rays such as electron beams, ultraviolet rays, or visible light. If the active energy ray is ultraviolet light, the irradiation intensity of the ultraviolet light is, for example, 10 to 5,000 mW / cm². 2 A suitable range is 10 to 10,000 mJ / cm², where the irradiation dose is, for example, 10 to 10,000 mJ / cm². 2 It would be good to set it within that range.

[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] There are no particular restrictions on the base material, but examples 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 copolymers, and cyclic polyolefin films.

[0096] The thickness of the substrate should be in the range of, for example, 20 μm to 1000 μm. When the substrate is a cellulose ester film, the film 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 comprises a polarizer and the hard coat layer of the present invention. The following describes each component of the polarizing plate of the present invention.

[0098] (Polarizer) A polarizer can be used in which a dichroic dye is adsorbed and oriented on a layer containing a polyvinyl alcohol (hereinafter sometimes referred to as "PVA")-based resin.

[0099] Known polarizers can be used, including, for example, a film formed by dyeing a PVA-based resin film with a dichroic dye and uniaxially stretching it; and a film formed by dyeing the PVA-based resin layer of a laminate, which is made by coating a substrate with a PVA-based resin solution, 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 polyvinyl acetate resins include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate with other monomers copolymerizable thereto. Examples of other monomers copolymerizable thereto 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, or polyvinyl butyral modified with aldehydes may also be used.

[0102] The degree of saponification of the PVA resin is preferably 85 mol% or more, more preferably 90 mol% or more, and even more preferably 99 mol% to 100 mol%. The degree of polymerization of the PVA 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 absorption dichroism at a wavelength between 380 nm and 780 nm. The transmittance of a 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 polarization degree of the polarizer is preferably 97.0% or higher, more preferably 99.0% or higher, and even more preferably 99.9% or higher.

[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, but may also have other layers. Examples of the layer configuration of the polarizing plate include a polarizer / adhesive layer / protective layer / hard coat layer, and a further layer having optical function, such as a phase difference layer, may be laminated on the hard coat layer.

[0106] (protective layer) The protective layer can be any known material, such as a film made of transparent resins including cellulose resins such as triacetylcellulose (TAC), polyester resins, polyvinyl alcohol resins, polycarbonate resins, polyamide resins, polyimide resins, polyethersulfone resins, polysulfone resins, polystyrene resins, polynorbornene resins, polyolefin resins, (meth)acrylic resins, and acetate 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 that makes up the adhesive layer can be any adhesive that is suitable for optical applications, and examples of such adhesives include water-based adhesives and photocuring adhesives.

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

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

[0111] Water-based adhesives containing PVA resin may further contain a crosslinking agent. Examples of such crosslinking agents include water-soluble epoxy compounds, dialdehydes, and isocyanates. When the PVA resin is an acetoacetyl group-containing PVA resin, the crosslinking agent is preferably one or more selected from glyoxal, glyoxylate, and methylolmelamine.

[0112] Water-based adhesives may contain organic solvents. The organic solvent is preferably an alcohol, given its miscibility with water, and among alcohols, methanol and / or ethanol are preferred. When the water-based adhesive contains 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 upon irradiation with active energy rays, including ultraviolet light. Examples include compositions containing photopolymerizable monomers such as photocurable epoxy monomers, photocurable acrylic monomers, and photocurable urethane monomers, as well as oligomers derived from these monomers, and substances that generate active species such as neutral radicals, anionic radicals, and cationic radicals upon irradiation 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 μm to 5 μm, more preferably in the range of 0.01 μm to 2 μm, and even more preferably in the range of 0.01 μm to 1 μm.

[0115] (optical functional layer) An optical functional layer is a layer that adds optical functionality to a polarizing plate, and an example of this is a phase difference layer. Examples of phase difference layers include a layer that provides a phase difference of λ / 2, a layer that provides a phase difference of λ / 4 (positive A plate), and a positive C plate. When a polarizer has a layer that provides a phase difference of λ / 4 as an optical functional layer, the polarizer can be a circular polarizer.

[0116] The optical functional layer may include an alignment layer and a substrate, or it may have two or more liquid crystal layers, alignment layers, and substrates. The protective layer described above can also serve as the phase difference layer, but the phase difference layer can also be laminated separately from the protective layer. This phase difference layer can be laminated to the polarizing plate via the adhesive layer described later.

[0117] Examples of phase difference layers include a birefringent film composed of a stretched film of a translucent thermoplastic resin, and a liquid crystal layer formed on a substrate film of a cellulose ester resin such as triacetylcellulose.

[0118] Examples of thermoplastic resins that constitute the phase difference layer include polycarbonate resins, polyester carbonate resins, polyester resins, polyvinyl acetal resins, polyarylate resins, cyclic olefin resins, cellulose resins, polyvinyl alcohol resins, polyamide resins, polyimide resins, polyether resins, polystyrene resins, and acrylic resins.

[0119] If the optical functional layer is a phase difference layer, the thickness of the phase difference layer can be appropriately determined according to the required optical properties, but for example, it is in the range of 50 to 300 μm.

[0120] Other examples of optical functional layers include light-gathering plates, brightness-enhancing films, reflective layers (reflective films), semi-transparent reflective layers (semi-transparent reflective films), light-diffusing layers (light-diffusing films), and anti-reflective films.

[0121] (Adhesive layer) An adhesive layer may be used in the lamination of the optical functional layer. This adhesive layer is used for bonding the optical functional layer and consists of an adhesive composition containing, for example, an adhesive resin such as (meth)acrylic resin, rubber resin, urethane resin, ester resin, silicone resin, or polyvinyl ether resin as a base polymer. The adhesive composition may be either photocurable or thermocurable.

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

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

[0124] The thickness of the 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 manufactured by known methods, 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, electroluminescent (EL) displays, plasma displays (PDs), and field emission displays (FEDs). [Examples]

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

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

[0129] [GPC measurement conditions] Measurement device: Tosoh Corporation high-speed GPC system "HLC-8320GPC" Column: Tosoh Corporation's "TSKGUARDCOLUMNSuperHZ-L" + Tosoh Corporation's "TSKgelSuperHZM-N" + Tosoh Corporation's "TSKgelSuperHZM-N" + Tosoh Corporation's "TSKgelSuperHZM-N" + Tosoh Corporation's "TSKgelSuperHZM-N" Detector: RI (Differential Refractometer) Data processing: EcoSEC Data Analysis version 1.07 manufactured by Tosoh Corporation. Column temperature: 40℃ Developing solvent: tetrahydrofuran Flow rate: 0.35mL / min Measurement sample: 7.5 mg of the sample was dissolved in 10 mL of tetrahydrofuran, and the resulting solution was filtered through a microfilter to be used as the measurement sample. Sample injection volume: 20 μL Standard sample: In accordance with the measurement manual for "HLC-8320GPC" mentioned above, the following monodisperse polystyrenes with known molecular weights were used.

[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 Tosoh Corporation's "F-10" F-20 manufactured by Tosoh Corporation Tosoh Corporation's "F-40" Tosoh Corporation's "F-80" Tosoh Corporation's "F-128" Tosoh Corporation's "F-288"

[0131] (Synthesis Example 1: Synthesis of Silicone-containing Random Copolymer (1)) 100.0 g of propylene glycol monomethyl ether acetate was charged into a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, 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 repeat number of propylene glycols: 4-6), and 7.5 g of t-butylperoxy-2-ethylhexanoate, a polymerization initiator, in 112.5 g of propylene glycol monomethyl ether acetate was set in the dropping device, and the solution was added dropwise over 2 hours while maintaining the temperature in the flask at 95°C. After the addition was complete, the mixture was reacted under a nitrogen stream at 95°C for 5 hours, and then the temperature was raised to 110°C and the mixture was reacted for 1 hour. After the reaction was complete, the solvent was removed by distillation under reduced pressure to obtain a silicone-containing random copolymer (1).

[0132] The molecular weight of the obtained 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 composition ratio, the content of silicone-containing polymerizable monomers in copolymer (1) was 33% by mass.

[0133] (Synthesis Example 2: Synthesis of Silicone-containing Random Copolymer (2)) 100.0 g of propylene glycol monomethyl ether acetate was charged into a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, 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 repeat number of propylene glycols: 4-6), and 7.5 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator) in 112.5 g of propylene glycol monomethyl ether acetate, was set in the dropping device and added dropwise over 2 hours while maintaining the temperature in the flask at 95°C. After the addition was complete, the mixture was reacted under a nitrogen stream at 95°C for 5 hours, and then the temperature was raised to 110°C and the mixture was reacted for 1 hour. After the reaction was complete, the solvent was removed by distillation under reduced pressure to obtain a silicone-containing random copolymer (2).

[0134] The molecular weight of the obtained 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 composition ratio, the content of silicone-containing polymerizable monomers in copolymer (2) was 44% by mass.

[0135] (Synthesis Example 3: Synthesis of Silicone-Containing Random Copolymer (3)) In a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, 100.0 g of butyl acetate was charged 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 t-butylperoxy-2-ethylhexanoate, a polymerization initiator, in 133.3 g of butyl acetate was set in the dropping device, and the solution was added dropwise over 2 hours while maintaining the temperature in the flask at 90°C. After the addition was complete, the mixture was reacted under a nitrogen stream at 90°C for 5 hours, and then the temperature was raised to 110°C and the mixture was reacted for 1 hour. After the reaction was complete, the solvent was removed by distillation under reduced pressure to obtain a silicone-containing random copolymer (3).

[0136] The molecular weight of the obtained silicone-containing random copolymer (3) was measured by GPC, and the weight-average molecular weight (Mw) was 16,000. Furthermore, based on the raw material composition ratio, the content of silicone-containing polymerizable monomers in copolymer (3) was 33% by 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 atmosphere. Then, 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 t-butylperoxy-2-ethylhexanoate, a polymerization initiator, were dissolved in 110.0 g of butyl acetate. This monomer and polymerization initiator solution was placed in a dropping apparatus and added dropwise over 2 hours while maintaining the flask temperature at 95°C. After the addition was complete, the mixture was reacted under a nitrogen stream at 95°C for 3 hours. After the reaction was complete, the solvent was removed by distillation under reduced pressure to obtain a silicone-containing random copolymer (4).

[0138] [ka] (In the above general formula (a1-1-1), the numerical mean of x1 is 10.)

[0139] The molecular weight of the obtained silicone-containing random copolymer (4) was measured by GPC, and the weight-average molecular weight (Mw) was 26,000. Furthermore, based on the raw material composition ratio, the content of silicone-containing polymerizable monomers in copolymer (4) was 33% by 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 UV-curable urethane acrylate resin ("Luxidia 17-806" manufactured by DIC Corporation, a butyl acetate solution containing 80% by mass of UV-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 hard coat layer coating composition was applied to a 188 μm thick PET film using a bar coater No. 13, and then the solvent was evaporated by placing the film in a drying oven set to 60°C for 5 minutes. The coating film on the PET film was cured using an ultraviolet curing apparatus (under a nitrogen atmosphere, using a high-pressure mercury lamp, with an ultraviolet irradiation dose of 200 mJ / cm²). 2 A hard coat film having a hard coat layer with a thickness of 8 μm on one side was fabricated by curing the coating film by irradiating it with ultraviolet light using ().

[0141] The smoothness of the hard coat layer of the fabricated hard coat film was evaluated using 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 its smoothness was evaluated according to the following criteria. ○: Almost no unevenness is observed on the surface of the hard coat layer. △: Some unevenness is observed on the surface of the hard coat layer. ×: Unevenness is observed throughout the surface of the hard coat layer.

[0142] [Table 1]

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

Claims

1. A hard coat layer forming composition containing an active energy ray curable compound and a silicone polymer, The silicone-containing polymer is a random copolymer comprising at least one 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 one or more polymerizable monomers (a2) selected from the group consisting of alkyl groups having 1 to 18 carbon atoms, aromatic groups having 6 to 18 carbon atoms, and polyoxyalkylene chains as polymerizable components, wherein the weight-average molecular weight (Mw) of the silicone-containing polymer is 8,000 or more, the content of the polymerizable monomer (a1) in the polymerizable components of the silicone-containing polymer is 15% by mass or more, and the polymerizable monomer (a2) is one or more selected from the group consisting of compounds represented by the following general formula (a2-1) and compounds represented by the following general formula (a2-2) as polymerizable components. 【Chemistry 1】 (In the above general formula (a), R １１ Each is independently an alkyl group having 1 to 6 carbon atoms or -OSi(R １４ ) ３ The group represented by (R １４ Each of these is an alkyl group having 1 to 3 carbon atoms. R １２ Each of these is an alkyl group having 1 to 6 carbon atoms, R １３ These are alkyl groups having 1 to 12 carbon atoms. x represents the number of repetitions and is an integer between 1 and 4. 【Chemistry 2】 (In the above general formulas (a2-1) and (a2-2), R 21 is a hydrogen atom or a methyl group. R22 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. n is an integer in the range of 1 to 4, and m represents the number of repetitions, with the average value of m being in the range of 1 to 200.

2. The hard coat layer forming composition 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). 【Transformation 3】 (In the above general formulas (a1-1) and (a1-2), R １１ 、R １２ 、R １３ and x are the same as R １１ 、R １２ 、R １３ 、R and x respectively in the general formula (a), R １５ is a hydrogen atom or a methyl group, L １ (It is a divalent organic group.)

3. The hard coat layer forming composition according to claim 1, wherein the polymerizable monomer (a2) comprises a compound represented by the general formula (a2-2).

4. The hard coat layer forming composition according to claim 1 or 2, wherein the silicone-containing polymer does not contain fluorine atoms.

5. The hard coat layer forming composition according to claim 1 or 2, comprising 0.01 to 5 parts by mass of the silicone-containing polymer per 100 parts by mass of the active energy ray curable compound.

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

7. A laminate comprising the film described in claim 6 on a substrate.

8. A polarizing plate having a polarizer and a hard coat layer, The hard coat layer contains a silicone polymer, The silicone-containing polymer is a random copolymer comprising at least one 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 one or more polymerizable monomers (a2) selected from the group consisting of alkyl groups having 1 to 18 carbon atoms, aromatic groups having 6 to 18 carbon atoms, and polyoxyalkylene chains as polymerizable components, wherein the weight-average molecular weight (Mw) of the silicone-containing polymer is 8,000 or more, the content of the polymerizable monomer (a1) in the polymerizable components of the silicone-containing polymer is 15% by mass or more, and the polymerizable monomer (a2) is one or more selected from the group consisting of compounds represented by the following general formula (a2-1) and compounds represented by the following general formula (a2-2). 【Chemistry 4】 (In the above general formula (a), R １１ Each is independently an alkyl group having 1 to 6 carbon atoms or -OSi(R １４ ) ３ The group represented by (R １４ Each of these is an alkyl group having 1 to 3 carbon atoms. R １２ Each of these is an alkyl group having 1 to 6 carbon atoms, R １３ These are alkyl groups having 1 to 6 carbon atoms. x represents the number of repetitions and is an integer between 1 and 4. 【Transformation 5】 (In the above general formulas (a2-1) and (a2-2), R 21 is a hydrogen atom or a methyl group. R22 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. n is an integer in the range of 1 to 4, and m represents the number of repetitions, with the average value of m being in the range of 1 to 200.

9. The polarizing plate according to claim 8, 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 6】 (In the above general formulas (a1-1) and (a1-2), R １１ , R １２ , R １３ and x are R in the general formula (a), respectively. １１ , R １２ , R １３ and are the same as x, R １５ is a hydrogen atom or a methyl group, L １ (It is a divalent organic group.)

10. An image display device comprising a polarizing plate according to claim 8 or 9.

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