Random copolymer, coating composition comprising same, and resist composition

Abstract

Provided is a copolymer which has leveling properties and recoating properties and functions as a silicone-based leveling agent. Specifically disclosed is a random copolymer comprising: a structural unit (A) derived from a polymerizable monomer (a1) having a functional group represented by-Si [OSi (R) 3] n [R '] 3-n and a (meth) acryloyl group; and a structural unit B derived from a polymerizable monomer (a2) having one or more groups selected from the group consisting of alkyl groups having 1-18 carbon atoms, aromatic groups having 6-18 carbon atoms, and polyoxyalkylene chain-containing groups, the content of the structural unit A being 50-80 mass% relative to the total of the structural unit A and the structural unit B, and the content of the structural unit B being 50-80 mass% relative to the total of the structural unit A and the structural unit B. And the random copolymer has a weight average molecular weight (Mw) of 10,000 or more.

Description

Technical Field

[0001] The present invention relates to a random copolymer, a coating composition containing the copolymer, and a resist composition. Background Art

[0002] A leveling agent is added to smooth the coating film obtained from a coating composition such as a coating paint composition or a resist composition. Specifically, by adding a leveling agent to the coating composition, the leveling agent aligns on the surface of the coating film, thereby reducing the surface tension of the coating film and obtaining the effect of smoothing the resulting coating film. In the coating film with a smoothed surface, the generation of craters or unevenness can be improved.

[0003] The leveling agent is used, for example, in automotive paints. The paint composition containing the leveling agent can impart high smoothness to the surface of the resulting coating film and can make the appearance of the automobile glossy.

[0004] As a leveling agent for automotive paints, a silicone-based leveling agent has been proposed (Patent Document 1).

[0005] The uses of the leveling agent are diverse. For example, it can also be used in a color resist composition used in the production of color filters for liquid crystal displays. The manufacture of color filters generally includes the following steps: coating a color resist composition on a glass substrate by a coating method such as spin coating or slit coating, exposing the dried coating film using a mask, and then developing to form a colored pattern. At this time, when the smoothness of the coating film is poor, there is unevenness in the film thickness, or there is coating unevenness, craters, etc., color unevenness of pixels may occur.

[0006] By adding a leveling agent to the color resist composition, the smoothness of the resulting coating film is improved, and the surfaces of red (R), green (G), blue (B) pixels, and a black matrix (BM) formed between these pixels can exhibit high smoothness, and a color filter with less color unevenness can be produced.

[0007] Patent Document 1 describes a silicone-based leveling agent synthesized by free radical polymerization. However, the silicone content in the actually evaluated leveling agent is low, and there is a problem that a sufficiently smooth coating film cannot be obtained.

[0008] In addition, Patent Document 2 describes a silicone-based leveling agent with good leveling properties synthesized by living polymerization. However, since it has a block structure, there are problems such as high liquid repellency of the coating film and poor recoatability.

[0009] Prior Art Documents

[0010] Patent Documents

[0011] Patent Document 1: Japanese Patent Laid-Open No. 2003-226834

[0012] Patent Document 2: WO 2021 / 131726 Summary of the Invention

[0013] Problems to be Solved by the Invention

[0014] An object of the present invention is to provide a copolymer that has leveling properties and recoatability and functions as a silicone-based leveling agent.

[0015] Means for Solving the Problems

[0016] The present inventors conducted intensive studies to solve the above problems and found that a leveling agent containing a random copolymer obtained by reacting a polymerizable monomer (a1) with a polymerizable monomer (a2) can achieve both leveling properties and recoatability. The polymerizable monomer (a1) has a functional group represented by -Si[OSi(R) 3 n [R’] 3-n and a (meth)acryloyl group, and the polymerizable monomer (a2) has one or more selected from 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, thereby completing the present invention.

[0017] That is, the present invention relates to a random copolymer containing: a structural unit A derived from a polymerizable monomer (a1) having a functional group represented by -Si[OSi(R) 3 n [R’] 3-n (n is an integer of 1 to 3; each R is independently an alkyl group having 1 to 3 carbon atoms; each R’ is independently an alkyl group having 1 to 3 carbon atoms) and a (meth)acryloyl group; and

[0018] a structural unit B derived from a polymerizable monomer (a2) having one or more selected from 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,

[0019] The content ratio of the structural unit A is 50% by mass to 80% by mass relative to the total of the structural unit A and the structural unit B, and

[0020] the weight average molecular weight (Mw) of the random copolymer is 10,000 or more.

[0021] In addition, the present invention relates to a coating composition containing the random copolymer.

[0022] ​​In addition, the present invention relates to a resist composition containing the random copolymer.

[0023] In addition, the present invention relates to an article containing the random copolymer.

[0024] In addition, the present invention relates to a method for producing a random copolymer by subjecting one or more of the compounds represented by the following formula (a2-1) and the compounds represented by the following formula (a2-2), and the compound represented by the following formula (a1-1) as reaction raw materials to radical polymerization.

[0025]

[0026] (In the formula (a1-1), formula (a2-1) and formula (a2-2),

[0027] R is independently an alkyl group having 1 to 3 carbon atoms,

[0028] R 1 is a hydrogen atom or a methyl group,

[0029] L 1 is a divalent organic group or a single bond,

[0030] R 21 is a hydrogen atom or a methyl group,

[0031] R 22 is an alkyl group having 1 to 18 carbon atoms,

[0032] R 23 is a hydrogen atom or a methyl group,

[0033] R 24 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms,

[0034] n is an integer in the range of 1 to 4, and m is an integer in the range of 1 to 200.)

[0035] Effects of the Invention

[0036] According to the present invention, it is possible to provide a copolymer that has leveling properties and recoatability and functions as a silicone-based leveling agent. Detailed Embodiments

[0037] Hereinafter, modes for carrying out the invention will be described.

[0038] It should be noted that in this specification, "x to y" represents a numerical range of "x or more and y or less". The upper limit value and the lower limit value described for the numerical range can be arbitrarily combined.

[0039] In addition, a mode obtained by combining two or more of the respective modes of the present invention described below is also a mode of the present invention.

[0040] In addition, in the description of the present application, "(meth)acrylate" means one or both of acrylate and methacrylate.

[0041] The random copolymer of one embodiment of the present invention includes: a structural unit A derived from a polymerizable monomer (a1), the polymerizable monomer (a1) having -Si[OSi(R) 3 n [R'] 3-n (where n is an integer from 1 to 3; each R is independently an alkyl group having 1 to 3 carbon atoms; each R' is independently an alkyl group having 1 to 3 carbon atoms) and an acryloyl group; and a structural unit B derived from a polymerizable monomer (a2), the polymerizable monomer (a2) having one or more selected from 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.

[0042] Moreover, relative to the total of the structural unit A and the structural unit B, the content rate of the structural unit A is 50% by mass to 80% by mass, and the weight-average molecular weight (Mw) of the random copolymer is 10,000 or more.

[0043] In the random copolymer of the present invention, by having the content rate of the structural unit A be 50% by mass to 80% and by randomly arranging -Si[OSi(R) 3 n [R'] 3-n shown functional groups in the polymer chain, it is possible to balance the leveling property and the recoatability.

[0044] The random copolymer of the present invention can be polymerized, for example, by subjecting the polymerizable monomer (a1) and the polymerizable monomer (a2) to radical polymerization.

[0045] Hereinafter, the polymerizable monomer (a1) and the polymerizable monomer (a2) constituting the random copolymer of the present invention will be described separately.

[0046] In the polymerizable monomer (a1), the -Si[OSi(R) 3 n [R'] 3-n shown functional group is preferably the -Si[OSi(R) 3 3 shown functional group, more preferably -Si[OSi(CH 3 ) 3 3 . When the -Si[OSi(R) 3 n [R'] 3-n shown functional group is -Si[OSi(CH 3 )​​​​​​3 3 When this is the case, the copolymer of the present invention can achieve a relatively high surface segregation ability.

[0047] In the present invention, the "polymerizable monomer" refers to a compound having a polymerizable unsaturated group. As the polymerizable unsaturated group of the polymerizable monomer (a1), any group containing a vinyl group is acceptable, and examples include: (meth)acryloyl group, (meth)acryloyloxy group, (meth)acrylamide group, vinyl ether group, allyl group, styryl group, maleimide group, etc. Among these, the (meth)acryloyl group or (meth)acryloyloxy group is preferred.

[0048] The polymerizable monomer (a1) is preferably a compound represented by the following formula (a1-1).

[0049]

[0050] (In the formula (a1-1),

[0051] R is independently an alkyl group having 1 to 3 carbon atoms,

[0052] R 1 is a hydrogen atom or a methyl group,

[0053] L 1 is a divalent organic group or a single bond.)

[0054] L 1 The divalent organic group of L is preferably an alkylene group having 1 to 50 carbon atoms or an alkoxy group having 1 to 50 carbon atoms.

[0055] As the alkylene group having 1 to 50 carbon atoms of L 1 examples include: methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group, n-decylene group, n-dodecylene group, isopropylidene group, 2-methylpropylene group, 2-methylhexylene group, tetramethylethylene group, etc.

[0056] L 1 The alkylene group having 1 to 50 carbon atoms of L is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and still more preferably a methylene group, an ethylene group, an n-propylene group or an isopropylidene group.

[0057] L 1 The alkoxy group having 1 to 50 carbon atoms of L is, for example, a group in which one or more of -CH 2 - in the above alkylene group is replaced by -O-.

[0058] L 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 still more preferably a methoxy group, an ethoxy group, a propoxy group, an oxytriethylene group, a butoxy group, an oxytetramethylene group, a pentyloxy group, a heptyloxy group or an octyloxy group.

[0059] In 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, a part of -CH 2 - may be replaced by a carbonyl group (-C(=O)-) or a phenylene group, and further, a hydroxyl group or the like may be substituted on the carbon atom.

[0060] The functional group represented by -Si[OSi(R) 3 3 shown is preferably -Si[OSi(CH 3 ) 3 3 , and this compound is represented by the following formula (a1-2).

[0061]

[0062] (In the formula (a1-2), R 1 is a hydrogen atom or a methyl group, and L 1 is a divalent organic group or a single bond.)

[0063] In the copolymer of the present invention, structural units A derived from two or more polymerizable monomers (a1) having different structures may be included. The polymerizable monomer (a1) is preferably a single polymerizable monomer.

[0064] The polymerizable monomer (a1) can be produced by a known method or a commercially available product can be used.

[0065] As a commercially available product of the polymerizable monomer (a1), for example, 3-(methacryloyloxy)propyltris(trimethylsiloxy)silane is commercially available.

[0066] In the copolymer of the present invention, the content of the structural unit A is 50% by mass or more, preferably 60% by mass or more, more preferably 65% by mass or more, based on the total of the structural unit A and the structural unit B. In addition, it is 80% by mass or less, preferably 75% by mass or less.

[0067] The content of the structural unit A can be adjusted according to the raw material input ratio of the polymerizable monomer (a1) when producing the copolymer of the present invention.

[0068] -Si[OSi(R) 3 n ​​​[R’] 3-n The content rate of the functional group shown is, for example, more than 30% by mass and 60% by mass or less of the total amount of the copolymer, preferably in the range of 40% to 60% by mass, and more preferably in the range of 50% to 60% by mass.

[0069] -Si[OSi(R) 3 n [R’] 3-n The content of the functional group shown can be adjusted according to the raw material input ratio of the polymerizable monomer (a1) when producing the copolymer of the present invention.

[0070] The polymerizable monomer (a2) is a polymerizable monomer having at least one selected from 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.

[0071] As the polymerizable unsaturated group of the polymerizable monomer (a2), any group containing a vinyl group may be used, and examples thereof include: (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamide group, vinyl ether group, allyl group, styryl group, maleimide group, etc. Among these, a (meth)acryloyl group or a (meth)acryloyloxy group is preferred.

[0072] The alkyl group having 1 to 18 carbon atoms of the polymerizable monomer (a2) may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group. Specific examples thereof include: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group, etc.

[0073] The alkyl group having 1 to 18 carbon atoms of the polymerizable monomer (a2) preferably has 1 to 6 carbon atoms.

[0074] As the aromatic group having 6 to 18 carbon atoms of the polymerizable monomer (a2), examples thereof include: phenyl group, naphthyl group, anthracen-1-yl group, phenanthren-1-yl group, etc.

[0075] The group containing a (poly)oxyalkylene chain of the polymerizable monomer (a2) refers to a monovalent group containing a repeating part of an oxyalkylene or a divalent linking group containing a repeating part of an oxyalkylene.

[0076] When the polymerizable unsaturated group of the polymerizable monomer (a2) is a (meth)acryloyl group, the polymerizable monomer having a group containing a (poly)oxyalkylene chain is, for example, a compound represented by the following general formula (a2-poa1) or general formula (a2-poa2).

[0077]

[0078] ​(In the formulas (a2-poa1) and (a2-poa2),

[0079] R a21 is independently a hydrogen atom or a methyl group;

[0080] R a22 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms;

[0081] p is an integer of 0 or more, q is an integer of 0 or more, r is an integer of 0 or more, and p + q + r is an integer of 1 or more;

[0082] X, Y, and Z are independently an alkylene group having 1 to 6 carbon atoms.)

[0083] In the formulas (a2-poa1) and (a2-poa2), -(XO) p -(YO) q -(ZO) r -R a22 and the group represented by -(XO) p -(YO) q -(ZO) r - correspond to groups containing (poly)oxyalkylene chains.

[0084] In the formulas (a2-poa1) and (a2-poa2), the alkylene groups having 1 to 6 carbon atoms for X, Y, and Z are preferably alkylene groups having 2 to 4 carbon atoms.

[0085] Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and a polymerizable unsaturated group of (meth)acryloyl group include: (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid isopropyl ester, (meth)acrylic acid n-butyl ester, (meth)acrylic acid sec-butyl ester, (meth)acrylic acid isobutyl ester, (meth)acrylic acid tert-butyl ester, (meth)acrylic acid n-pentyl ester, (meth)acrylic acid n-hexyl ester, (meth)acrylic acid n-heptyl ester, (meth)acrylic acid n-octyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid decyl ester, (meth)acrylic acid dodecyl ester, (meth)acrylic acid stearyl ester, (meth)acrylic acid isostearyl ester, etc., (meth)acrylic acid alkyl esters having 1 to 18 carbon atoms; (meth)acrylic acid dicyclopentyloxyethyl ester, (meth)acrylic acid isobornyloxyethyl ester, (meth)acrylic acid isobornyl ester, (meth)acrylic acid adamantyl ester, (meth)acrylic acid dimethyladamantyl ester, (meth)acrylic acid dicyclopentyl ester, (meth)acrylic acid dicyclopentenyl ester, etc., (meth)acrylic acid crosslinked cyclic alkyl esters having 1 to 18 carbon atoms, etc.

[0086] As the polymerizable monomer (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, for example, benzyl (meth)acrylate, 2-phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, etc. can be cited.

[0087] As the polymerizable monomer (a2) having an alkyl group with 1 to 18 carbon atoms and a polymerizable unsaturated group being a vinyl ether group, for example, 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, cyclohexyl vinyl ether, etc.; cycloalkyl vinyl ethers, etc.

[0088] As the polymerizable monomer (a2) having an aromatic group with 6 to 18 carbon atoms, for example, styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, etc. can be cited.

[0089] As the polymerizable monomer (a2) having an alkyl group with 1 to 18 carbon atoms and a polymerizable unsaturated group being a (meth)acryloylamide group, for example, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, diacetoneacrylamide, acryloylmorpholine, etc. can be cited.

[0090] As the polymerizable monomer (a2) having an alkyl group with 1 to 18 carbon atoms and a polymerizable unsaturated group being a maleimide group, for example, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, cyclohexyl maleimide, etc. can be cited.

[0091] As the polymerizable monomer (a2) having a group containing a polyoxyalkylene chain and a polymerizable unsaturated group being a (meth)acryloyl group, examples thereof 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 - poly(tetramethylene glycol) mono(meth)acrylate, poly(propylene glycol - tetramethylene glycol) mono(meth)acrylate, polypropylene glycol - poly(tetramethylene glycol) mono(meth)acrylate, poly(propylene glycol - 1,2 - butanediol) mono(meth)acrylate, polypropylene glycol - poly(1,2 - butanediol) mono(meth)acrylate, poly(ethylene glycol - 1,2 - butanediol) mono(meth)acrylate, polyethylene glycol - poly(1,2 - butanediol) mono(meth)acrylate, poly(tetraethylene glycol - 1,2 - butanediol) mono(meth)acrylate, poly(tetraethylene glycol - poly(1,2 - butanediol)) mono(meth)acrylate, 1,2 - butanediol mono(meth)acrylate, poly(ethylene glycol - trimethylene glycol) mono(meth)acrylate, polyethylene glycol - poly(trimethylene glycol) mono(meth)acrylate, poly(propylene glycol - trimethylene glycol) mono(meth)acrylate, polypropylene glycol - poly(trimethylene glycol) mono(meth)acrylate, poly(trimethylene glycol - tetramethylene glycol) mono(meth)acrylate, poly(trimethylene glycol - poly(tetramethylene glycol)) mono(meth)acrylate, poly(1,2 - butanediol - trimethylene glycol) mono(meth)acrylate, poly(1,2 - butanediol - poly(trimethylene glycol)) mono(meth)acrylate, 2 - hydroxyethyl (meth)acrylate, 2 - hydroxypropyl (meth)acrylate, 2 - hydroxybutyl (meth)acrylate, 4 - hydroxybutyl (meth)acrylate, poly(1,2 - butanediol - tetramethylene glycol) mono(meth)acrylate, poly(1,2 - butanediol - poly(tetramethylene glycol)) mono(meth)acrylate, and the like.

[0092] It should be noted that 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.

[0093] The polymerizable monomer (a2) is preferably at least one selected from the group consisting of the compound represented by the following formula (a2 - 1), the compound represented by the following formula (a2 - 2), and the compound represented by the following formula (a2 - 3), and more preferably at least one selected from the group consisting of the compound represented by the following formula (a2 - 1) and the compound represented by the following formula (a2 - 2).

[0094] When the copolymer of the present invention is used as a leveling agent, these compounds can exhibit high compatibility.

[0095]

[0096] (In the formulas (a2-1), (a2-2), and (a2-3),

[0097] R 21 is a hydrogen atom or a methyl group,

[0098] R 22 is an alkyl group having 1 to 18 carbon atoms,

[0099] R 23 is a hydrogen atom or a methyl group,

[0100] R 24 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms,

[0101] R 25 is a hydrogen atom or a methyl group,

[0102] R 26 are each independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms,

[0103] n is an integer in the range of 1 to 4, m is an integer in the range of 1 to 200, and l is an integer of 0 to 5.)

[0104] In the formulas (a2-1), (a2-2), and (a2-3), R 21 、R 23 、R 25 and R 27 are preferably each a hydrogen atom.

[0105] The polymerizable monomer (a2) can be produced by a known method.

[0106] In addition, commercially available products can be used as the polymerizable monomer (a2). For example, as commercially available products of the polymerizable monomer (a2) having a polyoxyalkylene chain-containing group and a polymerizable unsaturated group being a (meth)acryloyl group, there can be mentioned "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", "NK Ester AMP-60G" manufactured by Shin-Nakamura Chemical Co., Ltd.; "Blemmer PE-90", "Blemmer PE-200", "Blemmer PE-350", "Blemmer PME-100", "Blemmer PME-200", "Blemmer PME-400", "Blemmer PME-4000", "Blemmer PP-1000", "Blemmer PP-500", "Blemmer PP-800", "Blemmer 70PEP-350B", "Blemmer 55PET-800", "Blemmer 50POEP-800B", "Blemmer 10PPB-500B", "Blemmer NKH-5050", "Blemmer AP-400", "Blemmer AE-350" manufactured by NOF Corporation; Placcel F series manufactured by Daicel Corporation, etc.

[0107] The copolymer of the present invention may also be composed of two or more polymerizable monomers (a2) having different structures. The polymerizable monomer (a2) is preferably a single polymerizable monomer.

[0108] In the copolymer of the present invention, the content of the structural unit B relative to the total of the structural unit A and the structural unit B is 20% by mass or more. In addition, it is 50% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less.

[0109] The content of the structural unit B can be adjusted according to the raw material input ratio of the polymerizable monomer (a2) when manufacturing the copolymer of the present invention.

[0110] The copolymer of the present invention only needs to contain structural unit A and structural unit B. Within the range not damaging the effects of the present invention, other polymerizable monomers other than polymerizable monomer (a1) and polymerizable monomer (a2) can also be used as reaction raw materials.

[0111] The copolymer of the present invention is preferably a copolymer substantially composed of structural unit A and structural unit B, and more preferably a copolymer composed only of structural unit A and structural unit B. Here, "substantially composed" means that the total content ratio of structural unit A and structural unit B in the copolymer of the present invention is 80% by mass or more, 90% by mass or more, 95% by mass or more, or 99% by mass or more.

[0112] The copolymer of the present invention preferably does not contain fluorine atoms.

[0113] When the copolymer of the present invention is composed of polymerizable monomer (a1) and polymerizable monomer (a2), the copolymer of the present invention can be a copolymer that does not contain fluorine atoms.

[0114] The weight-average molecular weight (Mw) of the copolymer of the present invention is 10,000 or more. Preferably 15,000 or more, more preferably 20,000 or more. In addition, it is preferably 500,000 or less, more preferably 100,000 or less, and further preferably 40,000 or less.

[0115] In the present invention, the weight-average molecular weight (Mw) is a value obtained by measuring based on gel permeation chromatography (GPC) and performing polystyrene conversion. The value of the weight-average molecular weight (Mw) is measured by the method described in the examples.

[0116] [Manufacturing method of random copolymer]

[0117] The manufacturing method of the random copolymer of the present invention is not particularly limited, and it can be manufactured by a known method.

[0118] The copolymer of the present invention can be manufactured by solution polymerization method, bulk polymerization method, emulsion polymerization method, etc. based on polymerization mechanisms such as radical polymerization method, cationic polymerization method, anionic polymerization method. For example, if it is a radical polymerization method, the copolymer of the present invention can be manufactured by adding a polymerizable monomer mixture to an organic solvent and adding a general radical polymerization initiator.

[0119] As the above polymerization initiator, various polymerization initiators can be used. For example, peroxides such as tert-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, and diacyl peroxide; azo compounds such as azobisisobutyronitrile, dimethyl azobisisobutyrate, and phenylazotriphenylmethane; metal chelate compounds such as Mn(acac) 3 and the like.

[0120] As needed, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, ethyl mercaptoacetate, octyl mercaptoacetate, and thiol compounds having a coupling group such as γ-mercaptopropyltrimethoxysilane are used as additives such as chain transfer agents.

[0121] Examples of the above organic solvents include: alcohols such as ethanol, isopropyl alcohol, n-butanol, isobutanol, and tert-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and butyl lactate; monocarboxylic esters 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; polar solvents such as dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone; ethers such as methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, and ethyl cellosolve acetate; propylene glycols and their 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-based solvents such as 1,1,1-trichloroethane and chloroform; ethers such as tetrahydrofuran and dioxane; aromatic compounds such as benzene, toluene, and xylene; and furthermore, fluorinated inert liquids such as perfluorooctane and perfluoro-tri-n-butylamine can be cited.

[0122] These solvents can be used alone or in combination of two or more.

[0123] As the input ratio (by mass) of the polymerizable monomer (a1) and the polymerizable monomer (a2) when producing the copolymer of the present invention, for example, polymerizable monomer (a1):polymerizable monomer (a2) = 50:50 to 80:20, preferably polymerizable monomer (a1):polymerizable monomer (a2) = 60:40 to 80:20, more preferably polymerizable monomer (a1):polymerizable monomer (a2) = 65:35 to 80:20.

[0124] The polymerization temperature during radical polymerization is preferably in the range from room temperature to 120°C.

[0125] The copolymer of the present invention can also be produced by living polymerization such as living radical polymerization and living anionic polymerization of the polymerization components (living random copolymer).

[0126] In the above-mentioned living radical polymerization, the growth reaction is carried out by reversibly generating free radicals from dormant species in which the living polymerization terminal is protected by an atom or atomic group and reacting with monomers. Even when the first monomer is consumed, the growth terminal does not lose its activity and can react with the subsequently added second monomer to obtain a block polymer. Examples of such living radical polymerization include: atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer radical polymerization (RAFT), nitroxide-mediated radical polymerization (NMP), radical polymerization using organotellurium (TERP), etc. Among these methods, there is no particular limitation on which method to use, but in terms of ease of control, etc., ATRP is preferred. ATRP is carried out using an organic halide or a sulfonyl halide compound as a polymerization initiator and a metal complex containing a transition metal compound and a ligand as a catalyst.

[0127] Specific examples of the polymerization initiator 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, alkyl esters of C1-C6 2-halocarboxylic acids (such as methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate, ethyl 2-bromoisobutyrate, etc.) with C1-C6 alkyl groups.

[0128] More specific examples of the alkyl esters of C1-C6 2-halocarboxylic acids with C1-C6 alkyl groups include, for example: methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate, ethyl 2-bromoisobutyrate, etc.

[0129] The transition metal compound that can be used in ATRP is a compound represented by M n+ X n as shown.

[0130] As the transition metal M n+ X n of the transition metal compound represented by M n+ , it can be selected from 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+ , Rh4+ 、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+ Select from the group consisting of

[0131] M n+ X n X in the transition metal compound shown can be selected from a halogen atom, an alkoxy group having 1 to 6 carbon atoms, (SO 4 ) 1 / 2 ,(PO 4 ) 1 / 3 ,(HPO 4 ) 1 / 2 ,(H 2 PO 4 ), trifluoromethanesulfonate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate), SeR 11 , CN and R 12 COO. Here, R 11 represents an aryl group, a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and R 12 It 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 by 1 to 5 halogen atoms (preferably substituted by 1 to 3 fluorine or chlorine atoms).

[0132] M n+ X n In the transition metal compounds shown, n represents the formal charge on the metal and is an integer of 0-7.

[0133] As ligand compounds capable of coordinating with the transition metal of the above-mentioned transition metal compound, there can be listed: compounds having ligands containing one or more nitrogen atoms, oxygen atoms, phosphorus atoms or sulfur atoms that can coordinate with the transition metal via a σ bond, compounds having ligands containing two or more carbon atoms that can coordinate with the transition metal via a π bond, and compounds having ligands that can coordinate with the transition metal via a μ bond or an η bond.

[0134] The above-mentioned transition metal complex is not particularly limited. As preferred examples, transition metal complexes of Group 7, 8, 9, 10, and 11 can be cited. As further preferred examples, complexes of copper(0), copper(I), ruthenium(II), iron(II), or nickel(II) can be cited.

[0135] As specific examples of the catalyst that can be used in ATRP, when the central metal is copper, complexes formed with ligands such as 2,2'-bipyridine and its derivatives, 1,10-phenanthroline and its derivatives, polyamines such as tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexamethyltris(2-aminoethyl)amine can be cited. In addition, as ruthenium(II) complexes, dichlorotris(triphenylphosphine)ruthenium, dichlorotris(tributylphosphine)ruthenium, dichloro(cyclooctadiene)ruthenium, dichlorobenzene ruthenium, dichloro(p-cymene)ruthenium, dichloro(norbornadiene)ruthenium, cis-dichlorobis(2,2'-bipyridine)ruthenium, dichlorotris(1,10-phenanthroline)ruthenium, carbonylchlorohydridotris(triphenylphosphine)ruthenium, etc. can be cited. Further, as iron(II) complexes, bis(triphenylphosphine) complexes, triazacyclononane complexes, etc. can be cited.

[0136] In living radical polymerization, a solvent is preferably used.

[0137] As the solvent used in living radical polymerization, for example, 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; aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide, etc. can be cited.

[0138] The above solvents can be used alone or in combination of two or more.

[0139] The charging ratio of the polymerizable monomer can be the same as the charging ratio in the above radical polymerization method.

[0140] The polymerization temperature during the above living radical polymerization is preferably in the range of room temperature to 120 °C.

[0141] In the case of producing the copolymer of the present invention by living radical polymerization, metals resulting from the transition metal compound used in the polymerization may sometimes remain in the obtained polymer. The metals remaining in the obtained polymer can be removed using activated alumina, etc. after the polymerization is completed.

[0142] [Coating composition]

[0143] The copolymer of the present invention can preferably be used as a leveling agent for coating compositions, and the coating compositions of the present invention contain the copolymer of the present invention. The copolymer of the present invention can be a fluorine atom-free leveling agent, and thus is a leveling agent with low environmental accumulation and low environmental load.

[0144] The content of the copolymer of the present invention contained in the coating composition of the present invention varies depending on the type of the base resin, the coating method, the target film thickness, etc., but is preferably in the range of 0.0001 part by mass to 10 parts by mass, more preferably in the range of 0.001 part by mass to 5 parts by mass, and further preferably in the range of 0.01 part by mass to 2 parts by mass, relative to 100 parts by mass of the solid content of the coating composition. If the content of the copolymer of the present invention is within this range, the surface tension can be sufficiently reduced, the target leveling property can be obtained, and the occurrence of defects such as foaming during coating can be suppressed.

[0145] The use of the coating composition of the present invention is not particularly limited, and it can be used for any use as long as leveling property is required. For example, it can be cited: coating compositions for displays such as color filters (color resists), hard coatings for polarizing films, etc.

[0146] The coating composition of the present invention can be used, for example, as various coating compositions and photosensitive resin compositions.

[0147] When the coating composition of the present invention is used as a coating composition for paints, examples of the coating composition for paints include: paints using natural resins such as petroleum resin paints, shellac paints, rosin-based paints, cellulose-based paints, rubber-based paints, lacquer paints, urushiol resin paints, oil-based vehicle paints, etc.; paints using synthetic resins such as phenolic resin paints, alkyd resin paints, unsaturated polyester resin paints, amino resin paints, epoxy resin paints, vinyl resin paints, acrylic resin paints, polyurethane resin paints, silicone resin paints, fluororesin paints, etc.

[0148] By adding the copolymer of the present invention to the above coating compositions with different base resins, smoothness can be imparted to the resulting coating films.

[0149] In the coating composition for paints, colorants such as pigments, dyes, and carbon can be appropriately added as needed; inorganic powders such as silica, titanium dioxide, zinc oxide, alumina, zirconia, calcium oxide, and calcium carbonate; organic fine powders such as higher fatty acids, polyacrylic resins, and polyethylene; and various additives such as light resistance improvers, weather resistance improvers, heat resistance improvers, antioxidants, thickeners, and anti-settling agents.

[0150] Regarding the coating method of the coating composition, as long as it is a publicly known and commonly used coating method, any method can be used. For example, the following methods can be cited: roll coater, electrostatic coating, bar coater, gravure printing coater, knife coater, dip coating, spray coating, etc.

[0151] A photosensitive resin composition is a substance that changes physical properties such as the solubility, viscosity, transparency, refractive index, conductivity, and ion permeability of the resin by irradiating light such as visible light and ultraviolet light.

[0152] In the photosensitive resin composition, resist compositions (photoresist compositions, color resist compositions for color filters, etc.) require a high level of leveling property. Usually, the resist composition is coated by spin coating to a thickness of about 1 μm to 2 μm on a silicon wafer or a glass substrate on which various metals have been vapor-deposited. At this time, if there are deviations in the coating film thickness or coating unevenness, problems such as a decrease in the linearity and reproducibility of the pattern will occur, and a resist pattern with the target accuracy cannot be obtained. In addition to these problems, there are also various leveling-related problems such as dripping marks, overall unevenness, and a bead phenomenon where the film thickness at the edge is increased compared to the central part.

[0153] In the coating composition of the present invention, since the copolymer of the present invention can exhibit a high level of leveling property, a uniform coating film (cured product) can be formed. Therefore, when used as a resist composition, the above-mentioned problems can be solved.

[0154] When the coating composition of the present invention is used as a photoresist composition, the photoresist composition contains, in addition to the copolymer of the present invention, an alkali-soluble resin, a radiation-sensitive substance (photosensitive substance), a solvent, and the like.

[0155] The alkali-soluble resin contained in the photoresist composition refers to a resin that is soluble in an alkaline solution of the developer used when patterning the resist.

[0156] Examples of the alkali-soluble resin include: novolak resins obtained by condensing aromatic hydroxy compound derivatives such as phenol, cresol, xylenol, resorcinol, phloroglucinol, and hydroquinone with aldehyde compounds such as formaldehyde, acetaldehyde, and benzaldehyde; polymers or copolymers of vinylphenol compound derivatives such as o-vinylphenol, m-vinylphenol, p-vinylphenol, and α-methylvinylphenol; (meth)acrylic acid-based polymers or copolymers such as acrylic acid, methacrylic acid, and (meth)acrylic acid hydroxyethyl ester; polyvinyl alcohol; modified resins obtained by introducing radiation-sensitive groups such as quinone diazide groups, naphthoquinone azide groups, aromatic azide groups, and aromatic cinnamoyl groups into a part of the hydroxyl groups of these various resins; polyurethane resins containing acidic groups such as carboxylic acid and sulfonic acid in the molecule.

[0157] These alkali-soluble resins can be used alone or in combination of two or more.

[0158] The radiation-sensitive substance contained in the photoresist composition refers to a substance that changes the solubility of the alkali-soluble resin in the developer by irradiating energy rays such as ultraviolet rays, far ultraviolet rays, excimer lasers, X-rays, electron beams, ion beams, molecular beams, and γ-rays.

[0159] Examples of the radiation-sensitive substance include: quinone diazide compounds, diazo compounds, azide compounds, onium salt compounds, halogenated organic compounds, mixtures of halogenated organic compounds and organometallic compounds, organic acid ester compounds, organic acid amide compounds, organic acid imide compounds, poly(olefin sulfone) compounds, etc.

[0160] Examples of the quinone diazide compounds include: 1,2-benzoquinone diazide-4-sulfonate, 1,2-naphthoquinone diazide-4-sulfonate, 1,2-naphthoquinone diazide-5-sulfonate, 2,1-naphthoquinone diazide-4-sulfonate, 2,1-naphthoquinone diazide-5-sulfonate, and sulfonyl chlorides of quinone diazide derivatives such as 1,2-benzoquinone diazide-4-sulfonyl chloride, 1,2-naphthoquinone diazide-4-sulfonyl chloride, 1,2-naphthoquinone diazide-5-sulfonyl chloride, 2,1-naphthoquinone diazide-4-sulfonyl chloride, 2,1-naphthoquinone diazide-5-sulfonyl chloride, etc.

[0161] Examples of the diazo compounds include: salts of condensates of p-diazodiphenylamine with formaldehyde or acetaldehyde, diazo resin inorganic salts which are reaction products of hexafluorophosphate, tetrafluoroborate, perchlorate or periodate with the above condensate, and diazo resin organic salts which are reaction products of the above condensate with sulfonates as described in USP3300309.

[0162] Examples of the azide compounds include: azidochalcone acids, bisazidobenzylidene methylcyclohexanones, azidocinnamylidene acetophenones, aromatic azide compounds, aromatic bisazide compounds, etc.

[0163] Examples of the halogenated organic compounds include: halogen-containing oxadiazole compounds, halogen-containing triazine compounds, halogen-containing acetophenone compounds, halogen-containing benzophenone compounds, halogen-containing sulfoxide compounds, halogen-containing sulfone compounds, halogen-containing thiazole compounds, halogen-containing oxazole compounds, halogen-containing triazole compounds, halogen-containing 2-pyrone compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, halogen-containing heterocyclic compounds, sulfinyl halide compounds, etc.

[0164] In addition to the above, compounds used as halogen-based flame retardants such as tris(2,3-dibromopropyl) phosphate, tris(2,3-dibromo-3-chloropropyl) phosphate, chlorotetrabromomethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenyl allyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis(bromoethyl ether)tetrabromobisphenol A, bis(chloroethyl ether)tetrachlorobisphenol A, tris(2,3-dibromopropyl) isocyanurate, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxyethoxy-3,5-dibromophenyl)propane, etc., and compounds used as organochlorine pesticides such as dichlorodiphenyltrichloroethane, etc. are also exemplified as halogenated organic compounds.

[0165] Examples of the organic acid esters include carboxylic acid esters, sulfonic acid esters, etc. In addition, examples of the organic acid amides include carboxylic acid amides, sulfonic acid amides, etc. Further, examples of the organic acid imides include carboxylic acid imides, sulfonic acid imides, etc.

[0166] The radiation-sensitive substance can be used alone or in combination of two or more.

[0167] In the photoresist composition, the content of the radiation-sensitive substance is preferably in the range of 10 parts by mass to 200 parts by mass, more preferably in the range of 50 parts by mass to 150 parts by mass, relative to 100 parts by mass of the alkali-soluble resin.

[0168] Solvents for the photoresist composition include, for example: ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, and butyrolactone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol, heptanol, octanol, nonanol, and decanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dioxane; alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether; esters such as ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, propyl butyrate, ethyl lactate, and butyl lactate; monocarboxylic acid esters such as methyl 2-oxopropionate, ethyl 2-oxopropionate, propyl 2-oxopropionate, butyl 2-oxopropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, and butyl 2-methoxypropionate; cellosolve acetates such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, and butyl cellosolve acetate; propylene glycols such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether; halogenated hydrocarbons such as trichloroethylene, Freon solvents, hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs); perfluorinated solvents such as perfluorooctane; aromatics such as toluene and xylene; and polar solvents such as dimethylacetamide, dimethylformamide, N-methylacetamide, and N-methylpyrrolidone.

[0169] These solvents can be used alone or in combination of two or more.

[0170] When the coating composition of the present invention is used as a color resist composition, the color resist composition contains, in addition to the copolymer of the present invention, an alkali-soluble resin, a polymerizable compound, a colorant, and the like.

[0171] As the alkali-soluble resin contained in the color resist, the same resin as the alkali-soluble resin contained in the above photoresist composition can be used.

[0172] The polymerizable compound contained in the color resist composition refers to, for example, a compound having a photopolymerizable functional group capable of undergoing a polymerization or crosslinking reaction by irradiation with active energy rays such as ultraviolet rays.

[0173] Examples of the above-mentioned polymeric compounds include unsaturated carboxylic acids such as (meth)acrylic acid, esters of monohydroxy compounds and unsaturated carboxylic acids, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; esters obtained by the esterification reaction of unsaturated carboxylic acids with polycarboxylic acids and polyhydroxy compounds such as the above-mentioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds; polymeric compounds having a urethane skeleton obtained by reacting a polyisocyanate compound with a hydroxy compound containing a (meth)acryloyl group, polymeric compounds having an acid group, and the like.

[0174] The polymeric compound(s) may be used alone or in combination of two or more.

[0175] Examples of the esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include (meth)acrylates such as ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and (meth)acrylic acid glycerol ester.

[0176] In addition, it is also possible to list itaconic acid esters in which the (meth)acrylic acid moiety of these acrylates is partially replaced with itaconic acid, crotonic acid esters replaced with crotonic acid, maleic acid esters replaced with maleic acid, and the like.

[0177] Examples of the esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone di(meth)acrylate, resorcinol di(meth)acrylate, pyrogallol tri(meth)acrylate, and the like.

[0178] The ester obtained by the esterification reaction of an unsaturated carboxylic acid, a polycarboxylic acid, and a polyhydroxy compound may be a single substance or a mixture. Examples of such esters include esters obtained from (meth)acrylic acid, phthalic acid, and ethylene glycol; esters obtained from (meth)acrylic acid, maleic acid, and diethylene glycol; esters obtained from (meth)acrylic acid, terephthalic acid, and pentaerythritol; esters obtained from (meth)acrylic acid, adipic acid, butanediol, and glycerol, and the like.

[0179] Examples of the polymerizable compound having a urethane skeleton obtained by reacting the above-mentioned polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound include reaction products of aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate with (meth)acryloyl group-containing hydroxy compounds such as 2-hydroxyethyl (meth)acrylate and 3-hydroxy[1,1,1-tris(meth)acryloxymethyl]propane.

[0180] Examples of the polymerizable compound having an acid group include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids. A polyfunctional polymerizable compound having an acid group is preferably obtained by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride. As the aliphatic polyhydroxy compound used in the preparation of the polyfunctional polymerizable compound, pentaerythritol or dipentaerythritol is preferred.

[0181] In terms of improving developability, curability, etc., the acid value of the above-mentioned polyfunctional polymerizable compound is preferably in the range of 0.1 to 40, more preferably in the range of 5 to 30. When two or more polyfunctional polymerizable compounds having an acid group are used in combination, or when a polyfunctional polymerizable compound having an acid group and a polyfunctional polymerizable compound having no acid group are used in combination, the acid value of the mixture of the polymerizable compounds is preferably set within the above range.

[0182] Specific examples of the polymerizable compound having an acid group include a mixture mainly composed of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid ester of dipentaerythritol pentaacrylate, which is commercially available under the name of ARONIX TO-1382 (manufactured by Toagosei Co., Ltd.).

[0183] Examples of polymerizable compounds other than the above include (meth)acrylamides such as ethylene bis(meth)acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate.

[0184] In the color resist composition, the content of the polymerizable compound is preferably in the range of 5% by mass to 80% by mass, more preferably in the range of 10% by mass to 70% by mass, and further preferably in the range of 20% by mass to 50% by mass based on the total solid content of the color resist composition.

[0185] The colorant of the color resist composition is not particularly limited as long as it is a colorant capable of coloring, and can be, for example, a pigment or a dye.

[0186] The pigment can be any one of organic pigments and inorganic pigments. As the above-mentioned organic pigments, various color pigments such as red pigment, green pigment, blue pigment, yellow pigment, purple pigment, orange pigment, and brown pigment can be used. In addition, as the chemical structure of the organic pigment, for example, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanone-based, perylene-based, etc. can be cited. In addition, as the above-mentioned inorganic pigments, for example, barium sulfate, lead sulfate, titanium dioxide, lead yellow, iron oxide red, chromium oxide, etc. can be cited.

[0187] It should be noted that "C.I." below refers to the Color Index.

[0188] As the above-mentioned red pigment, for example, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, etc. can be cited. Among these, C.I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242 or 254 are preferred, and C.I. Pigment Red 177, 209, 224 or 254 are more preferred.

[0189] As the above-mentioned green pigments, for example, the following can be cited: C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, etc. Among these, C.I. Pigment Green 7, 36 or 58 is preferred.

[0190] As the above-mentioned blue pigments, for example, the following can be cited: C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc. Among these, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4 or 15:6 is preferred, and C.I. Pigment Blue 15:6 is more preferred.

[0191] As the above-mentioned yellow pigments, for example, the following can be cited: C.I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, etc. Among these, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185 is preferred, and C.I. Pigment Yellow 83, 138, 139, 150 or 180 is more preferred.

[0192] As the above-mentioned purple pigments, for example, C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc. can be cited. Among these, C.I. Pigment Violet 19 or 23 is preferred, and C.I. Pigment Violet 23 is more preferred.

[0193] As the above-mentioned orange pigments, for example, C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79, etc. can be cited. Among these, C.I. Pigment Orange 38 or 71 is preferred.

[0194] Since each pixel of the three primary colors of the color filter used in the liquid crystal display device and the organic electroluminescence (EL) display device is red (R), green (G), and blue (B), organic pigments of colors such as yellow, purple, and orange can also be used as hue adjustments based on the main components of the above-mentioned red pigment, green pigment, and blue pigment for the purpose of improving color reproducibility.

[0195] In order to improve the brightness of the color liquid crystal display device and the organic EL display device, the average particle size of the above-mentioned organic pigment is preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.3 μm or less. In order to achieve these average particle sizes, it is preferable to use the organic pigment after dispersion treatment.

[0196] The average primary particle size of the above-mentioned organic pigment is preferably 100 nm or less, more preferably 50 nm or less, further preferably 40 nm or less, and particularly preferably in the range of 10 nm to 30 nm.

[0197] It should be noted that the average particle size of the organic pigment is measured using a dynamic light scattering type particle size distribution meter. For example, it can be measured using a particle size distribution measuring device "UPA-EX150", "UPA-EX250", etc. manufactured by Nikkiso Co., Ltd.

[0198] As the colorant when the color resist composition is used for forming the black matrix (BM), there is no particular limitation as long as it is black, and examples include carbon black, lamp black, acetylene black, bone black, thermal carbon black, channel black, furnace black, graphite, iron black, titanium black, etc. Among these, from the viewpoints of light shielding rate and image characteristics, carbon black and titanium black are preferred.

[0199] Alternatively, it is also possible to mix two or more organic pigments to form a combination that results in black through color mixing.

[0200] Examples of commercially available products of the above carbon black include: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B, etc. manufactured by Mitsubishi Chemical Corporation; Printex 3, Printex 3OP, Printex 30, Printex 30OP, Printex 40, Printex 45, Printex 55, Printex60, Printex 75, Printex 80, Printex 85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Printex G, SpecialBlack 550, SpecialBlack 350, SpecialBlack 250, SpecialBlack 100, SpecialBlack 6, SpecialBlack 5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, ColorBlack FW200, Color Black S160, Color Black S170, etc. manufactured by Evonik Degussa Japan Co., Ltd.Examples include Monarch 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R, BLACK PEARLS480, PEARLS130, VULCAN XC72R, ELFTEX-8, etc. manufactured by Cabot Japan Co., Ltd. Examples also include RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000, etc. manufactured by Columbian Carbon Company.,

[0201] Among the above carbon blacks, carbon black covered with resin is preferably used as the one having high optical density and high surface resistivity required for the black matrix of the color filter.

[0202] Examples of commercially available products of the above titanium black include Titanium Black 10S, 12S, 13R, 13M, 13M-C, etc. manufactured by Mitsubishi Materials Corporation.

[0203] As the colorant for forming the black matrix (BM), two or more organic pigments can be mixed to form black by color mixing. Examples include black pigments mixed with three pigments of red, green, and blue.

[0204] Examples of colorants that can be used in combination for the preparation of black pigments include: Victoria Pure Blue (C.I. 42595), Auramine O (C.I. 41000), Cathilon Brilliant Flavine (Basic 13), Rhodamine 6GCP (C.I. 45160), Rhodamine B (C.I. 45170), Safranin OK 70:100 (C.I. 50240), Erioglaucin X (C.I. 42080), No. 120 / LIONOL Yellow (C.I. 21090), LIONLO Yellow GRO (C.I. 21090), SYMULER FAST Yellow 8GF (C.I. 21105), Benzidine Yellow 4T-564D (C.I. 21095), SYMULER FAST Red 4015 (C.I. 12355), LIONOL Red 7B4401 (C.I. 15850), Fastogen Blue TGR-L (C.I. 74160), LIONOL Blue SM (C.I. 26150), LIONOL Blue ES (C.I. Pigment Blue 15:6), LIONOGEN Red GD (C.I. Pigment Red 168), LIONOL Green 2YS (C.I. Pigment Green 36), etc.

[0205] As other colorants that can be mixed and used for preparing black pigments, for example, the following can be cited: C.I. Pigment Yellow 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. Pigment Orange 36, 43, 51, 55, 59, 61, C.I. Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. Pigment Violet 19, 23, 29, 30, 37, 40, 50, C.I. Pigment Blue 15, 15:1, 15:4, 22, 60, 64, C.I. Pigment Green 7, C.I. Pigment Brown 23, 25, 26, etc.

[0206] When carbon black is used as a black pigment, the average primary particle diameter of the carbon black is preferably in the range of 0.01 μm to 0.08 μm, and in terms of good developability, it is more preferably in the range of 0.02 μm to 0.05 μm.

[0207] The particle shape of carbon black is different from that of organic pigments, etc., and it exists in a state called structure where primary particles are fused with each other, and sometimes fine pores are formed on the particle surface by post-treatment. Therefore, in order to represent the particle shape of carbon black, usually in addition to the average particle diameter of the primary particles obtained by the same method as the above-mentioned organic pigments, it is also preferable to measure the dibutyl phthalate (DBP) absorption amount (JIS K6221) and the specific surface area based on the BET method (JIS K6217), and use them as indexes of structure and pore amount.

[0208] The dibutyl phthalate (hereinafter simply referred to as "DBP") absorption amount of carbon black is preferably in the range of 40 cm 3 / 100 g to 100 cm 3 / 100 g, and in terms of good dispersibility and developability, it is more preferably in the range of 50 cm 3 / 100 g to 80 cm 3 / 100 g. The specific surface area of carbon black based on the BET method is preferably in the range of 50 m 2 / g to 120 m 2 / g, and in terms of good dispersion stability, it is more preferably in the range of 60 m 2 / g to 95 m 2 / g.

[0209] For dyes used as colorants in the color resist composition, for example, the following can be cited: azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methylene dyes, etc.

[0210] Examples of the above azo dyes include C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive Red 17, C.I. Reactive Red 120, C.I. Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Mordant Red 7, C.I. Mordant Yellow 5, C.I. Mordant Black 7, etc.

[0211] Examples of the above anthraquinone dyes include C.I. Vat Blue 4, C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, C.I. Disperse Blue 60, etc.

[0212] Examples of the above phthalocyanine dyes include C.I. Vat Blue 5, etc. Examples of the above quinone imine dyes include C.I. Basic Blue 3, C.I. Basic Blue 9, etc. Examples of the above quinoline dyes include C.I. Solvent Yellow 33, C.I. Acid Yellow 3, C.I. Disperse Yellow 64, etc. Examples of the above nitro dyes include C.I. Acid Yellow 1, C.I. Acid Orange 3, C.I. Disperse Yellow 42, etc.

[0213] In terms of the excellent light resistance, weather resistance and fastness of the obtained coating film, the colorant of the color resist composition is preferably a pigment, but in order to adjust the hue, a dye may also be used in combination with the pigment as needed.

[0214] In the color resist composition, the content of the colorant is preferably 1% by mass or more in the total solid content of the color resist composition, more preferably in the range of 5% to 80% by mass, and still more preferably in the range of 5% to 70% by mass.

[0215] When the color resist composition is used for forming each pixel of red (R), green (G), and blue (B) in a color filter, the content of the colorant in the color resist composition is preferably in the range of 5% to 60% by mass in the total solid content of the color resist composition, more preferably in the range of 10% to 50% by mass.

[0216] When a color resist composition is used for forming a black matrix of a color filter, the content of the colorant in the color resist composition is preferably in the range of 20% by mass to 80% by mass of the total solid components of the color resist composition, and more preferably in the range of 30% by mass to 70% by mass.

[0217] In the color resist composition, when the colorant is a pigment, it is preferably used in the form of a pigment dispersion liquid prepared by dispersing the pigment in an organic solvent using a dispersant.

[0218] Examples of the above-mentioned dispersant include: surfactants; intermediates or derivatives of pigments; intermediates or derivatives of dyes; resinous dispersants such as polyamide-based resins, polyurethane-based resins, polyester-based resins, and acrylic resins. Among these, graft copolymers having a nitrogen atom, acrylic block copolymers having a nitrogen atom, urethane resin dispersants, etc. are preferred. Since these dispersants have a nitrogen atom, the dispersibility stability is improved by making the nitrogen atom have an affinity for the pigment surface and increasing the affinity of the part other than the nitrogen atom for the medium.

[0219] These dispersants can be used alone or in combination of two or more.

[0220] Examples of commercially available products of the above-mentioned dispersant include: "EFKA" series (such as "EFKA46", etc.) manufactured by BASF; "Disperbyk" series, "BYK" series (such as "BYK-160", "BYK-161", "BYK-2001", etc.) manufactured by BYK-Chemie Japan; "Solsperse" series manufactured by Lubrizol Japan Co., Ltd.; "KP" series manufactured by Shin-Etsu Chemical Co., Ltd., "Polyflow" series manufactured by Kyoeisha Chemical Co., Ltd.; "DISPARLON" series manufactured by Kusumoto Chemical Co., Ltd.; "AJISPER" series (such as "AJISPER PB-814", etc.) manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0221] Examples of the organic solvent used when preparing the above-mentioned pigment dispersion liquid include: acetate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxypropionate; aromatic solvents such as toluene, xylene, and methoxybenzene; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, and diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; nitrogen compound solvents such as N,N-dimethylformamide, γ-butyrolactam, and N-methyl-2-pyrrolidone; lactone solvents such as γ-butyrolactone; carbamates, etc.

[0222] These solvents can be used alone or in combination of two or more kinds.

[0223] Examples of the method for preparing the above pigment dispersion include: a method via a kneading and dispersing step and a fine-dispersing step of a colorant, a method using only the fine-dispersing step, etc. In the above kneading and dispersing step, a colorant, a part of an alkali-soluble resin, and, if necessary, the above dispersant are mixed and kneaded. The colorant can be dispersed by applying a strong shearing force while using a kneader.

[0224] Examples of the machine used in kneading include: two-roll mill, three-roll mill, ball mill, trommel, disperser, kneader, kneading extruder, homogenizer, mixer, single-screw or twin-screw extruder, etc.

[0225] Before the above kneading, the colorant is preferably made finer in particle size by a salt grinding method or the like.

[0226] In the above fine-dispersing step, by using a disperser, a substance obtained by adding a solvent to the composition containing a colorant obtained in the above kneading and dispersing step, or a substance obtained by mixing a colorant, an alkali-soluble resin, a solvent, and, if necessary, the above dispersant is mixed and dispersed together with a dispersion medium of fine particles of glass, zirconia, or ceramic, and the particles of the colorant can be dispersed to a minute state close to primary particles.

[0227] From the viewpoint of improving the transmittance, contrast, etc. of the color filter, the average particle diameter of the primary particles of the colorant is preferably 10 nm to 100 nm, more preferably 10 nm to 60 nm.

[0228] It should be noted that the average particle diameter of the colorant is measured by using a dynamic light scattering type particle size distribution meter. For example, it can be measured by using a particle size distribution measuring device "UPA-EX150", "UPA-EX250", etc. manufactured by Nikkiso Co., Ltd.

[0229] Examples

[0230] Hereinafter, specific examples are given to further illustrate the present invention in detail. It should be noted that the weight average molecular weight (Mw) of the synthesized resin is measured under the following GPC measurement conditions.

[0231] [GPC measurement conditions]

[0232] Measuring device: High-speed GPC device "HLC-8420GPC" manufactured by Tosoh Corporation

[0233] Column: "TSK GUARDCOLUMN SuperHZ-L" manufactured by Tosoh Corporation + "TSK gel SuperHZM-N" manufactured by Tosoh Corporation + "TSK gel SuperHZM-N" manufactured by Tosoh Corporation + "TSK gel SuperHZM-N" manufactured by Tosoh Corporation + "TSK gel SuperHZM-N" manufactured by Tosoh Corporation

[0234] Detector: RI (Differential Refractometer)

[0235] Data Processing: "EcoSEC Data Analysis Version 1.07" manufactured by Tosoh Corporation

[0236] Column Temperature: 40 °C

[0237] Eluent: Tetrahydrofuran

[0238] Flow Rate: 0.35 mL / min

[0239] Test Sample: A solution obtained by dissolving 7.5 mg of the sample in 10 mL of tetrahydrofuran and filtering the resulting solution through a microporous filter is used as the test sample.

[0240] Sample Injection Volume: 20 μL

[0241] Standard Sample: According to the measurement manual of the above-mentioned "HLC-8420GPC", the following monodisperse polystyrene with known molecular weight is used.

[0242] (Monodisperse Polystyrene)

[0243] "A-300" manufactured by Tosoh Corporation

[0244] "A-500" manufactured by Tosoh Corporation

[0245] "A-1000" manufactured by Tosoh Corporation

[0246] "A-2500" manufactured by Tosoh Corporation

[0247] "A-5000" manufactured by Tosoh Corporation

[0248] "F-1" manufactured by Tosoh Corporation

[0249] "F-2" manufactured by Tosoh Corporation

[0250] "F-4" manufactured by Tosoh Corporation

[0251] "F-10" manufactured by Tosoh Corporation

[0252] "F-20" manufactured by Tosoh Corporation

[0253] "F-40" manufactured by Tosoh Corporation

[0254] "F-80" manufactured by Tosoh Corporation

[0255] "F-128" manufactured by Tosoh Corporation

[0256] "F-288" manufactured by Tosoh Corporation

[0257] Example 1

[0258] In a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, 100.0 g of butyl acetate as a solvent was charged, and the temperature was raised to 90 °C while stirring under a nitrogen stream. Next, 67.0 g of 3-methacryloxypropyltris(trimethylsiloxy)silane (forming structural unit A), 33.0 g of propylene glycol-polybutylene glycol-monomethacrylate (forming structural unit B, manufactured by NOF Corporation, Blemmer 10PPB-500B), and 70.0 g of butyl acetate as a solvent were mixed to prepare a mixed solution A. In addition, 3.0 g of an initiator (Perbutyl O, manufactured by NOF Corporation) and 63.3 g of butyl acetate as a solvent were mixed to prepare a mixed solution B.

[0259] The mixed solution A and the mixed solution B were added dropwise into the glass flask at 90 °C over 120 minutes. After the dropping was completed, the mixture was stirred at 90 °C for 5 hours, and then the temperature was raised to 110 °C and stirred for 1 hour. After the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain a random copolymer (1).

[0260] Analysis by GPC showed that the weight-average molecular weight (Mw) was 17,000. In addition, based on the raw material input ratio, the content rate of the functional group represented by -Si[OSi(CH 3 ) 3 3 in the random copolymer (1) was 50% by mass.

[0261] Comparative Example 1

[0262] ​In a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, 100.0 g of butyl acetate as a solvent was charged, and the temperature was raised to 90 °C with stirring under a nitrogen stream. Next, 33.0 g of 3-methacryloxypropyltris(trimethylsiloxy)silane, 67.0 g of propylene glycol-polybutylene glycol-monomethacrylate, and 70.0 g of butyl acetate as a solvent were mixed to prepare a mixed solution A. In addition, 3.0 g of an initiator (Perbutyl O) and 63.3 g of butyl acetate as a solvent were mixed to prepare a mixed solution B.

[0263] The mixed solution A and the mixed solution B were added dropwise into the glass flask at 90 °C over 120 minutes. After the addition was completed, stirring was carried out at 90 °C for 5 hours, and then the temperature was raised to 110 °C and stirring was carried out for 1 hour. After the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain a random copolymer (2).

[0264] Analysis was performed by GPC, and the result was that Mw was 17,000. In addition, according to the raw material input ratio, the content rate of the functional group represented by -Si[OSi(CH 3 ) 3 3 in the random copolymer (2) was 24% by mass.

[0265] Comparative Example 2

[0266] In a flask that had been purged with nitrogen, 75.0 g of methyl ethyl ketone as a solvent and 33.5 g of 3-methacryloxypropyltris(trimethylsiloxy)silane were charged, and the temperature was raised to 50 °C with stirring under a nitrogen stream. Next, 4.2 g of 2,2'-bipyridine and 1.5 g of copper(I) chloride were added, and stirring was carried out for 30 minutes while maintaining the temperature inside the flask at 50 °C. Thereafter, 2.7 g of ethyl 2-bromoisobutyrate was added, and the reaction was carried out at 50 °C for 4 hours under a nitrogen stream to obtain a polymer segment containing a trimethylsilyl group.

[0267] Next, 16.5 g of propylene glycol-polybutylene glycol-monomethacrylate was added to the reaction system containing the polymer segment, and the reaction was carried out at 50 °C for 20 hours to obtain a reaction product. Next, 30 g of activated alumina was added to the obtained reaction product and stirred. After filtering the activated alumina, the solvent was removed by distillation under reduced pressure to obtain a block copolymer (3).

[0268] The molecular weight of the block copolymer (3) was measured by GPC. The results were that Mw was 7,100, Mn was 6,100, and Mw / Mn was 1.2. In addition, according to the raw material input ratio, the -Si[OSi(CH 3 ) 3 3 ​​The content rate of the functional group shown is 50% by mass.

[0269] [Film Formation and Evaluation of Coating Film]

[0270] (1) Evaluation Method for Smoothness of Coating Film

[0271] 3.0 g of a 40% by mass resin solution of an alkali-soluble resin (ACRYDIC ZL-295, manufactured by DIC Corporation), 1.2 g of Aronix M-402 (manufactured by Toagosei Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), 0.001 g of the copolymer obtained in the examples or comparative examples in terms of solid content, and 3.8 g of PGMEA were mixed to obtain a coating composition.

[0272] 3 mL of this composition was dropped onto the central part of a 10 cm × 10 cm chromium-plated glass substrate, spin-coated at a rotation speed of 1000 rpm for 10 seconds, and then heated and dried at 100°C for 100 seconds to produce an article (laminate) having a coating film layer. The coating film layer was visually observed, and the smoothness of the coating film layer was evaluated according to the following criteria.

[0273] ○: Almost no coating film unevenness was observed.

[0274] △: Some coating film unevenness was observed.

[0275] ×: Multiple coating film unevennesses were observed.

[0276] (2) Evaluation Method for Reworkability

[0277] To 3.0 g of a 40% by mass resin solution of an alkali-soluble resin and 1.2 g of Aronix M-402, the copolymer obtained in the examples or comparative examples was added at a solid content ratio of 1.0% by mass. It was diluted with PGMEA to prepare a solution such that the resin solid content concentration (NV) became 19.5%.

[0278] 1 mL of the prepared solution was dropped onto the central part of a 7 cm × 7 cm glass substrate, spin-coated at a rotation speed of 1000 rpm for 10 seconds, and then heated and dried at 80°C for 3 minutes to volatilize the solvent.

[0279] Next, the dried coating film was irradiated with ultraviolet rays (UV) using an ultraviolet curing device (in an air atmosphere, high-pressure mercury lamp, ultraviolet irradiation amount 0.5 kJ / m 2 ) to cure it. Thereafter, it was developed using a 0.5% KOH-based developer, and then heat-treated at 230°C for 20 minutes to obtain a cured film.

[0280] For the surface of the cured film, the contact angle of PGMEA was measured using a contact angle measuring device ("MODEL CA-W701" manufactured by Kyowa Interface Science Co., Ltd.). A small contact angle indicates good recoatability of the cured film. Based on the contact angle, the recoatability was evaluated according to the following criteria.

[0281] ○: The contact angle of PGMEA is 20 degrees or less

[0282] △: The contact angle of PGMEA exceeds 20 degrees and is 30 degrees or less

[0283] ×: The contact angle of PGMEA exceeds 30 degrees

[0284] [Table 1]

[0285]

[0286] It can be confirmed from Table 1 that the film obtained from the composition using the random copolymer of the examples is excellent in both leveling property and recoatability as compared with the comparative examples.

Claims

1. A random copolymer comprising: Structural unit A derived from polymerizable monomer (a1), the polymerizable monomer (a1) having -Si[OSi(R) 3 n [R’] 3-n the functional group shown and a (meth)acryloyl group, where n is an integer from 1 to 3, R is independently an alkyl group having 1 to 3 carbon atoms, and R’ is independently an alkyl group having 1 to 3 carbon atoms; and​ A structural unit B derived from a polymerizable monomer (a2), the polymerizable monomer (a2) having one or more selected from 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, Based on the total of the structural unit A and the structural unit B, the content of the structural unit A is 50% by mass to 80% by mass, and The weight-average molecular weight (Mw) of the random copolymer is 10,000 or more.

2. The random copolymer according to claim 1, which is obtained by radical polymerization of the polymerizable monomer (a1) and the polymerizable monomer (a2).

3. The random copolymer according to claim 1 or 2, wherein, The content rate of the -Si[OSi(R) 3 n [R’] 3-n group in the structural unit A is more than 30% by mass and 60% by mass or less, relative to the random copolymer.​ 4. The random copolymer according to any one of claims 1 to 3, wherein, The polymerizable monomer (a1) is a compound represented by the following formula (a1-1), In the formula (a1-1), R are each independently an alkyl group having 1 to 3 carbon atoms, R 1 is a hydrogen atom or a methyl group, L 1 is a divalent organic group or a single bond.

5. The random copolymer according to any one of claims 1 to 4, wherein, The -Si[OSi(R) 3 n [R’] 3-n The functional group shown is -Si[OSi(CH 3 ) 3 3 .​​ 6. The random copolymer according to any one of claims 1 to 5, wherein, The polymerizable monomer (a2) is a polymerizable monomer having an alkyl group having 1 to 18 carbon atoms and / or a group containing a polyoxyalkylene chain.

7. The random copolymer according to any one of claims 1 to 6, wherein, The polymerizable monomer (a2) is one or more selected from the group consisting of a compound represented by the following formula (a2-1) and a compound represented by the following formula (a2-2), In the formula (a2-1) and the formula (a2-2), 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 n is an integer in the range of 1 to 4, and m is an integer in the range of 1 to 200.

8. The random copolymer according to claim 7, wherein, R 21 and R 23 are each a hydrogen atom, respectively.

9. The random copolymer according to any one of claims 1 to 8 does not contain fluorine atoms.

10. A coating composition comprising the random copolymer according to any one of claims 1 to 9.

11. The coating composition according to claim 10, which is used for a display.

12. A resist composition comprising the random copolymer according to any one of claims 1 to 9.

13. An article comprising the random copolymer according to any one of claims 1 to 9.

14. A method for producing a random copolymer, in which any one or more of a compound represented by the following formula (a2-1) and a compound represented by the following formula (a2-2) and a compound represented by the following formula (a1-1) are used as reaction raw materials for radical polymerization, In the formula (a1-1), the formula (a2-1) and the formula (a2-2), R are each independently an alkyl group having 1 to 3 carbon atoms, R 1 is a hydrogen atom or a methyl group, L 1 is a divalent organic group or a single bond, 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, n is an integer in the range of 1 to 4, and m is an integer in the range of 1 to 200.

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