Polymers, coating compositions, resist compositions and articles

Abstract

Provided is a polymer functioning as a leveling agent that imparts high smoothness to a coating film. Specifically, this polymer comprises a polymer block (A1) of a polymerizable monomer (a1) having a group represented by general formula (1), wherein the content ratio of the polymer block (A1) exceeds 50 mass%.

Description

[Technical Field]

[0001] The present invention relates to a polymer, a coating composition comprising the polymer, a resist composition comprising the polymer, and an article comprising the polymer. [Background technology]

[0002] Leveling agents are added to smooth the coating film obtained by applying a coating composition such as a paint composition or a resist composition. Specifically, by adding a leveling agent to a coating composition, the leveling agent orients on the surface of the coating film, reducing the surface tension of the coating film and achieving a smooth coating film. A coating film with a smooth surface can reduce the occurrence of cissing and unevenness.

[0003] Leveling agents are used, for example, in automotive paints, and coating compositions containing leveling agents can impart high smoothness to the resulting coating surface and can impart gloss to the exterior of the automobile. Silicone leveling agents have been proposed as leveling agents for use in automotive paints (Patent Documents 1 and 2).

[0004] Leveling agents have a wide range of applications, including in color resist compositions used in the production of color filters for liquid crystal displays. The production of color filters generally involves applying a color resist composition to a glass substrate by a coating method such as spin coating or slit coating, exposing the dried coating to light using a mask, and then developing the resulting coating to form a colored pattern. If the coating is not smooth enough and has uneven thickness, or if there are coating irregularities or repelling defects, color unevenness in the pixels may occur. By adding a leveling agent to the color resist composition, the smoothness of the resulting coating film can be improved, and the surfaces of the red (R), green (G), and blue (B) pixels and the black matrix (BM) formed between these pixels can exhibit high smoothness, resulting in a color filter with minimal color unevenness. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-226834 [Patent Document 2] Japanese Patent Application Publication No. 2018-199765 Summary of the Invention [Problem to be solved by the invention]

[0006] The silicone leveling agent disclosed in Patent Document 1 is a random polymer obtained by polymerizing a silicone monomer and a (meth)acrylic acid ester monomer by free radical polymerization, and the leveling effect is insufficient because the silicone moieties are randomly arranged. Also, the silicone leveling agent disclosed in Patent Document 2 does not have a sufficient leveling effect because the content of silicone blocks is insufficient.

[0007] The problem to be solved by the present invention is to provide a polymer that functions as a leveling agent that imparts high smoothness to a coating film. [Means for solving the problem]

[0008] Means for Solving the Problems The present inventors have conducted extensive research to solve the above problems and have found that a polymer containing a polymer block of a polymerizable monomer having a specific silicone functional group, in which the content of the polymer block exceeds 50 mass %, exhibits high leveling properties that are suitable for use as a resist, thereby completing the present invention.

[0009] That is, the present invention relates to a polymer containing a polymer block (A1) of a polymerizable monomer (a1) having a group represented by the following general formula (1), wherein the content of the polymer block (A1) is more than 50 mass%:

[0010] [ka] (In the formula (1), R 11 are each independently an alkyl group having 1 to 6 carbon atoms or -OSi(R 14 )3, a group (R 14 are each independently an alkyl group having 1 to 3 carbon atoms, R 12 are each independently an alkyl group having 1 to 6 carbon atoms, R 13 is an alkyl group having 1 to 6 carbon atoms, n is an integer greater than or equal to 0.) [Effects of the Invention]

[0011] The present invention can provide a polymer that functions as a leveling agent that imparts high smoothness to a coating film. DETAILED DESCRIPTION OF THE INVENTION

[0012] An embodiment of the present invention will be described below. The present invention is not limited to the following embodiment, and can be implemented by making appropriate modifications within the scope that does not impair the effects of the present invention. In this specification, the term "(meth)acrylate" refers to either or both of acrylate and methacrylate.

[0013] [Polymer] The polymer of the present invention is a polymer containing a polymer block (A1) of a polymerizable monomer (a1) having a group represented by the following general formula (1), and the content of the polymer block (A1) is more than 50 mass %. Here, the content of the polymer block (A1) is a value based on the mass of the polymer of the present invention (mass of the polymer block (A1) / mass of the polymer).

[0014] [ka] (In the formula (1), R 11 are each independently an alkyl group having 1 to 6 carbon atoms or -OSi(R14 )3, a group (R 14 are each independently an alkyl group having 1 to 3 carbon atoms, R 12 are each independently an alkyl group having 1 to 6 carbon atoms, R 13 is an alkyl group having 1 to 6 carbon atoms, n is an integer greater than or equal to 0.)

[0015] The polymer block (A1) is a segment consisting of a repeating unit derived from the polymerizable monomer (a1). Here, the phrase "consisting of a repeating unit derived from the polymerizable monomer (a1)" means that the polymer block (A1) may contain a repeating unit derived from another polymerizable monomer as long as the effect of the present invention is not impaired. The polymer block (A1) is a segment consisting of a repeating unit derived from the polymerizable monomer (a1). 80% or more, 90% or more The content may be 95% by mass or more, 98% by mass or more, or 100% by mass.

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

[0017] In the formula (1), R 11 , R 12 , R 13 and R 14 is preferably a methyl group. In the formula (1), n ​​is preferably an integer in the range of 1 to 200, more preferably an integer in the range of 1 to 100, even more preferably an integer in the range of 1 to 50, and particularly preferably an integer in the range of 1 to 20.

[0018] The number average value of n in the polymer block (A1) is preferably in the range of 1 to 70, more preferably in the range of 5 to 50, even more preferably in the range of 5 to 20, and particularly preferably in the range of 5 to 15. In the present invention, the "number average value of n" means the average number of repeating units of siloxane bonds per polymerizable monomer for the polymerizable monomers constituting the polymer block (A1). When the number-average length of the silicone chain in the polymer block (A1) is within the above range, the polymer of the present invention exhibits high surface segregation ability and can prevent defects from occurring in the resulting coating film. The number-average value of n in the polymer block (A1) is measured by the method described in the Examples.

[0019] The polymerizable monomer (a1) is preferably a compound represented by the following general formula (a1-1).

[0020] [ka] (In the formula (a1-1), R 11 , R 12 and R 13 are R in the above formula (1), 11 , R 12 and R 13 is the same as R 15 is a hydrogen atom or a methyl group, L 1 is a divalent organic group or a single bond. n is an integer greater than or equal to 0.)

[0021] L 1 The divalent organic group is preferably an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms.

[0022] L 1Examples of the alkylene group having 1 to 50 carbon atoms include a 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, isopropylene group, 2-methylpropylene group, 2-methylhexylene group, and tetramethylethylene group.

[0023] 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.

[0024] L 1 The alkyleneoxy group having 1 to 50 carbon atoms is, for example, a group in which one —CH2— in the alkylene group is substituted with —O—. 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 even more preferably a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, an oxytrimethylene group, a butyleneoxy group, an oxytetramethylene group, a pentyleneoxy group, a heptyleneoxy group, or an octyleneoxy group.

[0025] 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, some of the -CH2- groups in these divalent organic groups may be replaced by carbonyl groups (-C(=O)-), phenylene groups, amide bonds or urethane bonds, and further, carbon atoms may be substituted by hydroxyl groups or the like.

[0026] The polymerizable monomer constituting the polymer block (A1) may be a polymerizable monomer (a1), and the polymer block (A1) may be composed of two or more polymerizable monomers (a1) having different structures. In this case, the polymerization form of the polymer block (A1) is not particularly limited, and the polymer block (A1) may have a random polymer structure of two or more polymerizable monomers (a1) having different structures, or a block polymer structure of two or more polymerizable monomers (a1) having different structures. The polymerizable monomer constituting the polymer block (A1) is preferably a single polymerizable monomer (a1).

[0027] Specific examples of the polymerizable monomer (a1) include α-(3-methacryloyloxy)propylpolydimethylsiloxane. The polymerizable monomer (a1) can be produced by a known method, and a commercially available product may also be used.

[0028] In the polymer of the present invention, the content of the polymer block (A1) is more than 50% by mass, preferably 51% by mass or more, and more preferably 55% by mass or more, based on the total amount of the polymer. The upper limit of the content of the polymer block (A1) is not particularly limited, but is, for example, 95% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 75% by mass or less, based on the total amount of the polymer. The content of the polymer block (A1) is a value calculated from the ratio of raw materials charged, and can be adjusted by the ratio of raw materials charged of the polymerizable monomer (a1) used to produce the polymer of the present invention.

[0029] The polymer of the present invention may contain polymer block (A1) in an amount of more than 50 mass % based on the total amount of the polymer, and the structure other than the polymer block (A1) is not particularly limited. Since the polymer of the present invention is suitably used as an additive for a coating composition, it is preferable that the polymer contain, as a structure other than the polymer block (A1), a structure that shows compatibility with the base polymer of the coating composition.

[0030] The polymer of the present invention is preferably a block copolymer further comprising, in addition to the polymer block (A1), a polymer block (A2) of a polymerizable monomer (a2) having one or more groups 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. The polymer block (A2) can exhibit high compatibility with the base polymer of the coating composition.

[0031] The polymer block (A2) is a segment consisting of a repeating unit derived from the polymerizable monomer (a2). Here, the phrase "consisting of a repeating unit derived from the polymerizable monomer (a2)" means that the polymer block (A2) may contain a repeating unit derived from another polymerizable monomer, provided that the effects of the present invention are not impaired. The polymer block (A2) may contain 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass of the repeating unit derived from the polymerizable monomer (a2).

[0032] The polymer block (A2) is a segment consisting of a repeating unit 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. In the present invention, the term "polymerizable monomer" means a compound having a polymerizable unsaturated group, and examples of the polymerizable unsaturated group possessed by the polymerizable monomer (a2) include a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acryloylamino group, a vinyl ether group, an allyl group, a styryl group, a maleimide group, etc. Among these, a (meth)acryloyl group and a (meth)acryloyloxy group are preferred because of the ease of availability of raw materials and good polymerization reactivity.

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

[0034] The alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (a2) may be substituted with one or more substituents such as a hydroxyl group, a phenyl group, or a phenoxy group. The alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (a2) includes, for example, a hydroxyalkyl group having 1 to 18 carbon atoms, a phenylalkyl group having 7 to 18 carbon atoms, and a phenoxyalkyl group having 7 to 18 carbon atoms. The alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (a2) is preferably an alkyl group having 1 to 8 carbon atoms.

[0035] Examples of the aromatic group having 6 to 18 carbon atoms contained in the polymerizable monomer (a2) include a phenyl group, a naphthyl group, an anthracen-1-yl group, and a phenanthrene-1-yl group. The aromatic group having 6 to 18 carbon atoms contained in the polymerizable monomer (a2) may be further substituted with a substituent such as a hydroxyl group, an alkyl group, or an alkoxy group, and includes, for example, a phenyl group substituted with an alkyl group having 1 to 6 carbon atoms.

[0036] The group containing a (poly)oxyalkylene chain contained in the polymerizable monomer (a2) is a monovalent group containing a repeating oxyalkylene moiety or a divalent linking group containing a repeating oxyalkylene moiety. When the polymerizable unsaturated group of the polymerizable monomer (a2) is a (meth)acryloyl group, the polymerizable monomer (a2) having a group containing a (poly)oxyalkylene chain is, for example, a compound represented by the following general formula (a2-poa1) or (a2-poa2).

[0037] [ka] (In the formulas (a2-poa1) and (a2-poa2), R a21 are each independently a hydrogen atom or a methyl group. R a22 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. p is an integer of 0 or greater, q is an integer of 0 or greater, r is an integer of 0 or greater, and p+q+r is an integer of 1 or greater. X, Y, and Z are each independently an alkylene group having 1 to 6 carbon atoms.

[0038] In the above formulas (a2-poa1) and (a2-poa2), -(XO) p -(YO) q -(ZO) r -R a22 and groups represented by -(XO) p -(YO) q -(ZO) r The group represented by - corresponds to a group containing a (poly)oxyalkylene chain.

[0039] In the above formulae (a2-poa1) and (a2-poa2), the alkylene group having 1 to 6 carbon atoms for X, Y and Z is preferably an alkylene group having 2 to 4 carbon atoms.

[0040] Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloyl group include methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate, s-butyl(meth)acrylate, isobutyl(meth)acrylate, t-butyl(meth)acrylate, n-pentyl(meth)acrylate, n-hexyl(meth)acrylate, n-heptyl(meth)acrylate, n-octyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, decyl(meth)acrylate, and methyl(meth)acrylate.

[0033] Examples of the methyl acrylate include alkyl esters of (meth)acrylic acid having 1 to 18 carbon atoms, such as dicyclopentanyloxylethyl (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 dicyclopentanyloxylethyl (meth)acrylate, isobornyloxylethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyl adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyl (meth)acrylate.

[0041] Examples of the polymerizable monomer (a2) having a hydroxyalkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxy(meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, and 2,3-dihydroxypropyl (meth)acrylate.

[0042] Examples of the polymerizable monomer (a2) having a phenylalkyl group having 7 to 18 carbon atoms or a phenoxyalkyl group having 7 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloyl group include benzyl (meth)acrylate, 2-phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate.

[0043] Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a vinyl ether group include alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether; cycloalkyl vinyl ethers; 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 1-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 1-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 3-hydroxy-2-methylpropyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, and cyclohexane-1,4-dimethanol monovinyl ether.

[0044] Examples of the polymerizable monomer (a2) having an alkyl group with 1 to 18 carbon atoms and an allyl group as the polymerizable unsaturated group include 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether.

[0045] Examples of the polymerizable monomer (a2) having an aromatic group with 6 to 18 carbon atoms include styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene.

[0046] Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloylamino group include N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, diacetoneacrylamide, and acroylmorpholine.

[0047] Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a maleimide group include methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide.

[0048] Examples of the polymerizable monomer (a2) having a group containing a polyoxyalkylene chain and in which the polymerizable unsaturated group is a (meth)acryloyl group include polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polytrimethylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, poly(ethylene glycol·propylene glycol) mono(meth)acrylate, polyethylene glycol·polypropylene glycol mono(meth)acrylate, poly(ethylene glycol·tetramethylene glycol) mono(meth)acrylate, polyethylene glycol·polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol·tetramethylene glycol) mono(meth)acrylate, polypropylene glycol·polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol·1,2-butylene glycol) mono(meth)acrylate, polypropylene glycol·poly1,2-butylene glycol mono(meth)acrylate, Poly(ethylene glycol·1,2-butylene glycol) mono(meth)acrylate, polyethylene glycol·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, Poly 1,Examples include 2-butylene glycol polytrimethylene glycol mono(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, poly(1,2-butylene glycol tetramethylene glycol) mono(meth)acrylate, and poly(1,2-butylene glycol polytetramethylene glycol mono(meth)acrylate). In addition, the above "poly(ethylene glycol-propylene glycol)" means a random copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol-polypropylene glycol" means a block copolymer of ethylene glycol and propylene glycol.

[0049] The polymerizable monomer (a2) is preferably a compound represented by the following general formula (a2-1) or (a2-2): These compounds can impart high compatibility to the polymer of the present invention when it is used as a leveling agent.

[0050] [ka] (In the above formulas (a2-1) and (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 of 1 to 4, and m is an integer of 1 to 200.

[0051] In the formulas (a2-1) and (a2-2), R 22 and R 24 The alkyl group having 1 to 18 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. In the formulas (a2-1) and (a2-2), R 22 and R 24 and are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom. In the formula (a2-2), n is preferably 3 (propylene oxide chain, PO chain) or 4 (butylene oxide chain, BO chain). In the formula (a2-2), m is preferably an integer in the range of 2 to 100, more preferably an integer in the range of 2 to 50, and even more preferably an integer in the range of 3 to 20.

[0052] The polymerizable monomer (a2) is preferably a compound represented by the following general formula (a2-3).

[0053] [ka] ((In the above formula (a2-3), R 25 is a hydrogen atom or a methyl group. R 26 are each independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. l is an integer from 0 to 5.

[0054] The polymerizable monomer (a2) can be produced by a known method. Commercially available polymerizable monomers (a2) may be used. For example, commercially available polymerizable monomers (a2) having a group containing a polyoxyalkylene chain and in which the polymerizable unsaturated group is a (meth)acryloyl group include "NK Ester M-20G," "NK Ester M-40G," "NK Ester M-90G," "NK Ester M-230G," "NK Ester AM-90G," "NK Ester AMP-10G," "NK Ester AMP-20G," and "NK Ester AMP-60G" manufactured by Shin-Nakamura Chemical Co., Ltd.; "Blenmar PE-90," "Blenmar PE-200," and "Blenmar PE-60G" manufactured by NOF Corporation; -PE-350", "Blenmar PME-100", "Blenmar PME-200", "Blenmar PME-400", "Blenmar PME-4000", "Blenmar PP-1000", "Blenmar PP-500", "Blenmar PP-800", "Blenmar 70PEP-350B", "Blenmar 55PET-800", "Blenmar 50POEP-800B", "Blenmar 10PPB-500B", "Blenmar NKH-5050", "Blenmar AP-400", "Blenmar AE-350", etc.

[0055] The polymerizable monomer constituting the polymer block (A2) may be a polymerizable monomer (a2) having one or more groups 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, and the polymer block (A2) may be composed of two or more polymerizable monomers (a2) having different structures. In this case, the polymerization form of the polymer block (A2) is not particularly limited, and the polymer block (A2) may have a random polymer structure of two or more polymerizable monomers (a2) having different structures, or a block polymer structure of two or more polymerizable monomers (a2) having different structures. The polymerizable monomer constituting the polymer block (A2) is preferably a single polymerizable monomer (a2).

[0056] When the polymer of the present invention has a polymer block (A1) and a polymer block (A2), the mass ratio of the polymer block (A1) to the polymer block (A2) is, for example, polymer block (A1):polymer block (A2)=51:49 to 95:5, preferably polymer block (A1):polymer block (A2)=51:49 to 90:10, and more preferably polymer block (A1):polymer block (A2)=51:49 to 75:25.

[0057] The polymer of the present invention is preferably a block copolymer essentially consisting of polymer block (A1) and polymer block (A2), more preferably a block copolymer consisting only of polymer block (A1) and polymer block (A2). Here, "essentially consisting of" means that the total content of polymer block (A1) and polymer block (A2) in the block copolymer of the present invention is more than 80% by mass, 90% by mass or more, 95% by mass or more, or 99% by mass or more.

[0058] When the polymer of the present invention is a block copolymer of polymer block (A1) and polymer block (A2), it may contain a polymer block of a polymerizable monomer other than the exemplary polymerizable monomer (a1) and polymerizable monomer (a2) within a range that does not impair the effects of the present invention.

[0059] The polymer of the present invention preferably does not contain fluorine atoms. A fluorine-atom-free polymer has low environmental accumulation and can reduce the environmental load. When the polymer of the present invention is a block copolymer comprising polymer block (A1) and polymer block (A2), the polymer of the present invention can be a polymer containing no fluorine atoms.

[0060] When the polymer of the present invention contains at least one polymer block (A1) and at least one polymer block (A2), the number of each polymer block and the bonding order are not particularly limited. The polymer of the present invention is preferably a polymer having a diblock copolymer structure of polymer block (A1) and polymer block (A2), more preferably a diblock copolymer of polymer block (A1) and polymer block (A2). In the present invention, the term "diblock copolymer" refers to a copolymer in which polymer block (A1) and polymer block (A2) are bonded to each other at their terminals directly or via a spacer.

[0061] In the case where the polymer of the present invention is a diblock copolymer of polymer block (A1) and polymer block (A2) and is produced by living polymerization, one of the polymer blocks (A1) and (A2) may contain the monomer structure of the other block, but the properties of the polymer of the present invention are not impaired. In this case, the polymer is also included in the diblock copolymer of polymer block (A1) and polymer block (A2).

[0062] The number average molecular weight (Mn) of the polymer of the present invention is preferably in the range of 1,000 to 500,000, more preferably in the range of 2,000 to 100,000, still more preferably in the range of 2,000 to 40,000, and particularly preferably in the range of 2,000 to 40,000. The weight average molecular weight (Mw) of the polymer of the present invention is preferably in the range of 1,000 to 500,000, more preferably in the range of 2,000 to 100,000, still more preferably in the range of 2,000 to 40,000, and particularly preferably in the range of 4,000 to 40,000. The dispersity (Mw / Mn) of the polymer of the present invention is preferably in the range of 1.0 to 2.0, more preferably in the range of 1.0 to 1.8, and even more preferably in the range of 1.0 to 1.5. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer of the present invention are measured by the method described in the examples.

[0063] The polymer of the present invention can be produced, for example, by subjecting reactant materials containing the polymerizable monomer (a1) and the polymerizable monomer (a2) to living polymerization such as living radical polymerization or living anionic polymerization. Here, the term "reaction raw materials" refers to raw materials that constitute the polymer of the present invention, and does not include raw materials that do not constitute the polymer of the present invention, such as solvents and catalysts.

[0064] For example, in living radical polymerization, a dormant species, whose active polymerization terminal is protected by an atom or atomic group, reversibly generates radicals and reacts with a monomer, resulting in a propagation reaction. Even when the first monomer is consumed, the propagating terminal does not lose its activity and continues to react with the successively added second monomer to produce a block polymer. Examples of such living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-fragmentation radical polymerization (RAFT), nitroxide-mediated radical polymerization (NMP), and organotellurium radical polymerization (TERP). While there are no particular restrictions on which of these methods to use, ATRP is preferred due to its ease of control. ATRP uses an organic halide or sulfonyl halide 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 in ATRP include 1-phenylethyl chloride, 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, α,α'-dichloroxylene, α,α'-dibromoxylene, hexakis(α-bromomethyl)benzene, and alkyl esters of 2-halogenated carboxylic acids having 1 to 6 carbon atoms (e.g., 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, etc.) having 1 to 6 carbon atoms. More specific examples of C1-C6 alkyl esters of C1-C6 2-halogenated carboxylic acids include methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate, and ethyl 2-bromoisobutyrate.

[0066] The transition metal compounds that can be used in ATRP are M n+ X n It is expressed as: M n+ X n The transition metal M of the transition metal compound represented by n+ As for 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 2+ , Ag + and Ag 2+ It can be selected from the group consisting of: M n+ X n X in the transition metal compound represented by the formula (I) is a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, (SO4) 1 / 2 , (PO4) 1 / 3 , (HPO4) 1 / 2 , (H2PO4), triflate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate), SeR 11 , CN and R 12 COO, where R 11represents an aryl group or a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), R 12 represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms (preferably a methyl group) which may be substituted 1 to 5 times with halogen (preferably 1 to 3 times with fluorine or chlorine). M n+ X n In the transition metal compound represented by the formula (I), n represents the formal charge on the metal and is an integer of 0 to 7.

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

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

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

[0070] The atom transfer radical polymerization (ATRP) is not limited to the above, and other ATRPs can also be used. For example, AGET ATRP, ARGET ATRP, ICAR ATRP, etc., as described in "Macromol. Rapid. Commun. 2018, 1800616" can also be used.

[0071] In the living radical polymerization, it is preferable to use a solvent. Examples of solvents used in living radical polymerization include ester-based solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ether-based solvents such as diisopropyl ether, dimethoxyethane, and diethylene glycol dimethyl ether; halogen-based solvents such as dichloromethane and dichloroethane; aromatic solvents such as toluene, xylene, and anisole; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol-based solvents such as methanol, ethanol, and isopropanol; and aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide. The above solvents may be used alone or in combination of two or more.

[0072] When the polymer of the present invention is a block copolymer of polymer block (A1) and polymer block (A2) (hereinafter, the block copolymer is referred to as "the block copolymer of the present invention"), the block copolymer of the present invention can be produced, for example, by Method 1 or 2 shown below. Method 1: A method in which a polymerizable monomer (a1) is subjected to living radical polymerization (preferably atom transfer radical polymerization) in the presence of a polymerization initiator, a transition metal compound, a ligand compound capable of forming a coordinate bond with the transition metal, and a solvent to obtain a polymer block (A1), and then a polymerizable monomer (a2) is added to the reaction system, and the polymerizable monomer (a2) is further subjected to living radical polymerization (preferably atom transfer radical polymerization) to form the polymer block (A1). Method 2: A method in which polymerizable monomer (a2) is subjected to living radical polymerization (preferably atom transfer radical polymerization) in the presence of a polymerization initiator, a transition metal compound, a ligand compound capable of forming a coordinate bond with the transition metal, and a solvent to obtain a polymer block (A2), and then polymerizable monomer (a1) is added to the reaction system to further subject the polymerizable monomer (a1) to living radical polymerization (preferably atom transfer radical polymerization) to obtain the polymer block (A2).

[0073] The charge ratio (by mass) of the polymerizable monomer (a1) to the polymerizable monomer (a2) when producing the block copolymer of the present invention is, for example, polymerizable monomer (a1):polymerizable monomer (a2)=51:49 to 95:5, preferably polymerizable monomer (a1):polymerizable monomer (a2)=51:49 to 90:10, and more preferably polymerizable monomer (a1):polymerizable monomer (a2)=51:49 to 75:25.

[0074] The polymerization temperature during the living radical polymerization is preferably in the range of room temperature to 120°C.

[0075] When the block copolymer of the present invention is produced by living radical polymerization, metals resulting from the transition metal compound used in the polymerization may remain in the resulting block copolymer. The metals remaining in the resulting block copolymer may be removed using activated alumina or the like after the polymerization is completed.

[0076] [Coating composition] The polymer of the present invention can be suitably used as a leveling agent for a coating composition, and the coating composition of the present invention contains the polymer of the present invention. The polymer of the present invention can be used as a fluorine-atom-free leveling agent, which does not contain fluorine atoms, and therefore is a leveling agent with low environmental accumulation and low environmental load.

[0077] The content of the polymer of the present invention contained in the coating composition of the present invention varies depending on the type of base resin, the coating method, the desired film thickness, etc., but is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 5 parts by mass, and even more preferably 0.01 to 2 parts by mass, per 100 parts by mass of the solid content of the coating composition. If the content of the polymer of the present invention is within this range, the surface tension can be sufficiently reduced, the desired leveling properties can be obtained, and problems such as foaming during coating can be suppressed.

[0078] The application of the coating composition of the present invention is not particularly limited, and it can be used for any application that requires leveling property. For example, the coating composition of the present invention can be used as various paint compositions or photosensitive resin compositions.

[0079] When the coating composition of the present invention is used as a paint composition, examples of the paint composition include paints using natural resins such as petroleum resin paints, shellac paints, rosin-based paints, cellulose-based paints, rubber-based paints, lacquer paints, cashew resin paints, and oil-based vehicle paints; and 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, and fluororesin paints. By adding the polymer of the present invention to the coating composition, smoothness can be imparted to the resulting coating film.

[0080] Various additives may be added to the coating composition as needed, such as colorants such as pigments, dyes, and carbon; inorganic powders such as silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, and calcium carbonate; organic fine powders such as higher fatty acids, polyacrylic resins, and polyethylene; and light resistance improvers, weather resistance improvers, heat resistance improvers, antioxidants, thickeners, and anti-settling agents.

[0081] The coating method for the coating composition of the present invention can be any known and commonly used coating method, and examples thereof include methods such as a slit coater, a slit and spin coater, a spin coater, a roll coater, electrostatic coating, a bar coater, a gravure coater, a die coater, a knife coater, inkjet coating, dipping coating, spray coating, shower coating, screen printing, gravure printing, offset printing, and reverse coating.

[0082] The photosensitive resin composition changes its physical properties such as solubility, viscosity, transparency, refractive index, conductivity, and ion permeability when irradiated with light such as visible light or ultraviolet light. Among photosensitive resin compositions, resist compositions (such as photoresist compositions and color resist compositions for color filters) require high leveling properties. Resist compositions are typically applied by spin coating to a thickness of approximately 1 to 2 μm on a silicon wafer or a glass substrate on which various metals have been vapor-deposited. If the applied film thickness fluctuates or unevenness occurs during this process, the linearity and reproducibility of the pattern deteriorate, resulting in the failure to obtain a resist pattern with the desired precision. In addition to these problems, various leveling-related issues also exist, such as drip marks, overall unevenness, and a beading phenomenon in which the film thickness is thicker at the edges than at the center. The coating composition of the present invention can solve the above-mentioned problems when used as a resist composition because the polymer of the present invention exhibits high leveling properties and can form a uniform coating film (cured product).

[0083] When the coating composition of the present invention is used as a photoresist composition, the photoresist composition contains an alkali-soluble resin, a radiation-sensitive substance (photosensitive substance), a solvent, and the like in addition to the polymer of the present invention.

[0084] The alkali-soluble resin contained in the photoresist composition is a resin that is soluble in an alkaline solution, which is the developer used when patterning the resist. Examples of alkali-soluble resins include novolak resins obtained by condensing an aromatic hydroxy compound derivative such as phenol, cresol, xylenol, resorcinol, phloroglucinol, or hydroquinone with an aldehyde compound such as formaldehyde, acetaldehyde, or benzaldehyde; polymers or copolymers of vinylphenol compound derivatives such as o-vinylphenol, m-vinylphenol, p-vinylphenol, or α-methylvinylphenol; (meth)acrylic acid polymers or copolymers such as acrylic acid, methacrylic acid, or hydroxyethyl (meth)acrylate; polyvinyl alcohol; modified resins in which radioactive ray-sensitive groups such as quinone diazide groups, naphthoquinone azide groups, aromatic azide groups, or aromatic cinnamoyl groups have been introduced via some of the hydroxyl groups of these various resins; and urethane resins containing acidic groups such as carboxylic acid and sulfonic acid in the molecule. These alkali-soluble resins may be used alone or in combination of two or more.

[0085] The radiation-sensitive substance contained in the photoresist composition is a substance that changes the solubility of the alkali-soluble resin in a developer when irradiated with energy rays such as ultraviolet rays, far ultraviolet rays, excimer laser light, X-rays, electron beams, ion beams, molecular beams, and gamma rays. Examples of radiation-sensitive substances 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, and poly(olefin sulfone) compounds.

[0086] Examples of the quinone diazide compounds include 1,2-benzoquinone azide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,1-naphthoquinone diazide-4-sulfonic acid ester, 2,1-naphthoquinone diazide-5-sulfonic acid ester, and sulfonic acid chlorides of quinone diazide derivatives such as 1,2-benzoquinone azide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 2,1-naphthoquinone diazide-4-sulfonic acid chloride, and 2,1-naphthoquinone diazide-5-sulfonic acid chloride.

[0087] Examples of the diazo compounds include salts of condensates of p-diazodiphenylamine with formaldehyde or acetaldehyde, inorganic diazo resin salts which are reaction products of the above condensates with hexafluorophosphates, tetrafluoroborates, perchlorates or periodates, and organic diazo resin salts which are reaction products of the above condensates with sulfonic acids, as described in U.S. Pat. No. 3,300,309.

[0088] Examples of the azide compounds include azidochalconic acid, diazidobenzalmethylcyclohexanones, azidocinnamylideneacetophenones, aromatic azide compounds, and aromatic diazide compounds.

[0089] Examples of the halogenated organic compound 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 trizole compounds, halogen-containing 2-pyrone compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, halogen-containing heterocyclic compounds, and sulfenyl halide compounds. In addition to the above, examples of halogenated organic compounds include 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, and 2,2-bis(4-hydroxyethoxy-3,5-dibromophenyl)propane, and compounds used as organic chloro-based pesticides such as dichlorophenyltrichloroethane.

[0090] Examples of the organic acid ester include carboxylic acid ester and sulfonic acid ester. Examples of the organic acid amide include carboxylic acid amide and sulfonic acid amide. Examples of the organic acid imide include carboxylic acid imide and sulfonic acid imide. The radiation sensitive substance may be used alone or in combination of two or more kinds.

[0091] In the photoresist composition, the content of the radiation-sensitive substance is preferably in the range of 10 to 200 parts by mass, and more preferably in the range of 50 to 150 parts by mass, per 100 parts by mass of the alkali-soluble resin.

[0092] Examples of solvents for photoresist compositions include ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, and butyrolactone; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 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; ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, and butyl methyl butylate. esters such as ethyl butyrate, butyl butyrate, propyl butyrate, ethyl lactate, butyl lactate, etc.; monocarboxylic acid esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, etc.; cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate. Cellosolve 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; diethylene glycols such as diethyl glycol monomethyl ether, diethyl glycol monoethyl ether, diethyl glycol dimethyl ether, diethyl glycol diethyl ether, and diethyl glycol methyl ethyl ether;Examples of suitable solvents include halogenated hydrocarbons such as trichloroethylene, chlorofluorocarbon solvents, HCFCs, and HFCs; fully fluorinated solvents such as perfluorooctane, aromatic solvents such as toluene and xylene; and polar solvents such as dimethylacetamide, dimethylformamide, N-methylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.

[0093] When the coating composition of the present invention is used as a color resist composition, the color resist composition contains an alkali-soluble resin, a polymerizable compound, a colorant, and the like in addition to the polymer of the present invention.

[0094] The alkali-soluble resin contained in the color resist can be the same as the alkali-soluble resin contained in the photoresist composition described above.

[0095] The polymerizable compound contained in the color resist composition is a compound having a photopolymerizable functional group that can undergo a polymerization or crosslinking reaction when irradiated with active energy rays such as ultraviolet rays. Examples of the polymerizable compound 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 esterification reactions of unsaturated carboxylic acids with polyvalent carboxylic acids and polyvalent hydroxy compounds such as the above-mentioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, polymerizable compounds having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound, and polymerizable compounds having an acid group. The polymerizable compounds may be used alone or in combination of two or more.

[0096] Examples of the esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include (meth)acrylic acid esters 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 glycerol (meth)acrylate. Further, examples of the (meth)acrylic acid portion of these acrylates include itaconic acid esters in which itaconic acid is substituted, crotonic acid esters in which crotonic acid is substituted, and maleic acid esters in which maleic acid is substituted.

[0097] Examples of the esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone di(meth)acrylate, resorcinol di(meth)acrylate, and pyrogallol tri(meth)acrylate. 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 an ester obtained from (meth)acrylic acid, phthalic acid, and ethylene glycol, an ester obtained from (meth)acrylic acid, maleic acid, and diethylene glycol, an ester obtained from (meth)acrylic acid, terephthalic acid, and pentaerythritol, and an ester obtained from (meth)acrylic acid, adipic acid, butanediol, and glycerin.

[0098] Examples of the polymerizable compound having a urethane skeleton obtained by reacting the 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; and aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate with a hydroxy compound having a (meth)acryloyl group, such as 2-hydroxyethyl (meth)acrylate and 3-hydroxy[1,1,1-tri(meth)acryloyloxymethyl]propane.

[0099] The polymerizable compound having an acid group is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and is preferably a polyfunctional polymerizable compound in which an acid group is provided by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. The aliphatic polyhydroxy compound used to prepare the polyfunctional polymerizable compound is preferably pentaerythritol or dipentaerythritol. The acid value of the polyfunctional polymerizable compound is preferably in the range of 0.1 to 40, more preferably in the range of 5 to 30, in order to improve developability, curability, etc. 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 not having an acid group are used in combination, it is preferable that the acid value of the mixture of polymerizable compounds be within the above range.

[0100] Specific examples of the polymerizable compound having an acid group include a mixture containing dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and a succinate ester of dipentaerythritol pentaacrylate as the main components, and this mixture is commercially available as Aronix TO-1382 (manufactured by Toagosei Co., Ltd.).

[0101] Examples of polymerizable compounds other than those mentioned above include (meth)acrylamides such as ethylene bis(meth)acrylamide; allyl esters such as diallyl phthalate; and compounds having a vinyl group such as divinyl phthalate.

[0102] In the color resist composition, the content of the polymerizable compound is preferably in the range of 5 to 80 mass % of the total solid content of the color resist composition, more preferably in the range of 10 to 70 mass %, and even more preferably in the range of 20 to 50 mass %.

[0103] The colorant for the color resist composition is not particularly limited as long as it is capable of imparting color, and may be, for example, a pigment or a dye. The pigment may be either an organic pigment or an inorganic pigment. Examples of the organic pigment include red, green, blue, yellow, purple, orange, and brown pigments. Examples of the chemical structure of the organic pigment include azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. Examples of the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide. In addition, "CI" below stands for color index.

[0104] Examples of the red pigment include CI 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, and 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, 1 49, 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 3, 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. Among these, CI Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, or 254 is preferred, and CI Pigment Red 177, 209, 224, or 254 is more preferred.

[0105] Examples of the green pigment include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, and 58. Among these, CI Pigment Green 7, 36, and 58 are preferred.

[0106] Examples of the blue pigment include CI 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, and 79. Among these, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 is preferred, and CI Pigment Blue 15:6 is more preferred.

[0107] Examples of the yellow pigment include CI 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, CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, or 185 is preferred, and CI Pigment Yellow 83, 138, 139, 150, or 180 is more preferred.

[0108] Examples of the purple pigment include CI 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, and 50. Among these, CI Pigment Violet 19 or 23 is preferred, and CI Pigment Violet 23 is more preferred.

[0109] Examples of the orange pigment include CI 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, and 79. Among these, CI Pigment Orange 38 or 71 is preferred.

[0110] The three primary color pixels of color filters used in liquid crystal display devices and organic EL display devices are red (R), green (G), and blue (B). Therefore, the red, green, and blue pigments are used as the main components, and organic pigments of colors such as yellow, purple, and orange may be used to adjust the hue in order to improve color reproducibility.

[0111] The average particle size of the organic pigment is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less, in order to enhance the brightness of color liquid crystal displays and organic EL display devices. The organic pigment is preferably used after being subjected to a dispersion treatment so as to have such an average particle size. The average primary particle size of the organic pigment is preferably 100 nm or less, more preferably 50 nm or less, even more preferably 40 nm or less, and particularly preferably in the range of 10 to 30 nm. The average particle size of the organic pigment is measured using a dynamic light scattering particle size distribution analyzer, and can be measured using, for example, Nanotrac particle size distribution analyzers "UPA-EX150" and "UPA-EX250" manufactured by Nikkiso Co., Ltd.

[0112] When the color resist composition is used to form a black matrix (BM), the colorant is not particularly limited as long as it is black, and examples thereof include carbon black, lamp black, acetylene black, bone black, thermal black, channel black, furnace black, graphite, iron black, titanium black, etc. Among these, carbon black and titanium black are preferred from the viewpoint of light-shielding rate and image characteristics. In addition, two or more organic pigments may be mixed to produce a black color.

[0113] Commercially available carbon black products include, for example, 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, and # 3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B manufactured by Evonik Degussa Japan Co., Ltd., and Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, and Printex A, Print ex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack 350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170, and examples thereof 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, and BLACK manufactured by Cabot Japan Co., Ltd.Examples include PEARLS480, PEARLS130, VULCAN XC72R, and ELFTEX-8, and examples thereof include RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, and RAVEN 1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000, and the like.

[0114] Among the above carbon blacks, resin-coated carbon black is preferred as it has the high optical density and high surface resistivity required for the black matrix of a color filter.

[0115] Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.

[0116] As a colorant used to form a black matrix (BM), two or more organic pigments may be mixed to produce a black color, and examples thereof include a black pigment made by mixing three color pigments: red, green, and blue. Colorants that can be mixed to prepare black pigments include Victoria Pure Blue (CI 42595), Auramine O (CI 41000), Catilon Brilliant Flavin (Basic 13), Rhodamine 6GCP (CI 45160), Rhodamine B (CI 45170), Safranin OK70:100 (CI 50240), Erioglaucine X (CI 42080), No. 120 / Lionol Yellow (CI 21090), Lionol Yellow GRO (CI 21090), and Shimla First Yellow. -8GF (CI 21105), Benzidine Yellow 4T-564D (CI 21095), Shimla First Red 4015 (CI 12355), Lionor Red 7B4401 (CI 15850), Firstgen Blue TGR-L (CI 74160), Lionor Blue SM (CI 26150), Lionor Blue ES (CI Pigment Blue 15:6), Lionor Red GD (CI Pigment Red 168), Lionor Green 2YS (CI Pigment Green 36), etc.

[0117] Other colorants that can be mixed and used to prepare a black pigment include, for example, CI Yellow Pigment 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, CI Orange Pigment 36, 43, 51, 55, 59, 61, CI Red Pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, CI Violet Pigment 19, 23, 29, 30, 37, 40, 50, CI Blue Pigment 15, 15:1, 15:4, 22, 60, 64, CI Green Pigment 7, and CI Brown Pigment 23, 25, 26.

[0118] When carbon black is used as the black pigment, the average primary particle size of the carbon black is preferably in the range of 0.01 to 0.08 μm, and more preferably in the range of 0.02 to 0.05 μm in view of good developability.

[0119] Carbon black has a particle shape that differs from that of organic pigments, etc., in that the primary particles are fused together to form what is called a structure, and fine pores may be formed on the particle surface through post-treatment. Therefore, to express the particle shape of carbon black, it is generally preferable to measure the DBP absorption (JIS K6221) and the specific surface area (JIS K6217) measured by the BET method in addition to the average particle size of the primary particles, which is determined in the same way as for the organic pigments, and use these as indicators of the structure and pore volume. The dibutyl phthalate (DBP) absorption of carbon black is 40 to 100 cm 3 The range of 50 to 80 cm / 100 g is preferable because of its good dispersibility and developability. 3 The specific surface area of ​​carbon black measured by the BET method is preferably in the range of 50 to 120 m 2 The range of 60 to 95 m / g is preferable because dispersion stability is good. 2 / g range is more preferable.

[0120] Examples of dyes that can be used as colorants in the color resist composition include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

[0121] Examples of the azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, and CI Mordant Black 7.

[0122] Examples of the anthraquinone dyes include CI Vat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Disperse Blue 60.

[0123] Examples of the phthalocyanine dyes include CI Pad Blue 5, examples of the quinoneimine dyes include CI Basic Blue 3 and CI Basic Blue 9, examples of the quinoline dyes include CI Solvent Yellow 33, CI Acid Yellow 3 and CI Disperse Yellow 64, and examples of the nitro dyes include CI Acid Yellow 1, CI Acid Orange 3 and CI Disperse Yellow 42.

[0124] It is preferable to use a pigment as the colorant for the color resist composition, since the resulting coating film will have excellent light resistance, weather resistance, and fastness. However, in order to adjust the hue, a dye may be used in combination with the pigment, if necessary.

[0125] In the color resist composition, the content of the colorant is preferably 1% by mass or more, more preferably in the range of 5 to 80% by mass, and even more preferably in the range of 5 to 70% by mass, based on the total solid content of the color resist composition.

[0126] When the color resist composition is used to form red (R), green (G), and blue (B) pixels of a color filter, the content of the colorant in the color resist composition is preferably in the range of 5 to 60 mass % of the total solid content of the color resist composition, and more preferably in the range of 10 to 50 mass %.

[0127] When the color resist composition is used to form a black matrix of a color filter, the content of the colorant in the color resist composition is preferably in the range of 20 to 80 mass % of the total solid content of the color resist composition, and more preferably in the range of 30 to 70 mass %.

[0128] In the color resist composition, when the colorant is a pigment, it is preferable to use the pigment as a pigment dispersion prepared by dispersing the pigment in an organic solvent using a dispersant. Examples of the dispersant include surfactants; pigment intermediates or derivatives; dye intermediates or derivatives; and resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins. Among these, graft copolymers having nitrogen atoms, acrylic block copolymers having nitrogen atoms, and urethane resin dispersants are preferred. Since these dispersants contain nitrogen atoms, the nitrogen atoms have affinity for the pigment surface, and the portions other than the nitrogen atoms increase affinity for the medium, thereby improving dispersion stability. These dispersants may be used alone or in combination of two or more.

[0129] Commercially available dispersants include the "EFKA" series (such as "EFKA 46") manufactured by BASF; the "Disperbyk" series and "BYK" series (such as "BYK-160", "BYK-161", and "BYK-2001") manufactured by BYK Japan Co., Ltd.; the "Solsperse" series manufactured by Lubrizol Japan Co., Ltd.; the "KP" series manufactured by Shin-Etsu Chemical Co., Ltd.; the "Polyflow" series manufactured by Kyoeisha Chemical Co., Ltd.; the "Disparon" series manufactured by Kusumoto Chemical Co., Ltd.; and the "Ajisper" series (such as "Ajisper PB-814") manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0130] Examples of organic solvents used in preparing the pigment dispersion include acetate-based solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate-based solvents such as ethoxypropionate; aromatic solvents such as toluene, xylene, and methoxybenzene; ether-based solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, and diethylene glycol dimethyl ether; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon-based solvents such as hexane; nitrogen compound-based solvents such as N,N-dimethylformamide, γ-butyrolactam, and N-methyl-2-pyrrolidone; lactone-based solvents such as γ-butyrolactone; and carbamic acid esters. These solvents may be used alone or in combination of two or more.

[0131] The pigment dispersion liquid can be prepared by a method including a colorant kneading / dispersing step and a fine-dispersing step, or by a method including only the fine-dispersing step. In the kneading / dispersing step, the colorant, a portion of the alkali-soluble resin, and, if necessary, the dispersant are mixed and kneaded. The colorant can be dispersed by dispersing the mixture while applying a strong shear force using a kneader. Examples of machines used for kneading include two-roll mills, three-roll mills, ball mills, tron ​​mills, dispersers, kneaders, co-kneaders, homogenizers, blenders, and single- or twin-screw extruders. It is preferable that the particle size of the colorant be reduced by salt milling or the like before the above kneading.

[0132] In the fine dispersion step, a solvent is added to the composition containing the colorant obtained in the kneading and dispersion step, or a mixture of a colorant, an alkali-soluble resin, a solvent, and, if necessary, the dispersant is mixed and dispersed together with a dispersion medium such as fine particles of glass, zirconia, or ceramic using a disperser, thereby dispersing the colorant particles to a fine state close to primary particles.

[0133] From the viewpoint of improving the transmittance, contrast, etc. of the color filter, the average particle size of the primary particles of the colorant is preferably 10 to 100 nm, more preferably 10 to 60 nm. The average particle size of the colorant is measured with a dynamic light scattering particle size distribution analyzer, and can be measured with, for example, Nanotrac particle size distribution analyzers "UPA-EX150" and "UPA-EX250" manufactured by Nikkiso Co., Ltd.

[0134] Although the coating composition has been exemplified above as a paint composition, a photoresist composition, and a color resist composition, the coating composition is not limited to these.

[0135] Specific examples of uses of the coating composition of the present invention include anti-glare (AG) hard coating materials, anti-reflection (LR) coating materials, low refractive index layer coating materials, high refractive index layer coating materials, clear hard coating materials, and polymerizable liquid crystal coating materials, which are coating materials for various display screens such as liquid crystal displays (hereinafter abbreviated as "LCD"), plasma displays (hereinafter abbreviated as "PDP"), organic light-emitting diode displays (hereinafter abbreviated as "OLED"), and quantum dot displays (hereinafter abbreviated as "QDD"); color resists, inkjet inks, printing inks, or paints for forming each pixel such as RGB in color filters (hereinafter abbreviated as "CF") of LCDs, etc.; black resists, inkjet inks, printing inks, or paints for forming black matrices, black column spacers, and black photospacers in CFs of LCDs, etc.; transparent protective film paints for protecting the CF surfaces used in CFs of LCDs, etc.; resin compositions for liquid crystal materials, column spacers, and photospacers in LCDs; resin compositions for pixel partition walls of LCDs, PDPs, OLEDs, QDDs, etc., positive photoresists for forming electrodes, protective Films, insulating films, plastic housings, paints for plastic housings, bezel (frame) inks; prism sheets and light diffusion films used as backlight components for LCDs; paints for organic insulating films in LCD liquid crystal TFT arrays; protective coating materials for the internal polarizer surface of LCDs; phosphors for PDPs; organic EL materials and encapsulants (protective films, gas barriers) for OLEDs; quantum dot inks, encapsulants, and protective films for QDDs; high-refractive index lenses, low-refractive index encapsulants, and LED pixels for micro (mini) LED displays; positive photoresists, chemically amplified photoresists, anti-reflective films, and other materials used in semiconductor manufacturing. Layer materials (SOC, SOG), underlayer films, buffer coats, developers, rinse solutions, pattern collapse prevention agents, polymer residue removers, cleaning agents and other chemicals, nanoimprint release agents; resin compositions for semiconductor post-processing or printed wiring boards (epoxy resins, phenolic resins, polyphenylene ether resins, liquid crystal polymers, polyimide resins, bismaleimide resins, bisallylnadiimide resins, benzoxazine resins and other resin compositions), copper-clad laminates, resin-coated copper foils, build-up films, passivation films, interlayer insulating films, flexible copper-clad laminates, dry film resists;Color resists for image sensors; liquid repellents for solder flux; dispersants, paints, and green sheets for multilayer ceramic capacitors; cathode materials, anode materials, separators, and electrolytes for lithium-ion batteries; automotive exterior paints, rubber, elastomers, glass, vapor deposition anchor coats, headlamp lenses, solid lubricant paints, heat dissipation substrates, interior paints, and repair paints; wallpaper, flooring, kitchen components, bathroom and toilet components for residential facilities; inkjet inks for printed materials, offset printing inks, gravure printing inks, screen printing inks, photoresists for the printing plate manufacturing process, photosensitive materials for lithographic printing plates (PS plates), packaging adhesives, and ballpoint pen inks; primers for easily adhering plastic films; water repellents for textiles; anti-diffusion agents for grease; cleaning solutions for cleaning the surfaces of various products or parts; hard coating materials for optical recording media such as CDs, DVDs, and Blu-ray discs; smartphones or Examples of suitable applications include paints or hard coatings for mobile phone housings or screens; hard coatings for transfer films for insert molds (IMD, IMF); release films; paints or coatings for various plastic molded products such as home appliance housings; printing inks or paints for various building materials such as decorative panels; coatings for residential window glass; woodworking paints for furniture; coatings for artificial and synthetic leather; coatings for rubber rollers in office equipment such as copy machines and printers; coatings for the glass of reading parts in office equipment such as copy machines and scanners; optical lenses or coatings for cameras, video cameras, glasses, contact lenses, etc.; coatings for watch crystals and glass such as wristwatches; coatings for windows of various vehicles such as automobiles and railway cars; anti-reflective coatings for solar cell cover glass or films; paints or coatings for FRP bathtubs; PCMs for metal building materials or home appliances; and single-layer or multi-layer coating compositions for photofabrication processes.

[0136] The polymer of the present invention has excellent surface tension reducing ability, and therefore, not only can it be expected to have leveling properties, but also various functions such as wettability, penetration, cleanability, water repellency, oil repellency, antifouling properties, lubricity, antiblocking properties, and release properties. Furthermore, when the polymer of the present invention is blended into a paint or coating agent containing fine particles, it can be expected to improve the dispersibility of the fine particles, and thus not only have leveling properties but also function as a dispersant for the fine particles. Furthermore, when the polymer of the present invention is added to a pressure-sensitive adhesive composition used for pressure-sensitive adhesive tapes, etc., in addition to the above-mentioned coating composition, it can be expected to have not only leveling properties, but also various functions such as reducing peel force, suppressing peel force fluctuations, and suppressing peel electrification. [Example]

[0137] The present invention will be specifically described below with reference to examples and comparative examples. The present invention is not limited to the following examples.

[0138] In the examples and comparative examples, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured by gel permeation chromatography (GPC) and converted into polystyrene equivalent values. The GPC measurement conditions are as follows:

[0139] [GPC measurement conditions] Measurement equipment: Tosoh Corporation's high-speed GPC equipment "HLC-8420GPC" Column: Tosoh Corporation "TSK GUARDCOLUMN SuperHZ-L" + Tosoh Corporation "TSK gel SuperHZM-N" + Tosoh Corporation "TSK gel SuperHZM-N" + Tosoh Corporation "TSK gel SuperHZM-N" + Tosoh Corporation "TSK gel SuperHZM-N" Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "EcoSEC Data Analysis Version 1.07" 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 prepare a measurement sample. Sample injection volume: 20 μl Standard sample: In accordance with the measurement manual for the above-mentioned "HLC-8420GPC," the following monodisperse polystyrene with known molecular weight was used.

[0140] (monodisperse polystyrene) Tosoh Corporation "A-300" Tosoh Corporation "A-500" Tosoh Corporation "A-1000" Tosoh Corporation "A-2500" Tosoh Corporation "A-5000" "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation Tosoh Corporation "F-128" Tosoh Corporation "F-288"

[0141] (Example 1: Synthesis of Block Copolymer (1)) A nitrogen-purged flask was charged with 22.5 g of polypropylene glycol monomethacrylate (average repeat number of propylene glycol: 4-6) and 75.0 g of methyl ethyl ketone as a solvent, and the mixture was heated to 50°C while stirring under a nitrogen stream. Next, 3.2 g of 2,2'-bipyridyl and 1.1 g of cuprous chloride were charged, and the mixture was stirred for 30 minutes while maintaining the temperature inside the flask at 50°C. 2.0 g of ethyl 2-bromoisobutyrate was then added, and the mixture was reacted for 6 hours at 50°C under a nitrogen stream to obtain a polypropylene glycol monomethacrylate polymer block. Next, 27.5 g of a silicone-containing polymerizable unsaturated monomer represented by the following formula (A1-1) was added to the reaction system containing the polypropylene glycol monomethacrylate polymer block, and the mixture was allowed to react at 50°C for 20 hours to obtain a reaction product. Next, 30.0 g of activated alumina was added to the reaction product and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain block copolymer (1).

[0142] [ka] (In the formula (A1-1), the number average of n1 is 10.)

[0143] Regarding the obtained block copolymer (1), 29 The number average of repeating units of siloxane bonds in the polymer block of the silicone group-containing polymerizable unsaturated monomer represented by formula (A1-1) contained in block copolymer (1) was measured by SiNMR analysis. As a result, the number average of repeating units of siloxane bonds was found to be 10.

[0144] the above 29 In the Si NMR analysis, the repeating units of the siloxane bond were calculated from the integral value of Si when the integral value of Si at both ends of the siloxane moiety was set to 2.00 under the following conditions. Equipment: JEOL Ltd. ECA 500 Measurement mode: Decoupling with inverse gate Solvent: deuterated chloroform Sample concentration: 30wt%

[0145] The molecular weight of the resulting block copolymer (1) was measured by GPC, and the weight average molecular weight (Mw) was 8,300, the number average molecular weight (Mn) was 7,300, and the dispersity (Mw / Mn) was 1.1. Furthermore, based on the raw material charging ratio, the content of the polymer block of the polymerizable unsaturated monomer having a silicone group in the block copolymer (1) was 55% by mass.

[0146] (Example 2: Synthesis of Block Copolymer (2)) A nitrogen-purged flask was charged with 30.0 g of poly(1,2-butylene glycol mono(meth)acrylate (average repeat number of 1,2-butylene glycol: 6) and 66.7 g of methyl ethyl ketone as a solvent, and the mixture was heated to 60°C while stirring under a nitrogen stream. Next, 2.1 g of 2,2'-bipyridyl and 0.7 g of cuprous chloride were charged, and the mixture was stirred for 30 minutes while maintaining the temperature inside the flask at 60°C. After that, 1.3 g of ethyl 2-bromoisobutyrate was added, and the mixture was reacted for 6 hours at 60°C under a nitrogen stream, yielding a polymer block of poly(1,2-butylene glycol mono(meth)acrylate). Next, 36.7 g of the silicone-containing polymerizable unsaturated monomer represented by formula (A1-1) was added to the reaction system containing the poly(1,2-butylene glycol mono(meth)acrylate polymer block, and the mixture was allowed to react at 60°C for 20 hours to obtain a reaction product. Next, 30.0 g of activated alumina was added to the reaction product and stirred. After filtering the activated alumina, the solvent was removed under reduced pressure to obtain block copolymer (2).

[0147] The molecular weight of the resulting block copolymer (2) was measured by GPC, and the weight average molecular weight (Mw) was 14,000, the number average molecular weight (Mn) was 12,000, and the dispersity (Mw / Mn) was 1.2. Furthermore, based on the raw material charging ratio, the content of the polymer block of the polymerizable unsaturated monomer having a silicone group in the block copolymer (2) was 55% by mass.

[0148] (Example 3: Synthesis of block copolymer (3)) A nitrogen-purged flask was charged with 30.0 g of poly(1,2-butylene glycol mono(meth)acrylate (average repeat number of 1,2-butylene glycol: 6) and 66.7 g of methyl ethyl ketone as a solvent, and the mixture was heated to 60°C while stirring under a nitrogen stream. Next, 1.2 g of 2,2'-bipyridyl and 0.4 g of cuprous chloride were charged, and the mixture was stirred for 30 minutes while maintaining the temperature inside the flask at 60°C. 0.8 g of ethyl 2-bromoisobutyrate was then added, and the mixture was reacted for 6 hours at 60°C under a nitrogen stream to obtain a polymer block of poly(1,2-butylene glycol mono(meth)acrylate). Next, 36.7 g of the silicone-containing polymerizable unsaturated monomer represented by formula (A1-1) was added to the reaction system containing the poly(1,2-butylene glycol mono(meth)acrylate polymer block, and the mixture was allowed to react at 60°C for 20 hours to obtain a reaction product. Next, 30.0 g of activated alumina was added to the reaction product and stirred. After filtering the activated alumina, the solvent was removed by distillation under reduced pressure to obtain block copolymer (3).

[0149] The molecular weight of the resulting block copolymer (3) was measured by GPC, and the weight average molecular weight (Mw) was 18,000, the number average molecular weight (Mn) was 15,000, and the dispersity (Mw / Mn) was 1.2. Furthermore, based on the raw material charging ratio, the content of the polymer block of the polymerizable unsaturated monomer having a silicone group in the block copolymer (3) was 55% by mass.

[0150] (Example 4: Synthesis of block copolymer (4)) A nitrogen-purged flask was charged with 30.0 g of poly(1,2-butylene glycol mono(meth)acrylate) (average repeat number of 1,2-butylene glycol: 6) and 66.7 g of methyl ethyl ketone as a solvent, and the mixture was heated to 60°C while stirring under a nitrogen stream. Next, 1.4 g of 2,2'-bipyridyl and 0.5 g of cuprous chloride were charged, and the mixture was stirred for 30 minutes while maintaining the temperature inside the flask at 60°C. 0.9 g of ethyl 2-bromoisobutyrate was then added, and the mixture was reacted for 6 hours at 60°C under a nitrogen stream to obtain a polymer block of poly(1,2-butylene glycol mono(meth)acrylate). Next, 36.7 g of a silicone-containing polymerizable unsaturated monomer represented by the following formula (A1-2) was added to the reaction system containing the poly(1,2-butylene glycol mono(meth)acrylate polymer block, and the mixture was reacted at 60°C for 20 hours to obtain a reaction product. Next, 30.0 g of activated alumina was added to the reaction product and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain block copolymer (4).

[0151] [ka] (In the formula (A1-2), the number average of n2 is 65.)

[0152] The molecular weight of the resulting block copolymer (4) was measured by GPC, and the weight average molecular weight (Mw) was 18,000, the number average molecular weight (Mn) was 15,000, and (Mw / Mn) was 1.2. Furthermore, based on the raw material charging ratio, the content of the polymer block of the polymerizable unsaturated monomer having a silicone group in the block copolymer (4) was 55% by mass.

[0153] (Example 5: Synthesis of block copolymer (5)) A nitrogen-purged flask was charged with 20.0 g of poly(1,2-butylene glycol mono(meth)acrylate (average repeat number of 1,2-butylene glycol: 6) and 66.7 g of methyl ethyl ketone as a solvent, and the mixture was heated to 60°C while stirring under a nitrogen stream. Next, 2.1 g of 2,2'-bipyridyl and 0.7 g of cuprous chloride were charged, and the mixture was stirred for 30 minutes while maintaining the temperature inside the flask at 60°C. After that, 1.3 g of ethyl 2-bromoisobutyrate was added, and the mixture was reacted for 6 hours at 60°C under a nitrogen stream, yielding a polymer block of poly(1,2-butylene glycol mono(meth)acrylate). Next, 46.7 g of the silicone-containing polymerizable unsaturated monomer represented by formula (A1-1) was added to the reaction system containing the poly(1,2-butylene glycol mono(meth)acrylate polymer block, and the mixture was reacted at 60°C for 20 hours to obtain a reaction product. Next, 30.0 g of activated alumina was added to the reaction product and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain block copolymer (5).

[0154] The molecular weight of the resulting block copolymer (5) was measured by GPC, and the weight average molecular weight (Mw) was 14,000, the number average molecular weight (Mn) was 12,000, and the dispersity (Mw / Mn) was 1.2. Furthermore, based on the ratio of the raw materials charged, the content of the polymer block of the polymerizable unsaturated monomer having a silicone group in the block copolymer (2) was 70% by mass.

[0155] (Comparative Example 1: Synthesis of Block Copolymer (1')) A nitrogen-purged flask was charged with 27.5 g of polypropylene glycol monomethacrylate (average propylene glycol repeat number 4-6) and 75.0 g of methyl ethyl ketone as a solvent, and the mixture was heated to 50°C while stirring under a nitrogen stream. Next, 3.2 g of 2,2'-bipyridyl and 1.1 g of cuprous chloride were charged, and the mixture was stirred for 30 minutes while maintaining the temperature inside the flask at 50°C. 2.0 g of ethyl 2-bromoisobutyrate was then added, and the mixture was reacted for 6 hours at 50°C under a nitrogen stream to obtain a polymer block of polypropylene glycol monomethacrylate. Next, 22.5 g of the silicone-containing polymerizable unsaturated monomer represented by formula (A1-1) was added to the reaction system containing the polypropylene glycol monomethacrylate polymer block, and the mixture was allowed to react at 50°C for 20 hours to obtain a reaction product. Next, 30.0 g of activated alumina was added to the reaction product and stirred. After filtering the activated alumina, the solvent was removed under reduced pressure to obtain block copolymer (1').

[0156] The molecular weight of the resulting block copolymer (1') was measured by GPC, and the weight average molecular weight (Mw) was 7,100, the number average molecular weight (Mn) was 6,200, and the dispersity (Mw / Mn) was 1.1. Furthermore, based on the raw material charging ratio, the content of the polymer block of the polymerizable unsaturated monomer having a silicone group in the block copolymer (1') was 45 mass %.

[0157] (Comparative Example 2: Synthesis of Block Copolymer (2')) A nitrogen-purged flask was charged with 37.5 g of polypropylene glycol monomethacrylate (average repeat number of propylene glycol: 4-6) and 75.0 g of methyl ethyl ketone as a solvent, and the mixture was heated to 50°C while stirring under a nitrogen stream. Next, 3.2 g of 2,2'-bipyridyl and 1.1 g of cuprous chloride were charged, and the mixture was stirred for 30 minutes while maintaining the temperature inside the flask at 50°C. 2.0 g of ethyl 2-bromoisobutyrate was then added, and the mixture was reacted for 6 hours at 50°C under a nitrogen stream to obtain a polymer block of polypropylene glycol monomethacrylate. Next, 12.5 g of the silicone-containing polymerizable unsaturated monomer represented by formula (A1-1) was added to the reaction system containing the polypropylene glycol monomethacrylate polymer block, and the mixture was allowed to react at 50°C for 20 hours to obtain a reaction product. Next, 30.0 g of activated alumina was added to the reaction product and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain block copolymer (2').

[0158] The molecular weight of the resulting block copolymer (2') was measured by GPC, and the weight average molecular weight (Mw) was 8,300, the number average molecular weight (Mn) was 7,000, and the dispersity (Mw / Mn) was 1.2. Furthermore, based on the ratio of the raw materials charged, the content of the polymer block of the polymerizable unsaturated monomer having a silicone group in the block copolymer (2') was 25% by mass.

[0159] (Comparative Example 3: Synthesis of random copolymer (3')) A nitrogen-purged flask was charged with 133.3 g of butyl acetate as a solvent and heated to 100°C while stirring under a nitrogen stream. Next, a mixed solution of monomers and a polymerization initiator, prepared by dissolving 55.0 g of the polymerizable unsaturated monomer having a silicone group represented by the formula (A1-1) above, 45.0 g of polypropylene glycol monomethacrylate, and 6.0 g of t-butylperoxy-2-ethylhexanoate in 100.0 g of butyl acetate, was placed in a dropping device, and the mixture was added dropwise over 2 hours while maintaining the temperature inside the flask at 100°C. After the dropwise addition, the mixture was reacted for 4 hours at 100°C under a nitrogen stream to obtain a random copolymer (3') of the polymerizable unsaturated monomer having a silicone group represented by the formula (A1-1) above and polypropylene glycol monomethacrylate.

[0160] The molecular weight of the resulting random copolymer (3') was measured by GPC, and the weight average molecular weight (Mw) was 6,000, the number average molecular weight (Mn) was 2,500, and (Mw / Mn) was 2.4. Furthermore, based on the ratio of the raw materials charged, the content of the polymer block of the polymerizable unsaturated monomer having a silicone group in the random copolymer (3') was 55% by mass.

[0161] (Comparative Example 4: Synthesis of random copolymer (4')) A nitrogen-purged flask was charged with 133.3 g of butyl acetate as a solvent and heated to 100°C while stirring under a nitrogen stream. Next, a monomer / polymerization initiator solution consisting of 55.0 g of the silicone-containing polymerizable unsaturated monomer represented by formula (A1-1) above, 45.0 g of poly(1,2-butylene glycol mono(meth)acrylate), and 6.0 g of t-butylperoxy-2-ethylhexanoate dissolved in 100.0 g of butyl acetate was placed in a dropping apparatus and added dropwise over 2 hours while maintaining the flask at 100°C. After the addition was completed, the mixture was allowed to react for 4 hours at 100°C under a nitrogen stream, yielding a random copolymer (4') of the silicone-containing polymerizable unsaturated monomer represented by formula (A1-1) above and poly(1,2-butylene glycol mono(meth)acrylate.

[0162] The molecular weight of the resulting random copolymer (4') was measured by GPC, and the weight average molecular weight (Mw) was 11,000, the number average molecular weight (Mn) was 2,800, and (Mw / Mn) was 4.1. Furthermore, based on the ratio of the raw materials charged, the content of the polymer block of the polymerizable unsaturated monomer having a silicone group in the random copolymer (4') was 55% by mass.

[0163] (Coating film formation and evaluation) Using the block copolymer (1) produced in Example 1, a coating film was formed as follows. A resist composition was prepared by mixing 3.0 g of a 40 mass % alkali-soluble resin solution (Acrydic ZL-295, manufactured by DIC Corporation), 1.2 g of Aronix M-402 (manufactured by Toagosei Chemical Industry Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), 0.001 g (in terms of solid content) of block copolymer (1), and 3.8 g of propylene glycol monomethyl ether acetate (PGMEA). 3 ml of the obtained resist composition was dropped onto the center of a 10 cm × 10 cm chrome-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 a laminate having a coating layer.

[0164] The smoothness of the coating layer of the prepared laminate was evaluated by the following method, and the results are shown in Table 1. (Smoothness) The coating layer of the resulting laminate was visually observed, and the smoothness of the coating layer was evaluated according to the following criteria. ◯: Almost no unevenness in the coating film is observed. △: Unevenness in the coating film was observed in some areas. ×: Unevenness in the coating film was observed throughout.

[0165] The same evaluations as in Example 1 were carried out except that the polymers produced in Examples 2 to 5 and Comparative Examples 1 to 4 were used instead of the block copolymer (1). The results are shown in Table 1.

[0166] [Table 1]

[0167] As shown in the results in Table 1, the compositions of Examples 1 to 5, which contain a polymer containing a polymer block (silicone block) of a polymerizable unsaturated monomer having a silicone group and in which the silicone block content exceeds 50% by mass, provide excellent coating film smoothness. On the other hand, the compositions containing a polymer with an insufficient silicone block content (Comparative Examples 1 and 2) and a polymer without a silicone block (Comparative Examples 3 and 4) provide insufficient coating film smoothness.

[0168] The developability of the coating layer of the laminate produced in Example 1 was also evaluated. Specifically, the produced laminate was immersed in a 5% aqueous solution of an inorganic alkaline resist developer (Semiclean DL-A10, manufactured by Yokohama Yushi Kogyo Co., Ltd.) for 120 seconds, then rinsed with pure water for 120 seconds, and dried. No coating layer remained on the laminate of Example 1 after immersion in the developer, demonstrating that the polymer of the present invention can be used as a suitable leveling agent for resist compositions.

Claims

1. A resist composition comprising a polymer including: a polymer block (A1) which is a segment consisting of a repeating unit derived from a polymerizable monomer (a1) having a group represented by the following general formula (1); and a polymer block (A2) which is a segment consisting of a repeating unit derived from a polymerizable monomer (a2), which is a compound represented by the following general formula (a2-1) or (a2-2): the content of the polymer block (A1) in the polymer is more than 50% by mass, the mass ratio of the polymer block (A1) to the polymer block (A2) satisfies polymer block (A1):polymer block (A2)=51:49 to 75:25, A resist composition in which the content of the polymer is 0.0001 to 10 parts by mass per 100 parts by mass of the solid content of the resist composition. 【Chemistry 1】 (In the formula (1), R １１ are each independently an alkyl group having 1 to 6 carbon atoms or —OSi(R １４ ) ３ A group represented by R １４ are each independently an alkyl group having 1 to 3 carbon atoms, R １２ are each independently an alkyl group having 1 to 6 carbon atoms, R １３ is an alkyl group having 1 to 6 carbon atoms, n is an integer of 0 or more. 【Chemistry 2】 (In the above formulas (a2-1) and (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 ranging from 1 to 4, and m is an integer ranging from 1 to 200.

2. 2. The resist composition according to claim 1, wherein the polymerizable monomer (a1) is a compound represented by the following general formula (a1-1): 【Transformation 3】 (In the formula (a1-1), R １１ , R １２ and R １３ are R in the formula (1), respectively. １１ , R １２ and R １３ is the same as R １５ is a hydrogen atom or a methyl group, L １ is a divalent organic group or a single bond. n is an integer of 0 or more.

3. 3. The resist composition according to claim 1, wherein the number average value of n in the polymer block (A1) is in the range of 1 to 70.

4. 4. The resist composition according to claim 1, wherein the total content of the polymer block (A1) and the polymer block (A2) is 80% by mass or more relative to the total mass of the polymer.

5. 5. The resist composition according to claim 1, wherein the polymer is a diblock copolymer in which the polymer block (A1) and the polymer block (A2) are bonded together.

6. 6. The resist composition according to claim 1, which does not contain fluorine atoms.

7. 7. The resist composition according to claim 1, wherein the number average molecular weight of the polymer is in the range of 1,000 to 500,000.

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