Coating composition and photoresist composition

Abstract

This invention provides a polymer that functions as a leveling agent, imparting a high degree of smoothness to the coating film without creating defects on the surface. Specifically, this invention is a polymer containing polysiloxane chains, wherein the polymer has polysiloxane chains at one end, the number of such polysiloxane chains having an average molecular weight in the range of 2,000 to 20,000, and the polymer does not contain polymerizable unsaturated groups.

Description

Technical Field

[0001] This invention relates to polymers containing polysiloxane chains and coating compositions comprising such polymers. Prior Technology

[0002] Leveling agents are added to smooth the coating film obtained from coating components such as paint components and photoresist components. Specifically, by adding a leveling agent to the coating component, the leveling agent will orient itself on the coating surface, reducing the surface tension of the coating film and thus achieving the effect of smoothing the resulting coating film. A smoothed coating film can improve the occurrence of shrinkage and unevenness.

[0003] Leveling agents have various uses, such as in color photoresist compositions used to manufacture color filters for liquid crystal displays. The manufacturing of color filters generally involves the following steps: coating the color photoresist composition onto a glass substrate using methods such as transfer coating or slot coating; exposing the dried coating with a mask; and then developing to form a colored pattern. However, if the coating has poor smoothness, resulting in uneven film thickness, or if there are issues such as uneven coating or shrinkage, there is a risk of uneven pixel color.

[0004] By adding a leveling agent to the color photoresist composition, the smoothness of the resulting coating film can be improved, resulting in high smoothness of the surfaces of red (R), green (G), and blue (B) pixels and the black matrix (BM) formed between these pixels, thus forming a color filter with less color unevenness.

[0005] As a leveling agent that makes the coating film smooth, a polymeric leveling agent has been proposed (Patent Document 1). [Previous Technical Documents] [Patent Literature]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2002-179991 Summary of the Invention

[0007] [The problem the invention aims to solve]

[0008] The polymer leveling agent in Patent Document 1 introduces macromonomers into the matrix molecules through free radical copolymerization or ionic copolymerization. When the aforementioned macromonomers have polysiloxane chains, the following problem arises: the polymer leveling agent in Patent Document 1 becomes a polymer with multiple polysiloxane chains, but leveling agents with multiple polysiloxane chains can become a cause of defects on the coating surface.

[0009] The problem to be solved by the present invention is to provide a polymer that functions as a leveling agent without causing defects on the coating surface and imparts high smoothness to the coating. [Methods used to solve problems]

[0010] In order to solve the above-mentioned problems, the inventors of this case conducted detailed research and found that if the polymer containing polysiloxane chains has a specific polysiloxane chain at one end and does not contain polymerizable unsaturated groups, then the coating surface will not produce defects, and excellent leveling performance can be obtained, thus completing the present invention.

[0011] That is, the present invention relates to a polymer containing polysiloxane chains, which is a polymer with polysiloxane chains at one end, wherein the number of the aforementioned polysiloxane chains has an average molecular weight in the range of 2,000 to 20,000, and the polymer does not contain polymerizable unsaturated groups. [Effects of the Invention]

[0012] According to the present invention, a polymer is provided that functions as a leveling agent without causing defects on the coating surface and imparts high smoothness to the coating. Simple Explanation of the Diagram

[0013] none. Implementation

[0014] [The form in which the invention is carried out]

[0015] The following describes one embodiment of the present invention. The present invention is not limited to the following embodiment; appropriate modifications may be made to implement it without impairing its effectiveness. Furthermore, in this specification, "(meth)acrylate" refers to one or both of acrylate and methacrylate.

[0016] [polymer] The polymer of the present invention comprises polysiloxane chains with an average molecular weight of 2,000 to 20,000 at one end and does not contain polymerizable unsaturated groups. Furthermore, "one-sided end" refers to any end of the main chain of a polymer (the longest molecular chain that makes up the polymer's molecular chain).

[0017] The polymer of this invention has a specific polysiloxane chain only at one end and does not contain polymerizable unsaturated groups. Therefore, when this polymer is used as an additive in a coating composition, it does not compromise the compatibility of the coating composition with the matrix polymer or solvent, thus exhibiting leveling properties. Because compatibility is not compromised, defects on the resulting coating surface are prevented.

[0018] The number of polysiloxane chains mentioned above has an average molecular weight in the range of 2,000 to 20,000, more preferably in the range of 3,000 to 20,000, even more preferably in the range of 3,500 to 15,000, and even more preferably in the range of 4,000 to 12,000. The number of polysiloxane chains and the average molecular weight were measured using the method described in the examples.

[0019] The aforementioned proportion of polysiloxane chains is, for example, in the range of 5 to 95% by mass, preferably in the range of 10 to 90% by mass, more preferably in the range of 15 to 80% by mass, and even more preferably in the range of 20 to 70% by mass. Here, the polysiloxane chain ratio is a value based on the mass of the polymer of the present invention (mass of polysiloxane chain / mass of polymer). The polysiloxane chain ratio is a value calculated from the raw material loading ratio during manufacturing, which can be adjusted by the raw material loading ratio of the polysiloxane compound used in the manufacturing of the polymer of the present invention.

[0020] The polysiloxane chain of the polymer of the present invention is preferably represented by the polysiloxane chain of the following formula (1).

[0021] (in the aforementioned formula (1),) R11, R12, R13, R14 and R15 are each independently an alkyl or phenyl group having 1 to 18 carbon atoms. L 11 is a divalent organic group or a single bond. (n is an integer.)

[0022] The alkyl groups of R11, R12, R13, R14 and R15 with 1 to 18 carbon atoms are preferably alkyl groups with 1 to 6 carbon atoms. R11, R12, R13 and R14 are preferably methyl, and R15 is preferably an alkyl group having 1 to 6 carbon atoms.

[0023] n is preferably an integer in the range of 5 to 300, more preferably an integer in the range of 10 to 250, even more preferably an integer in the range of 20 to 200, and most preferably an integer in the range of 25 to 200.

[0024] The divalent organic group of L 11 is preferably an alkyl group with 1 to 50 carbon atoms or an alkyloxy group with 1 to 50 carbon atoms.

[0025] Examples of alkyl groups with 1 to 50 carbon atoms in L11 include: methylene, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecylene, isopropyl, 2-methylpropyl, 2-methylhexyl, tetramethylethyl, etc.

[0026] The alkyl group of L 11 with 1 to 50 carbon atoms is preferably an alkyl group with 1 to 15 carbon atoms, more preferably an alkyl group with 1 to 5 carbon atoms, and even more preferably methylene, ethyl, n-propyl or isopropyl.

[0027] L 11 is an alkyl group with 1 to 50 carbon atoms, for example, formed by replacing one or more -CH 2- of the aforementioned alkyl groups with -O-. L 11 preferably has an alkyloxy group with 1 to 50 carbon atoms, preferably an alkyloxy group with 1 to 15 carbon atoms, more preferably an alkyloxy group with 1 to 8 carbon atoms, and even more preferably a methyleneoxy group, an ethyloxy group, an propyloxy group, an oxytrimethylene group, an butyloxy group, an oxytetramethylene group, an pentyloxy group, an heptyloxy group, or an octyloxy group.

[0028] When the divalent organic group of L 11 is an alkyl group or an alkyloxy group with 1 to 50 carbon atoms, a portion of the -CH 2- of such divalent organic group can be substituted into a carbonyl group (-C(=O)-), an phenyl group, an amino acid bond or an amino carbamate bond. Furthermore, the carbon atom can also be substituted by a hydroxyl group or the like.

[0029] The polymer of the present invention is not particularly limited in structure as long as the ends have the aforementioned polysiloxane chains and do not contain polymerizable unsaturated groups. The polymer of the present invention is suitable for use as an additive in coating compositions; therefore, it is preferred that the polymer portion comprises a structure that exhibits compatibility with the matrix polymer of the coating composition.

[0030] The polymer of the present invention is preferably a polymer in which a polymeric monomer (2) is used as a polymeric component and has a polysiloxane chain at one end. The polymeric monomer (2) has one or more selected from alkyl groups having 1 to 18 carbon atoms, aromatic groups having 6 to 18 carbon atoms, groups containing polyoxyalkyl chains, and groups containing polyester chains. The polymer of the polymeric monomer (2) exhibits high compatibility with the matrix polymer of the coating composition. Furthermore, "polymer components" refers to the components that make up the polymer, and does not include solvents and polymerization initiators that do not constitute the polymer.

[0031] In this invention, "polymerizable monomer" refers to a compound having a polymerizable unsaturated group. Examples of polymerizable unsaturated groups in polymerizable monomer (2) include: (meth)acryl, (meth)acryloxy, (meth)acrylamide, vinyl ether, allyl, styrene, (meth)acrylamide, maleimide, etc. Among these, (meth)acryl and (meth)acryloxy are preferred in terms of ease of obtaining raw materials and good polymerization reactivity.

[0032] The polymerizable monomer (2) has an alkyl group with 1 to 18 carbon atoms, which can be any of the straight-chain alkyl, branched alkyl and cyclic alkyl groups. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, tributyl, n-hexyl, cyclohexyl, n-octyl, hexadecyl, etc. The polymerizable monomer (2) preferably has an alkyl group with 1 to 18 carbon atoms, which is preferably an alkyl group with 1 to 6 carbon atoms.

[0033] The polymerizable monomer (2) may have an alkyl group with 1 to 18 carbon atoms, or an ether bond. The -CH 2- in the alkyl group with ether bond of 1 to 18 carbon atoms is replaced by an ether bond (-O-) group, including alkyloxyalkyl with 2 to 18 carbon atoms, polyoxyalkylalkyl with 3 to 18 carbon atoms, and oxocyclic alkyl with 2 to 18 carbon atoms.

[0034] Aromatic groups with 6 to 18 carbon atoms that are polymerizable monomers (2) can be listed as: phenyl, naphthyl, anthracene-1-yl, phenanthrene-1-yl, etc.

[0035] The polymeric monomer (2) has a group containing a (poly)oxyalkyl chain, which is a monovalent group containing a repeating part of the oxyalkyl group or a divalent linker containing a repeating part of the oxyalkyl group.

[0036] When the polymerizable unsaturated group of the polymerizable monomer (2) is (meth)acrylic acid, the polymerizable monomer having a group containing a (poly)oxyalkyl chain is, for example, a compound represented by the following general formula (2-poa1) or (2-poa2).

[0037] (In the aforementioned formulas (2-poa1) and (2-poa2), Ra21 can be independently represented by either a hydrogen atom or a methyl group. Ra22 is an alkyl group having 1 to 18 hydrogen atoms or carbon atoms. p is an integer greater than or equal to 0, q is an integer greater than or equal to 0, and r is an integer greater than or equal to 0. p+q+r is an integer greater than or equal to 1. X, Y, and Z are each independently an alkyl group having 1 to 6 carbon atoms.

[0038] In the above formulas (2-poa1) and (2-poa2), the radicals represented by -(XO) p-(YO) q-(ZO) rRa22 and -(XO) p-(YO) q-(ZO) r- correspond to radicals containing (poly)oxyalkyl chains.

[0039] In the above formulas (2-poa1) and (2-poa2), the alkyl groups of X, Y and Z with 1 to 6 carbon atoms are preferably alkyl groups with 2 to 4 carbon atoms.

[0040] Examples of polymerizable monomers (2) having an alkyl group having 1 to 18 carbon atoms and a polymerizable unsaturated group of (meth)acrylic acid include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, dibutyl methacrylate, isobutyl methacrylate, tributyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-... Ethylhexyl acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate, isooctadecyl acrylate, and other alkyl esters of (meth)acrylic acid with 1 to 18 carbon atoms; dicyclopentyloxyethyl acrylate, isocamphenoxyethyl acrylate, isocamphenyl acrylate, adamantyl acrylate, dimethyl adamantyl acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, and other bridged cyclic alkyl esters of (meth)acrylic acid with 1 to 18 carbon atoms.

[0041] Examples of polymerizable monomers (2) that have 1 to 18 carbon atoms in a hydroxyalkyl group and whose polymerizable unsaturated group is (meth)acrylic acid group include: 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxy methacrylate, 1,4-cyclohexanediethanol mono(meth)acrylate, 2,3-dihydroxypropyl methacrylate, etc.

[0042] Examples of polymerizable monomers (2) that are phenylalkyl or phenoxyalkyl with 7 to 18 carbon atoms and whose polymerizable unsaturated group is (meth)acrylyl are: benzyl (meth)acrylate, 2-phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, etc.

[0043] Examples of polymerizable monomers (2) that have alkyl groups having 1 to 18 carbon atoms and whose polymerizable unsaturated group is vinyl ether group include: methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tributyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, etc., alkyl vinyl ethers, 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, cyclohexane-1,4-diethanol monovinyl ether, etc.

[0044] Examples of polymerizable monomers (2) that are alkyl groups having 1 to 18 carbon atoms and whose polymerizable unsaturated group is allyl include: 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, etc.

[0045] Examples of polymerizable monomers (2) that have an aromatic group having 6 to 18 carbon atoms include styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, etc.

[0046] Examples of polymerizable monomers (2) that are alkyl groups having 1 to 18 carbon atoms and whose polymerizable unsaturated group is (meth)acrylamide include: N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, diacetoneacrylamide, and acrylamide. Phospholine (acryloylmorpholine), etc.

[0047] Examples of polymerizable monomers (2) that are alkyl groups having 1 to 18 carbon atoms and whose polymerizable unsaturated group is maleimide include: methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, cyclohexylmaleimide, etc.

[0048] Examples of polymerizable monomers (2) that have a polyoxyalkylene chain and a polymerizable unsaturated group of (meth)acrylic acid include: polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, poly(1,3-propylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, poly(ethylene glycol / propylene glycol) mono(meth)acrylate, polyethylene glycol / polypropylene glycol mono(meth)acrylate, poly(ethylene glycol / butylene glycol) mono(meth)acrylate, polyethylene glycol / Polybutylene glycol mono(meth)acrylate, poly(propylene glycol / butylene glycol) mono(meth)acrylate, polypropylene glycol / polybutylene glycol mono(meth)acrylate, poly(propylene glycol / 1,2-butanediol) mono(meth)acrylate, polypropylene glycol / poly1,2-butanediol mono(meth)acrylate, poly(ethylene glycol·1,2-butanediol) mono(meth)acrylate, polyethylene glycol·poly1,2-butanediol mono(meth)acrylate, poly(tetraethylene glycol / 1,2-butanediol) mono(meth)acrylate Ester, Poly(tetraethylene glycol) / Poly(1,2-butanediol) mono(meth)acrylate, Poly(1,2-butanediol) mono(meth)acrylate, Poly(ethylene glycol / 1,3-propanediol) mono(meth)acrylate, Poly(ethylene glycol) / Poly(1,3-propanediol) mono(meth)acrylate, Poly(propylene glycol / 1,3-propanediol) mono(meth)acrylate, Poly(propylene glycol / Poly(1,3-propanediol) mono(meth)acrylate, Poly(1,3-propanediol / ...but ...) / ...butanediol) mono(meth)acrylate, Poly(1,3-propanediol) / ...butanediol) mono(meth)acrylate, Poly(1,3-propanediol) / ...butanediol) mono(meth)acrylate, Poly(1,3-propanediol) / ...butanediol) mono(meth)acrylate, Poly(1,2-propanediol) mono(meth)acrylate, Poly(1,2-butanediol) mono(meth)acrylate, Poly(1,2-butanediol) mono(meth)acrylate, Poly(1,2-butanediol) mono(meth)acrylate, Poly(1,2-butanediol) mono(meth)acrylate, Poly(1,2-butanediol) mono(meth)acrylate, Poly(1,2-butanediol) mono(meth)acrylate, Poly(1,2-butanediol) mono(meth)acrylate, Poly(1,2-butane Polybutylene glycol mono(meth)acrylate, poly(1,2-butanediol / 1,3-propanediol) mono(meth)acrylate, poly(1,2-butanediol / poly(1,3-propanediol) mono(meth)acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, poly(1,2-butanediol·butylene glycol) mono(meth)acrylate, poly(1,2-butanediol / polybutylene glycol) mono(meth)acrylate, etc. Furthermore, the aforementioned "poly(ethylene glycol / propylene glycol)" refers to a random copolymer of ethylene glycol and propylene glycol, while "polyethylene glycol / polypropylene glycol" refers to a block copolymer of ethylene glycol and propylene glycol.

[0049] The polymerizable monomer (2) is preferably selected from one or more compounds represented by formula (2-1), formula (2-2), formula (2-3), formula (2-4) and formula (2-5), and more preferably selected from one or more compounds represented by formula (2-1), formula (2-2), formula (2-3) and formula (2-4). These compounds exhibit high compatibility when the polymers of the present invention are used as leveling agents.

[0050] (In the aforementioned equations (2-1), (2-2), (2-3), (2-4) and (2-5), R 21 is a hydrogen atom or a methyl group. R 22 is an alkyl group having 1 to 18 carbon atoms. R 23 is a hydrogen atom or a methyl group. R 24 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. R 25 is a hydrogen atom or a methyl group. R 26 is an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms and containing an ether bond. R 27 is a hydrogen atom or a methyl group. R 28 is an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms and containing an ether bond. L2 is a divalent organic group. R 29 is a hydrogen atom or a methyl group. R 30 are each independently an alkyl group or an alkoxy group having 1 to 6 carbon atoms. n is an integer in the range of 1 to 4, m is an integer in the range of 1 to 200, p is an integer in the range of 1 to 10, q is an integer in the range of 1 to 100, and l is an integer in the range of 0 to 5.

[0051] The divalent organogroups of L2 in the aforementioned formulas (2-3) and (2-4) can be listed as being the same as the divalent organogroups of L11.

[0052] Polymerizable monomers (2) can be manufactured by known methods. Furthermore, commercially available products can also be used for polymerizable monomers (2). For example, commercially available products containing a polyoxyalkylene chain and a (meth)acrylic acid group as the polymerizable unsaturated group (2) can be listed as follows: "NK ESTER M-20G", "NK ESTER M-40G", "NK ESTER M-90G", "NK ESTER M-230G", "NK ESTER AM-90G", "NK ESTER AMP-10G", "NK ESTER AMP-20G", "NK ESTER AMP-60G" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and "Blemmer PE-90", "Blemmer PE-200", "Blemmer PE-350", "Blemmer PME-100", "Blemmer PME-200", "Blemmer PME-400", "Blemmer PME-4000", "Blemmer PME-4000", "Blemmer PME-4000", "Blemmer PME-4000", "Blemmer PME-4000", "Blemmer PME-2 ... PP-1000, Blemmer PP-500, Blemmer PP-800, Blemmer 70PEP-350B, Blemmer 55PET-800, Blemmer 50POEP-800B, Blemmer 10PPB-500B, Blemmer NKH-5050, Blemmer AP-400, Blemmer AE-350, Placcel F series manufactured by DAICL Co., Ltd., and Viscoat series manufactured by Osaka Organic Chemical Industry Co., Ltd., etc.

[0053] The polymer of the present invention is a polymer having one or more polymerizable monomers (2) selected from alkyl groups with 1 to 18 carbon atoms, aromatic groups with 6 to 18 carbon atoms, and groups containing polyoxyalkyl chains. When the polymer has a polysiloxane chain at one end, the polymerizable monomer (2) may be a single type or two or more types may be used together. Furthermore, when the polymer is a copolymer of two or more polymeric monomers (2), the polymerization form of the copolymer is not particularly limited. It can be a random copolymer of two or more polymeric monomers (2) with different structures, or a block copolymer of two or more polymeric monomers (2) with different structures.

[0054] The polymer of the present invention is a polymer having one or more polymeric monomers (2) selected from alkyl groups with 1 to 18 carbon atoms, aromatic groups with 6 to 18 carbon atoms, and groups containing polyoxyalkyl chains as polymeric components, and when it is a polymer with polysiloxane chains at one end, the polymer of the present invention may also contain polymer portions of polymeric monomers other than polymeric monomers (2). The aforementioned polymeric component may be, for example, at least 90% by mass of a polymeric monomer (2), preferably at least 95% by mass of a polymeric monomer (2), and more preferably containing only a polymeric monomer (2). That is, the polymer of the present invention is preferably a polymer having one or more polymeric monomers (2) selected from alkyl groups having 1 to 18 carbon atoms, aromatic groups having 6 to 18 carbon atoms, and groups containing polyoxyalkylene chains, and is a polymer having a polysiloxane chain at one end.

[0055] The polymer of this invention does not contain polymerizable unsaturated groups. The polymer of the present invention is suitable as a leveling agent for coatings. However, when it contains polymerizable unsaturated groups that may react with the matrix polymer contained in the coating composition, the desired effect may be impaired. Examples of polymerizable unsaturated groups include: (meth)acrylyl, (meth)acryloxy, (meth)acrylamide, vinyl ether, allyl, styryl, maleimino, and other groups containing carbon-carbon unsaturated double bonds (C=C).

[0056] The polymer of the present invention is preferably free of reactive functional groups. In this invention, "reactive functional group" refers to a functional group that can react with other functional groups to form cross-linked structures, etc. Examples include: isocyanate group, epoxy group, carboxyl group, carboxylic acid halide group, carboxylic anhydride group, etc. The polymer of the present invention is suitable as a leveling agent for coatings. However, when it contains reactive functional groups that may react with the matrix polymer contained in the coating composition, the desired effect may be impaired.

[0057] 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, and even more 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, and even more preferably in the range of 2,000 to 40,000. The dispersion (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) values ​​of the polymers of the present invention were measured by the method of the embodiments.

[0058] [Polymer Manufacturing Methods] The polymer of the present invention can be manufactured by the following method: in a reaction system containing compound (1) and polymerizable monomer (2), free radicals are generated from the aforementioned compound (1), and the aforementioned polymerizable monomer (2) is used to perform living free radical polymerization on the aforementioned compound (1), wherein the compound (1) has functional groups with free radical generation ability at one end of a polysiloxane chain in the range of number average molecular weight of 2,000 to 20,000.

[0059] As functional groups possessed by compound (1) that have the ability to generate free radicals, examples include: organic groups with halogen atoms, organic groups with alkyl telluryl groups, organic groups with dithioester groups, organic groups with peroxide groups, organic groups with azo groups, etc. From the perspectives of ease of synthesis, ease of polymerization control, and diversity of applicable polymerizable monomers, the functional group possessed by compound (1) with the ability to generate free radicals is preferably an organic group with halogen atoms.

[0060] Examples of organic groups containing halogen atoms include, for example, organic groups containing 2-bromo-2-methylpropoxy, 2-bromo-propoxy, p-chlorosulfonylbenzooxy, etc.

[0061] The compound (1) having a polysiloxane chain with a number average molecular weight in the range of 2,000 to 20,000 and having a functional group at one end capable of generating free radicals on one side is preferably a compound represented by the following formula (1-1).

[0062] (In the aforementioned equation (1-1), R11, R12, R13, R14 and R15 are each independently an alkyl or phenyl group having 1 to 18 carbon atoms. L 11 is a divalent organic group or a single bond. n is an integer. X is a functional group capable of generating free radicals.

[0063] In the aforementioned equation (1-1), the preferred states of R11, R12, R13, R14, R15, L11 and n are the same as the preferred states of R11, R12, R13, R14, R15, L11 and n in the aforementioned equation (1).

[0064] In the aforementioned formula (1-1), the functional group of X that has the ability to generate free radicals is, for example, a functional group with halogen atoms, preferably a functional group represented by the following formula (X-1).

[0065] (In the aforementioned formula (X-1), R HAL represents halogen atoms. R16 and R17 are each independently alkyl groups having 1 to 6 carbon atoms. Q represents either an oxygen atom or a sulfur atom.

[0066] Specific examples of compounds (1) whose polysiloxane chains have functional groups with free radical generation ability at one end are as follows: compounds represented by formulas (A-1) to (A-5).

[0067] (In the aforementioned formulas (A-1) to (A-5), n is an integer, preferably an integer between 27 and 270.) R is a divalent organic group or a single bond.

[0068] Compounds (1) in which the number average molecular weight is in the range of 2,000 to 20,000 and one end of a polysiloxane chain has a functional group with free radical generation capability can be manufactured by conventional methods (e.g., Japanese Patent No. 6405647).

[0069] The polymeric monomer (2) used in the manufacturing method of the polymer of the present invention is the same as the polymeric monomer (2) described in the polymer of the present invention.

[0070] As for the mass ratio of compound (1) to polymerizable monomer (2) in manufacturing the polymer of the present invention, for example, the content of compound (1) in the total reactants can be in the range of 5 to 95% by mass. For example, the mass ratio of compound (1): polymerizable monomer (2) is 5:95 to 95:5, more preferably compound (1): polymerizable monomer (2) is 10:90 to 90:10, more preferably compound (1): polymerizable monomer (2) is 15:85 to 80:20, and even more preferably compound (1): polymerizable monomer (2) is 20:80 to 70:30.

[0071] In the aforementioned living radical polymerization, dormant species protected by atoms or groups at the active polymerization terminus reversibly generate free radicals that react with monomers to carry out the growth reaction. Even if the first monomer is consumed, the growth terminus does not lose its activity and reacts with successively added second monomers to obtain a block polymer. Examples of such living radical polymerization include: atom-moving radical polymerization (ATRP), reversible addition-cracking radical polymerization (RAFT), nitrogen oxide radical polymerization (NMP), and organotelluric radical polymerization (TERP). While there is no limitation on the method used, ATRP is preferred due to ease of control. ATRP uses organohalides or sulfonyl halides as polymerization initiators and metal complexes containing transition metal compounds and ligands as catalysts for polymerization. In the polymer manufacturing method of the present invention, compound (1) can function as a polymerization initiator, enabling compound (1) to undergo living radical polymerization with polymerizable monomer (2).

[0072] The transition metal compounds that can be used in ATRP are denoted as Mn+Xn. The transition metal Mn+, representing the transition metal compound Mn+Xn, can be selected from the group consisting of Cu+, Cu2+, Fe2+, Fe3+, Ru2+, Ru3+, Cr2+, Cr3+, Mo0, Mo+, Mo2+, Mo3+, W2+, W3+, Rh3+, Rh4+, Co+, Co2+, Re2+, Re3+, Ni0, Ni+, Mn3+, Mn4+, V2+, V3+, Zn+, Zn2+, Au+, Au2+, Ag+, and Ag2+. In the transition metal compound Mn+X, X can be selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, (SO4)1 / 2, (PO4)1 / 3, (HPO4)1 / 2, (H2PO4), trifluoromethanesulfonate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate), SeR11, CN, and R12COO. Here, R11 represents an aryl group, a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and R12 represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms (preferably methyl) that may be halogenated 1 to 5 times (preferably fluorine or chlorine substituted 1 to 3 times). In M n+X n, n represents the formal charge on the metal, which is an integer from 0 to 7.

[0073] Examples of coordination compounds that can coordinate with transition metals among the aforementioned transition metal compounds include: compounds having coordination ligands containing one or more nitrogen, oxygen, phosphorus, or sulfur atoms that can coordinate with transition metals through σ bonds; compounds having coordination ligands containing two or more carbon atoms that can coordinate with transition metals through π bonds; and compounds having coordination ligands that can coordinate with transition metals through μ or η bonds.

[0074] The aforementioned transition metal complexes are not particularly limited, but preferably include transition metal complexes of groups 7, 8, 9, 10, and 11, and even more preferably include complexes of 0-valent copper, 1-valent copper, 2-valent ruthenium, 2-valent iron, or 2-valent nickel.

[0075] Specific examples of catalysts usable in ATRP, when the central metal is copper, include its complexes with the following ligands: 2,2'-bipyridine and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris(2-aminoethyl)amine, tris(2-(dimethylamino)ethyl)amine, tris(2-pyridylmethyl)amine, and other polyamines. Furthermore, examples of divalent ruthenium complexes include: dichlorotriphenylphosphine ruthenium, dichlorotributylphosphine ruthenium, dichlorocyclooctadiene ruthenium, dichlorobenzene ruthenium, dichloro-p-isopropyltoluene ruthenium, dichloronorbornene ruthenium, cis-dichlorobis(2,2'-bipyridine)ruthenium, dichlorotris(1,10-phenanthroline)ruthenium, and carbonylchlorohydrotriphenylphosphine ruthenium. Furthermore, examples of divalent iron complexes include: bis(triphenylphosphine) complexes and triazacyclononane complexes.

[0076] Atom-moving radical polymerization (ATRP) is not limited to the above and can also be carried out by other ATRP methods. For example, AGET ATRP, ARGET ATRP, ICAR ATRP, etc., as described in "Macromol.Rapid.Commun.2018,1800616" can also be used.

[0077] In living radical polymerization, solvents are preferred. Solvents used in living radical polymerization include, for example: ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ether solvents such as diisopropyl ether, dimethoxyethane, and diethylene glycol dimethyl ether; halogen solvents such as dichloromethane and dichloroethane; aromatic solvents such as toluene, xylene, and anisole; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, and isopropanol; and aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide. The above solvents can be used alone or in combination of two or more.

[0078] The preferred polymerization temperature for the aforementioned living free radical polymerization is in the range of room temperature to 120°C.

[0079] When the polymer of this invention is manufactured by living radical polymerization, the resulting polymer may contain residual metals derived from the transition metal compounds used in the polymerization. These residual metals can be removed by using activated alumina or similar methods after polymerization.

[0080] [Coating Composition] The polymer of this invention is suitable for use as a leveling agent in coating compositions comprising the polymer of this invention. The polymer of this invention can be used as a fluorine-free leveling agent, thus exhibiting low environmental accumulation and a small environmental burden.

[0081] The content of the polymer of the present invention in the coating composition varies depending on the type of matrix resin, coating method, target film thickness, etc., but is preferably 0.0001 to 10 parts by weight, more preferably 0.001 to 5 parts by weight, and even more preferably 0.01 to 2 parts by weight relative to 100 parts by weight 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, achieving the desired leveling properties, and preventing blistering and other defects during coating.

[0082] The application of the coating composition of the present invention is not particularly limited, and it can be used for any application requiring smoothness. The coating composition of the present invention can be used as, for example, various coating compositions and photosensitive resin compositions.

[0083] When the coating composition of the present invention is used as a coating composition, examples of coating compositions that use natural resins include: petroleum resin coatings, shellac coatings, rosin-based coatings, cellulose-based coatings, rubber-based coatings, lacquer coatings, cashew resin coatings, and oil-based coal slurry coatings; and coatings that use synthetic resins include phenolic resin coatings, alkyd resin coatings, unsaturated polyester resin coatings, amino resin coatings, epoxy resin coatings, vinyl resin coatings, acrylic resin coatings, polyurethane resin coatings, polysiloxane resin coatings, and fluoropolymer coatings. By adding the polymer of the present invention to the above-mentioned coating composition, the resulting coating film can be given smoothness.

[0084] Various additives can be appropriately added to the composition of coatings as needed: colorants such as pigments, dyes, and carbon; inorganic powders such as silicon dioxide, titanium dioxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, and calcium carbonate; organic micro powders such as higher fatty acids, polyacrylic resin, and polyethylene; lightfastness enhancers, weather resistance enhancers, heat resistance enhancers, antioxidants, thickeners, and anti-settling agents, etc.

[0085] Regarding the coating method of the coating composition of the present invention, any conventional coating method can be used, such as: slot coating, slot and spin coating, spin coating, roller coating, electrostatic coating, bar coating, gravure coating, die coating, knife coating, inkjet, dip coating, spray coating, rinse coating, screen printing, gravure printing, offset printing, reverse coating, etc.

[0086] Photosensitive resin composition refers to resins whose physical properties, such as solubility, viscosity, transparency, refractive index, conductivity, and ion penetration, change when exposed to visible light, ultraviolet light, or other light sources. Among photosensitive resin compositions, photoresist components (photoresist components, color photoresist components for color filters, etc.) require a high degree of flatness. Photoresist components are typically spin-coated onto silicon wafers or glass substrates deposited with various metals to achieve a thickness of approximately 1-2 μm. If the coating thickness varies or unevenness occurs, the linearity and reproducibility of the pattern decrease, resulting in problems such as the inability to obtain photoresist patterns with the target precision. Furthermore, in addition to these problems, various flatness-related issues arise, including drip marks, overall unevenness, and bead phenomena where the edges are thicker than the center. In the coating composition of the present invention, the polymer of the present invention can exhibit high leveling properties and form a uniform coating film (hardened material), thus solving the above-mentioned problems when used as a photoresist composition.

[0087] When the coating composition of the present invention is used as a photoresist composition, the photoresist composition contains, in addition to the polymer of the present invention, an alkali-soluble resin, a radiation-sensitive substance (photosensitive substance), a solvent, etc.

[0088] The alkali-soluble resin contained in the photoresist composition is a resin that can be dissolved in the developing solution used during photoresist patterning, i.e., an alkaline solution. Examples of alkali-soluble resins include: phenolic varnish resins obtained by condensing aromatic hydroxyl compound derivatives such as phenol, cresol, xylenol, resorcinol, phloroglucinol, and hydroquinone with aldehyde compounds such as formaldehyde, acetaldehyde, and benzaldehyde; polymers or copolymers of vinylphenol compound derivatives such as o-vinylphenol, m-vinylphenol, p-vinylphenol, and α-methylvinylphenol; (meth)acrylic acid polymers or copolymers such as acrylic acid, methacrylic acid, and hydroxyethyl (meth)acrylate; polyvinyl alcohol; modified resins by introducing radiosensitive groups such as quinone diazido, naphthoquinone azido, aromatic azido, and aromatic cinnamyl into a portion of the hydroxyl groups of these resins; and aminoformate resins containing acidic groups such as carboxylic acid and sulfonic acid in their molecules. These alkali-soluble resins can be used alone or in combination with two or more.

[0089] The radiosensitive substances contained in photoresist are substances that alter the solubility of alkali-soluble resin in developer by irradiation with energy lines such as ultraviolet light, far ultraviolet light, excimer laser light, X-rays, electron beams, ion beams, molecular beams, and gamma rays. Examples of radiosensitive substances include: quinone diazido compounds, diazo compounds, azido compounds, onium chlorides, halogenated organic compounds, mixtures of halogenated organic compounds and organometallic compounds, organic acid esters, organic acid amides, organic acid amides, poly(olefinic) compounds, etc.

[0090] Examples of the aforementioned quinone diazido group compounds include, for example, 1,2-benzoquinone azido-4-sulfonate, 1,2-naphthoquinone diazido-4-sulfonate, 1,2-naphthoquinone diazido-5-sulfonate, 2,1-naphthoquinone diazido-4-sulfonate, 2,1-naphthoquinone diazido-5-sulfonate, other quinone diazido-4-sulfochloro, 1,2-naphthoquinone diazido-4-sulfochloro, 1,2-naphthoquinone diazido-5-sulfochloro, 2,1-naphthoquinone diazido-4-sulfochloro, 2,1-naphthoquinone diazido-5-sulfochloro, and sulfochloro of other quinone diazido group derivatives.

[0091] Examples of the aforementioned diazo compounds include: salts of condensates of diphenylamine with formaldehyde or acetaldehyde; hexafluorophosphates, tetrafluoroborates, perchlorates or periodates reacting with the aforementioned condensates, i.e., inorganic salts of diazo resins; and organic salts of diazo resins reacting with the aforementioned condensates as described in USP3,300,309, i.e., organic salts of diazo resins.

[0092] Examples of the aforementioned azido compounds include: azidochalcone acids, diazidobenzylidene methylcyclohexanones, azidobenzylidene allyl acetophenones, aromatic azido compounds, and aromatic diazido compounds.

[0093] Examples of the aforementioned halogenated organic compounds include: halogenated diazole compounds, halogenated triazole compounds, halogenated acetophenone compounds, halogenated benzophenone compounds, halogenated ternary compounds, halogenated ternary compounds, halogenated thiazole compounds, halogenated diazole compounds, halogenated triazole compounds, halogenated 2-piperazine compounds, halogenated aliphatic hydrocarbon compounds, halogenated aromatic hydrocarbon compounds, halogenated heterocyclic compounds, and sulfonylurea halides. In addition to the above, examples of halogenated organic compounds include: trichloro(2,3-dibromopropyl) phosphate, trichloro(2,3-dibromo-3-chloropropyl) phosphate, tetrachlorobromomethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenylallyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis(bromoethyl ether)tetrabromobisphenol A, bis(chloroethyl ether)tetrachlorobisphenol A, trichloro(2,3-dibromopropyl) triisocyanate, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxyethoxy-3,5-dibromophenyl)propane, etc., which are used as halogenated flame retardants; and dichlorophenyltrichloroethane, etc., which are used as organochlorine pesticides.

[0094] Examples of organic acid esters include carboxylic acid esters and sulfonate esters. Examples of organic acid amides include carboxylated amides and sulfonated amides. Examples of organic acid amides include carboxylated amides and sulfonated amides. A single type of radiation-sensitive substance may be used alone or in combination with two or more types.

[0095] In the photoresist composition, the content of the radiation-sensitive substance is preferably in the range of 10 to 200 parts by weight relative to 100 parts by weight of the alkali-soluble resin, and more preferably in the range of 50 to 150 parts by weight.

[0096] Solvents used as components of photoresist include, for example: ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, and butyrolactone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol, heptanol, octanol, nonanol, and decanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dialkylene; and ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monopropyl ether. Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and other alcohol ethers; ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, propyl butyrate, ethyl lactate, butyl lactate, and other esters; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, 2- Monocarboxylic acid esters such as butyl hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, and butyl 2-methoxypropionate; cerusoxene esters such as cerusoxene acetate, methyl cerusoxene acetate, ethyl cerusoxene acetate, propyl cerusoxene acetate, and butyl cerusoxene acetate; and propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate. Propylene glycols such as esters; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether; trichloroethylene, chlorofluorocarbon solvents, HCFCs, HFCs, and other halogenated hydrocarbons; fully fluorinated solvents such as perfluorooctane; aromatic solvents such as toluene and xylene; polar solvents such as dimethylacetamide, dimethylformamide, N-methylacetamide, and N-methylpyrrolidone. These solvents can be used alone or in combination with two or more.

[0097] When the coating composition of the present invention is used as a color photoresist composition, the color photoresist composition contains, in addition to the polymer of the present invention, an alkali-soluble resin, a polymeric compound, a colorant, etc.

[0098] The alkali-soluble resin contained in the color photoresist can be the same as the alkali-soluble resin contained in the above-mentioned photoresist composition.

[0099] The polymerizable compounds contained in colored photoresist components refer to compounds, for example, those with photopolymerizable functional groups that can undergo polymerization or cross-linking reactions when irradiated by active energy lines such as ultraviolet light. Examples of such polymerizable compounds include: esters of 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 and polycarboxylic acids, as well as polyvalent hydroxy compounds such as the aforementioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds; polymerizable compounds having a carbamate backbone formed by reacting polyisocyanate compounds with hydroxy compounds containing (meth)acrylic acid groups; and polymerizable compounds having acid groups. Polymers can be used alone or in combination with two or more compounds.

[0100] Examples of esters of the aforementioned aliphatic polyhydroxy compounds and unsaturated carboxylic acids include: ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyltetrol di(meth)acrylate, neopentyltetrol tri(meth)acrylate, neopentyltetrol tetra(meth)acrylate, dinepentyltetrol tetra(meth)acrylate, dinepentyltetrol penta(meth)acrylate, dinepentyltetrol hexa(meth)acrylate, glycerol (meth)acrylate, etc. Alternatively, examples include: esters in which a portion of the (meth)acrylic acid of these acrylates is replaced with icosinic acid, esters in which icosinic acid is replaced with crotonic acid, and esters in which maleic acid is replaced with maleic acid.

[0101] Examples of esters of the aforementioned aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone di(meth)acrylate, resorcinol di(meth)acrylate, and gallnutol tri(meth)acrylate. Esters obtained from the esterification of unsaturated carboxylic acids, polycarboxylic acids, and polyvalent hydroxyl compounds can be single substances or mixtures. Examples of such esters include: esters obtained from (meth)acrylic acid, phthalic acid, and ethylene glycol; esters obtained from (meth)acrylic acid, maleic acid, and diethylene glycol; esters obtained from (meth)acrylic acid, terephthalic acid, and neopentyl terephthalol; and esters obtained from (meth)acrylic acid, adipic acid, butanediol, and glycerol.

[0102] Examples of polymeric compounds with a carbamate backbone formed by reacting the aforementioned polyisocyanate compounds with hydroxyl compounds containing (meth)acrylic acid groups include: aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; and aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate reacting with hydroxyl compounds containing (meth)acrylic acid groups such as 2-(meth)acrylate hydroxyethyl ester and 3-hydroxy[1,1,1-tris(meth)acrylic acidoxymethyl]propane.

[0103] The aforementioned polymerizable compound having an acid group is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, preferably a polyfunctional polymerizable compound having an acid group by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl group of the aliphatic polyhydroxy compound. The aliphatic polyhydroxy compound used in the preparation of this polyfunctional polymerizable compound is preferably neopentyl tetrol or dinepentyl tetrol. The acid value of the aforementioned polyfunctional polymerizable compounds is preferably in the range of 0.1 to 40, and more preferably in the range of 5 to 30, from the perspective of improving developability and curing properties. When using two or more polyfunctional polymerizable compounds with acid groups, or when using a polyfunctional polymerizable compound with acid groups and a polyfunctional polymerizable compound without acid groups, it is preferable that the acid value of the mixture of polymerizable compounds is within the above-mentioned range.

[0104] As a specific example of the aforementioned polymerizable compound with acid groups, a mixture with dinepentylenetetroxide hexaacrylate, dinepentylenetetroxide pentaacrylate and dinepentylenetetroxide pentaacrylate succinate as the main components can be listed. This mixture is commercially available Aronix TO-1382 (manufactured by Dong-A Synthetic Co., Ltd.).

[0105] Examples of polymerizable compounds other than those mentioned above include: methyl methacrylates such as ethyl bis(meth)acrylamide; allyl esters such as diallyl phthalate; and compounds containing vinyl groups such as divinyl phthalate.

[0106] In the color photoresist composition, the content of polymeric compounds is preferably in the range of 5 to 80% by mass of all solid components of the color photoresist composition, more preferably in the range of 10 to 70% by mass, and even more preferably in the range of 20 to 50% by mass.

[0107] As a colorant in a colored photoresist, there are no particular limitations as long as it is capable of coloring; for example, it can be a pigment or a dye. Pigments can be either organic or inorganic. As for the aforementioned organic pigments, pigments of various hues such as red, green, blue, yellow, purple, orange, and brown can be used. Furthermore, examples of the chemical structures of organic pigments include: azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, diazonium, indanthrene, and perylene. As for the aforementioned inorganic pigments, examples include: barium sulfate, lead sulfate, titanium dioxide, lead yellow, iron oxide red, and chromium oxide. In addition, the "CI" mentioned below refers to the Color Index.

[0108] Examples of red pigments mentioned above 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, 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 The following are examples of pigments: 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, etc. Among these, CI Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, or 254 are preferred, and CI Pigment Red 177, 209, 224, or 254 are even more preferred.

[0109] Examples of the aforementioned green pigments 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, or 58 are preferred.

[0110] Examples of the aforementioned blue pigments 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 are preferred, and CI Pigment Blue 15:6 is even more preferred.

[0111] Examples of yellow pigments mentioned above 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. Of these, CI pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185 are preferred, and CI pigment yellow 83, 138, 139, 150 or 180 are even more preferred.

[0112] Examples of the aforementioned purple pigments 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 even more preferred.

[0113] Examples of the aforementioned orange pigments 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.

[0114] The color filters used in liquid crystal display devices and organic EL display devices use red (R), green (G), and blue (B) as the three primary colors of each pixel. Therefore, red, green, and blue pigments are used as the main components to improve color reproduction. Yellow, purple, orange, and other organic pigments can also be used for hue adjustment.

[0115] To improve the brightness of color liquid crystal display devices and organic EL display devices, the average particle size of the aforementioned organic pigments is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less. To achieve such an average particle size, it is preferable to disperse the organic pigments before use. The average primary particle size of the aforementioned organic pigments is preferably below 100 nm, more preferably below 50 nm, even more preferably below 40 nm, and most preferably in the range of 10 to 30 nm. In addition, the average particle size of organic pigments is measured using a dynamic light scattering particle size analyzer, such as the Nanotrac particle size distribution measuring device "UPA-EX150" and "UPA-EX250" manufactured by Nikkiso Co., Ltd.

[0116] When colored photoresist components are used to form a black matrix (BM), the colorant is not particularly limited as long as it is black, and examples 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 blocking rate and image characteristics. Furthermore, it is also acceptable to mix two or more organic pigments to form black through color mixing.

[0117] Commercially available carbon black products, such as those manufactured by Mitsubishi Chemical Corporation, include: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, and # 960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B, etc.; Examples include: Evonik Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex made by Degussa Japan Co., Ltd. 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, etc.;Examples include: Monarch 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R; BLACK PEARLS 480, PEARLS 130; VULCAN XC72R; ELFTEX-8, etc., manufactured by CABOT JAPAN Co., Ltd.; and COLUMBIAN. RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVE made by CARBON N1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000, etc. ;

[0118] Among the aforementioned carbon blacks, those with high optical concentration and high surface resistivity required for a black matrix with color filters are preferably resin-coated carbon blacks.

[0119] Commercially available titanium black products, such as those manufactured by Mitsubishi Materials Co., Ltd., include titanium black 10S, 12S, 13R, 13M, and 13M-C.

[0120] As a coloring agent used to form black matrix (BM), two or more organic pigments can be mixed to form black by mixing colors. Examples of black pigments can be made by mixing red, green and blue pigments. Examples of colorants that can be mixed and used to prepare black pigments include: Victoria Pure Blue (CI42595), Auramine O (CI41000), Cathilon Brilliant Flavin (Basic 13), Rose Red 6GCP (CI45160), Rose Red B (CI45170), Safranbolus OK70:100 (CI50240), Erioglaucine X (CI42080), Lionol Yellow No. 120 (CI21090), Lionol Yellow GRO (CI21090), Shimura Fast Yellow 8GF (CI21105), Benzidine Yellow 4T-564D (CI21095), and Shimura Fast Red. Red 4015 (CI12355), Lenor Red 7B4401 (CI15850), Fastogen Blue TGR-L (CI74160), Lenor Blue SM (CI26150), Lenor Blue ES (CI Pigment Blue 15:6), Lenor Red GD (CI Pigment Red 168), Lenor Green 2YS (CI Pigment Green 36).

[0121] Other colorants that can be mixed and used to prepare black pigments include, for example: CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166; CI orange pigments 36, 43, 51, 55, 59, 61; CI red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240; CI purple pigments 19, 23, 29, 30, 37, 40, 50; CI blue pigments 15, 15:1, 15:4, 22, 60, 64; CI green pigment 7; CI brown pigments 23, 25, 26, etc.

[0122] When carbon black is used as a black pigment, the average primary particle size of the carbon black is preferably in the range of 0.01 to 0.08 μm, and from the perspective of good developability, it is even more preferably in the range of 0.02 to 0.05 μm.

[0123] The particle shape of carbon black differs from that of organic pigments. It exists in a state of structure, formed by the fusion of primary particles, and sometimes fine pores are formed on the particle surface due to post-processing. Therefore, in order to represent the particle shape of carbon black, in addition to the average particle size of the primary particles obtained by the same method as for organic pigments, it is generally preferable to measure the DBP absorbance (JIS K6221) and the specific surface area obtained by the BET method (JIS K6217) as indicators of structure and porosity. The preferred absorption of carbon black by dibutyl phthalate (hereinafter referred to as "DBP") is in the range of 40~100 cm³ / 100g, and more preferably in the range of 50~80 cm³ / 100g for good dispersibility / developability. The preferred specific surface area of ​​carbon black obtained by the BET method is in the range of 50~120 m² / g, and more preferably in the range of 60~95 ​​m² / g for good dispersion stability.

[0124] In colored photoresist compositions, dyes used as colorants can be categorized as follows: azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methylene dyes.

[0125] Examples of the aforementioned 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, CI Mordant Black 7, etc.

[0126] Examples of anthraquinone dyes mentioned above include: CI Umbrella 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, CI Disperse Blue 60, etc.

[0127] Examples of phthalocyanine dyes include CI Umbrella Blue 5; examples of quinone imine dyes include CI Basic Blue 3 and CI Basic Blue 9; examples of quinoline dyes include CI Solvent Yellow 33, CI Acid Yellow 3, and CI Disperse Yellow 64; and examples of nitro dyes include CI Acid Yellow 1, CI Acid Orange 3, and CI Disperse Yellow 42.

[0128] From the perspective of the excellent lightfastness, weather resistance and density of the resulting coating, pigments are preferred as colorants for colored photoresist compositions. However, dyes can also be used in combination with pigments to adjust the hue as needed.

[0129] In the colored photoresist composition, the content of the colorant is preferably more than 1% by mass of all solid components of the colored photoresist composition, more preferably in the range of 5 to 80% by mass, and even more preferably in the range of 5 to 70% by mass.

[0130] When a color photoresist composition is used to form the red (R), green (G), and blue (B) pixels of a color filter, the content of the colorant in the color photoresist composition is preferably in the range of 5 to 60% by mass of all solid components of the color photoresist composition, and more preferably in the range of 10 to 50% by mass.

[0131] When a colored photoresist composition is used to form the black matrix of a colored filter, the content of the colorant in the colored photoresist composition is preferably in the range of 20 to 80% by mass of all solid components of the colored photoresist composition, and more preferably in the range of 30 to 70% by mass.

[0132] In colored photoresist compositions, when the colorant is a pigment, it is preferable to use it as a pigment dispersion, which is prepared by dispersing the pigment in an organic solvent using a dispersant. Examples of dispersants include: surfactants; pigment intermediates or derivatives; dye intermediates or derivatives; and resin-type dispersants such as polyamine resins, polyurethane resins, polyester resins, and acrylic resins. Among these, graft copolymers containing nitrogen atoms, acrylic block copolymers containing nitrogen atoms, and polyurethane resin dispersants are preferred. Because these dispersants contain nitrogen atoms, which have an affinity for pigment surfaces, the dispersion stability is improved by increasing the affinity of the components other than the nitrogen atoms for the medium. These dispersants can be used alone or in combination of two or more.

[0133] Commercially available products that are the aforementioned dispersants include: BASF's "Efka" series ("Efka46", etc.); BYK-Chemie Japan Co., Ltd.'s "Disperbyk" series and "BYK" series ("BYK-160", "BYK-161", "BYK-2001", etc.); Japan Lubrizol Co., Ltd.'s "Solsperse" series; Shin-Etsu Chemical Co., Ltd.'s "KP" series; Kyoeisha Chemical Co., Ltd.'s "Polyflo" series; Kusumoto Chemical Co., Ltd.'s "Disparion" series; Ajisper series ("Ajisper PB-814", etc.) manufactured by Ajinomoto Precision Technology Co., Ltd., etc.

[0134] Examples of organic solvents used in preparing the aforementioned pigment dispersions include: acetate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxypropionate; aromatic solvents such as toluene, xylene, and methoxybenzene; ether solvents such as butyl celecoxib, propylene glycol monomethyl ether, diethylene glycol ethyl ether, and diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; nitrogen compound solvents such as N,N-dimethylformamide, γ-butyrolactone, and N-methyl-2-pyrrolidone; lactone solvents such as γ-butyrolactone; and carbamates. These solvents can be used alone or in combination with two or more.

[0135] Methods for preparing the aforementioned pigment dispersion include: methods involving a kneading and dispersing step and a micro-dispersing step, and methods involving only a micro-dispersing step. In the aforementioned kneading and dispersing step, the colorant, a portion of the alkali-soluble resin, and the aforementioned dispersant as required are mixed and kneaded. By applying strong shear force using a kneading machine and dispersing, the colorant can be dispersed. Examples of machines used for kneading include: two-roll mills, three-roll mills, ball mills, rotary mills, dispersers, kneaders, co-kneaders, homogenizers, blenders, and single-shaft or twin-shaft extruders. The colorant is preferably made by pre-refining the particle size using a salt milling method or similar method before the above-mentioned kneading.

[0136] In the aforementioned micro-dispersion step, a solvent is added to a composition containing the colorant obtained in the aforementioned kneading and dispersing step, or a mixture of colorant, alkali-soluble resin, solvent, and the aforementioned dispersant as needed is mixed and dispersed using a disperser with a medium for dispersing glass, zirconium dioxide, or ceramic particles, thereby dispersing the colorant particles to a state close to that of primary particles.

[0137] From the perspective of improving the transmittance and contrast of color filters, the average particle size of the primary particles of the colorant is preferably 10~100nm, and more preferably 10~60nm. Furthermore, the average particle size of the colorant is measured using a dynamic light scattering particle size analyzer, such as the Nanotrac particle size distribution measuring devices "UPA-EX150" and "UPA-EX250" manufactured by Nikkiso Co., Ltd.

[0138] While the above examples illustrate coating components, photoresist components, and colored photoresist components as coating components, they are not limited to these.

[0139] Specific examples of the applications of the coating composition of the present invention include: anti-glare (AG) hard coatings, anti-reflective (LR) coatings, low refractive index layer coatings, high refractive index layer coatings, transparent hard coatings, and polymeric liquid crystal coatings for coating materials used in various display screens such as liquid crystal displays (hereinafter referred to as "LCD"), plasma displays (hereinafter referred to as "PDP"), organic EL displays (hereinafter referred to as "OLED"), and quantum dot displays (hereinafter referred to as "QDD"); color photoresists, inkjet inks, printing inks, or coatings used to form each pixel such as RGB in color filters (hereinafter referred to as "CF") of LCDs; black photoresists, inkjet inks, printing inks, or coatings used to form black matrices, black column spacers, and black light spacers in CFs such as LCDs; coatings for transparent protective films used to protect the surface of CFs in LCDs; resin compositions for liquid crystal materials, column spacers, and light spacers in LCDs; resin compositions for pixel separators in LCDs, PDPs, OLEDs, QDDs, etc. Positive photoresist, protective film, insulating film, plastic frame, coating for plastic frame, bezel printing ink for polarization; prisms and light diffusion films for LCD backlight components; coatings for organic insulating films of LCD TFT arrays; protective coatings for the surface of LCD internal polarizers; phosphors for PDPs; organic EL materials and sealing materials (protective films, gas barrier films) for OLEDs; quantum dot printing inks, sealing materials, and protective films for QDDs; high refractive index lenses and low refractive index sealants for mini LED displays. Materials, LED pixels; positive photoresist, chemically amplified photoresist, anti-reflective film, multilayer materials (SOC, SOG), underlayer film, buffer coating, developer, rinsing solution, anti-pattern collapse agent, polymer residue removal solution, cleaning agent and other chemical solutions used in semiconductor manufacturing; nanoimprint release agent; resin components used in semiconductor back-end processes or printed wiring boards (epoxy resin, phenolic resin, polyphenylene ether resin, liquid crystal polymer, polyimide resin, bismaleimide resin, dielyl dimethyl etherimide). Resin compositions such as nadimide resin, benzo[a]pyrene resin, copper laminates, resin-coated copper foil, build-up films, passivation films, interlayer insulating films, flexible copper laminates, dry film photoresists; color photoresists for image sensors; flux repellents; dispersants, coatings, and green sheets for multilayer ceramic capacitors; positive electrode materials, negative electrode materials, separators, and electrolytes for lithium-ion batteries; exterior coatings, rubber, elastomers, glass, vapor-deposited material primers, headlight lenses, solid lubricant coatings, heat dissipation substrates, interior coatings, and repair coatings for automobiles; wallpaper, flooring materials, kitchen components, and bathroom / toilet components for residential equipment.Inkjet printing inks, offset printing inks, gravure printing inks, screen printing inks for printing products; photoresist for printing plate manufacturing; photosensitive materials for offset printing plates (PS plates); encapsulating adhesives; ballpoint pen inks; primers for easy adhesion to plastic films; water-repellent agents for fibers; non-diffusing agents for greases; cleaning fluids for cleaning the surfaces of various products or parts; hard coatings for optical recording media such as CDs, DVDs, and Blu-ray discs; coatings or hard coatings for the casings or screens of smartphones or mobile phones; hard coatings for transfer films used in embedded molds (IMD, IMF); release films; coatings or coating materials for various plastic molded products such as appliance casings; decorative panels, etc. Printing inks or coatings for various building materials; coatings for residential window glass; woodworking coatings for furniture, etc.; coatings for artificial / synthetic leather; coatings for rubber rollers in OA equipment such as photocopiers and printers; coatings for glass in the reading parts of OA equipment such as photocopiers and scanners; optical lenses or their coatings for cameras, video recorders, eyeglasses, contact lenses, etc.; coatings for windshields and glass of watches and clocks; coatings for windows of various vehicles such as automobiles and trains; coatings for anti-reflective films on the glass or film coverings of solar cells; coatings or coatings for FRP bath tubs; PCM for metal building materials or household appliances; single-layer or multi-layer coating compositions for photosensitive etching processes, etc.

[0140] The polymer of this invention, due to its excellent surface tension reduction properties, is expected to provide various functions beyond just leveling, including wettability, penetration, cleaning, water repellency, oil repellency, antifouling, lubrication, anti-caking, and release properties. Furthermore, when incorporated into coatings or coating agents containing microparticles, the polymer of this invention can improve the dispersibility of the microparticles, thus providing not only leveling properties but also the function of acting as a dispersant for the microparticles. Moreover, in addition to the aforementioned coating components, the polymer of this invention, when added to adhesive components used in adhesive tapes, provides not only leveling properties but also the ability to reduce peel force, suppress peel force fluctuations, and suppress peel charge. [Example]

[0141] The present invention will be specifically described below through examples and comparative examples. Furthermore, the present invention is not limited to the following embodiments.

[0142] In the examples and comparative examples, the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) and converted to polystyrene. The measurement conditions for GPC are as follows.

[0143] [GPC Measurement Conditions] Measuring device: TOSOH Corporation high-speed GPC device "HLC-8420GPC" Column: "TSK GUARDCOLUMN SuperHZ-L" manufactured by TOSOH Corporation + "TSK gel SuperHZM-N" manufactured by TOSOH Corporation + "TSK gel SuperHZM-N" manufactured by TOSOH Corporation + "TSK gel SuperHZM-N" manufactured by TOSOH Corporation + "TSK gel SuperHZM-N" manufactured by TOSOH Corporation Detector: RI (Differential Refractometer) Data Processing: Prepared by TOSOH Inc. "EcoSEC Data Analysis version 1.07" Column temperature: 40℃ Developing solvent: tetrahydrofuran Flow rate: 0.35 mL / min Test sample: Dissolve 7.5 mg of the test sample in 10 mL of tetrahydrofuran, filter the resulting solution through a microfilter, and use the resulting solution as the test sample. Sample injection volume: 20 μL Standard sample: According to the aforementioned measurement manual "HLC-8420GPC", the following monodisperse polystyrene with known molecular weight was used.

[0144] (Monodisperse polystyrene) Made by TOSOH Corporation, "A-300" Made by TOSOH Corporation, "A-500" Made by TOSOH Corporation, "A-1000" Made by TOSOH Corporation, "A-2500" Made by TOSOH Corporation, "A-5000" TOSOH Corporation's "F-1" Made by TOSOH Corporation, "F-2" "F-4" manufactured by TOSOH Corporation TOSOH Corporation's "F-10" TOSOH Corporation manufactured the "F-20" TOSOH Corporation manufactured the "F-40" "F-80" manufactured by TOSOH Corporation "F-128" manufactured by TOSOH Corporation "F-288" manufactured by TOSOH Corporation

[0145] (Example 1: Synthesis of a polymer (1) with polysiloxane chains at one end of the polymer backbone) In a glass flask equipped with a stirrer, thermometer, cooling tube, and dropping device, 136.76 g of n-heptane as a solvent, 300.00 g of a polysiloxane compound with hydroxyl groups on one side as represented by formula (a-1), and 10.48 g of triethylamine as a catalyst are placed inside. The temperature inside the flask is maintained at 5°C, and the mixture is stirred for 30 minutes.

[0146] (In the formula, n1 has an average value of 65;) The molecular weight (Mn) of the polysiloxane chain is 5,000.

[0147] Add 19.10 g of 2-bromoisobutyric acid bromide to the above mixture and stir at room temperature for 3 hours. Then mix 341.89 g of n-heptane and 600 g of 0.36% hydrochloric acid, stir, and allow to stand to separate and remove the hydrochloric acid layer. Next, mix 600 g of saturated sodium bicarbonate aqueous solution, stir, and allow to stand to separate and remove the saturated sodium bicarbonate aqueous solution layer. Finally, mix 600 g of ion-exchanged water, stir, and allow to stand to separate and remove the ion-exchanged water layer. Next, 8 g of magnesium sulfate was added as a dehydrating agent, the mixture was shaken and dehydrated, and the dehydrating agent was filtered off. Then, the solvent was distilled off under reduced pressure, and the resulting residue was dissolved in 313.31 g of isopropyl ether. 300 g of 0.36% hydrochloric acid was mixed, stirred, and allowed to stand to separate and remove the hydrochloric acid layer. Next, 300 g of 1% sodium hydroxide aqueous solution was mixed, stirred, and allowed to stand to separate and remove the 1% sodium hydroxide aqueous solution layer. Then, 300 g of ion-exchanged water was mixed, stirred, and allowed to stand to separate and remove the ion-exchanged water layer. Next, 8 g of magnesium sulfate was added as a dehydrating agent, the mixture was shaken and dehydrated, and the dehydrating agent was filtered off. Then, the solvent was distilled off under reduced pressure to obtain the compound represented by formula (A-4).

[0148]

[0149] In a nitrogen-substituted flask, 37.8 g of poly(1,2-butanediol) mono(meth)acrylate (1,2-butanediol has an average repeatability of 6) and 79.0 g of methyl ethyl ketone (MEK) as a solvent were placed, and the mixture was heated to 50°C under a nitrogen atmosphere with stirring. Then, 4.2 g of 2,2'-bipyridine and 1.5 g of cuprous chloride were added as catalysts, and the flask was maintained at 50°C with stirring for 30 minutes. Afterward, 12.3 g of the compound represented by the aforementioned formula (A-4) was added as a polymerization initiator, and living polymerization was carried out at 50°C for 8 hours under a nitrogen atmosphere. 30g of activated alumina was added to the obtained reactants and stirred. After filtering the activated alumina, the solvent was removed by vacuum distillation to obtain a polymer (1) with polysiloxane chains at one end of the polymer backbone.

[0150] The molecular weight of polymer (1) was measured by GPC, and the weight average molecular weight (Mw) was 25,000, the number average molecular weight (Mn) was 23,000, and the (Mw / Mn) ratio was 1.1. Furthermore, the proportion of polysiloxane chains in polymer (1) is 24 by mass.

[0151] (Example 2: Synthesis of a polymer (2) with polysiloxane chains at one end of the polymer backbone) In a nitrogen-substituted flask, 32.8 g of polypropylene glycol monomethacrylate (with an average repeat of 4-6 for propylene glycol) and 79.0 g of methyl ethyl ketone (MEK) as a solvent were placed, and the mixture was heated to 50°C under a nitrogen atmosphere with stirring. Then, 4.2 g of 2,2'-bipyridine as a catalyst and 1.5 g of cuprous chloride were added, and the flask was maintained at 50°C with stirring for 30 minutes. Afterward, 17.2 g of the compound represented by the aforementioned formula (A-4) was added as a polymerization initiator, and living polymerization was carried out at 50°C for 8 hours under a nitrogen atmosphere. 30g of activated alumina was added to the obtained reactants and stirred. After filtering the activated alumina, the solvent was removed by vacuum distillation to obtain a polymer (2) with polysiloxane chains at one end of the polymer backbone.

[0152] The molecular weight of polymer (2) was measured by GPC, and the weight average molecular weight (Mw) was 16,000, the number average molecular weight (Mn) was 14,000, and the (Mw / Mn) ratio was 1.1. Furthermore, the proportion of polysiloxane chains in polymer (2) is 32% by mass.

[0153] (Example 3: Synthesis of a polymer (3) with polysiloxane chains at one end) In a nitrogen-substituted flask, 32.8 g of poly(1,2-butanediol) mono(meth)acrylate (1,2-butanediol has an average repeatability of 6) and 79.0 g of methyl ethyl ketone (MEK) as a solvent were placed, and the mixture was heated to 50°C under a nitrogen atmosphere with stirring. Then, 4.2 g of 2,2'-bipyridine and 1.5 g of cuprous chloride were added as catalysts, and the flask was maintained at 50°C with stirring for 30 minutes. Afterward, 17.2 g of the compound represented by the aforementioned formula (A-4) was added as a polymerization initiator, and living polymerization was carried out at 50°C for 8 hours under a nitrogen atmosphere. Add 30g of activated alumina to the obtained reactants and stir. After filtering the activated alumina, remove the solvent by vacuum distillation to obtain a polymer (3) with polysiloxane chains at one end of the polymer backbone.

[0154] The molecular weight of polymer (3) was measured by GPC, and the weight average molecular weight (Mw) was 16,000, the number average molecular weight (Mn) was 13,000, and the (Mw / Mn) ratio was 1.2. Furthermore, the proportion of polysiloxane chains in polymer (3) is 32% by mass.

[0155] (Example 4: Synthesis of a polymer (4) with polysiloxane chains at one end) In a nitrogen-substituted flask, 19.1 g of poly(1,2-butanediol) mono(meth)acrylate (1,2-butanediol has an average repeat number of 6) and 79.0 g of methyl ethyl ketone (MEK) as a solvent were placed, and the mixture was heated to 50°C under a nitrogen atmosphere with stirring. Then, 4.2 g of 2,2'-bipyridine and 1.5 g of cuprous chloride were added as catalysts, and the flask was maintained at 50°C with stirring for 30 minutes. Afterward, 31.0 g of the compound represented by the aforementioned formula (A-4) was added as a polymerization initiator, and living polymerization was carried out at 50°C for 8 hours under a nitrogen atmosphere. 30g of activated alumina was added to the obtained reactants and stirred. After filtering the activated alumina, the solvent was removed by vacuum distillation to obtain a polymer (4) with polysiloxane chains at one end of the polymer backbone.

[0156] The molecular weight of polymer (4) was measured by GPC. The result showed that the weight average molecular weight (Mw) was 11,000, the number average molecular weight (Mn) was 10,000, and the (Mw / Mn) ratio was 1.1. Furthermore, the proportion of polysiloxane chains in polymer (4) is 58% by mass.

[0157] (Example 5: Synthesis of a polymer (5) with polysiloxane chains at one end) Place 136.76 g of n-heptane as a solvent, 300.00 g of a polysiloxane compound with hydroxyl groups on one side, represented by formula (a-2), and 10.48 g of triethylamine as a catalyst into a glass flask equipped with a stirrer, thermometer, cooling tube, and dropping device. Maintain the temperature inside the flask at 5°C and stir for 30 minutes.

[0158] (In the formula, n2 has an average value of 132.) The molecular weight (Mn) of the polysiloxane chain is 10,000.

[0159] 19.10 g of 2-bromoisobutyric acid bromide was added to the above mixture and stirred at room temperature for 3 hours. Then, 341.89 g of n-heptane and 600 g of 0.36% hydrochloric acid were mixed, stirred, and allowed to stand to separate and remove the hydrochloric acid layer. Next, 600 g of saturated sodium bicarbonate aqueous solution was mixed, stirred, and allowed to stand to separate and remove the saturated sodium bicarbonate aqueous solution layer. Finally, 600 g of ion-exchanged water was mixed, stirred, and allowed to stand to separate and remove the ion-exchanged water layer. Next, 8g of magnesium sulfate was added as a dehydrating agent, the mixture was shaken and dehydrated, and the dehydrating agent was filtered off. Then, the solvent was removed by distillation under reduced pressure, and the resulting residue was dissolved in 313.31g of isopropyl ether. 300g of 0.36% hydrochloric acid was mixed, stirred, and allowed to stand to separate and remove the hydrochloric acid layer. Next, 300g of 1% sodium hydroxide aqueous solution was mixed, stirred, and allowed to stand to separate and remove the 1% sodium hydroxide aqueous solution layer. Then, 300g of ion-exchanged water was mixed, stirred, and allowed to stand to separate and remove the ion-exchanged water layer. Next, 8g of magnesium sulfate was added as a dehydrating agent, the mixture was shaken and dehydrated, and the dehydrating agent was filtered off. Then, the solvent was removed by distillation under reduced pressure, thereby obtaining the compound represented by formula (A-5).

[0160]

[0161] In a nitrogen-substituted flask, 21.7 g of poly(1,2-butanediol) mono(meth)acrylate (1,2-butanediol has an average repeat number of 6) and 61.5 g of methyl ethyl ketone (MEK) as a solvent were placed, and the mixture was heated to 60°C under a nitrogen atmosphere with stirring. Then, 0.62 g of 2,2'-bipyridine and 0.2 g of cuprous chloride were added as catalysts, and the flask was maintained at 60°C with stirring for 30 minutes. Afterward, 20.0 g of the compound represented by the aforementioned formula (A-5) was added as a polymerization initiator, and living polymerization was carried out at 60°C for 18 hours under a nitrogen atmosphere. Add 30g of activated alumina to the obtained reactants and stir. After filtering the activated alumina, remove the solvent by vacuum distillation to obtain a polymer (5) with polysiloxane chains at one end of the polymer backbone.

[0162] The molecular weight of polymer (5) was measured by GPC, and the weight average molecular weight (Mw) was 22,000, the number average molecular weight (Mn) was 20,000, and the (Mw / Mn) ratio was 1.1. Furthermore, the proportion of polysiloxane chains in polymer (5) is 47% by mass.

[0163] (Comparative Example 1: Synthesis of free radical copolymers using polysiloxane monomers (1')) 200.0 g of butyl acetate as a solvent was placed in a nitrogen-substituted flask, and the mixture was heated to 90 °C under a nitrogen stream while stirring. Then, 63.2 g of a polymerizable unsaturated monomer with a polysiloxane chain represented by formula (A'), 136.8 g of poly(1,2-butanediol) mono(meth)acrylate (the average repeat number of 1,2-butanediol is 6), and 3.0 g of tributylperoxy-2-ethylhexanoate as a polymerization initiator were dissolved in 266.0 g of butyl acetate to form a monomer polymerization initiator solution. This solution was placed in a dropping apparatus, and the flask was kept at 90 °C for 2 hours for the dropping process. After the dropping process was completed, the mixture was reacted at 90 °C for 6 hours under a nitrogen stream to obtain a random copolymer (1'). Random copolymers (1') are polymers with multiple polysiloxane chains in the polymer chain.

[0164] (In the formula, the average quantity of n3 is 65;) The molecular weight (Mn) of the polysiloxane chain is 5,000.

[0165] The molecular weight of the random copolymer (1') was measured by GPC, and the weight average molecular weight (Mw) was 14,000, the number average molecular weight (Mn) was 1,700, and the (Mw / Mn) ratio was 7.8. Furthermore, the proportion of polysiloxane chains in the random copolymer (1') is 31% by mass.

[0166] (Comparative Example 2: Synthesis of free radical copolymers using polysiloxane monomers (2')) 200.0 g of butyl acetate as a solvent was placed in a nitrogen-substituted flask, and the mixture was heated to 90 °C under a nitrogen stream while stirring. Then, 63.2 g of a polymerizable unsaturated monomer with a polysiloxane chain represented by the aforementioned formula (A'), 136.8 g of poly(1,2-butanediol) mono(meth)acrylate (the average repeat number of 1,2-butanediol is 6), and 3.0 g of tributylperoxy-2-ethylhexanoate as a polymerization initiator were dissolved in 100.0 g of butyl acetate to form a monomer polymerization initiator solution. This solution was placed in a dropping apparatus, and the flask was kept at 90 °C for 2 hours for the dropping process. After the dropping process was completed, the mixture was reacted at 90 °C for 6 hours under a nitrogen stream to obtain a random copolymer (2').

[0167] The molecular weight of the random copolymer (2') was measured by GPC, and the weight average molecular weight (Mw) was 34,000, the number average molecular weight (Mn) was 3,400, and the (Mw / Mn) ratio was 9.9. Furthermore, the proportion of polysiloxane chains in the random copolymer (2') is 31% by mass.

[0168] The following evaluation was performed using the polymer (1) manufactured in Example 1. The results are shown in Table 1. In Table 1, "Si chain" refers to "polysiloxane chain".

[0169] (Film formation and evaluation of coatings) A photoresist composition was prepared by mixing 3.0 g of 40% by weight alkali-soluble resin solution (ACRYDIC ZL-295, manufactured by DIC Corporation), 1.2 g of Aronix M-402 (manufactured by Dong-A Synthetic Chemicals Co., Ltd., a mixture of dinepentylenetetroxide pentaacrylate and dinepentylenetetroxide hexaacrylate), 0.001 g of polymer (1) with a solid content equivalent to 3.8 g, and 3.8 g of propylene glycol monomethyl ether acetate (PGMEA). 3 ml of the obtained photoresist composition was dropped onto the center of a 10 cm × 10 cm chrome-plated glass substrate. The substrate was spin-coated at 1,000 rpm for 10 seconds and then dried at 100°C for 100 seconds to create a laminate with a coating layer.

[0170] The smoothness and coating defects of the fabricated laminate were evaluated using the following methods. The results are shown in Table 1.

[0171] (Smoothness) The smoothness of the coating layer obtained by visual observation is evaluated according to the following criteria. AA: No uneven coating was observed. A: Almost no coating unevenness was observed. C: Uneven coating was observed throughout.

[0172] (Coating defects) The coating defects of the laminate obtained by visual observation are evaluated according to the following criteria. A: Almost no coating defects were observed. B: Several coating defects were observed. C: Numerous coating defects were observed.

[0173] Polymers prepared in Examples 2-5 and Comparative Examples 1-2 were used instead of polymer (1), and the same evaluation was performed as in Example 1. The results are shown in Table 1.

[0174] Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 leveling agent Single-sided terminal Si chain Polymer (1) (1 Si chain) Single-sided end Si chain Polymer (2) (1 Si chain) Single-sided end Si chain Polymer (3) (1 Si chain) Single-sided end Si chain Polymer (4) (1 Si chain) Single-sided end Si chain Polymer (5) (1 Si chain) Unregulated Copolymer (1') (Multiple Si chains) Unregulated copolymer (2') (Multiple Si chains) Si chain molecular weight [Mn] 5000 5000 5000 5000 10000 5000 5000 Si chain ratio [quality%] twenty four 32 32 58 47 31 31 Coating Smoothness A A A AA A A A Coating defects A A A A A C C

[0175] As shown in Table 1, when polymers with polysiloxane chains only at the ends (polymers (1) to (5)) are used as leveling agents, excellent smoothness can be obtained and almost no coating defects are generated. On the other hand, it is found that the polymers (random copolymers (1') and (2')) of Comparative Examples 1 and 2, which have multiple polysiloxane chains, generate a large number of coating defects, even though the content of polysiloxane chains is approximately the same as that of polymer (1) in Example 1.

[0176] none.

Claims

1. A coating composition comprising a polymer containing polysiloxane chains, wherein the polymer containing polysiloxane chains is a polymer having polysiloxane chains only at one end and not containing polymerizable unsaturated groups, wherein one or more polymerizable monomers (2) selected from the group consisting of compounds represented by formula (2-1), formula (2-2), formula (2-3), and formula (2-4) are used as polymeric components; the average molecular weight of the polysiloxane chains is in the range of 2,000 to 20,000, and the ratio of the polysiloxane chains (mass of polysiloxane chains / mass of polymer containing polysiloxane chains) is in the range of 15% to 80% by mass. (In formulas (2-1), (2-2), (2-3), and (2-4), R21 is a hydrogen atom or a methyl group, R22 is an alkyl group with 1 to 18 carbon atoms, R23 is a hydrogen atom or a methyl group, R24 is a hydrogen atom or an alkyl group with 1 to 18 carbon atoms, R25 is a hydrogen atom or a methyl group, R26 is an alkyl group with 1 to 18 carbon atoms or an alkyl group with 1 to 18 carbon atoms having an ether bond, R27 is a hydrogen atom or a methyl group, R28 is an alkyl group with 1 to 18 carbon atoms or an alkyl group with 1 to 18 carbon atoms having an ether bond, L2 is a divalent organogroup, n is an integer in the range of 1 to 4, m is an integer in the range of 1 to 200, p is an integer in the range of 1 to 10, and q is an integer in the range of 1 to 100).

2. The coating composition of claim 1, wherein the polymer containing polysiloxane chains does not contain any of the following groups: isocyanate group, epoxy group, carboxyl group, carboxyl halide group and carboxylic anhydride group.

3. The coating composition of claim 1 or 2, wherein the polysiloxane chain is a polysiloxane chain represented by the following formula (1), (in formula (1), R11, R12, R13, R14 and R15 are each independently an alkyl or phenyl group having 1 to 18 carbon atoms, L11 is a divalent organic group or a single bond, and n is an integer).

4. The coating composition of claim 1 or 2, wherein the polymer containing polysiloxane chains is contained in the range of 0.0001 to 10 parts by mass relative to 100 parts by mass of the solid components of the coating composition.

5. A photoresist composition comprising a polymer containing polysiloxane chains, wherein the polymer containing polysiloxane chains is a polymer having polysiloxane chains only at one end and not containing polymerizable unsaturated groups, wherein one or more polymerizable monomers (2) selected from the group consisting of compounds represented by formula (2-1), formula (2-2), formula (2-3), and formula (2-4) are used as polymeric components; the average molecular weight of the polysiloxane chains is in the range of 2,000 to 20,000, and the ratio of the polysiloxane chains (mass of polysiloxane chains / mass of polymer containing polysiloxane chains) is in the range of 15 to 80% by mass, wherein in formulas (2-1), (2-2), (2-3), and (2-4), R21 is a hydrogen atom or a methyl group, and R22 is an alkyl group having 1 to 18 carbon atoms. R23 is a hydrogen atom or a methyl group; R24 is a hydrogen atom or an alkyl group with 1 to 18 carbon atoms; R25 is a hydrogen atom or a methyl group; R26 is an alkyl group with 1 to 18 carbon atoms, or an alkyl group with 1 to 18 carbon atoms and an ether bond; R27 is a hydrogen atom or a methyl group; R28 is an alkyl group with 1 to 18 carbon atoms, or an alkyl group with 1 to 18 carbon atoms and an ether bond; L2 is a divalent organogroup; n is an integer in the range of 1 to 4; m is an integer in the range of 1 to 200; p is an integer in the range of 1 to 10; q is an integer in the range of 1 to 100.

6. The photoresist composition of claim 5, wherein the polymer containing the polysiloxane chain does not contain any of the following groups: isocyanate group, epoxy group, carboxyl group, carboxyl halide group and carboxylic anhydride group.

7. The photoresist composition of claim 5 or 6, wherein the polysiloxane chain is a polysiloxane chain represented by the following formula (1), (in formula (1), R11, R12, R13, R14 and R15 are each independently an alkyl or phenyl group with 1 to 18 carbon atoms, L11 is a divalent organic group or a single bond, and n is an integer).

8. The photoresist composition of claim 5 or 6, wherein the polymer containing the polysiloxane chain is contained in the range of 0.0001 to 10 parts by mass relative to 100 parts by mass of the solid component of the photoresist composition.

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