Polymer and coating composition containing the polymer

Abstract

Provided is a polymer that functions as a leveling agent that provides high smoothness to a coating film. Specifically, a polymer comprising: a polymer block (A1) of a polymerizable monomer (a1), wherein the polymerizable monomer (a1) has -Si[OSi(R) 3 ] n [R'] 3‑n (n is an integer of 1 to 3. R is independently an alkyl group having 1 to 3 carbon atoms. R' is independently an alkyl group having 1 to 3 carbon atoms). A coating composition, a resist composition or an article comprising the polymer.

Description

Technical Field

[0001] The present invention relates to polymers and coating compositions comprising the polymers. Background Art

[0002] The leveling agent is added to smooth the coating film obtained by applying a coating composition such as a coating composition or an anti-corrosion composition. Specifically, by adding the leveling agent to the coating composition, the leveling agent is oriented on the surface of the coating film, the surface tension of the coating film is reduced, and the obtained coating film is smoothed. For the coating film with a smoothed surface, the occurrence of shrinkage and unevenness can be reduced.

[0003] Leveling agents are used, for example, in automotive coatings. A coating composition containing a leveling agent can impart high smoothness to the surface of the resulting coating film and can provide gloss to the appearance of the automobile.

[0004] As a leveling agent used for automobile coatings, silicone-based leveling agents have been proposed (Patent Documents 1 and 2).

[0005] The purpose of leveling agent is various, for example, it is also applied to the color resist composition used in the preparation of the color filter for liquid crystal display. In the manufacture of color filter, the following steps are included: the color resist composition is usually applied on the glass substrate by a coating method such as spin coating and slit coating, and the dried coating film is exposed using a mask, and then, developed to form a colored pattern. At this time, when the smoothness of the coating film is not good, there is unevenness in the film thickness, or when there is uneven coating, shrinkage, etc., there is a concern about uneven color of pixels.

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

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2003-226834

[0010] Patent Document 2: Japanese Patent Application Publication No. 2018-199765 Summary of the invention

[0011] Problem that the invention aims to solve

[0012] The silicone-based leveling agent disclosed in Patent Document 1 is a random polymer obtained by free radical polymerization of silicone monomers and (meth)acrylate monomers, and the silicone sites are randomly arranged, so the leveling effect is not sufficient. In addition, the silicone-based leveling agent disclosed in Patent Document 2 requires an organopolysiloxane chain with a large molecular weight, and there is a concern that defects may occur in the coating film obtained from the organopolysiloxane chain.

[0013] An object of the present invention is to provide a polymer that functions as a leveling agent that provides high smoothness to a coating film.

[0014] Solutions for solving problems

[0015] The present inventors have conducted intensive research to solve the above-mentioned problems and found that: n [R'] 3-n The polymer having a polymer block of a polymerizable monomer having the functional group shown above exhibits high leveling properties that can withstand resist applications, thereby completing the present invention.

[0016] That is, the present invention relates to a polymer comprising: a polymer block (A1) of a polymerizable monomer (a1), wherein the polymerizable monomer (a1) has -Si[OSi(R)3] n [R'] 3-n (n is an integer of 1 to 3. Each R is independently an alkyl group having 1 to 3 carbon atoms. Each R' is independently an alkyl group having 1 to 3 carbon atoms).

[0017] Effects of the Invention

[0018] According to the present invention, a polymer that functions as a leveling agent that provides high smoothness to a coating film can be provided. DETAILED DESCRIPTION

[0019] Hereinafter, an embodiment of the present invention will be described. The present invention is not limited to the following embodiment, and can be implemented with appropriate modifications within a range that does not impair the effects of the present invention.

[0020] In the present specification, "(meth)acrylate" means one or both of acrylate and methacrylate.

[0021] [polymer]

[0022] The polymer of the present invention comprises: a polymer block (A1) of a polymerizable monomer (a1), wherein the polymerizable monomer (a1) has: -Si[OSi(R)3] n [R'] 3-n(n is an integer of 1 to 3. Each R is independently an alkyl group having 1 to 3 carbon atoms. Each R' is independently an alkyl group having 1 to 3 carbon atoms).

[0023] The polymer block (A1) is derived from -Si[OSi(R)3] n [R'] 3-n (n is an integer of 1 to 3. R is independently an alkyl group having 1 to 3 carbon atoms. R' is independently an alkyl group having 1 to 3 carbon atoms). A segment formed by a repeating structure of a polymerizable monomer (a1) having a functional group represented by (n is an integer of 1 to 3. R is independently an alkyl group having 1 to 3 carbon atoms. R' is independently an alkyl group having 1 to 3 carbon atoms). Here, for "formed by a repeating structure derived from a polymerizable monomer (a1)", the polymer block (A1) may contain a repeating structure derived from other polymerizable monomers within a range that does not impair the effects of the present invention. The polymer block (A1) may contain 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass of the repeating structure derived from the polymerizable monomer (a1).

[0024] In the present invention, "polymerizable monomer" refers to a compound having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group possessed by the polymerizable monomer (a1) include C=C-containing groups such as (meth)acryloyl, (meth)acryloyloxy, (meth)acryloylamino, vinyl ether, allyl, styryl, and maleimide. Among these, (meth)acryloyl and (meth)acryloyloxy are preferred from the viewpoint of easy availability of raw materials and good polymerization reactivity.

[0025] In the polymerizable monomer (a1), -Si[OSi(R)3] n [R'] 3-n The functional group represented by is preferably a functional group represented by -Si[OSi(R)3]3, and more preferably -Si[OSi(CH3)3]3. -Si[OSi(R)3] n [R'] 3-n When the functional group shown is -Si[OSi(CH3)3]3, the polymer of the present invention can obtain high surface segregation ability.

[0026] The polymerizable monomer (a1) is preferably a compound represented by the following formula (a1-1).

[0027]

[0028] (In the above formula (a1-1),

[0029] Each R is independently an alkyl group having 1 to 3 carbon atoms.

[0030] R 1 A hydrogen atom or a methyl group.

[0031] L 1 is a divalent organic group or a single bond. )

[0032] L 1 The divalent organic group is preferably an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms.

[0033] As L 1 The alkylene group having 1 to 50 carbon atoms includes methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene, n-dodecylene, isopropylene, 2-methylpropylene, 2-methylhexylene and tetramethylethylene.

[0034] L 1 The alkylene group having 1 to 50 carbon atoms is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, further preferably a methylene group, an ethylene group, a n-propylene group or an isopropylene group.

[0035] L 1 The alkyleneoxy group having 1 to 50 carbon atoms is, for example, a group in which one -CH2- in the aforementioned alkylene group is substituted by -O-.

[0036] L 1 The alkyleneoxy group having 1 to 50 carbon atoms is preferably an alkyleneoxy group having 1 to 15 carbon atoms, more preferably an alkyleneoxy group having 1 to 8 carbon atoms, further preferably a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, an oxytrimethylene group, a butyleneoxy group, an oxytetramethylene group, a pentyleneoxy group, a heptyleneoxy group or an octyleneoxy group.

[0037] L 1 When the divalent organic group is an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms, a part of -CH2- in these divalent organic groups can be substituted by a carbonyl group (-C(=O)-), a phenylene group, an amide bond or a carbamate bond, and further, a hydroxyl group or the like can replace a carbon atom.

[0038] The functional group represented by -Si[OSi(R)3]3 of the compound represented by the above formula (a1-1) is preferably -Si[OSi(CH3)3]3, and the compound is represented by the following formula (a1-2).

[0039]

[0040] (In the above formula (a1-2),

[0041] R 1 A hydrogen atom or a methyl group.

[0042] L 1is a divalent organic group or a single bond. )

[0043] The polymerizable monomer constituting the polymer block (A1) is only required to have -Si[OSi(R)3] n [R'] 3-n The polymerizable monomer (a1) having the functional group shown in the figure can be used, and the polymer block (A1) can also be composed of two or more polymerizable monomers (a1) having different structures. In this case, the polymerization form of the polymer block (A1) is not particularly limited, and the polymer block (A1) can be a random polymer structure of two or more polymerizable monomers (a1) having different structures, or a block polymer structure of two or more polymerizable monomers (a1) having different structures.

[0044] The polymerizable monomer constituting the polymer block (A1) is preferably a single polymerizable monomer (a1).

[0045] The polymerizable monomer (a1) can be produced by a known method, or a commercially available product can be used.

[0046] As a commercially available product of the polymerizable monomer (a1), for example, 3-(methacryloyloxy)propyltris(trimethylsiloxy)silane is commercially available.

[0047] In the polymer of the present invention, the content ratio of the polymer block (A1) is, for example, preferably 5 mass % or more, 10 mass % or more, 15 mass % or more, 20 mass % or more, 30 mass % or more, 50 mass % or more, 60 mass % or more, or 65 mass % or more relative to the total amount of the polymer.

[0048] The upper limit of the content of the polymer block (A1) is not particularly limited, but is, for example, 95 mass % or less, preferably 90 mass % or less, more preferably 85 mass % or less, and further preferably 75 mass % or less, based on the total amount of the polymer.

[0049] The content ratio of the polymer block (A1) can be adjusted by adjusting the raw material input ratio of the polymerizable monomer (a1) for producing the polymer of the present invention.

[0050] In the polymer of the present invention, -Si[OSi(R)3] n [R'] 3-n The content of the functional group is, for example, 5 to 95 mass %, preferably 10 to 90 mass %, more preferably 15 to 85 mass %, further preferably 20 to 65 mass %, particularly preferably 45 to 65 mass %.

[0051] -Si[OSi(R)3] n [R'] 3-nThe content of the functional group shown above can be adjusted by adjusting the raw material input ratio of the polymerizable monomer (a1) used when producing the polymer of the present invention.

[0052] The polymer of the present invention preferably further comprises a polymer block (A2) having at least one polymerizable monomer (a2) selected from an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, and a group containing a polyoxyalkylene chain. The polymer block (A2) can impart compatibility to the polymer of the present invention.

[0053] The polymer block (A2) is a segment formed of a repeating structure derived from a polymerizable monomer (a2) having one or more selected from an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, and a group containing a polyoxyalkylene chain.

[0054] In the present invention, "polymerizable monomer" refers to a compound having a polymerizable unsaturated group. The polymerizable unsaturated group possessed by the polymerizable monomer (a2) may be any group containing a vinyl group, and may include (meth)acryloyl, (meth)acryloyloxy, (meth)acryloylamino, vinyl ether, allyl, styryl, maleimide, etc. Among these, (meth)acryloyl and (meth)acryloyloxy are preferred from the perspective of easy availability of raw materials and good polymerization reactivity.

[0055] The alkyl group having 1 to 18 carbon atoms possessed by the polymerizable monomer (a2) may be a straight-chain alkyl group, a branched alkyl group or a cyclic alkyl group. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, cyclohexyl, n-octyl, hexadecyl and the like.

[0056] The alkyl group having 1 to 18 carbon atoms in the polymerizable monomer (a2) may be substituted with one or more substituents such as hydroxyl group, phenyl group, phenoxy group, etc.

[0057] Examples of the alkyl group having 1 to 18 carbon atoms in the polymerizable monomer (a2) include a hydroxyalkyl group having 1 to 18 carbon atoms, a phenylalkyl group having 7 to 18 carbon atoms, and a phenoxyalkyl group having 7 to 18 carbon atoms.

[0058] The alkyl group having 1 to 18 carbon atoms in the polymerizable monomer (a2) is preferably an alkyl group having 1 to 8 carbon atoms.

[0059] Examples of the aromatic group having 6 to 18 carbon atoms in the polymerizable monomer (a2) include phenyl, naphthyl, anthracene-1-yl, phenanthrene-1-yl and the like.

[0060] The aromatic group having 6 to 18 carbon atoms in the polymerizable monomer (a2) may be further substituted with a substituent such as a hydroxyl group, an alkyl group, or an alkoxy group, and includes, for example, a phenyl group substituted with an alkyl group having 1 to 6 carbon atoms.

[0061] The polyoxyalkylene chain-containing group contained in the polymerizable monomer (a2) refers to a monovalent group containing a repeating portion of an oxyalkylene group or a divalent linking group containing a repeating portion of an oxyalkylene group.

[0062] When the polymerizable unsaturated group of the polymerizable monomer (a2) is a (meth)acryloyl group, the polymerizable monomer (a2) having a group containing a polyoxyalkylene chain is, for example, a compound represented by the following formula (a2-poa1) or (a2-poa2).

[0063]

[0064] (In the above formulas (a2-poa1) and (a2-poa2),

[0065] R a21 Each is independently a hydrogen atom or a methyl group.

[0066] R a22 It is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.

[0067] p is an integer greater than or equal to 0, q is an integer greater than or equal to 0, r is an integer greater than or equal to 0, and p+q+r is an integer greater than or equal to 1.

[0068] X, Y and Z are each independently an alkylene group having 1 to 6 carbon atoms.

[0069] In the above formulas (a2-poa1) and (a2-poa2), -(XO) p -(YO) q -(ZO) r -R a22 The groups shown and -(XO) p -(YO) q -(ZO) r - The group shown corresponds to a group containing a polyoxyalkylene chain.

[0070] Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and a polymerizable unsaturated group being a (meth)acryloyl group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethyl (meth)acrylate. Alkyl (meth)acrylates having 1 to 18 carbon atoms such as hexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate; bridged cyclic alkyl (meth)acrylates having 1 to 18 carbon atoms such as dicyclopentyloxyethyl (meth)acrylate, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyl (meth)acrylate.

[0071] Examples of the polymerizable monomer (a2) having a hydroxyalkyl group having 1 to 18 carbon atoms and a (meth)acryloyl group as the polymerizable unsaturated group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxy (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, and 2,3-dihydroxypropyl (meth)acrylate.

[0072] Examples of the polymerizable monomer (a2) having a phenylalkyl group having 7 to 18 carbon atoms or a phenoxyalkyl group having 7 to 18 carbon atoms, in which the polymerizable unsaturated group is a (meth)acryloyl group, include benzyl (meth)acrylate, 2-phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate.

[0073] Examples of the polymerizable monomer (a2) having a group containing a polyoxyalkylene chain and in which the polymerizable unsaturated group is a (meth)acryloyl group include polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polytrimethylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, poly(ethylene glycol·propylene glycol) mono(meth)acrylate, polyethylene glycol·polypropylene glycol mono(meth)acrylate, poly(ethylene glycol·tetramethylene glycol) mono(meth)acrylate, and polyethylene glycol. Polypropylene glycol·polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol·tetramethylene glycol) mono(meth)acrylate, polypropylene glycol·polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol·1,2-butylene glycol) mono(meth)acrylate, polypropylene glycol·poly1,2-butylene glycol mono(meth)acrylate, poly(ethylene glycol·1,2-butylene glycol) mono(meth)acrylate, polyethylene glycol·poly1,2-butylene glycol mono(meth)acrylate, poly(tetraethylene glycol·1,2-butylene glycol) mono(meth)acrylate acrylate, polyethylene glycol·poly 1,2-butylene glycol mono(meth)acrylate, poly 1,2-butylene glycol mono(meth)acrylate, poly(ethylene glycol·trimethylene glycol) mono(meth)acrylate, polyethylene glycol·polytrimethylene glycol mono(meth)acrylate, poly(propylene glycol·trimethylene glycol) mono(meth)acrylate, polypropylene glycol·polytrimethylene glycol mono(meth)acrylate, poly(trimethylene glycol·tetramethylene glycol) mono(meth)acrylate, polytrimethylene glycol·polytetramethylene glycol) mono(meth)acrylate Methyl glycol mono(meth)acrylate, poly(1,2-butylene glycol·trimethylene glycol) mono(meth)acrylate, poly(1,2-butylene glycol·polytrimethylene glycol) mono(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, poly(1,2-butylene glycol·tetramethylene glycol) mono(meth)acrylate, poly(1,2-butylene glycol·polytetramethylene glycol) mono(meth)acrylate, and the like.

[0074] It should be noted that the above-mentioned “poly(ethylene glycol·propylene glycol)” refers to a random copolymer of ethylene glycol and propylene glycol, and “polyethylene glycol·polypropylene glycol” refers to a block copolymer of ethylene glycol and propylene glycol.

[0075] Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and a polymerizable unsaturated group being a vinyl ether group include alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether, cycloalkyl vinyl ether, 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-dimethanol monovinyl ether, etc.

[0076] Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and an allyl group as the polymerizable unsaturated group include 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether.

[0077] Examples of the polymerizable monomer (a2) having an aromatic group having 6 to 18 carbon atoms include styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene.

[0078] Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and a (meth)acryloylamino group as the polymerizable unsaturated group include N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, diacetoneacrylamide, acryloylmorpholine, and the like.

[0079] Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and a maleimide group as the polymerizable unsaturated group include methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide.

[0080] The polymerizable monomer (a2) is preferably a compound represented by the following formula (a2-1) or (a2-2). These compounds can impart high compatibility when the polymer of the present invention is used as a leveling agent.

[0081]

[0082] (In the above formulas (a2-1) and (a2-2),

[0083] R 2 A hydrogen atom or a methyl group.

[0084] R 3 It is an alkyl group having 1 to 18 carbon atoms.

[0085] R 4 A hydrogen atom or a methyl group.

[0086] R 5 It is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.

[0087] n is an integer of 1 to 4, and m is an integer of 1 to 100. )

[0088] In the above formulae (a2-1) and (a2-2), R 3 and R 5 The alkyl group having 1 to 18 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms.

[0089] In the above formula (a2-2), m is preferably an integer of 2-50, more preferably an integer of 3-20.

[0090] The polymerizable monomer (a2) is preferably a compound represented by the following formula (a2-3).

[0091]

[0092] ((In the above formula (a2-3),

[0093] R 6 A hydrogen atom or a methyl group.

[0094] R 7 Each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.

[0095] l is an integer from 0 to 5.)

[0096] The polymerizable monomer (a2) can be produced by a known method.

[0097] In addition, a commercially available item can be used as the polymerizable monomer (a2). For example, commercially available products of the polymerizable monomer (a2) having a group containing a polyoxyalkylene chain and in which the polymerizable unsaturated group is a (meth)acryloyl group include "NK Ester M-20G", "NK Ester M-40G", "NK Ester M-90G", "NK Ester M-230G", "NK Ester AM-90G", "NK Ester AMP-10G", "NK Ester AMP-20G", and "NK Ester AMP-60G" manufactured by Shin-Nakamura Chemical Co., Ltd., "BLEMMER PE-90", "BLEMMER PE-200", "BLEMMER PE-350", "BLEMMER PME-100", "BLEMMER PME-200", "BLEMMER PME-400", "BLEMMER PME-4000", "BLEMMER PP-1000", "BLEMMER PP-500", "BLEMMER PP-800", and "BLEMMER PE-90" manufactured by NOF Corporation. 70PEP-350B", "BLEMMER55PET-800", "BLEMMER 50POEP-800B", "BLEMMER 10PPB-500B", "BLEMMER NKH-5050", "BLEMMER AP-400", "BLEMMER AE-350", etc.

[0098] The monomer constituting the polymer block (A2) only needs to be a polymerizable monomer (a2) having one or more selected from an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, and a group containing a polyoxyalkylene chain. The polymer block (A2) may be composed of two or more polymerizable monomers (a2) having different structures. In this case, the polymerization form of the polymer block (A2) is not particularly limited. The polymer block (A2) may be a random polymer structure of two or more polymerizable monomers (a2) having different structures, or a block polymer structure of two or more polymerizable monomers (a2) having different structures.

[0099] The polymerizable monomer constituting the polymer block (A2) is preferably a single polymerizable monomer (a2).

[0100] The mass ratio of polymer block (A1) to polymer block (A2) in the polymer of the present invention is, for example, polymer block (A1):polymer block (A2) = 5:95 to 95:5, and preferably polymer block (A1):polymer block (A2) = 20:80 to 90:10.

[0101] The polymer of the present invention may contain polymer blocks of other polymerizable monomers other than the polymerizable monomers (a1) and (a2) as long as the effects of the present invention are not impaired.

[0102] The polymer of the present invention is preferably a block copolymer comprising a polymer block (A1) and a polymer block (A2), more preferably a block copolymer substantially formed by a polymer block (A1) and a polymer block (A2), and further preferably a block copolymer consisting only of a polymer block (A1) and a polymer block (A2). Here, "substantially formed" means that the total content of the polymer block (A1) and the polymer block (A2) in the polymer of the present invention is 80% by mass or more, 90% by mass or more, 95% by mass or more, or 99% by mass or more.

[0103] The polymer of the present invention preferably does not contain fluorine atoms. By using a polymer without fluorine atoms, the accumulation of fluorine atoms in the environment is reduced, and the environmental load can be reduced.

[0104] When the polymer of the present invention is a block copolymer composed of the polymer block (A1) and the polymer block (A2), the polymer of the present invention may be a polymer containing no fluorine atoms.

[0105] The polymer of the present invention only needs to contain at least one polymer block (A1). For example, when the polymer of the present invention is a block copolymer containing a polymer block (A1) and a polymer block (A2), the number and bonding order of each polymer block are not particularly limited.

[0106] The polymer of the present invention is preferably a diblock copolymer in which one polymer block (A1) and one polymer block (A2) are bonded to each other.

[0107] 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, further preferably in the range of 2,000 to 40,000, particularly preferably in the range of 4,000 to 40,000.

[0108] 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, further preferably in the range of 2,000 to 40,000, particularly preferably in the range of 4,000 to 40,000.

[0109] The degree of 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.

[0110] In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​obtained by polystyrene conversion based on gel permeation chromatography (GPC). In addition, the measurement conditions of GPC are as follows.

[0111] [GPC measurement conditions]

[0112] Measuring device: High-speed GPC device "HLC-8320GPC" manufactured by Tosoh Corporation

[0113] Column: "TSK GUARDCOLUMN SuperHZ-L" made by Tosoh Co., Ltd. + "TSK gelSuperHZM-N" made by Tosoh Co., Ltd. + "TSK gel SuperHZM-N" made by Tosoh Co., Ltd. + "TSK gelSuperHZM-N" made by Tosoh Co., Ltd. + "TSK gel SuperHZM-N" made by Tosoh Co., Ltd.

[0114] Detector: RI (differential refractometer)

[0115] Data processing: Tosoh Corporation "EcoSEC Data Analysis version 1.07"

[0116] Column temperature: 40°C

[0117] Developing solvent: tetrahydrofuran

[0118] Flow rate: 0.35mL / min

[0119] Measurement sample: 7.5 mg of a sample was dissolved in 10 ml of tetrahydrofuran, and the obtained solution was filtered through a microfilter to obtain a measurement sample.

[0120] Sample injection volume: 20μl

[0121] Standard sample: According to the measurement manual of the aforementioned "HLC-8320GPC", the following monodisperse polystyrene having a known molecular weight was used.

[0122] (monodisperse polystyrene)

[0123] "A-300" manufactured by Tosoh Corporation

[0124] "A-500" manufactured by Tosoh Corporation

[0125] "A-1000" manufactured by Tosoh Corporation

[0126] "A-2500" manufactured by Tosoh Corporation

[0127] "A-5000" manufactured by Tosoh Corporation

[0128] "F-1" manufactured by Tosoh Corporation

[0129] "F-2" manufactured by Tosoh Corporation

[0130] "F-4" manufactured by Tosoh Corporation

[0131] "F-10" manufactured by Tosoh Corporation

[0132] "F-20" manufactured by Tosoh Corporation

[0133] "F-40" manufactured by Tosoh Corporation

[0134] "F-80" manufactured by Tosoh Corporation

[0135] "F-128" manufactured by Tosoh Corporation

[0136] "F-288" manufactured by Tosoh Corporation

[0137] When the polymer of the present invention is a block copolymer comprising a polymer block (A1) and a polymer block (A2), the block copolymer can be produced, for example, by subjecting a reaction raw material comprising a polymerizable monomer (a1) and a polymerizable monomer (a2) to living polymerization such as living radical polymerization or living anion polymerization.

[0138] It should be noted that the "reaction raw materials" herein refer to raw materials constituting the polymer of the present invention, and do not include raw materials such as solvents and catalysts that do not constitute the polymer of the present invention.

[0139] For example, for the aforementioned active radical polymerization, the dormant species protected by atoms or atomic groups at the active polymerization end reversibly produces free radicals to react with monomers so that the growth reaction proceeds, and even if the first monomer is consumed, the growth end will not lose activity, and can react with the second monomer added in sequence to obtain a block polymer. As an example of such active radical polymerization, atom transfer radical polymerization (ATRP), reversible addition-fragmentation free radical polymerization (RAFT), free radical polymerization via nitroxide free radicals (NMP), free radical polymerization using organic tellurium (TERP), etc. can be cited. Any method therein can be used without particular limitation, and ATRP is preferred from the ease of control, etc. ATRP is performed as follows: an organic halide or a halogenated sulfonyl compound, etc. are used as a polymerization initiator, and a metal complex formed by a transition metal compound and a ligand is used as a catalyst for polymerization.

[0140] Specific examples of the polymerization initiator that can be used in ATRP include 1-phenylethyl chloride, 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, α,α'-dichloroxylene, α,α'-dibromoxylene, hexa(α-bromomethyl)benzene, 2-halogenated carboxylic acids having 1 to 6 carbon atoms (e.g., 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, etc.), alkyl esters having 1 to 6 carbon atoms, and the like.

[0141] More specific examples of the C1-6 alkyl ester of a C1-6 2-halogenated carboxylic acid include methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate, and ethyl 2-bromoisobutyrate.

[0142] Transition metal compounds that can be used in ATRP include M n+ X n shown.

[0143] As M n+ X n The transition metal M of the transition metal compound shown n+ , can be selected from Cu+, Cu 2+ , Fe 2+ , Fe 3+ 、Ru 2+ 、Ru 3+ Cr 2+ Cr 3+ 、Mo 0 、Mo + 、Mo 2+ 、Mo 3+ , W 2+ , W 3+ , Rh 3+ , Rh 4+ 、Co + 、Co 2+ 、Re 2+ 、Re 3+ 、Ni 0 、Ni + , Mn 3+ , Mn 4+ 、V 2+ 、V 3+ 、Zn + 、Zn 2+ 、Au + 、Au 2+ 、Ag + and Ag 2+ Composed of groups.

[0144] M n+ X nX of the transition metal compound shown can be selected from 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), SeR 11 , CN and R 12 COO group. Here, R 11 represents an aryl group, a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and R 12 It represents a hydrogen atom, and a linear or branched alkyl group having 1 to 6 carbon atoms (preferably a methyl group) which is optionally substituted 1 to 5 times by halogen (preferably substituted 1 to 3 times by fluorine or chlorine).

[0145] M n+ X n In the transition metal compounds shown, n represents the formal charge on the metal and is an integer of 0-7.

[0146] As ligand compounds capable of coordination bonding with the transition metal of the above-mentioned transition metal compound, there can be mentioned: compounds having a transition metal and a ligand containing one or more nitrogen atoms, oxygen atoms, phosphorus atoms or sulfur atoms which can coordinate via a σ bond, compounds having a transition metal and a ligand containing two or more carbon atoms which can coordinate via a π bond, and compounds having a transition metal and a ligand which can coordinate via a μ bond or an η bond.

[0147] The above-mentioned transition metal complex is not particularly limited. Preferred examples include transition metal complexes of Groups 7, 8, 9, 10, and 11. Further preferred examples include complexes of 0-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel.

[0148] Specific examples of catalysts that can be used in ATRP include, when the central metal is copper, complexes with ligands such as 2,2'-bipyridine and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris(2-aminoethyl)amine and other polyamines. In addition, as divalent ruthenium complexes, dichlorotris(triphenylphosphine)ruthenium, dichlorotris(tributylphosphine)ruthenium, dichloro(cyclooctadiene)ruthenium, dichlorophenylruthenium, dichloro-p-methylisopropylphenylruthenium, dichloro(norbornadiene)ruthenium, cis-dichlorobis(2,2'-bipyridine)ruthenium, dichlorotris(1,10-phenanthroline)ruthenium, carbonylchlorohydrotris(triphenylphosphine)ruthenium, etc. Further, as divalent iron complexes, bistriphenylphosphine complexes, triazacyclononane complexes, etc. can be mentioned.

[0149] In the living radical polymerization, it is preferred to use a solvent.

[0150] Examples of the solvent used in the living radical polymerization include ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ether solvents such as diisopropyl ether, dimethoxyethane, and diethylene glycol dimethyl ether; halogen solvents such as dichloromethane and dichloroethane; aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, and isopropanol; and non-protonic polar solvents such as dimethylformamide and dimethyl sulfoxide.

[0151] The above solvents may be used alone or in combination of two or more.

[0152] When the polymer of the present invention is a block copolymer comprising a polymer block (A1) and a polymer block (A2) (hereinafter, this copolymer is referred to as "the block copolymer of the present invention"), the block copolymer of the present invention can be produced by, for example, the method 1 or 2 described below.

[0153] Method 1: In the presence of a polymerization initiator, a transition metal compound, a ligand compound capable of forming a coordination bond with the transition metal, and a solvent, a polymerizable monomer (a1) is subjected to living radical polymerization (preferably atom transfer radical polymerization) to obtain a polymer block (A1), and then a polymerizable monomer (a2) is added to the reaction system to further subject the polymer block (A1) to living radical polymerization (preferably atom transfer radical polymerization) with the polymerizable monomer (a2).

[0154] Method 2: In the presence of a polymerization initiator, a transition metal compound, a ligand compound capable of forming a coordination bond with the transition metal, and a solvent, a polymerizable monomer (a2) is subjected to living free radical polymerization (preferably atom transfer radical polymerization) to obtain a polymer block (A2), and then a polymerizable monomer (a1) is added to the reaction system to further subject the polymer block (A2) to living free radical polymerization (preferably atom transfer radical polymerization) with the polymerizable monomer (a1).

[0155] The charging ratio (mass) of the polymerizable monomer (a1) and the polymerizable monomer (a2) when producing the block copolymer of the present invention is, for example, polymerizable monomer (a1):polymerizable monomer (a2)=5:95 to 95:5, preferably polymerizable monomer (a1):polymerizable monomer (a2)=20:80 to 90:10.

[0156] The polymerization temperature in the living radical polymerization is preferably in the range of room temperature to 120°C.

[0157] When the block copolymer of the present invention is produced by living radical polymerization, a metal derived from the transition metal compound used in the polymerization may remain in the obtained block copolymer. The metal remaining in the obtained block copolymer can be removed using activated alumina or the like after the polymerization is completed.

[0158] [Coating composition]

[0159] The polymer of the present invention can be suitably used as a leveling agent for a coating composition, and the coating composition of the present invention comprises the polymer of the present invention. The polymer of the present invention can form a fluorine-free leveling agent that does not contain fluorine atoms, and therefore is a leveling agent with low environmental accumulation and low environmental load.

[0160] The content of the polymer of the present invention contained in the coating composition of the present invention varies depending on the type of base resin, coating method, target film thickness, etc., and is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 5 parts by mass, and further preferably 0.01 to 2 parts by mass relative to 100 parts by mass of the solid content of the coating composition. If the content of the polymer of the present invention is within this range, the surface tension can be sufficiently reduced, the target leveling property can be obtained, and the occurrence of undesirable conditions such as blistering during coating can be suppressed.

[0161] The application of the coating composition of the present invention is not particularly limited, and the coating composition of the present invention can be used in any application as long as leveling properties are required. The coating composition of the present invention can be used as, for example, various coating compositions and photosensitive resin compositions.

[0162] When the coating composition of the present invention is formed into a coating composition, examples of the coating composition include coatings using natural resins such as petroleum resin coatings, shellac coatings, rosin-based coatings, cellulose-based coatings, rubber-based coatings, lacquer coatings, cashew resin coatings, and oily vehicle coatings; and coatings using synthetic resins such as 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, silicone resin coatings, and fluororesin coatings.

[0163] By adding the polymer of the present invention to the above-mentioned coating composition, smoothness can be imparted to the resulting coating film.

[0164] The coating composition may contain colorants such as pigments, dyes, and carbon; inorganic powders such as silicon dioxide, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, and calcium carbonate; organic micropowders such as higher fatty acids, polyacrylic resins, and polyethylene; and various additives such as light resistance improvers, weather resistance improvers, heat resistance improvers, antioxidants, thickeners, and anti-settling agents.

[0165] Any coating method can be used for the coating composition of the present invention as long as it is a known and commonly used coating method, for example, a slit coater, a slit & spin coater, a spin coater, a roll coater, an electrostatic coating, a rod coater, a gravure coater, a die coater, a knife coater, inkjet, dip coating, spray coating, shower coating, screen printing, gravure printing, offset printing, reverse coating and the like can be mentioned.

[0166] When a photosensitive resin composition is irradiated with light such as visible light or ultraviolet light, physical properties such as solubility, viscosity, transparency, refractive index, conductivity, and ion permeability of the resin change.

[0167] Among the photosensitive resin compositions, the resist compositions (photoresist compositions, color resist compositions for color filters, etc.) require a high degree of leveling. The resist composition is usually applied by spin coating on a silicon wafer or a glass substrate on which various metals are evaporated so that the thickness is about 1 to 2 μm. At this time, when the coating film thickness fluctuates or uneven coating occurs, the linearity and reproducibility of the pattern are reduced, resulting in the problem that the resist pattern with the target accuracy cannot be obtained. In addition, in addition to these problems, there are various problems related to leveling, such as dripping marks, overall unevenness, and beading phenomenon in which the film thickness of the edge portion is thicker than that of the center portion.

[0168] In the coating composition of the present invention, the polymer of the present invention can form a uniform coating film (cured product) by exerting high leveling properties. Therefore, when used as a resist composition, the above-mentioned problems can be solved.

[0169] When the coating composition of the present invention is formed into a photoresist composition, the photoresist composition contains an alkali-soluble resin, a radiation-sensitive substance (photosensitive substance), a solvent, and the like in addition to the polymer of the present invention.

[0170] The alkali-soluble resin contained in the photoresist composition refers to a resin that is soluble in an alkaline solution, which is a developer used when patterning the resist.

[0171] Examples of the alkali-soluble resin include novolac resins obtained by condensing aromatic hydroxy compound derivatives such as phenol, cresol, xylenol, resorcinol, phloroglucinol, and hydroquinone with aldehyde compounds such as formaldehyde, acetaldehyde, and benzaldehyde; polymers or copolymers of vinyl phenol 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 obtained by introducing radiation-sensitive groups such as quinonediazide groups, naphthoquinoneazide groups, aromatic azide groups, and aromatic cinnamoyl groups into a part of the hydroxyl groups of these various resins; and polyurethane resins containing acidic groups such as carboxylic acids and sulfonic acids in the molecules.

[0172] These alkali-soluble resins may be used alone or in combination of two or more.

[0173] The radiation-sensitive substance contained in the photoresist composition is a substance that changes the solubility of the alkali-soluble resin in the developer by irradiation with energy rays such as ultraviolet rays, extreme ultraviolet rays, excimer lasers, X-rays, electron beams, ion beams, molecular beams, and gamma rays.

[0174] Examples of radiation-sensitive substances include quinonediazide compounds, diazo compounds, azide compounds, onium salt compounds, halogenated organic compounds, mixtures of halogenated organic compounds and organic metal compounds, organic acid ester compounds, organic acid amide compounds, organic acid imide compounds, and poly(olefin sulfone) compounds.

[0175] Examples of the quinonediazide compound include 1,2-benzoquinoneazide-4-sulfonate, 1,2-naphthoquinonediazide-4-sulfonate, 1,2-naphthoquinonediazide-5-sulfonate, 2,1-naphthoquinonediazide-4-sulfonate, 2,1-naphthoquinonediazide-5-sulfonate, and sulfonic acid chlorides of quinonediazide derivatives such as 1,2-benzoquinoneazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 2,1-naphthoquinonediazide-4-sulfonic acid chloride, and 2,1-naphthoquinonediazide-5-sulfonic acid chloride.

[0176] Examples of the diazo compounds include salts of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde, diazo resin inorganic salts obtained by reacting hexafluorophosphates, tetrafluoroborate, perchlorate or periodate with the above condensates, and diazo resin organic salts obtained by reacting the above condensates with sulfonic acids as described in USP 3,300,309.

[0177] Examples of the azide compounds include azidochalcone acid, diazidobenzylidenemethylcyclohexanones, azidocinnamylideneacetophenones, aromatic azide compounds, and aromatic diazide compounds.

[0178] Examples of the halogenated organic compound include halogen-containing oxadiazole compounds, halogen-containing triazine compounds, halogen-containing acetophenone compounds, halogen-containing benzophenone compounds, halogen-containing sulfoxide compounds, halogen-containing sulfone compounds, halogen-containing thiazole compounds, halogen-containing oxazole compounds, halogen-containing triazole compounds, halogen-containing 2-pyrone compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, halogen-containing heterocyclic compounds, and sulfenyl halide compounds.

[0179] In addition to the above, compounds used as halogen flame retardants such as tris(2,3-dibromopropyl)phosphate, tris(2,3-dibromo-3-chloropropyl)phosphate, chlorotetrabromomethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenyl allyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis(bromoethyl ether)tetrabromobisphenol A, bis(chloroethyl ether)tetrachlorobisphenol A, tris(2,3-dibromopropyl)isocyanurate, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, and 2,2-bis(4-hydroxyethoxy-3,5-dibromophenyl)propane, and compounds used as organochlorine pesticides such as dichlorophenyltrichloroethane can also be exemplified as the halogenated organic compound.

[0180] Examples of the organic acid ester include carboxylic acid ester and sulfonic acid ester. Examples of the organic acid amide include carboxylic acid amide and sulfonic acid amide. Examples of the organic acid imide include carboxylic acid imide and sulfonic acid imide.

[0181] The radiation sensitive substance may be used alone or in combination of two or more.

[0182] In the photoresist composition, the content of the radiation sensitive substance is preferably in the range of 10 to 200 parts by mass, more preferably in the range of 50 to 150 parts by mass, based on 100 parts by mass of the alkali-soluble resin.

[0183] Examples of the solvent for the photoresist composition include ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, and butyrolactone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol, heptanol, octanol, nonanol, and decanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ... Alcohol ethers such as glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether; esters such as ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, propyl butyrate, ethyl lactate, butyl lactate, methyl 2-oxopropionate, ethyl 2-oxopropionate, propyl 2-oxopropionate, Monocarboxylic acid esters such as butyl 2-oxopropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, and butyl 2-methoxypropionate; cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, and butyl cellosolve acetate; propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate Propylene glycol; diethylene glycol such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether; halogenated hydrocarbons such as trichloroethylene, Freon solvents, HCFC, HFC; fully fluorinated solvents such as perfluorooctane, aromatics such as toluene and xylene; polar solvents such as dimethylacetamide, dimethylformamide, N-methylacetamide, N-methylpyrrolidone.

[0184] These solvents may be used alone or in combination of two or more.

[0185] When the coating composition of the present invention is formed into a color resist composition, the color resist composition contains an alkali-soluble resin, a polymerizable compound, a colorant, and the like in addition to the polymer of the present invention.

[0186] As the alkali-soluble resin contained in the color resist, the same alkali-soluble resin as that contained in the above-mentioned photoresist composition can be used.

[0187] The polymerizable compound contained in the color resist composition refers to, for example, a compound having a photopolymerizable functional group that can undergo polymerization or crosslinking reaction when irradiated with active energy rays such as ultraviolet rays.

[0188] Examples of the polymerizable compounds include: esters of unsaturated carboxylic acids such as (meth)acrylic acid, 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 of unsaturated carboxylic acids with polyvalent carboxylic acids and polyhydroxy compounds such as the aforementioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds; polymerizable compounds having a carbamate skeleton obtained by reacting a polyisocyanate compound with a hydroxy compound containing a (meth)acryloyl group; polymerizable compounds having an acid group, etc.

[0189] The polymerizable compound may be used alone or in combination of two or more.

[0190] Examples of the esters of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include (meth)acrylates such as ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and glycerol (meth)acrylate.

[0191] In addition, examples include itaconate esters obtained by replacing the (meth)acrylic acid portion of these acrylates with itaconic acid, crotonate esters obtained by replacing the (meth)acrylic acid portion with crotonic acid, or maleate esters obtained by replacing the (meth)acrylic acid portion with maleic acid.

[0192] Examples of the esters of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone di(meth)acrylate, resorcinol di(meth)acrylate, and pyrogallol tri(meth)acrylate.

[0193] The ester obtained by the esterification reaction of unsaturated carboxylic acid, polycarboxylic acid and polyhydroxy compound may be a single substance or a mixture. Examples of such esters include esters obtained from (meth)acrylic acid, phthalic acid and ethylene glycol, esters obtained from (meth)acrylic acid, maleic acid and diethylene glycol, esters obtained from (meth)acrylic acid, terephthalic acid and pentaerythritol, and esters obtained from (meth)acrylic acid, adipic acid, butanediol and glycerol.

[0194] Examples of the polymerizable compound having a urethane skeleton obtained by reacting the polyisocyanate compound with the hydroxy compound containing a (meth)acryloyl group include: aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate, and reaction products of hydroxy compounds having a (meth)acryloyl group such as 2-hydroxyethyl (meth)acrylate and 3-hydroxy〔1,1,1-tri(meth)acryloyloxymethyl〕propane.

[0195] The 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 acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound. The aliphatic polyhydroxy compound used in the preparation of the polyfunctional polymerizable compound is preferably pentaerythritol or dipentaerythritol.

[0196] From the viewpoint of improving developability, curability, etc., the acid value of the polyfunctional polymerizable compound is preferably in the range of 0.1 to 40, and more preferably in the range of 5 to 30. When two or more polyfunctional polymerizable compounds having an acid group are used in combination, and when a polyfunctional polymerizable compound having an acid group and a polyfunctional polymerizable compound having no acid group are used in combination, it is preferred that the acid value of the mixture of the polymerizable compounds be within the above range.

[0197] Specific examples of the polymerizable compound having an acid group include a mixture mainly composed of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and succinate of dipentaerythritol pentaacrylate. This mixture is commercially available as Aronix TO-1382 (manufactured by Toagosei Co., Ltd.).

[0198] Examples of polymerizable compounds other than the above include (meth)acrylamide such as ethylenebis(meth)acrylamide; allyl esters such as diallyl phthalate; and compounds having a vinyl group such as divinyl phthalate.

[0199] The content of the polymerizable compound in the color resist composition is preferably in the range of 5 to 80% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 50% by mass, based on the total solid content of the color resist composition.

[0200] The colorant of the color resist composition is not particularly limited as long as it can color the composition, and may be, for example, a pigment or a dye.

[0201] Any of organic pigments and inorganic pigments can be used as the pigment. As the aforementioned organic pigment, pigments of various colors such as red pigment, green pigment, blue pigment, yellow pigment, purple pigment, orange pigment, brown pigment can be used. In addition, as the chemical structure of the organic pigment, for example, azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrone, perylene, etc. can be cited. In addition, as the aforementioned inorganic pigment, for example, barium sulfate, lead sulfate, titanium oxide, yellow lead, ferric oxide, chromium oxide, etc. can be cited.

[0202] It should be noted that the "CI" below means a color index.

[0203] Examples of the red pigment include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:4 :3、57、57:1、57:2、58:4、60、63、63:1、63:2、64、64:1、68、69、81、81:1、81:2、81:3、81:4、83、88、90:1、101、101:1、104、108、108:1、109、112、113、114、122、123、144、146、147、1 49, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232 , 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, etc. Among these, CI Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242 or 254 is preferred, and CI Pigment Red 177, 209, 224 or 254 is more preferred.

[0204] Examples of the green pigment include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, and 58. Among these, CI Pigment Green 7, 36, or 58 is preferred.

[0205] Examples of the blue pigment include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 is preferred, and CI Pigment Blue 15:6 is more preferred.

[0206] Examples of the yellow pigment include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, etc. Among these, CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185 is preferred, and CI Pigment Yellow 83, 138, 139, 150 or 180 is more preferred.

[0207] Examples of the violet pigment include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, CI Pigment Violet 19 or 23 is preferred, and CI Pigment Violet 23 is more preferred.

[0208] Examples of the orange pigment include CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79. Among these, CI Pigment Orange 38 or 71 is preferred.

[0209] The pixels of the three primary colors of the color filters used in liquid crystal display devices and organic EL display devices are red (R), green (G), and blue (B). Therefore, the aforementioned red pigment, green pigment, and blue pigment are mainly used, and in order to improve color reproduction, organic pigments of colors such as yellow, purple, and orange can also be used for hue adjustment.

[0210] In order to improve the brightness of color liquid crystal display devices and organic EL display devices, the average particle size of the organic pigment is preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.3 μm or less. The organic pigment is preferably dispersed and used to have these average particle sizes.

[0211] The average primary particle size of the organic pigment is preferably 100 nm or less, more preferably 50 nm or less, further preferably 40 nm or less, and particularly preferably in the range of 10 to 30 nm.

[0212] The average particle size of the organic pigment is measured by a dynamic light scattering particle size distribution analyzer, for example, Nanotrac particle size distribution measuring apparatus "UPA-EX150" or "UPA-EX250" manufactured by Nikkiso Co., Ltd.

[0213] When the color resist composition is used to form a black matrix (BM), there is no particular limitation on the colorant as long as it is black, and examples thereof include carbon black, lamp black, acetylene black, bone black, thermal black, channel black, furnace black, black lead, iron black, titanium black, etc. Among these, carbon black and titanium black are preferred from the viewpoint of light shielding rate and image characteristics.

[0214] Alternatively, two or more organic pigments may be mixed to form a black color.

[0215] Examples of commercially available carbon blacks 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, #1050, #1100, #1200, #1300, #1400, #1500, #1600, #1700, #1800, #1900, #2000, #2100, #2200, #2300, #2400, #2500, #2600, #2700, #2800, #2900, #3000, #3100 960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B, etc., and 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, ColoRBlack FW18, ColoRBlackFW18, ColoRBlack FW200, Color Black S160, ColoRBlack Examples of S170 include Cabot Japan Co., Ltd.Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch14 00, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN XC72R, ELFTEX-8, etc., Colombian Carbon can be cited Company-made RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVE N1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000, etc. .

[0216] Among the above carbon blacks, carbon black coated with a resin is preferred because it has high optical density and high surface resistivity required for a black matrix of a color filter.

[0217] Examples of commercially available products of the titanium black include titanium black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.

[0218] As a colorant used in forming the black matrix (BM), two or more organic pigments may be mixed to form black by color mixing, and a black pigment obtained by mixing three colors of red, green, and blue pigments may be used.

[0219] Examples of colorants that can be mixed for preparing black pigments include Victoria Brilliant Blue (CI42595), Auramine O (CI41000), Cachiron Brilliant Flavin (BASIC 13), Rhodamine 6GCP (CI45160), Rhodamine B (CI45170), Safranin OK70:100 (CI50240), Erio Grausin X (CI42080), No.120 / Leonor Yellow (CI21090), Leonor Yellow GRO (CI21090), Shimla First Yellow 8GF (CI21105), Benzidine Yellow 4T-564D (CI21095), Shimla First Red 4015 (CI12355), Lionor Red 7B4401 (CI15850), First Gen Blue TGR-L (CI74160), Lionol Blue SM (CI26150), Lionol Blue ES (CI Pigment Blue 15:6), Rio Nogen Red GD (CI Pigment Red 168), Lionol Green 2YS (CI Pigment Green 36), etc.

[0220] As other colorants that can be mixed for preparing the black pigment, for example, CI yellow pigment 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, CI orange pigment 36, 43, 51, 55, 59, 61, CI red pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, CI violet pigment 19, 23, 29, 30, 37, 40, 50, CI blue pigment 15, 15:1, 15:4, 22, 60, 64, CI green pigment 7, CI brown pigment 23, 25, 26, etc. can be mentioned.

[0221] When carbon black is used as the black pigment, the average primary particle size of the carbon black is preferably in the range of 0.01 to 0.08 μm, and more preferably in the range of 0.02 to 0.05 μm from the viewpoint of improving the developability.

[0222] The particle shape of carbon black is different from that of organic pigments, etc., and the primary particles exist in a state called a structure formed by mutual fusion, and sometimes fine pores are formed on the particle surface by post-treatment. Therefore, in order to express the particle shape of carbon black, in addition to the average particle size of the primary particles obtained by the same method as the above-mentioned organic pigments, it is usually preferred to measure the DBP absorption (JIS K6221) and the specific surface area based on the BET method (JIS K6217) as indicators of the structure and pore amount.

[0223] The dibutyl phthalate (hereinafter referred to as "DBP") absorption of carbon black is preferably 40 to 100 cm 3 The range of 50 to 80 cm / 100 g is more preferable from the viewpoint of good dispersibility and developability. 3 The specific surface area of ​​carbon black based on the BET method is preferably 50 to 120 m 2 The range of 60 to 95 m / g is more preferable from the viewpoint of good dispersion stability. 2 / g range.

[0224] Examples of dyes used as colorants in the color resist composition include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

[0225] Examples of the azo dye 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, CIBASIC Blue 41, CIBASIC Red 18, CI Medium Red 7, CI Medium Yellow 5, and CI Medium Black 7.

[0226] Examples of the anthraquinone dye include CI Vat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Disperse Blue 60.

[0227] Examples of the aforementioned phthalocyanine dyes include CI Vat Blue 5, examples of the aforementioned quinoneimine dyes include CIBASIC Blue 3, CIBASIC Blue 9, etc., examples of the aforementioned quinoline dyes include CI Solvent Yellow 33, CI Acid Yellow 3, CI Disperse Yellow 64, and examples of the aforementioned nitro dyes include CI Acid Yellow 1, CI Acid Orange 3, CI Disperse Yellow 42, and the like.

[0228] As the colorant of the color resist composition, a pigment is preferably used because the obtained coating film has excellent light resistance, weather resistance and fastness. In order to adjust the color tone, a pigment and a dye may be used in combination as necessary.

[0229] The content of the colorant in the color resist composition is preferably 1% by mass or more, more preferably in the range of 5 to 80% by mass, and even more preferably in the range of 5 to 70% by mass, based on the total solid content of the color resist composition.

[0230] When the color resist composition is used to form each of red (R), green (G), and blue (B) pixels of a color filter, the content of the colorant in the color resist composition is preferably in the range of 5 to 60% by mass, more preferably in the range of 10 to 50% by mass, based on the total solid content of the color resist composition.

[0231] When the color resist composition is used to form a black matrix of a color filter, the content of the colorant in the color resist composition is preferably in the range of 20 to 80% by mass, more preferably in the range of 30 to 70% by mass, based on the total solid content of the color resist composition.

[0232] In the color resist composition, when the colorant is a pigment, it is preferred to use a pigment dispersion prepared by dispersing the pigment in an organic solvent using a dispersant.

[0233] As the above-mentioned dispersant, surfactants; intermediates or derivatives of pigments; intermediates or derivatives of dyes; resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins, etc. can be cited. Among these, graft copolymers having nitrogen atoms, acrylic block copolymers having nitrogen atoms, polyurethane resin dispersants, etc. are preferred. These dispersants have nitrogen atoms, so the nitrogen atoms have affinity for the pigment surface, and the dispersion stability is improved by increasing the affinity of the part other than the nitrogen atoms to the medium.

[0234] These dispersants may be used alone or in combination of two or more.

[0235] Commercially available products of the above-mentioned dispersants include the "Efka" series ("Efka 46" etc.) manufactured by BASF; the "Disperbyk" series and the "BYK" series ("BYK-160", "BYK-161", "BYK-2001" etc.) manufactured by BYK Japan Co., Ltd.; the "Solsperse" series manufactured by Japan Lubrizol Co., Ltd.; the "KP" series manufactured by Shin-Etsu Chemical Co., Ltd., the "Polyflow" series manufactured by Kyoeisha Chemical Co., Ltd.; the "DISPARLON" series manufactured by Kusumoto Chemicals Co., Ltd.; and the "Ajisper" series ("Ajisper PB-814" etc.) manufactured by Ajinomoto Fine Techno Co., Ltd.

[0236] Examples of the organic solvent used in the preparation of the pigment dispersion include acetate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxy propionate; aromatic solvents such as toluene, xylene, and methoxybenzene; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, and diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; nitrogen compound solvents such as N,N-dimethylformamide, γ-butyrolactam, and N-methyl-2-pyrrolidone; lactone solvents such as γ-butyrolactone; carbamates, etc.

[0237] These solvents may be used alone or in combination of two or more.

[0238] The pigment dispersion can be prepared by a method including a colorant kneading and dispersing step and a micro-dispersing step, or a method including a micro-dispersing step alone. In the kneading and dispersing step, the colorant, a part of the alkali-soluble resin, and the dispersant as required are mixed and kneaded. The colorant can be dispersed by applying a strong shear force while using a kneading machine.

[0239] Examples of the machine used for kneading include a two-roll mill, a three-roll mill, a ball mill, a trommel, a disperser, a kneader, a co-kneader, a homogenizer, a stirrer, and a single-screw or twin-screw extruder.

[0240] The colorant is preferably reduced to a fine particle size by a salt milling method or the like before the kneading.

[0241] In the above-mentioned fine dispersion step, a composition containing a colorant obtained in the above-mentioned kneading and dispersing step is prepared by adding a solvent, or a composition containing a colorant, an alkali-soluble resin, a solvent and the above-mentioned dispersant as needed is mixed and dispersed together with a dispersion medium for fine particles of glass, zirconium oxide or ceramics using a disperser, so that the particles of the colorant can be dispersed to a microscopic state close to primary particles.

[0242] From the viewpoint of improving the transmittance and contrast of the color filter, the average particle size of the primary particles of the colorant is preferably 10 to 100 nm, more preferably 10 to 60 nm. It should be noted that the average particle size of the colorant is measured by a dynamic light scattering particle size distribution meter, for example, Nanotrac (Nanotrac) particle size distribution measuring device "UPA-EX150", "UPA-EX250" and the like manufactured by Nikkiso Co., Ltd.

[0243] In the above, the coating composition, the photoresist composition, and the color resist composition are exemplified as the coating composition, but the coating composition is not limited to these.

[0244] Specific examples of the use of the coating composition of the present invention include: coating materials for various display screens such as liquid crystal displays (hereinafter, abbreviated as "LCD"), plasma displays (hereinafter, abbreviated as "PDP"), organic EL displays (hereinafter, abbreviated as "OLED"), quantum dot displays (hereinafter, abbreviated as "QDD"), namely anti-glare (AG: anti-glare) hard coating materials, anti-reflection (LR) coating materials, low refractive index layer coating materials, high refractive index layer coating materials, transparent hard coating materials, polymerizable liquid crystal coating materials; color resists, inkjet inks, printing inks or coatings for forming each pixel such as RGB of color filters (hereinafter, abbreviated as "CF") such as LCDs; black matrices for forming CFs such as LCDs; , black resist, inkjet ink, printing ink or coating for black column spacers, black optical spacers; coating for transparent protective film used in CF of LCD, etc. to protect the surface of CF; LCD liquid crystal material, column spacer, optical spacer resin composition; LCD, PDP, OLED, QDD, etc. pixel partition wall resin composition, electrode formation positive photoresist, protective film, insulating film, plastic shell, plastic shell coating, baffle (frame) ink; LCD backlight component, i.e. prism sheet, light diffusion film; LCD liquid crystal TFT array organic insulating film coating; LCD internal polarizing plate surface protective coating material; PDP phosphor; OLED organic EL material, sealing material (protective film, gas barrier); QDD Quantum dot ink, sealing materials, protective films; high refractive index prisms, low refractive index seals, LED pixels for micro (mini) LED displays; positive photoresists, chemically amplified photoresists, anti-reflective films, multilayer materials (SOC, SOG), lower films, buffer coatings, developers, rinsers, anti-pattern tilt agents, polymer residue removers, cleaning agents and other chemical solutions, nanoimprint release agents used in semiconductor manufacturing; resin compositions for semiconductor post-processing or printed circuit boards (epoxy resins, phenolic resins, polyphenylene ether resins, liquid crystal polymers, polyimide resins, bismaleimide resins, bisallyl nadic imide resins, benzoxazine resins and other resin compositions), copper-clad laminates, copper foil with resins, laminates Thin films, passivation films, interlayer insulating films, flexible copper-clad laminates, dry film resists; color resists for image sensors; liquid repellents for solder flux; dispersants, coatings, and green sheets for laminated ceramic capacitors; positive electrode materials, negative electrode materials, separators, and electrolytes for lithium-ion batteries; exterior coatings, rubber, elastomers, glass, vapor-deposited anchor coatings, headlight prisms, solid lubricating coatings, heat-dissipating substrates, interior coatings, and repair coatings for automobiles; wallpaper, flooring materials, kitchen components, and bathroom / toilet components for residential equipment; inkjet inks, offset printing inks, gravure printing inks, screen printing inks, photoresists for printing plate manufacturing processes, photosensitive materials for lithographic printing plates (PS plates), packaging adhesives, and ballpoint pen inks for printed materials;Primers for easy adhesion of plastic films, etc.; water repellents for fibers; non-diffusing agents for grease; cleaning liquids for cleaning the surfaces of various products or parts; hard coating materials for optical storage media such as CDs, DVDs, and Blu-ray discs; coatings or hard coating materials for housings or screens for smartphones or mobile phones; hard coating materials for transfer films for embedded molds (IMD, IMF); mold release films; coatings or coating materials for various plastic molded products such as housings of home appliances; printing inks or coatings for various building materials such as decorative panels; coating materials for window glass in houses; woodworking coatings for furniture, etc.; artificial / composite Coating materials for finished leather; coating materials for rubber rollers for OA equipment such as copiers and printers; coating materials for glass of the reading part of OA equipment such as copiers and scanners; optical prisms or coating materials for cameras, video cameras, glasses, contact lenses, etc.; coating materials for windshields and glasses of clocks such as watches; coating materials for windows of various vehicles such as automobiles and railway vehicles; coating materials for anti-reflective films for protective glass or thin films for solar cells; coating materials or coating materials for FRP baths; PCM for metal building materials or home appliances; single-layer or multi-layer coating compositions for photolithography processes, etc.;

[0245] The polymer of the present invention has excellent surface tension reduction ability, therefore, can not only expect leveling property, can also expect each function of wettability, permeability, cleaning property, water repellency, oil repellency, antifouling property, lubricity, anti-blocking property, demoulding property. In addition, if the polymer of the present invention is compounded in the coating or coating agent containing microparticles, then improve the dispersibility of microparticles, can not only expect leveling property, can also expect the function as the dispersant of microparticles. In addition, the polymer of the present invention is also added to the adhesive composition used in the adhesive tape etc. except the above-mentioned coating composition, thus can not only expect leveling property, can also expect each function of the reduction of peeling force, the suppression of peeling force variation, the suppression of stripping charge.

[0246] Example

[0247] Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples.

[0248] Example 1

[0249] (Preparation of Block Copolymer)

[0250] In a flask purged with nitrogen, 15.0 g of 3-methacryloxypropyl tris(trimethylsiloxy)silane and 79.0 g of methyl ethyl ketone as a solvent were added, and the temperature was raised to 50°C while stirring under a nitrogen stream. Then, 4.2 g of 2,2'-bipyridine and 1.5 g of cuprous chloride were added, and the flask was stirred for 30 minutes while maintaining the temperature at 50°C. After that, 2.7 g of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 50°C for 3 hours under a nitrogen stream to obtain a polymer block of 3-methacryloxypropyl tris(trimethylsiloxy)silane.

[0251] Next, 35.0 g of polypropylene glycol monomethacrylate (average number of repetitions of propylene glycol is 4 to 6) was added to the reaction system containing the polymer block of 3-methacryloxypropyl tris(trimethylsiloxy)silane, and the mixture was reacted at 50° C. for 18 hours to obtain a reactant. Then, 30 g of activated alumina was added to the obtained reactant and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a block copolymer (1).

[0252] The molecular weight of the obtained block copolymer (1) was measured by GPC, and the weight average molecular weight (Mw) was 10300, the number average molecular weight (Mn) was 9200, and (Mw / Mn) was 1.1. In addition, based on the raw material input ratio, the content of the functional group represented by -Si[OSi(CH3)3]3 in the block copolymer (1) was 22% by mass.

[0253] (Film formation and evaluation)

[0254] A coating composition was prepared by mixing 3.0 g of a 40% by mass alkali-soluble resin solution (ACRYDIC ZL-295, manufactured by DIC Corporation), 1.2 g of Aronix M-402 (manufactured by Toagosei Chemical Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), 0.001 g of the block copolymer (1) in terms of solid content, and 3.8 g of propylene glycol monomethyl ether acetate (PGMEA).

[0255] 3 ml of the obtained coating composition was dripped onto the central part of a 10 cm × 10 cm chrome-plated glass substrate, and spin-coated at a rotation speed of 1000 rpm and a rotation time of 10 seconds, and then heated at 100° C. for 100 seconds and dried to prepare a laminate having a coating layer. The coating layer of the obtained laminate was visually observed, and the smoothness of the coating layer was evaluated according to the following criteria. The results are shown in Table 1.

[0256] ◎: Almost no uneven coating was observed.

[0257] ○: Uneven coating was observed in part.

[0258] ×: Uneven coating was observed throughout.

[0259] The coating layer of the obtained laminate was measured for a total of 400 points using a reflection spectrophotometer (FE-3000, manufactured by Otsuka Electronics Co., Ltd.) to calculate the thickness standard deviation. The smaller the value, the less uneven the coating is, and the coating layer can be evaluated as smooth.

[0260] Example 2

[0261] In a flask purged with nitrogen, 33.5 g of 3-methacryloxypropyl tris(trimethylsiloxy)silane and 75.0 g of methyl ethyl ketone as a solvent were added, and the temperature was raised to 50°C while stirring under a nitrogen stream. Then, 4.2 g of 2,2'-bipyridine and 1.5 g of cuprous chloride were added, and the flask was stirred for 30 minutes while maintaining the temperature at 50°C. After that, 2.7 g of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 50°C for 4 hours under a nitrogen stream to obtain a polymer block of 3-methacryloxypropyl tris(trimethylsiloxy)silane.

[0262] Then, 16.5 g of polypropylene glycol monomethacrylate (average number of repetitions of propylene glycol is 4 to 6) was added to the reaction system containing the polymer block of 3-methacryloxypropyl tris(trimethylsiloxy)silane, and the mixture was reacted at 50° C. for 20 hours to obtain a reactant. Then, 30 g of activated alumina was added to the obtained reactant and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a block copolymer (2).

[0263] The molecular weight of the obtained block copolymer (2) was measured by GPC, and the weight average molecular weight (Mw) was 7100, the number average molecular weight (Mn) was 6100, and (Mw / Mn) was 1.2. The content of the functional group represented by -Si[OSi(CH3)3]3 in the obtained block copolymer (2) was 49% by mass.

[0264] The coating composition was prepared in the same manner as in Example 1 except that the block copolymer (2) was used instead of the block copolymer (1), and a coating film was formed and evaluated.

[0265] Example 3

[0266] In a flask purged with nitrogen, 33.5 g of 3-methacryloxypropyl tris(trimethylsiloxy)silane and 75.0 g of methyl ethyl ketone as a solvent were added, and the temperature was raised to 60°C while stirring under a nitrogen stream. Then, 4.2 g of 2,2'-bipyridine and 1.5 g of cuprous chloride were added, and the flask was stirred for 30 minutes while maintaining the temperature at 60°C. After that, 2.7 g of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60°C for 8 hours under a nitrogen stream to obtain a polymer block of 3-methacryloxypropyl tris(trimethylsiloxy)silane.

[0267] Next, 16.5 g of poly 1,2-butylene glycol monomethacrylate (average number of repetitions of 1,2-butylene glycol is 6) was added to the reaction system containing the polymer block of 3-methacryloxypropyl tris(trimethylsiloxy)silane, and the mixture was reacted at 60° C. for 20 hours to obtain a reactant. Then, 30 g of activated alumina was added to the obtained reactant and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a block copolymer (3).

[0268] The molecular weight of the obtained block copolymer (3) was measured by GPC, and the weight average molecular weight (Mw) was 10300, the number average molecular weight (Mn) was 7900, and (Mw / Mn) was 1.3. The content of the functional group represented by -Si[OSi(CH3)3]3 in the obtained block copolymer (3) was 49% by mass.

[0269] The coating composition was prepared in the same manner as in Example 1 except that the block copolymer (3) was used instead of the block copolymer (1), and a coating film was formed and evaluated.

[0270] Comparative Example 1

[0271] In a flask purged with nitrogen, 15.0 g of 3-methacryloxypropyl tris(trimethylsiloxy)silane, 35.0 g of polypropylene glycol monomethacrylate (average number of repetitions of propylene glycol is 4 to 6), and 79.0 g of methyl ethyl ketone as a solvent were added, and the temperature was raised to 50°C while stirring under a nitrogen stream. Next, 4.2 g of 2,2'-bipyridine and 1.5 g of cuprous chloride were added, and the flask was kept at 50°C while stirring for 30 minutes. After that, 2.6 g of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 50°C for 8 hours under a nitrogen stream to obtain a reactant. Then, 30 g of activated alumina was added to the obtained reactant and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a random copolymer (1').

[0272] The molecular weight of the random copolymer (1') obtained was measured by GPC, and the weight average molecular weight (Mw) was 5100, the number average molecular weight (Mn) was 5900, and (Mw / Mn) was 1.2. In addition, the content of the functional group represented by -Si[OSi(CH3)3]3 in the random copolymer (1') obtained was 22% by mass.

[0273] The coating composition was prepared in the same manner as in Example 1 except that the random copolymer (1′) was used instead of the block copolymer (1), and a coating film was formed and evaluated.

[0274] Comparative Example 2

[0275] In a flask purged with nitrogen, 137.8 g of butyl acetate as a solvent was placed, and the temperature was raised to 100° C. under a nitrogen stream while stirring. Then, a monomer polymerization initiator solution of 31.0 g of 3-methacryloxypropyl tris(trimethylsiloxy)silane, 72.3 g of polypropylene glycol monomethacrylate (average number of repeats of propylene glycol is 4 to 6), and 7.8 g of tert-butyl peroxy-2-ethylhexanoate as a polymerization initiator dissolved in 103.3 g of butyl acetate was set in a dropping device, and the mixture was dropped over 2 hours while the temperature in the flask was kept at 100° C. After the dropwise addition, the mixture was reacted at 100° C. for 5 hours under a nitrogen stream to obtain a random copolymer (2′).

[0276] The molecular weight of the random copolymer (2') obtained was measured by GPC, and the weight average molecular weight (Mw) was 4400, the number average molecular weight (Mn) was 1700, and (Mw / Mn) was 2.7. In addition, the content of the functional group represented by -Si[OSi(CH3)3]3 in the random copolymer (2') obtained was 22% by mass.

[0277] The coating composition was prepared in the same manner as in Example 1 except that the random copolymer (2′) was used instead of the block copolymer (1), and the coating film was formed and evaluated.

[0278] Comparative Example 3

[0279] In a flask purged with nitrogen, 137.3 g of butyl acetate as a solvent was placed, and the temperature was raised to 100° C. under a nitrogen stream while stirring. Next, a monomer polymerization initiator solution of 67.0 g of 3-methacryloxypropyl tris(trimethylsiloxy)silane, 33.0 g of polypropylene glycol monomethacrylate (average number of repeats of propylene glycol is 4 to 6), and 6.0 g of tert-butyl peroxy-2-ethylhexanoate as a polymerization initiator dissolved in 100.0 g of butyl acetate was set in a dropping device, and the mixture was dropped over 3 hours while the temperature in the flask was kept at 100° C. After the dropwise addition, the mixture was reacted at 100° C. for 5 hours under a nitrogen stream to obtain a random copolymer (3′).

[0280] The content of the functional group represented by -Si[OSi(CH3)3]3 in the obtained random copolymer (3') was 49 mass %.

[0281] The molecular weight of the random copolymer (3') obtained was measured by GPC, and the weight average molecular weight (Mw) was 6100, the number average molecular weight (Mn) was 2600, and (Mw / Mn) was 2.3. In addition, the content of the functional group represented by -Si[OSi(CH3)3]3 in the random copolymer (3') obtained was 49 mass %.

[0282] The coating composition was prepared in the same manner as in Example 1 except that the random copolymer (3′) was used instead of the block copolymer (1), and the coating film was formed and evaluated.

[0283] [Table 1]

[0284]

[0285] The coating layer of the laminated bodies prepared in Examples 1 and 2 was also evaluated for its developability. Specifically, the prepared laminated bodies were immersed in a 5% aqueous solution of an inorganic alkaline resist developer (SEMICLEAN DL-A10, manufactured by Yokohama Oil & Fats Industries, Ltd.) for 120 seconds, then rinsed with pure water for 120 seconds, and dried. No coating layer remained in the laminated bodies of Examples 1 and 2 after immersion in the developer, indicating that the polymer of the present invention can be used as a leveling agent suitable for the resist composition.

Claims

1. A leveling agent, which is a polymer, the polymer comprising: a polymer block (A1) and a polymer block (A2) of a polymerizable monomer (a1), wherein the polymerizable monomer (a1) has -Si[OSi(R)3] n [R'] 3-n The functional group shown is: n is an integer of 1 to 3, R is independently an alkyl group having 1 to 3 carbon atoms, and R' is independently an alkyl group having 1 to 3 carbon atoms. The polymer block (A2) is a polymer block of a polymerizable monomer (a2-2) having a group containing a polyoxyalkylene chain; or a polymerizable monomer (a2-2) having a group containing a polyoxyalkylene chain and one or more selected from a polymerizable monomer (a2-1) having an alkyl group having 1 to 18 carbon atoms and a polymerizable monomer (a2-3) having an aromatic group having 6 to 18 carbon atoms, The content of the polymer block (A1) is 15% by mass or more and 95% by mass or less relative to the total amount of the polymer, and the total content of the polymer block (A1) and the polymer block (A2) is 80% by mass or more.

2. The leveling agent according to claim 1, wherein The polymerizable monomer (a1) is a compound represented by the following formula (a1-1), In the formula (a1-1), R is each independently an alkyl group having 1 to 3 carbon atoms, R 1 is a hydrogen atom or a methyl group, L 1 It is a divalent organic group or a single bond.

3. The leveling agent according to claim 1, wherein -Si[OSi(R)3] n [R'] 3-n The functional group shown is -Si[OSi(CH3)3]3.

4. The leveling agent according to claim 1 or 2, wherein The polymerizable monomer (a2-1) is a compound represented by the following formula (a2-1), and the polymerizable monomer (a2-2) is a compound represented by the following formula (a2-2), In the formulas (a2-1) and (a2-2), R 2 is a hydrogen atom or a methyl group, R 3 is an alkyl group having 1 to 18 carbon atoms, R 4 is a hydrogen atom or a methyl group, R 5 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, n is an integer of 1-4, and m is an integer of 1-100. The leveling agent according to claim 1 or 2, which does not contain fluorine atoms.

6. The leveling agent according to claim 1 or 2, wherein The mass ratio of the polymer block (A1) to the polymer block (A2) is in the range of polymer block (A1): polymer block (A2) = 20:80 to 90:

10.

7. The leveling agent according to claim 1 or 2, wherein the number average molecular weight is in the range of 1,000 to 500,000.

8. A coating composition comprising a leveling agent, wherein the leveling agent is a polymer comprising a polymer block (A1) of a polymerizable monomer (a1) and a polymer block (A2), wherein the polymerizable monomer (a1) has -Si[OSi(R)3] n [R'] 3-n The functional group shown is: n is an integer of 1 to 3, R is independently an alkyl group having 1 to 3 carbon atoms, and R' is independently an alkyl group having 1 to 3 carbon atoms. The polymer block (A2) is a polymer block of a polymerizable monomer (a2-2) having a group containing a polyoxyalkylene chain; or a polymerizable monomer (a2-2) having a group containing a polyoxyalkylene chain and one or more selected from a polymerizable monomer (a2-1) having an alkyl group having 1 to 18 carbon atoms and a polymerizable monomer (a2-3) having an aromatic group having 6 to 18 carbon atoms, The content of the polymer block (A1) is 15% by mass or more and 95% by mass or less relative to the total amount of the polymer, and the total content of the polymer block (A1) and the polymer block (A2) is 80% by mass or more, The polymer is contained in an amount of 0.0001 to 10 parts by mass based on 100 parts by mass of the solid content of the coating composition.

9. An anti-corrosion composition comprising a polymer and an alkali-soluble resin, wherein the polymer comprises a polymer block (A1) and a polymer block (A2) of a polymerizable monomer (a1), wherein the polymerizable monomer (a1) has -Si[OSi(R)3] n [R'] 3-n The functional group shown is: n is an integer of 1 to 3, R is independently an alkyl group having 1 to 3 carbon atoms, and R' is independently an alkyl group having 1 to 3 carbon atoms. The polymer block (A2) is a polymer block of a polymerizable monomer (a2-2) having a group containing a polyoxyalkylene chain; or a polymerizable monomer (a2-2) having a group containing a polyoxyalkylene chain and one or more selected from a polymerizable monomer (a2-1) having an alkyl group having 1 to 18 carbon atoms and a polymerizable monomer (a2-3) having an aromatic group having 6 to 18 carbon atoms, The content of the polymer block (A1) is 15% by mass or more and 95% by mass or less relative to the total amount of the polymer, and the total content of the polymer block (A1) and the polymer block (A2) is 80% by mass or more. 10 . An article comprising the leveling agent according to claim 1 .

11. A method for producing a leveling agent according to any one of claims 1 to 7, wherein the leveling agent is a block copolymer, and the block copolymer is obtained by living polymerization of a compound represented by the following formula (a1-1) and a compound represented by the following formula (a2-2) as reaction raw materials, or by living polymerization of a compound represented by the following formula (a1-1), a compound represented by the following formula (a2-2) and a compound represented by the following formula (a2-1) as reaction raw materials, In the formulas (a1-1), (a2-1) and (a2-2), R is independently an alkyl group having 1 to 3 carbon atoms, 1 is a hydrogen atom or a methyl group, L 1 is a divalent organic group or a single bond, R 2 is a hydrogen atom or a methyl group, R 3 is an alkyl group having 1 to 18 carbon atoms, R 4 is a hydrogen atom or a methyl group, R 5 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, n is an integer of 1 to 4, and m is an integer of 1 to 100.

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