Copolymer and coating composition or resist composition containing copolymer

Abstract

Provided is a copolymer which can function as a leveling agent giving high smoothness to a coating film even with a small amount added.　The copolymer contains a polymerizable monomer (a1) having a functional group represented by -Si[OSi(R)3]n[R']3-n (n is an integer of 1-3. Each R independently represents a C1-3 alkyl group. Each R' independently represents a C1-3 alkyl group.) and an acryloyl group, and a polymerizable monomer (a2) having at least one selected from a C1-18 alkyl group, a C6-18 aromatic group, a group containing a polyoxyalkylene chain, and a group containing a polyester chain, as polymerization components.

Description

Copolymer and coating composition or resist composition containing said copolymer

[0001] The present invention relates to a copolymer and a coating or resist composition containing the copolymer.

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

[0003] Leveling agents are used in, for example, automotive paints, and coating compositions containing a leveling agent can impart high smoothness to the resulting coating film surface and can impart gloss to the automotive exterior. Silicone-based leveling agents have been proposed as leveling agents for use in automotive paints (Patent Document 1).

[0004] The uses of leveling agents are diverse and are not limited to the above-mentioned coating material application. In applications other than coating materials, leveling agents are also added to resist compositions, and leveling agents for such resists have also been proposed (Patent Document 2).

[0005] Japanese Patent Application Laid-Open No. 2003-226834 International Publication No. 2021 / 131726

[0006] In resist applications requiring nanometer-order miniaturization, there is a need to minimize additives contained in resists that can adversely affect miniaturization processing, and leveling agents that can achieve leveling effects even at low addition amounts are needed. Patent Documents 1 and 2 disclose silicone-based leveling agents that use silicone (meth)acrylate as the silicone monomer, but the leveling agents actually evaluated in the examples are those using silicone methacrylate. Because the main chain consisting of the methacrylate skeleton is rigid, the leveling effect obtained is insufficient, and a certain amount of addition is required to achieve the desired leveling effect (Patent Documents 1 and 2).

[0007] The problem to be solved by the present invention is to provide a copolymer that can function as a leveling agent that imparts high smoothness to a coating film even when added in a small amount. Another problem to be solved by the present invention is to provide a coating composition that can form a coating film that exhibits high smoothness even when the leveling agent content is small. Another problem to be solved by the present invention is to provide a coating film that exhibits high smoothness even when the leveling agent content is small.

[0008] As a result of extensive research to solve the above problems, the present inventors have found that -Si[OSi(R) ３ ] ｎ [R'] ３－ｎ The inventors have found that a copolymer containing, as polymerization components, a polymerizable monomer (a1) having a functional group represented by the following formula (n is an integer ranging from 1 to 3; each R is independently an alkyl group having 1 to 3 carbon atoms; and each R' is independently an alkyl group having 1 to 3 carbon atoms) and an acryloyl group, and 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, a group containing a polyoxyalkylene chain, and a group containing a polyester chain, exhibits high leveling properties that can withstand resist applications even when added in a small amount, and have completed the present invention.

[0009] That is, the present invention relates to the following copolymers, etc.

[0010] The present invention provides a copolymer that can function as a leveling agent that imparts high smoothness to a coating film even when added in a small amount.The present invention provides a coating composition that can form a cured product that exhibits high smoothness even when the leveling agent content is small.The present invention provides a cured product that exhibits high smoothness even when the leveling agent content is small.

[0011] An embodiment of the present invention will be described below. The present invention is not limited to the following embodiment, and can be carried out by making appropriate modifications within the scope that does not impair the effects of the present invention. In this specification, "(meth)acrylate" means either or both of acrylate and methacrylate.

[0012] [Copolymer] The copolymer of the present invention is a copolymer of —Si[OSi(R) ３ ] ｎ [R'] ３－ｎ (n is an integer ranging from 1 to 3. Each R is independently an alkyl group having 1 to 3 carbon atoms. Each R' is independently an alkyl group having 1 to 3 carbon atoms) and an acryloyl group, and a polymerizable monomer (a2) having one or more groups selected from an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, a group containing a polyoxyalkylene chain, and a group containing a polyester chain, as polymerization components. Here, "polymerization components" means components that constitute the copolymer of the present invention, and does not include components that do not constitute the copolymer of the present invention, such as solvents and polymerization initiators.

[0013] In the present invention, the term "polymerizable monomer" refers to a compound having a polymerizable unsaturated group, and the polymerizable monomer (a1) has an acryloyl group as the polymerizable unsaturated group. In the copolymer of the present invention, the polymerizable unsaturated group of the polymerizable monomer (a1) exhibiting surface uneven distribution ability is an acryloyl group, so that the portion of the main chain structure of the copolymer exhibiting surface uneven distribution ability becomes a flexible acryloyl skeleton, thereby enhancing the surface uneven distribution ability of the copolymer. The acryloyl group, which is the polymerizable unsaturated group of the polymerizable monomer (a1), is preferably an acryloyloxy group (acrylate group (CH ２ ═CH—C(═O)—O— group).

[0014] The number of polymerizable unsaturated groups that the polymerizable monomer has may be one or two or more.

[0015] The polymerizable monomer (a1) and the polymerizable monomer (a2) constituting the copolymer of the present invention will be described below.

[0016] In the polymerizable monomer (a1), —Si[OSi(R) ３ ] ｎ [R'] ３－ｎ The functional group represented by is preferably —Si[OSi(R) ３ ] ３ is a functional group represented by the formula:３ ) ３ ] ３ It is. -Si[OSi(R) ３ ] ｎ [R'] ３－ｎ The functional group represented by -Si[OSi(CH ３ ) ３ ] ３ When the above formula (1) is satisfied, the copolymer of the present invention can have a higher surface localization ability.

[0017] The polymerizable monomer (a1) is preferably a compound represented by the following formula (a1-1): (In the formula (a1-1), each R is independently an alkyl group having 1 to 3 carbon atoms. L １ is a divalent organic group or a single bond.

[0018] L １ The "single bond" in the formula (I) means that O and Si are directly bonded to each other. 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.

[0019] L １ Examples of the alkylene group having 1 to 50 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, an n-decylene group, an n-dodecylene group, an isopropylene group, a 2-methylpropylene group, a 2-methylhexylene group, and a tetramethylethylene group.

[0020] L １ The alkylene group having 1 to 50 carbon atoms is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group, an ethylene group, an n-propylene group, or an isopropylene group.

[0021] L １ The alkyleneoxy group having 1 to 50 carbon atoms may be, for example, one or more —CH ２ - is a group in which - is substituted with -O-. １The alkyleneoxy group having 1 to 50 carbon atoms is preferably an alkyleneoxy group having 1 to 15 carbon atoms, more preferably an alkyleneoxy group having 1 to 8 carbon atoms, and even more preferably a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, an oxytrimethylene group, a butyleneoxy group, an oxytetramethylene group, a pentyleneoxy group, a heptyleneoxy group, or an octyleneoxy group.

[0022] 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, these divalent organic groups are -CH ２ A part of the - may be replaced by a carbonyl group (-C(=O)-), a phenylene group, an amide bond or a urethane bond.

[0023] 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 carbon atom of these groups may further be substituted with a substituent such as a hydroxyl group.

[0024] The compound represented by formula (a1-1) -Si[OSi(R) ３ ] ３ The functional group represented by -Si[OSi(CH ３ ) ３ ] ３ The compound is preferably represented by the following formula (a1-2):

[0025] (In the above formula (a1-2), L １ is a divalent organic group or a single bond.

[0026] The polymerizable monomer (a1) can be produced by a known method, or a commercially available product such as 3-acryloyloxypropyltris(trimethylsiloxy)silane can be used.

[0027] In the copolymer of the present invention, the lower limit of the content of the polymerizable monomer (a1) is, for example, 5% by mass or more, preferably 10% by mass or more, 15% by mass or more, 20% by mass or more, 30% by mass or more, 50% by mass or more, 60% by mass or more, and 65% by mass or more, in that order. The upper limit of the content of the polymerizable monomer (a1) is not particularly limited, but is, for example, 95% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 75% by mass or less, relative to the total amount of the copolymer. The combination of the upper and lower limits of the content of the polymerizable monomer (a1) can be, for example, a range of 20% to 90% by mass of the total amount of the polymerizable components of the copolymer. The content of the polymerizable monomer (a1) can be adjusted by the raw material charge ratio of the polymerizable monomer (a1) when producing the copolymer of the present invention.

[0028] In the copolymer of the present invention, —Si[OSi(R) ３ ] ｎ [R'] ３－ｎ The content of the functional group represented by -Si[OSi(R) is, for example, in the range of 5 to 95 mass % of the total amount of the copolymer, preferably in the range of 10 to 90 mass %, more preferably in the range of 20 to 80 mass %, even more preferably in the range of 30 to 70 mass %, and particularly preferably in the range of 35 to 65 mass %. ３ ] ｎ [R'] ３－ｎ The content of the functional group represented by the formula (I) can be adjusted by the raw material charge ratio of the polymerizable monomer (a1) when producing the copolymer of the present invention.

[0029] The polymerizable monomer (a2) is a polymerizable monomer having one or more selected from an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, a group containing a polyoxyalkylene chain, and a group containing a polyester chain.

[0030] Examples of the polymerizable unsaturated group contained in the polymerizable monomer (a2) include C═C-containing groups such as a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acryloylamino group, a vinyl ether group, an allyl group, a styryl group, and a maleimide group. Among these, a (meth)acryloyl group or a (meth)acryloyloxy group is preferred, an acryloyl group is more preferred, and an acryloyloxy group (acrylate group (CH ２ ═CH—C(═O)—O— group).

[0031] When the polymerizable unsaturated group in the polymerizable monomer (a2) is an acryloyl group, both the portion of the main chain structure of the copolymer of the present invention that exhibits surface uneven distribution (the structure derived from the polymerizable monomer (a1)) and the portion that exhibits compatibility (the structure derived from the polymerizable monomer (a2)) have a flexible acryloyl skeleton, which can suppress "pin unevenness" in the cured film obtained from the coating composition described below. Regarding "pin unevenness," the coating composition is generally dried in a reduced-pressure drying apparatus after film formation to evaporate the solvent in the coating film, and the coating film on the substrate is dried while supported by support pins in the drying apparatus chamber. During this process, a temperature difference occurs between the portion where the support pins contact the substrate and the other portion, and the drying unevenness in the coating film due to the difference in drying speed is called "pin unevenness."

[0032] The alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (a2) may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, a hexadecyl group, etc. The alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (a2) is preferably an alkyl group having 1 to 6 carbon atoms.

[0033] Examples of the aromatic group having 6 to 18 carbon atoms contained in the polymerizable monomer (a2) include a phenyl group, a naphthyl group, an anthracen-1-yl group, and a phenanthrene-1-yl group.

[0034] The group containing a (poly)oxyalkylene chain contained in the polymerizable monomer (a2) is a monovalent group containing a repeating oxyalkylene moiety or a divalent linking group containing a repeating oxyalkylene moiety.

[0035] The group containing a polyester chain contained in the polymerizable monomer (a2) is a monovalent group containing a repeating ester bond moiety or a divalent linking group containing a repeating ester bond moiety.

[0036] The alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (a2) may further have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, etc. The aromatic group having 6 to 18 carbon atoms contained in the polymerizable monomer (a2) may further have a substituent, and examples of the substituent include a hydroxyl group, an alkyl group, etc.

[0037] The polymerizable monomer (a2) may be at least one selected from, for example, a polymerizable monomer having an alkyl group having 1 to 18 carbon atoms, a polymerizable monomer having an aromatic group having 6 to 18 carbon atoms, a polymerizable monomer having a group containing a polyoxyalkylene chain, and a polymerizable monomer having a group containing a polyester chain, and it is preferable that the polymerizable monomer (a2) essentially contains a polymerizable monomer having a group containing a polyoxyalkylene chain.

[0038] Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloyl group include methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate, s-butyl(meth)acrylate, isobutyl(meth)acrylate, t-butyl(meth)acrylate, n-pentyl(meth)acrylate, n-hexyl(meth)acrylate, n-heptyl(meth)acrylate, n-octyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, decyl(meth)acrylate, and methyl(meth)acrylate. (meth)acrylic acid alkyl esters having 1 to 18 carbon atoms, such as dicyclopentanyloxylethyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate; and (meth)acrylic acid bridged cyclic alkyl esters having 1 to 18 carbon atoms, such as dicyclopentanyloxylethyl (meth)acrylate, isobornyloxylethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyl (meth)acrylate.

[0039] Examples of the polymerizable monomer (a2) having a hydroxyalkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxy(meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, and 2,3-dihydroxypropyl (meth)acrylate.

[0040] Examples of the polymerizable monomer (a2) having a phenylalkyl group having 7 to 18 carbon atoms or a phenoxyalkyl group having 7 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloyl group include benzyl (meth)acrylate, 2-phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate.

[0041] Examples of the polymerizable monomer (a2) having a group containing a polyoxyalkylene chain and in which the polymerizable unsaturated group is a (meth)acryloyl group include polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polytrimethylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, poly(ethylene glycol.propylene glycol) mono(meth)acrylate, polyethylene glycol.polypropylene glycol mono(meth)acrylate, poly(ethylene glycol.tetramethylene glycol) mono(meth)acrylate, polyethylene glycol.polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol.tetramethylene glycol) mono(meth)acrylate, polypropylene glycol.polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol.1,2-butylene glycol) mono(meth)acrylate, polypropylene glycol.poly1,2-butylene glycol mono(meth)acrylate, Poly(ethylene glycol·1,2-butylene glycol) mono(meth)acrylate, polyethylene glycol·poly 1,2-butylene glycol mono(meth)acrylate, poly(tetraethylene glycol·1,2-butylene glycol) mono(meth)acrylate, polytetraethylene 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, poly(1,2-butylene glycol / trimethylene glycol) mono(meth)acrylate, poly 1,Examples include 2-butylene glycol-polytrimethylene glycol mono(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, poly(1,2-butylene glycol-tetramethylene glycol) mono(meth)acrylate, and poly(1,2-butylene glycol-polytetramethylene glycol mono(meth)acrylate). The above "poly(ethylene glycol-propylene glycol)" refers to a random copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol-polypropylene glycol" refers to a block copolymer of ethylene glycol and propylene glycol.

[0042] Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a vinyl ether group include alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether, cycloalkyl vinyl ethers, and 2-hydroxyethyl vinyl ethers. ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 1-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 1-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 3-hydroxy-2-methylpropyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, and cyclohexane-1,4-dimethanol monovinyl ether.

[0043] Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is an allyl group include 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether.

[0044] 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.

[0045] Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloylamino group include N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, diacetoneacrylamide, and acroylmorpholine.

[0046] Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a maleimide group include methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide.

[0047] The polymerizable monomer (a2) is preferably at least one selected from the group consisting of compounds represented by the following formula (a2-1), compounds represented by the following formula (a2-2), compounds represented by the following formula (a2-3), compounds represented by the following formula (a2-4), and compounds represented by the following formula (a2-5), and more preferably at least one selected from the group consisting of compounds represented by the following formula (a2-1), compounds represented by the following formula (a2-2), compounds represented by the following formula (a2-3), and compounds represented by the following formula (a2-4). These compounds can exhibit high compatibility when the copolymer of the present invention is used as a leveling agent.

[0048] (In the above formulas (a2-1), (a2-2), (a2-3), (a2-4) and (a2-5), R ２１ is a hydrogen atom or a methyl group, R ２２is an alkyl group having 1 to 18 carbon atoms; R ２３ is a hydrogen atom or a methyl group, R ２４ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms; R ２５ is a hydrogen atom or a methyl group, R ２６ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms and an ether bond, and R ２７ is a hydrogen atom or a methyl group, R ２８ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms and an ether bond; L ２ is a divalent organic group or a single bond, R ２９ is a hydrogen atom or a methyl group, R ３０ are each independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, n is an integer ranging from 1 to 4, m is the number of repetitions, p is an integer ranging from 1 to 10, q is the number of repetitions, and l is an integer ranging from 0 to 5.

[0049] In the formula (a2-2), the m n's in the parentheses may be the same or different from each other. In the formula (a2-3), the q p's in the parentheses may be the same or different from each other. In the formula (a2-4), the q p's in the parentheses may be the same or different from each other.

[0050] R ２２ , R ２４ , R ２６ and R ２８ The alkyl group having 1 to 18 carbon atoms may further have a substituent, and examples of the substituent include a hydroxyl group and an aryl group. ２６ and R ２８ The alkyl group having 1 to 18 carbon atoms and an ether bond may further have a substituent, and examples of the substituent include a hydroxyl group and an aryl group. ３０ The alkyl group having 1 to 6 carbon atoms may further have a substituent, and examples of the substituent include a hydroxyl group and an aryl group. ３０The alkoxy group having 1 to 6 carbon atoms may further have a substituent, and examples of the substituent include a hydroxyl group and an aryl group.

[0051] L in the formulas (a2-3) and (a2-4) ２ The divalent organic group is L １ The divalent organic groups are the same as those mentioned above.

[0052] In all of the compounds represented by the formulas (a2-1), (a2-2), (a2-3), (a2-4) and (a2-5), the polymerizable unsaturated group is preferably an acryloyl group. ２１ , R ２３ , R ２５ , R ２７ and R ２９ are preferably hydrogen atoms.

[0053] In the general formula (a2-2), m represents the number of repetitions, and may be, for example, an integer of 1 or greater. The number average of m is, for example, in the range of 1 to 200, preferably in the range of 1 to 150, and more preferably in the range of 1 to 100. The number average of m can be confirmed by measuring the number average molecular weight of the polymerizable monomer (a2) by the method described in the Examples.

[0054] In the general formulae (a2-3) and (a2-4), q represents the number of repetitions, and may be, for example, an integer of 1 or greater. The number average of q is, for example, in the range of 1 to 100, preferably in the range of 1 to 80, and more preferably in the range of 1 to 50. The number average of q can be confirmed by measuring the number average molecular weight of the polymerizable monomer (a2) by the method described in the Examples.

[0055] The polymerizable monomer (a2) preferably contains one or more selected from the group consisting of the compound represented by the formula (a2-2), the compound represented by the formula (a2-3), and the compound represented by the formula (a2-4). When the polymerizable monomer (a2) contains one or more selected from the group consisting of the compound represented by the formula (a2-2), the compound represented by the formula (a2-3), and the compound represented by the formula (a2-4), it is preferable that the total amount of the compound represented by the formula (a2-2), the compound represented by the formula (a2-3), and the compound represented by the formula (a2-4) is 50 mass% or more relative to the total amount of the polymerizable monomer (a2).

[0056] The polymerizable monomer (a2) can be produced by a known method. Alternatively, a commercially available product may 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., and "BLEMMER PE-90", "BLEMMER PE-200", "BLEMMER PE-350", and "BLEMMER PME-100" manufactured by NOF Corporation. Examples of such polymers include "Blenmer PME-200," "Blenmer PME-400," "Blenmer PME-4000," "Blenmer PP-1000," "Blenmer PP-500," "Blenmer PP-800," "Blenmer 70PEP-350B," "Blenmer 55PET-800," "Blenmer 50POEP-800B," "Blenmer 10PPB-500B," "Blenmer NKH-5050," "Blenmer AP-400," "Blenmer AE-350," the Plaxel F series manufactured by Daicel Corporation, and the Viscoat series manufactured by Osaka Organic Chemical Industry Ltd.

[0057] The polymerization form of the copolymer of the present invention is not particularly limited, and may be a random polymer structure of the polymerizable monomer (a1) and the polymerizable monomer (a2), or a block polymer structure of the polymerizable monomer (a1) and the polymerizable monomer (a2).

[0058] The copolymer of the present invention is preferably a block copolymer containing a polymer block (A1) of a polymerizable monomer (a1) and a polymer block (A2) of a polymerizable monomer (a2). The polymer block (A1) is a segment in which two or more polymerizable monomers (a1) are polymerized, and the polymer block (A2) is a segment in which two or more polymerizable monomers (a2) are polymerized.

[0059] When the copolymer of the present invention is a block copolymer containing polymer block (A1) and polymer block (A2), recoatability can be improved. In a multilayer resist process, multiple resist layers are formed by coating resist compositions one on top of another. When the resist layer contains a leveling agent, the surface tension-reducing ability of the leveling agent reduces the wettability of the resist layer, which can make it difficult to further stack layers on the resist layer. This ease of stacking on the resist layer is referred to as "recoatability." When the copolymer of the present invention is a block copolymer containing polymer block (A1) and polymer block (A2), the recoatability can be improved.

[0060] When the copolymer of the present invention is a block copolymer containing a polymer block (A1) of a polymerizable monomer (a1) and a polymer block (A2) of a polymerizable monomer (a2), the polymerizable monomer constituting the polymer block (A1) may be the polymerizable monomer (a1), and the polymer block (A1) may be composed of two or more polymerizable monomers (a1) having different structures. In this case, the polymerization form of the polymer block (A1) is not particularly limited, and the polymer block (A1) may 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. The polymerizable monomer constituting the polymer block (A1) is preferably a single polymerizable monomer (a1).

[0061] When the copolymer of the present invention is a block copolymer containing a polymer block (A1) of a polymerizable monomer (a1) and a polymer block (A2) of a polymerizable monomer (a2), the polymerizable monomer constituting the polymer block (A2) may be the polymerizable monomer (a2), and the polymer block (A2) may be composed of two or more polymerizable monomers (a2) having different structures. In this case, the polymerization form of the polymer block (A2) is not particularly limited, and the polymer block (A2) may 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. The polymerizable monomer constituting the polymer block (A2) is preferably a single polymerizable monomer (a2).

[0062] When the copolymer of the present invention is a block copolymer containing a polymer block (A1) of a polymerizable monomer (a1) and a polymer block (A2) of a polymerizable monomer (a2), the block copolymer of the present invention is sufficient to contain at least one polymer block (A1) and at least one polymer block (A2), and the number and bonding order of the polymer blocks are not particularly limited. The block copolymer of the present invention is preferably a diblock copolymer in which one polymer block (A1) and one polymer block (A2) are bonded.

[0063] The mass ratio of the polymerizable monomer (a1) to the polymerizable monomer (a2) in the polymerization components of the 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, more preferably polymerizable monomer (a1):polymerizable monomer (a2)=30:70 to 80:20, and even more preferably polymerizable monomer (a1):polymerizable monomer (a2)=50:50 to 80:20.

[0064] The copolymer of the present invention may be any copolymer containing polymerizable monomer (a1) and polymerizable monomer (a2) as polymerization components, and may contain other polymerizable monomers as polymerization components other than polymerizable monomer (a1) and polymerizable monomer (a2) as long as the effects of the present invention are not impaired. The copolymer of the present invention is preferably a copolymer essentially consisting of polymerizable monomer (a1) and polymerizable monomer (a2), more preferably a copolymer consisting only of polymerizable monomer (a1) and polymerizable monomer (a2). Here, "essentially consisting of" refers to a case where the total content of polymerizable monomer (a1) and polymerizable monomer (a2) in the polymerization components of the copolymer of the present invention is 80% by mass or more, 90% by mass or more, 95% by mass or more, or 99% by mass or more.

[0065] In the copolymer of the present invention, it is preferable that 50% by mass or more of the polymerization components other than the polymerizable monomer (a1) are monomers having an acryloyl group as a polymerizable unsaturated group, and the higher the proportion of the polymerization components other than the polymerizable monomer (a1) is, the more preferable it is, for example, 70% by mass, 80% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass.

[0066] The copolymer of the present invention preferably does not contain fluorine atoms. For example, when the copolymer of the present invention is composed of the polymerizable monomer (a1) and the polymerizable monomer (a2), the copolymer of the present invention can be a copolymer not containing fluorine atoms.

[0067] The number average molecular weight (Mn) of the copolymer of the present invention is preferably in the range of 1,000 to 500,000, more preferably in the range of 2,000 to 100,000, and even more preferably in the range of 2,000 to 40,000. The weight average molecular weight (Mw) of the copolymer of the present invention is, for example, in the range of 1,000 to 500,000, preferably in the range of 2,000 to 100,000, more preferably in the range of 2,000 to 40,000, and even more preferably in the range of 12,000 to 40,000. The dispersity (Mw / Mn) of the copolymer 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.

[0068] In the present invention, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured by gel permeation chromatography (GPC) and converted into polystyrene equivalents. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the copolymer of the present invention are measured by the method described in the Examples.

[0069] [Method for Producing Copolymer] The method for producing the copolymer of the present invention is not particularly limited, and the copolymer can be produced by a known method. The copolymer of the present invention can be produced by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, or the like, based on a polymerization mechanism such as a radical polymerization method, a cationic polymerization method, or an anionic polymerization method. For example, in the case of a radical polymerization method, the copolymer of the present invention can be produced by charging a polymerizable monomer mixture into an organic solvent and adding a general-purpose radical polymerization initiator.

[0070] As the polymerization initiator, various types can be used, for example, peroxides such as t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, and diacyl peroxide, azo compounds such as azobisisobutyronitrile, dimethyl azobisisobutyrate, and phenylazotriphenylmethane, Mn(acac) ３ If necessary, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, ethyl thioglycolic acid, or octyl thioglycolic acid, or a thiol compound having a coupling group such as γ-mercaptopropyltrimethoxysilane may be used as an additive such as a chain transfer agent.

[0071] Examples of the organic solvent include alcohols such as ethanol, isopropyl alcohol, n-butanol, iso-butanol, and tert-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and butyl lactate; monocarboxylic acid esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, and butyl 2-methoxypropionate; dimethylformamide, dimethyl sulfoxide, N-methyl Examples of the solvent include polar solvents such as pyrrolidone, ethers such as methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, and ethyl cellosolve acetate, propylene glycols and esters thereof such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate, halogenated solvents such as 1,1,1-trichloroethane and chloroform, ethers such as tetrahydrofuran and dioxane, aromatic solvents such as benzene, toluene, and xylene, and fluorinated inert liquids such as perfluorooctane and perfluorotri-n-butylamine. These solvents can be used alone or in combination of two or more.

[0072] The copolymer of the present invention is preferably produced by subjecting polymerization components containing the polymerizable monomer (a1) and the polymerizable monomer (a2) to living polymerization such as living radical polymerization or living anionic polymerization.

[0073] In living radical polymerization, a dormant species, whose active polymerization terminal is protected by an atom or atomic group, reversibly generates radicals and reacts with a monomer, thereby causing a propagation reaction. Even when a first monomer is consumed, the propagating terminal does not lose its activity and reacts with a second monomer that is successively added to produce a block polymer. Examples of such living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-fragmentation radical polymerization (RAFT), nitroxide-mediated radical polymerization (NMP), and organotellurium radical polymerization (TERP). While there are no particular restrictions on which of these methods is used, ATRP is preferred due to its ease of control. ATRP uses an organic halide or a sulfonyl halide compound as a polymerization initiator and a metal complex composed of a transition metal compound and a ligand as a catalyst.

[0074] Specific examples of polymerization initiators that can be used in ATRP include 1-phenylethyl chloride, 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, α,α'-dichloroxylene, α,α'-dibromoxylene, hexakis(α-bromomethyl)benzene, and C1-6 alkyl esters of C2-halogenated carboxylic acids (e.g., 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, etc.). More specific examples of C1-6 alkyl esters of C2-halogenated carboxylic acids include, for example, methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate, and ethyl 2-bromoisobutyrate.

[0075] The transition metal compounds that can be used in ATRP are M ｎ＋ X ｎ It is expressed as follows: M ｎ＋ X ｎ The transition metal M of the transition metal compound represented by ｎ＋ As the ＋ , 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＋ M ｎ＋ X ｎ X in the transition metal compound represented by the formula (I) is a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, (SO ４ ) １／２ , (PO ４ ) １／３ , (HPO ４ ) １／２ , (H ２ P.O. ４ ), triflate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate), SeR １１ , C.N. and R. １２ COO, where R １１ represents an aryl group or a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), R １２ represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms (preferably a methyl group) which may be substituted 1 to 5 times with halogen (preferably 1 to 3 times with fluorine or chlorine). ｎ＋ X ｎ In the transition metal compound represented by the formula (I), n represents the formal charge on the metal and is an integer of 0 to 7.

[0076] Examples of the ligand compound capable of forming a coordinate bond to the transition metal of the transition metal compound include a compound having a ligand containing one or more nitrogen atoms, oxygen atoms, phosphorus atoms, or sulfur atoms that can be coordinated to the transition metal via a σ bond, a compound having a ligand containing two or more carbon atoms that can be coordinated to the transition metal via a π bond, and a compound having a ligand that can be coordinated to the transition metal via a μ bond or an η bond.

[0077] The transition metal complex is not particularly limited, but preferred examples include complexes of transition metals of Groups 7, 8, 9, 10, and 11, and more preferred examples include complexes of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel.

[0078] Specific examples of catalysts that can be used in ATRP include complexes with ligands such as 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, and polyamines such as tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexamethyltris(2-aminoethyl)amine when the central metal is copper. Examples of divalent ruthenium complexes include dichlorotris(triphenylphosphine)ruthenium, dichlorotris(tributylphosphine)ruthenium, dichloro(cyclooctadiene)ruthenium, dichlorobenzeneruthenium, dichloro-p-cymeneruthenium, dichloro(norbornadiene)ruthenium, cis-dichlorobis(2,2'-bipyridine)ruthenium, dichlorotris(1,10-phenanthroline)ruthenium, and carbonylchlorohydridotris(triphenylphosphine)ruthenium. Examples of divalent iron complexes include bistriphenylphosphine complexes and triazacyclononane complexes.

[0079] In living radical polymerization, it is preferable to use a solvent. Examples of solvents used in living radical polymerization include ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ether solvents such as diisopropyl ether, dimethoxyethane, and diethylene glycol dimethyl ether; halogenated solvents such as dichloromethane and dichloroethane; aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, and isopropanol; and aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide. The above solvents may be used alone or in combination of two or more.

[0080] The copolymer of the present invention can be produced, for example, by any of Methods 1 to 3 shown below. Method 1: A method in which polymerizable monomer (a1) and polymerizable monomer (a2) are subjected to living radical polymerization (preferably atom transfer radical polymerization) in the presence of a polymerization initiator, a transition metal compound, a ligand compound capable of forming a coordinate bond with the transition metal, and a solvent. Method 2: A method in which polymerizable monomer (a1) is subjected to living radical polymerization (preferably atom transfer radical polymerization) in the presence of a polymerization initiator, a transition metal compound, a ligand compound capable of forming a coordinate bond with the transition metal, and a solvent to obtain a polymer block (A1), and then polymerizable monomer (a2) is added to the reaction system to further subject polymerizable monomer (a2) to living radical polymerization (preferably atom transfer radical polymerization) to the polymer block (A1). Method 3: A method in which a polymerizable monomer (a2) is subjected to living radical polymerization (preferably atom transfer radical polymerization) in the presence of a polymerization initiator, a transition metal compound, a ligand compound capable of forming a coordinate bond with the transition metal, and a solvent to obtain a polymer block (A2), and then a polymerizable monomer (a1) is added to the reaction system, and the polymerizable monomer (a1) is further subjected to living radical polymerization (preferably atom transfer radical polymerization) to form the polymer block (A2).

[0081] The charge ratio (by mass) of the polymerizable monomer (a1) to the polymerizable monomer (a2) when producing the 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, more preferably polymerizable monomer (a1):polymerizable monomer (a2)=30:70 to 80:20, and even more preferably polymerizable monomer (a1):polymerizable monomer (a2)=50:50 to 80:20.

[0082] The polymerization temperature during the living radical polymerization is preferably in the range of room temperature to 120°C.

[0083] When the copolymer of the present invention is produced by living radical polymerization, metals resulting from the transition metal compound used in the polymerization may remain in the resulting copolymer. The metals remaining in the resulting copolymer may be removed using activated alumina or the like after the polymerization is completed.

[0084] [Coating composition] The copolymer of the present invention can be suitably used as a leveling agent for a coating composition, and the coating composition of the present invention contains the copolymer of the present invention. The copolymer of the present invention can be used as a fluorine atom-free leveling agent, which does not contain fluorine atoms, and is therefore a leveling agent with low environmental accumulation and low environmental load.

[0085] The content of the copolymer of the present invention in the coating composition of the present invention varies depending on the type of base resin, coating method, desired film thickness, etc., but is, for example, in the range of 0.0001 to 10 parts by mass, preferably 0.0001 to 5 parts by mass, more preferably 0.0001 to 1 part by mass, and even more preferably 0.0001 to 0.05 parts by mass, per 100 parts by mass of the solid content of the coating composition. The copolymer of the present invention can exert a leveling effect even in a small amount. Note that the "solid content of the coating composition" refers to the components other than water and solvent contained in the coating composition.

[0086] The application of the coating composition of the present invention is not particularly limited, and it can be used for any application that requires leveling property. For example, the coating composition of the present invention can be used as various paint compositions or photosensitive resin compositions.

[0087] When the coating composition of the present invention is used as a paint composition, examples of the paint composition include paints using natural resins such as petroleum resin paints, shellac paints, rosin-based paints, cellulose-based paints, rubber-based paints, lacquer paints, cashew resin paints, and oil-based vehicle paints, and paints using synthetic resins such as phenolic resin paints, alkyd resin paints, unsaturated polyester resin paints, amino resin paints, epoxy resin paints, vinyl resin paints, acrylic resin paints, polyurethane resin paints, silicone resin paints, and fluororesin paints. Adding the copolymer of the present invention to the above paint compositions can impart smoothness to the resulting coating film.

[0088] Various additives may be added to the coating composition as needed, such as colorants such as pigments, dyes, and carbon; inorganic powders such as silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, and calcium carbonate; organic fine powders such as higher fatty acids, polyacrylic resins, and polyethylene; and light resistance improvers, weather resistance improvers, heat resistance improvers, antioxidants, thickeners, and anti-settling agents.

[0089] The coating method for the coating composition of the present invention can be any known and commonly used coating method, and examples thereof include methods such as a slit coater, a slit and spin coater, a spin coater, a roll coater, electrostatic coating, a bar coater, a gravure coater, a die coater, a knife coater, inkjet coating, dipping coating, spray coating, shower coating, screen printing, gravure printing, offset printing, and reverse coating.

[0090] Photosensitive resin compositions exhibit physical properties such as solubility, viscosity, transparency, refractive index, conductivity, and ion permeability that change upon irradiation with light such as visible light or ultraviolet light. Among photosensitive resin compositions, resist compositions (e.g., photoresist compositions, color resist compositions for color filters) require high leveling properties. Resist compositions are typically applied by spin coating to a thickness of approximately 1 to 2 μm on silicon wafers or glass substrates vapor-deposited with various metals. If the coating film thickness fluctuates or coating unevenness occurs, the linearity and reproducibility of the pattern deteriorate, resulting in the failure to obtain a resist pattern with the desired precision. In addition to these problems, various leveling-related issues also exist, such as drop marks, overall unevenness, and a beading phenomenon in which the film thickness is thicker at the edges than at the center. The coating composition of the present invention can solve the above-mentioned problems when used as a resist composition because the copolymer of the present invention exhibits high leveling properties and can form a uniform coating film (cured product).

[0091] When the coating composition of the present invention is used as a photoresist composition, the photoresist composition contains an alkali-soluble resin, a radiation-sensitive substance (photosensitive substance), a solvent, and the like in addition to the copolymer of the present invention.

[0092] The alkali-soluble resin contained in the photoresist composition is a resin that is soluble in an alkaline solution, which is the developer used for patterning the resist. Examples of alkali-soluble resins include novolak resins obtained by condensing an aromatic hydroxy compound derivative such as phenol, cresol, xylenol, resorcinol, phloroglucinol, or hydroquinone with an aldehyde compound such as formaldehyde, acetaldehyde, or benzaldehyde; polymers or copolymers of vinylphenol compound derivatives such as o-vinylphenol, m-vinylphenol, p-vinylphenol, or α-methylvinylphenol; (meth)acrylic acid polymers or copolymers such as acrylic acid, methacrylic acid, or hydroxyethyl (meth)acrylate; polyvinyl alcohol; modified resins obtained by introducing radioactive ray-sensitive groups such as quinone diazide groups, naphthoquinone azide groups, aromatic azide groups, or aromatic cinnamoyl groups via some of the hydroxyl groups of these various resins; and urethane resins containing acidic groups such as carboxylic acid or sulfonic acid in the molecule. These alkali-soluble resins may be used alone or in combination of two or more.

[0093] When the coating composition of the present invention is used as a photoresist composition, the content of the copolymer of the present invention is, for example, 0.05 parts by mass or less, and preferably in the range of 0.0001 to 0.05 parts by mass, per 100 parts by mass of the alkali-soluble resin.

[0094] The radiation-sensitive substance contained in the photoresist composition is a substance that changes the solubility of an alkali-soluble resin in a developer by irradiation with energy rays such as ultraviolet rays, far ultraviolet rays, excimer laser light, X-rays, electron beams, ion beams, molecular beams, gamma rays, etc. Examples of radiation-sensitive substances include quinone diazide compounds, diazo compounds, azide compounds, onium salt compounds, halogenated organic compounds, mixtures of halogenated organic compounds and organometallic compounds, organic acid ester compounds, organic acid amide compounds, organic acid imide compounds, poly(olefin sulfone) compounds, etc.

[0095] Examples of the quinone diazide compounds include 1,2-benzoquinone azide-4-sulfonic acid esters, 1,2-naphthoquinone diazide-4-sulfonic acid esters, 1,2-naphthoquinone diazide-5-sulfonic acid esters, 2,1-naphthoquinone diazide-4-sulfonic acid esters, 2,1-naphthoquinone diazide-5-sulfonic acid esters, and sulfonic acid chlorides of quinone diazide derivatives such as 1,2-benzoquinone azide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 2,1-naphthoquinone diazide-4-sulfonic acid chloride, and 2,1-naphthoquinone diazide-5-sulfonic acid chloride.

[0096] Examples of the diazo compounds include salts of condensates of p-diazodiphenylamine with formaldehyde or acetaldehyde, inorganic diazo resin salts which are reaction products of the above condensates with hexafluorophosphates, tetrafluoroborates, perchlorates or periodates, and organic diazo resin salts which are reaction products of the above condensates with sulfonic acids, as described in U.S. Pat. No. 3,300,309.

[0097] Examples of the azide compounds include azidochalconic acid, diazidobenzalmethylcyclohexanones, azidocinnamylideneacetophenones, aromatic azide compounds, and aromatic diazide compounds.

[0098] Examples of the halogenated organic compound include halogen-containing oxadiazole compounds, halogen-containing triazine compounds, halogen-containing acetophenone compounds, halogen-containing benzophenone compounds, halogen-containing sulfoxide compounds, halogen-containing sulfone compounds, halogen-containing thiazole compounds, halogen-containing oxazole compounds, halogen-containing trizole compounds, halogen-containing 2-pyrone compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, halogen-containing heterocyclic compounds, and sulfenyl halide compounds. In addition to the above, compounds used as halogen-based flame retardants such as tris(2,3-dibromopropyl)phosphate, tris(2,3-dibromo-3-chloropropyl)phosphate, chlorotetrabromomethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenyl allyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis(bromoethyl ether)tetrabromobisphenol A, bis(chloroethyl ether)tetrachlorobisphenol A, tris(2,3-dibromopropyl)isocyanurate, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, and 2,2-bis(4-hydroxyethoxy-3,5-dibromophenyl)propane, and compounds used as organic chloro-based pesticides such as dichlorophenyltrichloroethane are also exemplified as halogenated organic compounds.

[0099] Examples of the organic acid ester include carboxylic acid esters and sulfonic acid esters. Examples of the organic acid amide include carboxylic acid amides and sulfonic acid amides. Examples of the organic acid imide include carboxylic acid imides and sulfonic acid imides. The radiation-sensitive substance may be used alone or in combination of two or more.

[0100] In the photoresist composition, the content of the radiation-sensitive substance is preferably in the range of 10 to 200 parts by weight, and more preferably in the range of 50 to 150 parts by weight, per 100 parts by weight of the alkali-soluble resin.

[0101] Examples of solvents for photoresist compositions include ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, and butyrolactone; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, pentanol, heptanol, octanol, nonanol, and decanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dioxane; alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether; ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, and butyl methyl butylate. esters such as ethyl butyrate, butyl butyrate, propyl butyrate, ethyl lactate, and butyl lactate; monocarboxylic acid esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, and butyl 2-methoxypropionate; cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, and butyl cellosolve acetate. propylene glycols such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate; diethylene glycols such as diethyl glycol monomethyl ether, diethyl glycol monoethyl ether, diethyl glycol dimethyl ether, diethyl glycol diethyl ether, and diethyl glycol methyl ethyl ether;Examples of suitable solvents include halogenated hydrocarbons such as trichloroethylene, chlorofluorocarbon solvents, HCFCs, and HFCs; fully fluorinated solvents such as perfluorooctane; aromatic solvents such as toluene and xylene; and polar solvents such as dimethylacetiamide, dimethylformamide, N-methylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.

[0102] When the coating composition of the present invention is used as a color resist composition, the color resist composition contains an alkali-soluble resin, a polymerizable compound, a colorant, and the like in addition to the copolymer of the present invention.

[0103] The alkali-soluble resin contained in the color resist can be the same as the alkali-soluble resin contained in the photoresist composition described above.

[0104] The polymerizable compound contained in the color resist composition is a compound having a photopolymerizable functional group that can polymerize or crosslink when exposed to active energy rays such as ultraviolet rays. Examples of the polymerizable compound include unsaturated carboxylic acids such as (meth)acrylic acid, esters of monohydroxy compounds and unsaturated carboxylic acids, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, esters obtained by esterification of unsaturated carboxylic acids with polycarboxylic acids and polyhydroxy compounds such as the above-mentioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, polymerizable compounds having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound, and polymerizable compounds having an acid group. The polymerizable compounds may be used alone or in combination of two or more.

[0105] Examples of the esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and glycerol (meth)acrylate. Other examples include itaconic acid esters in which the (meth)acrylic acid portion of these acrylates is replaced with itaconic acid, crotonic acid esters in which the (meth)acrylic acid portion is replaced with crotonic acid, or maleic acid esters in which the (meth)acrylic acid portion is replaced with maleic acid.

[0106] Examples of the esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone di(meth)acrylate, resorcinol di(meth)acrylate, and pyrogallol tri(meth)acrylate. The esters obtained by the esterification reaction of unsaturated carboxylic acids, polycarboxylic acids, and polyhydroxy compounds 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 glycerin.

[0107] Examples of the polymerizable compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound include reaction products of aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; and aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate with a hydroxy compound having a (meth)acryloyl group, such as 2-hydroxyethyl(meth)acrylate and 3-hydroxy[1,1,1-tri(meth)acryloyloxymethyl]propane.

[0108] The polymerizable compound having an acid group is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and is preferably a polyfunctional polymerizable compound obtained by reacting a non-aromatic carboxylic acid anhydride with the unreacted hydroxyl groups of the aliphatic polyhydroxy compound to provide an acid group. The aliphatic polyhydroxy compound used to prepare the polyfunctional polymerizable compound is preferably pentaerythritol or dipentaerythritol. The acid value of the polyfunctional polymerizable compound is preferably in the range of 0.1 to 40, more preferably 5 to 30, because this improves developability, curability, and the like. When two or more polyfunctional polymerizable compounds having an acid group are used in combination, or when a polyfunctional polymerizable compound having an acid group and a polyfunctional polymerizable compound not having an acid group are used in combination, it is preferable that the acid value of the mixture of polymerizable compounds be within the above range.

[0109] Specific examples of the polymerizable compound having an acid group include a mixture containing dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and a succinate ester of dipentaerythritol pentaacrylate as main components, and this mixture is commercially available as Aronix TO-1382 (manufactured by Toagosei Co., Ltd.).

[0110] Other polymerizable compounds include (meth)acrylamides such as ethylenebis(meth)acrylamide; allyl esters such as diallyl phthalate; and compounds having a vinyl group such as divinyl phthalate.

[0111] In the color resist composition, the content of the polymerizable compound is preferably in the range of 5 to 80 mass % of the total solid content of the color resist composition, more preferably in the range of 10 to 70 mass %, and even more preferably in the range of 20 to 50 mass %.

[0112] The colorant for the color resist composition is not particularly limited as long as it is capable of coloring, and may be, for example, a pigment or a dye. The pigment may be either an organic or inorganic pigment. Examples of the organic pigment include red, green, blue, yellow, purple, orange, and brown pigments. Examples of the chemical structure of the organic pigment include azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. Examples of the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide. The abbreviation "C.I." in the following text stands for Color Index.

[0113] Examples of the red pigment include C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1 , 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 16 6, 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, 234 5, 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, C.I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242 or 254 is preferred, and C.I. Pigment Red 177, 209, 224 or 254 is more preferred.

[0114] Examples of the green pigment include C.I. 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, C.I. Pigment Green 7, 36, or 58 is preferred.

[0115] Examples of the blue pigment include C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 is preferred, and C.I. Pigment Blue 15:6 is more preferred.

[0116] Examples of the yellow pigment include C.I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 1 38, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, etc. Among these, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185 is preferred, and C.I. Pigment Yellow 83, 138, 139, 150 or 180 is more preferred.

[0117] Examples of the purple pigment include C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, C.I. Pigment Violet 19 or 23 is preferred, and C.I. Pigment Violet 23 is more preferred.

[0118] Examples of the orange pigment include C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79. Among these, C.I. Pigment Orange 38 or 71 is preferred.

[0119] The three primary color pixels of color filters used in liquid crystal display devices and organic EL display devices are red (R), green (G), and blue (B). Therefore, the red pigment, green pigment, and blue pigment are used as main components, and organic pigments of colors such as yellow, purple, and orange may be used to adjust the hue in order to improve color reproducibility.

[0120] The average particle size of the organic pigment is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less, in order to enhance the brightness of color liquid crystal displays and organic EL display devices. It is preferable to use the organic pigment after dispersing it so that the average particle size falls within these ranges. The average primary particle size of the organic pigment is preferably 100 nm or less, more preferably 50 nm or less, even more preferably 40 nm or less, and particularly preferably in the range of 10 to 30 nm. The average particle size of the organic pigment is measured using a dynamic light scattering particle size distribution analyzer, and can be measured using, for example, a Nanotrac particle size distribution analyzer "UPA-EX150" or "UPA-EX250" manufactured by Nikkiso Co., Ltd.

[0121] When the color resist composition is used to form a black matrix (BM), the colorant is not particularly limited as long as it is black, and examples thereof include carbon black, lamp black, acetylene black, bone black, thermal black, channel black, furnace black, graphite, iron black, and titanium black. Among these, carbon black and titanium black are preferred from the viewpoint of light-shielding rate and image characteristics. Furthermore, a combination of two or more organic pigments may be used to produce a black color by mixing them.

[0122] Commercially available carbon black products include, for example, MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150, and # 3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B, and the like manufactured by Evonik Degussa Japan Co., Ltd. are also suitable. A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack 350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170, and the like, and Monarch 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R, and the like manufactured by Cabot Japan Co., Ltd.BLACK PEARLS480, PEARLS130, VULCAN XC72R, ELFTEX-8, etc., and RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, ...2, RAVEN13, RAVEN14, RAVEN15, RAVEN16, RAVEN17, RAVEN18, RAVEN19, RAVEN20, RAVEN21, RAVEN222, RAVEN23, RAVEN24 1000, RAVEN 1020, RAVEN 1040, RAVEN 1060U, RAVEN 1080U, RAVEN 1170, RAVEN 1190U, RAVEN 1250, RAVEN 1500, RAVEN 2000, RAVEN 2500U, RAVEN 3500, RAVEN 5000, RAVEN 5250, RAVEN 5750, RAVEN 7000, and the like.

[0123] Among the above carbon blacks, resin-coated carbon black is preferred as it has the high optical density and high surface resistivity required for the black matrix of a color filter.

[0124] Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.

[0125] As a colorant used for forming a black matrix (BM), two or more organic pigments may be mixed to produce a black color, and examples thereof include a black pigment obtained by mixing three color pigments, i.e., red, green, and blue. Examples of colorants that can be mixed to prepare a black pigment include Victoria Pure Blue (C.I. 42595), Auramine O (C.I. 41000), Catilon Brilliant Flavin (Basic 13), Rhodamine 6 GCP (C.I. 45160), Rhodamine B (C.I. 45170), Safranin OK70:100 (C.I. 50240), Erioglaucine X (C.I. 42080), No. 120 / Lionol Yellow (C.I. 21090), Lionol Yellow GRO (C.I. 21090), Shimler Fast Yellow 8GF (C.I. 21105), Benzidine Yellow 4T-564D (C.I. 21095), Shimler First Red 4015 (C.I. 12355), Lionol Red 7B4401 (C.I. 15850), Firstgen Blue TGR-L (C.I. 74160), Lionol Blue SM (C.I. 26150), Lionol Blue ES (C.I. Pigment Blue 15:6), Lionogen Red GD (C.I. Pigment Red 168), Lionol Green 2YS (C.I. Pigment Green 36), and the like.

[0126] Other colorants that can be mixed and used to prepare a black pigment include, for example, C.I. Yellow Pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. Orange Pigments 36, 43, 51, 55, 59, 61, C.I. Red Pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. Violet Pigments 19, 23, 29, 30, 37, 40, 50, C.I. Examples of suitable pigments include C.I. blue pigments 15, 15:1, 15:4, 22, 60, and 64, C.I. green pigment 7, and C.I. brown pigments 23, 25, and 26.

[0127] When carbon black is used as the black pigment, the average primary particle size of the carbon black is preferably in the range of 0.01 to 0.08 μm, and more preferably in the range of 0.02 to 0.05 μm in view of good developability.

[0128] Carbon black has a particle shape different from that of organic pigments and exists in a state called a structure in which primary particles are fused together, and fine pores may be formed on the particle surface by post-treatment. Therefore, to express the particle shape of carbon black, it is generally preferable to measure the DBP absorption (JIS K6221) and the specific surface area (JIS K6217) measured by the BET method in addition to the average particle size of the primary particles, which is determined by the same method as for the organic pigments, and use these as indicators of the structure and pore volume. The dibutyl phthalate (hereinafter abbreviated as "DBP") absorption of carbon black is 40 to 100 cm. ３ / 100g, and in view of good dispersibility and developability, the range of 50 to 80 cm ３ The specific surface area of ​​carbon black measured by the BET method is preferably in the range of 50 to 120 m ２ / g, and in view of good dispersion stability, a range of 60 to 95 m ２ / g is more preferred.

[0129] Examples of dyes that can be used as colorants in the color resist composition include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

[0130] Examples of the azo dyes include C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive Red 17, C.I. Reactive Red 120, C.I. Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Examples of suitable pigments include C.I. Mordant Red 7, C.I. Mordant Yellow 5, and C.I. Mordant Black 7.

[0131] Examples of the anthraquinone dye include C.I. Vat Blue 4, C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, and C.I. Disperse Blue 60.

[0132] Examples of the phthalocyanine dyes include C.I. Pad Blue 5, examples of the quinoneimine dyes include C.I. Basic Blue 3 and C.I. Basic Blue 9, examples of the quinoline dyes include C.I. Solvent Yellow 33, C.I. Acid Yellow 3 and C.I. Disperse Yellow 64, and examples of the nitro dyes include C.I. Acid Yellow 1, C.I. Acid Orange 3 and C.I. Disperse Yellow 42.

[0133] It is preferable to use a pigment as the colorant for the color resist composition, since the resulting coating film will have excellent light resistance, weather resistance, and fastness. However, in order to adjust the hue, a dye may be used in combination with the pigment, if necessary.

[0134] In the color resist composition, the content of the colorant is preferably 1% by mass or more, more preferably in the range of 5 to 80% by mass, and even more preferably in the range of 5 to 70% by mass, based on the total solid content of the color resist composition.

[0135] When the color resist composition is used to form red (R), green (G), and blue (B) pixels of a color filter, the content of the colorant in the color resist composition is preferably in the range of 5 to 60 mass % of the total solid content of the color resist composition, and more preferably in the range of 10 to 50 mass %.

[0136] When the color resist composition is used to form a black matrix of a color filter, the content of the colorant in the color resist composition is preferably in the range of 20 to 80 mass % of the total solid content of the color resist composition, and more preferably in the range of 30 to 70 mass %.

[0137] In the color resist composition, when the colorant is a pigment, it is preferable to use a pigment dispersion prepared by dispersing the pigment in an organic solvent using a dispersant. Examples of the dispersant include surfactants; pigment intermediates or derivatives; dye intermediates or derivatives; and resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins. Among these, graft copolymers containing nitrogen atoms, acrylic block copolymers containing nitrogen atoms, and urethane resin dispersants are preferred. Because these dispersants contain nitrogen atoms, the nitrogen atoms have affinity for the pigment surface, and the portions other than the nitrogen atoms increase affinity for the medium, thereby improving dispersion stability. These dispersants may be used alone or in combination of two or more.

[0138] Commercially available dispersants include the "EFKA" series (such as "EFKA 46") manufactured by BASF; the "Disperbyk" series and the "BYK" series (such as "BYK-160", "BYK-161", and "BYK-2001") manufactured by BYK Japan K.K.; the "Solsperse" series manufactured by The Lubrizol Japan 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 (such as "AJISPER PB-814") manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0139] Examples of organic solvents used in preparing the pigment dispersion include acetate-based solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate-based solvents such as ethoxypropionate; aromatic solvents such as toluene, xylene, and methoxybenzene; ether-based solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, and diethylene glycol dimethyl ether; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon-based solvents such as hexane; nitrogen compound-based solvents such as N,N-dimethylformamide, γ-butyrolactam, and N-methyl-2-pyrrolidone; lactone-based solvents such as γ-butyrolactone; carbamic acid esters, etc. These solvents may be used alone or in combination of two or more.

[0140] Methods for preparing the pigment dispersion include a method that includes a colorant kneading / dispersing step and a fine-dispersing step, and a method that includes only the fine-dispersing step. In the kneading / dispersing step, the colorant, a portion of the alkali-soluble resin, and, if necessary, the dispersant are mixed and kneaded. The colorant can be dispersed by dispersing while applying strong shear force using a kneader. Machines that can be used for kneading include two-roll mills, three-roll mills, ball mills, tron ​​mills, dispersers, kneaders, co-kneaders, homogenizers, blenders, and single- or twin-screw extruders. It is preferable to refine the particle size of the colorant by a salt milling method or the like before the above kneading.

[0141] In the fine dispersion step, a solvent is added to the composition containing the colorant obtained in the kneading and dispersion step, or a mixture of a colorant, an alkali-soluble resin, a solvent, and, if necessary, the dispersant is mixed and dispersed together with a dispersion medium such as fine particles of glass, zirconia, or ceramic using a disperser, thereby dispersing the colorant particles to a fine state close to primary particles.

[0142] From the viewpoint of improving the transmittance, contrast, etc. of the color filter, the average particle size of the primary particles of the colorant is preferably 10 to 100 nm, and more preferably 10 to 60 nm. The average particle size of the colorant is measured with a dynamic light scattering particle size distribution analyzer, and can be measured with, for example, Nanotrac particle size distribution analyzers "UPA-EX150" and "UPA-EX250" manufactured by Nikkiso Co., Ltd.

[0143] Although the coating composition has been exemplified above as a paint composition, a photoresist composition, and a color resist composition, the coating composition is not limited to these.

[0144] Specific examples of applications 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"), and quantum dot displays (hereinafter abbreviated as "QDD"), such as anti-glare (AG) hard coating materials, anti-reflection (LR) coating materials, low refractive index layer coating materials, high refractive index layer coating materials, clear hard coating materials, and polymerizable liquid crystal coating materials; color filters (hereinafter abbreviated as "CF") for LCDs, etc.; "); black resists, inkjet inks, printing inks or paints for forming black matrices, black column spacers and black photospacers of CFs of LCDs and the like; paints for transparent protective films for protecting the CF surfaces used in CFs of LCDs and the like; resin compositions for liquid crystal materials, column spacers and photospacers of LCDs; resin compositions for pixel partition walls of LCDs, PDPs, OLEDs, QDDs and the like, positive photoresists for forming electrodes, protective Films, insulating films, plastic housings, paints for plastic housings, bezel (frame) inks; prism sheets and light diffusion films that are backlight components for LCDs; paints for organic insulating films in LCD liquid crystal TFT arrays; protective coating materials for the internal polarizer surfaces of LCDs; phosphors for PDPs; organic EL materials and sealing materials (protective films, gas barriers) for OLEDs; quantum dot inks, sealing materials, and protective films for QDDs; high refractive index lenses, low refractive index sealing, and LED pixels for micro (mini) LED displays; positive photoresists, chemically amplified photoresists, anti-reflective films, and multilayers used in semiconductor manufacturing Materials (SOC, SOG), underlayer films, buffer coats, developers, rinse solutions, pattern collapse prevention agents, polymer residue removers, cleaning agents and other chemical solutions, nanoimprint release agents; resin compositions for semiconductor post-processing or printed wiring boards (resin compositions such as epoxy resins, phenolic resins, polyphenylene ether resins, liquid crystal polymers, polyimide resins, bismaleimide resins, bisallylnadimide resins, and benzoxazine resins), copper-clad laminates, resin-coated copper foils, build-up films, passivation films, interlayer insulating films, flexible copper-clad laminates, and dry film resists;color resists for image sensors; liquid repellents for solder flux; dispersants, paints, and green sheets for multilayer ceramic capacitors; cathode materials, anode materials, separators, and electrolytes for lithium-ion batteries; automotive exterior paints, rubber, elastomers, glass, vapor deposition anchor coats, headlamp lenses, solid lubricant paints, heat dissipation substrates, interior paints, and repair paints; wallpaper, flooring materials, kitchen components, bathroom and toilet components for housing facilities; inkjet inks for printed materials, offset printing inks, gravure printing inks, screen printing inks, photoresists for the printing plate manufacturing process, photosensitive materials for lithographic printing plates (PS plates), package adhesives, and ballpoint pen inks; primers for easily adhering plastic films; water repellents for fibers; non-diffusing agents for grease; cleaning solutions for cleaning the surfaces of various products or parts; hard coating materials for optical recording media such as CDs, DVDs, and Blu-ray discs; smartphones or Examples of suitable coating materials include paints or hard coating materials for mobile phone housings or screens; hard coating materials for transfer films for insert molds (IMD, IMF); release films; paints or coating materials for various plastic molded products such as home appliance housings; printing inks or paints for various building materials such as decorative panels; coating materials for residential window glass; woodworking paints for furniture, etc.; coating materials for artificial and synthetic leather; coating materials for rubber rollers in office equipment such as copy machines and printers; coating materials for the glass of the reading parts of office equipment such as copy machines and scanners; optical lenses or coating materials for cameras, video cameras, glasses, contact lenses, etc.; coating materials for the crystal glass and glass of watches such as wristwatches; coating materials for the windows of various vehicles such as automobiles and railway cars; anti-reflective coating paints for solar cell cover glass or films; paints or coating materials for FRP bathtubs; PCMs for metal building materials or home appliances; single-layer or multi-layer coating compositions for photofabrication processes, etc.;

[0145] The copolymer of the present invention has excellent surface tension reducing ability, and therefore, not only can it be expected to have leveling properties, but also various functions such as wettability, penetration, cleanability, water repellency, oil repellency, stain resistance, lubricity, anti-blocking properties, and release properties. Furthermore, when the copolymer of the present invention is blended into a paint or coating agent containing fine particles, it improves the dispersibility of the fine particles, and is expected to function not only as a leveling property but also as a dispersant for the fine particles. Furthermore, when the copolymer of the present invention is added to a pressure-sensitive adhesive composition used for pressure-sensitive adhesive tapes, etc., in addition to the above-mentioned coating composition, it can be expected to have not only leveling properties, but also various functions such as reducing peel force, suppressing peel force fluctuations, and suppressing peel electrification.

[0146] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0147] In the examples and comparative examples, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​calculated in terms of polystyrene based on gel permeation chromatography (GPC) measurements. The GPC measurement conditions are as follows:

[0148] [GPC measurement conditions] Measurement apparatus: High-speed GPC apparatus "HLC-8320GPC" manufactured by Tosoh Corporation Column: "TSK GUARDCOLUMN SuperHZ-L" manufactured by Tosoh Corporation + "TSK gel SuperHZM-N" manufactured by Tosoh Corporation + "TSK gel SuperHZM-N" manufactured by Tosoh Corporation + "TSK gel SuperHZM-N" manufactured by Tosoh Corporation + "TSK gel SuperHZM-N" manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: "EcoSEC Data Analysis Version 1.07" manufactured by Tosoh Corporation Column temperature: 40°C Developing solvent: tetrahydrofuran Flow rate: 0.35 mL / min Measurement sample: 7.5 mg of sample was dissolved in 10 mL of tetrahydrofuran, and the resulting solution was filtered through a microfilter to prepare a measurement sample. Sample injection amount: 20 μL. Standard sample: The following monodisperse polystyrene with known molecular weight was used in accordance with the measurement manual for the "HLC-8320GPC."

[0149] (Monodisperse polystyrene) "A-300" manufactured by Tosoh Corporation "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation "F-128" manufactured by Tosoh Corporation "F-288" manufactured by Tosoh Corporation

[0150] Synthesis Example 1: Synthesis of Random Copolymer (Main Chain: Acrylate Skeleton) A nitrogen-purged, three-necked glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 30.0 g of propylene glycol monomethyl ether acetate as a solvent, and the temperature was raised to 75°C while stirring under a nitrogen stream. A reaction solution was separately prepared by mixing 25.0 g of 3-acryloyloxypropyltris(trimethylsiloxy)silane, 12.5 g of polypropylene glycol monoacrylate (average number of propylene glycol repeats: 6), 0.375 g of t-butylperoxy-2-ethylhexanoate as an initiator, and 7.50 g of propylene glycol monomethyl ether acetate as a solvent, and this reaction solution was added dropwise to the flask over 120 minutes. After completion of the dropwise addition, the flask was stirred at 75°C for 5 hours, then heated to 110°C and further stirred for 1 hour. After completion of the reaction, the solvent was removed by distillation under reduced pressure, yielding random copolymer (1).

[0151] The molecular weight of the copolymer (1) obtained was measured by GPC, and the weight average molecular weight (Mw) was 15,700, and the (Mw / Mn) was 1.64. In addition, from the raw material charging ratio, it was found that -Si[OSi(CH ３ ) ３ ] ３ The content of the functional group represented by the formula (I) was 48 mass %.

[0152] Synthesis Example 2: Synthesis of Random Copolymer (Main Chain: Acrylate Skeleton) A three-necked glass flask equipped with a stirrer, thermometer, condenser, and dropping device and purged with nitrogen was charged with 25.0 g of propylene glycol monomethyl ether acetate as a solvent, and the temperature was raised to 80°C while stirring under a nitrogen stream. A reaction solution was separately prepared by mixing 16.7 g of 3-acryloyloxypropyltris(trimethylsiloxy)silane, 8.33 g of polypropylene glycol monoacrylate (average number of propylene glycol repeats: 6), 0.250 g of t-butylperoxy-2-ethylhexanoate as an initiator, and 12.5 g of propylene glycol monomethyl ether acetate as a solvent, and this reaction solution was added dropwise to the flask over 120 minutes. After completion of the dropwise addition, the flask was stirred at 80°C for 5 hours, then heated to 110°C and further stirred for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain random copolymer (2).

[0153] The molecular weight of the copolymer (2) obtained was measured by GPC, and the weight average molecular weight (Mw) was 10,300, and the (Mw / Mn) was 1.45. In addition, from the raw material charging ratio, it was found that -Si[OSi(CH ３ ) ３ ] ３ The content of the functional group represented by the formula (I) was 48 mass %.

[0154] Synthesis Example 3: Synthesis of Block Copolymer (Main Chain: Acrylate Skeleton) A three-necked glass flask equipped with a stirrer, a thermometer, and a condenser and purged with nitrogen was charged with 20.0 g of polypropylene glycol monoacrylate (average number of propylene glycol repeats: 6) and 25.0 g of butyl acetate as a solvent, and the mixture was heated to 60°C with stirring under a nitrogen stream. 0.76 g of N,N,N',N",N"-pentamethyldiethylenetriamine and 0.63 g of cuprous bromide were further charged, and the mixture was stirred for 30 minutes while maintaining the temperature inside the flask at 60°C. 1.42 g of ethyl 2-bromoisobutyrate was added to this reaction solution, and the mixture was reacted for 3 hours at 50°C under a nitrogen stream to obtain a polymer block of polypropylene glycol monoacrylate. 40.6 g of 3-acryloyloxypropyltris(trimethylsiloxy)silane was added to this reaction solution, and the mixture was reacted for 20 hours at 60°C. Methyl ethyl ketone was added, and the mixture was washed with a 20% aqueous solution of citric acid, a 5% aqueous solution of sodium hydroxide, and a 20% aqueous solution of sodium chloride. The solvent was removed under reduced pressure to obtain a block copolymer (3) of a polymer block of polypropylene glycol monoacrylate and a polymer block of 3-acryloyloxypropyltris(trimethylsiloxy)silane.

[0155] The molecular weight of the copolymer (3) obtained was measured by GPC, and the weight average molecular weight (Mw) was 113.00, and the (Mw / Mn) was 1.44. In addition, from the raw material charging ratio, it was found that -Si[OSi(CH ３ ) ３ ] ３ The content of the functional group represented by the formula (I) was 48 mass %.

[0156] Synthesis Example 4: Synthesis of Random Copolymer (Main Chain: Acrylate Skeleton + Methacrylate Skeleton) A three-necked glass flask equipped with a stirrer, thermometer, condenser, and dropping device and purged with nitrogen was charged with 25.0 g of propylene glycol monomethyl ether acetate as a solvent, and the temperature was raised to 80°C while stirring under a nitrogen stream. A reaction solution was separately prepared by mixing 16.7 g of 3-acryloyloxypropyltris(trimethylsiloxy)silane, 8.33 g of polypropylene glycol monomethacrylate (average propylene glycol repeat number: 4 to 6), 0.50 g of t-butylperoxy-2-ethylhexanoate as an initiator, and 12.5 g of propylene glycol monomethyl ether acetate as a solvent, and this reaction solution was added dropwise to the flask over 120 minutes. After completion of the dropwise addition, the flask was stirred at 80°C for 5 hours, then heated to 110°C and further stirred for 1 hour. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a random copolymer (4).

[0157] The molecular weight of the obtained copolymer (4) was measured by GPC, and the weight average molecular weight (Mw) was 14,700, and the (Mw / Mn) was 1.78. In addition, from the raw material charging ratio, it was found that -Si[OSi(CH ３ ) ３ ] ３ The content of the functional group represented by the formula (I) was 48 mass %.

[0158] Comparative Synthesis Example 1: Synthesis of Random Copolymer (Main Chain: Methacrylate Skeleton + Acrylate Skeleton) A three-necked glass flask equipped with a stirrer, thermometer, condenser, and dropping device and purged with nitrogen was charged with 25.0 g of propylene glycol monomethyl ether acetate as a solvent, and the temperature was raised to 100°C while stirring under a nitrogen stream. A reaction solution was separately prepared by mixing 16.7 g of 3-methacryloyloxypropyltris(trimethylsiloxy)silane, 8.33 g of polypropylene glycol monoacrylate (average number of propylene glycol repeats: 6), 0.50 g of t-butylperoxy-2-ethylhexanoate as an initiator, and 12.5 g of propylene glycol monomethyl ether acetate as a solvent, and this reaction solution was added dropwise to the flask over 120 minutes. After completion of the dropwise addition, the flask was stirred at 80°C for 5 hours, then heated to 110°C and further stirred for 1 hour. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a random copolymer (1').

[0159] The molecular weight of the copolymer (1') obtained was measured by GPC, and the weight average molecular weight (Mw) was 16,400, and the (Mw / Mn) was 2.13. In addition, from the raw material charging ratio, it was found that -Si[OSi(CH ３ ) ３ ] ３ The content of the functional group represented by the formula (I) was 48 mass %.

[0160] Comparative Synthesis Example 2: Synthesis of Random Copolymer (Main Chain: Methacrylate Skeleton + Methacrylate Skeleton) A three-necked glass flask equipped with a stirrer, thermometer, condenser, and dropping device and purged with nitrogen was charged with 60.0 g of butyl acetate as a solvent, and the temperature was raised to 100°C while stirring under a nitrogen stream. A reaction solution was separately prepared by mixing 40.0 g of 3-methacryloyloxypropyltris(trimethylsiloxy)silane, 20.0 g of polypropylene glycol monomethacrylate (average number of propylene glycol repeats: 4 to 6), 1.2 g of t-butylperoxy-2-ethylhexanoate as an initiator, and 22.9 g of butyl acetate as a solvent, and this reaction solution was added dropwise to the flask over 120 minutes. After completion of the dropwise addition, the mixture was stirred at 100°C for 4 hours, then heated to 110°C and further stirred for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain random copolymer (2').

[0161] The molecular weight of the copolymer (2') obtained was measured by GPC, and the weight average molecular weight (Mw) was 18,000, and the (Mw / Mn) was 1.86. In addition, from the raw material charging ratio, it was found that -Si[OSi(CH ３ ) ３ ] ３ The content of the functional group represented by the formula (I) was 48 mass %.

[0162] Comparative Synthesis Example 3: Synthesis of Block Copolymer (Main Chain: Methacrylate Skeleton + Methacrylate Skeleton) 75.0 g of methyl ethyl ketone as a solvent and 16.5 g of polypropylene glycol monomethacrylate (average number of propylene glycol repeats: 4 to 6) were placed in a nitrogen-purged three-neck glass flask equipped with a stirrer, a thermometer, and a condenser, and the mixture was heated to 60°C with stirring under a nitrogen stream. 4.24 g of 2,2'-bipyridyl, 2.31 g of N,N,N',N'',N''-pentamethyldiethylenetriamine, 1.21 g of cuprous chloride, and 0.303 g of cupric bromide were further placed in the flask, and the mixture was stirred for 30 minutes while maintaining the temperature inside the flask at 50°C. 2.65 g of ethyl 2-bromoisobutyrate was added to the reaction solution, and the mixture was reacted for 5 hours at 50°C under a nitrogen stream to obtain a polymer block of polypropylene glycol monomethacrylate. To this reaction solution, 33.5 g of 3-methacryloyloxypropyltris(trimethylsiloxy)silane was added and reacted at 50°C for 18 hours, after which 30 g of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a block copolymer (3') of a polymer block of polypropylene glycol monomethacrylate and a polymer block of 3-methacryloyloxypropyltris(trimethylsiloxy)silane.

[0163] The molecular weight of the copolymer (3') obtained was measured by GPC, and the weight average molecular weight (Mw) was 8,300, and the (Mw / Mn) was 1.19. In addition, from the raw material charging ratio, it was found that -Si[OSi(CH ３ ) ３ ] ３ The content of the functional group represented by the formula (I) was 48 mass %.

[0164] (Examples 1-3 and Comparative Examples 1-2: Preparation and Evaluation of Coating Compositions) A coating composition was prepared by mixing 3.0 g of a 40 mass % resin solution of an alkali-soluble resin (Acrydic ZL-295, manufactured by DIC Corporation), 1.2 g of Aronix M-402 (manufactured by Toagosei Chemical Industry Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), 0.0005 g (in terms of solid content) of a copolymer shown in Table 1 below as a leveling agent, and 3.8 g of propylene glycol monomethyl ether acetate (PGMEA).

[0165] (Leveling Properties) 3 ml of the obtained coating composition was dropped onto the central portion of a 10 cm x 10 cm chrome-plated glass substrate, spin-coated at a rotation speed of 400 rpm for 20 seconds, and then heated and dried at 100°C for 100 seconds to produce a laminate having a coating layer. The film thickness of 400 points in a 7 x 7 cm central portion of the coating layer of the obtained laminate was measured using a reflection spectrophotometer (FE-3000, manufactured by Otsuka Electronics Co., Ltd.), and the standard deviation was calculated to evaluate the smoothness of the coating layer according to the following criteria. The results are shown in Table 1. AA: Standard deviation of film thickness less than 150 A: Standard deviation of film thickness 150 or more but less than 200 B: Standard deviation of film thickness 200 or more but less than 250 C: Standard deviation of film thickness 250 or more

[0166]

[0167] In Table 1, "Ac" means "a monomer in which the polymerizable unsaturated group is an acrylate group," and "Mc" means "a monomer in which the polymerizable unsaturated group is a methacrylate group." For example, in the case of Copolymer (4) in Example 3, the silicone monomer is an acrylate monomer, and the compatible monomer is a methacrylate monomer.

[0168] The results in Table 1 show that copolymers in which the structure derived from the silicone monomer has an acrylate skeleton can provide excellent leveling properties even at low addition amounts, compared to copolymers in which the structure derived from the silicone monomer has a methacrylate skeleton.

[0169] (Examples 4-5, Reference Example 1, and Comparative Examples 3-4: Preparation and Evaluation of Coating Compositions) Coating compositions were prepared in the same manner as in Example 1, using the copolymers shown in Table 2 below as leveling agents. Pin unevenness was evaluated using the obtained coating compositions by the following method. The results are shown in Table 2.

[0170] (Evaluation of pin unevenness) 3 ml of the obtained coating composition was dropped onto the center of a 10 cm x 10 cm chrome-plated glass substrate and spin-coated at a rotation speed of 400 rpm for 20 seconds to obtain a coated substrate. SUS pins were attached to the four corners of a hot plate, and the obtained coated substrate was placed on the support pins and heated and dried at 100°C for 100 seconds to produce a laminate having a coating layer. The coating layer of the obtained laminate was visually observed, and pin unevenness of the coating layer was evaluated according to the following criteria. The results are shown in Table 2. "Pin unevenness" refers to film thickness unevenness (drying unevenness) occurring mainly at the contact point between the support pin and the coated substrate. ◯: Almost no film thickness unevenness was observed around the pin. ×: Film thickness unevenness was observed around the pin.

[0171]

[0172] The results in Table 2 show that a copolymer in which the structure derived from the silicone monomer is an acrylate skeleton and the structure derived from the compatible monomer is also composed of an acrylate skeleton can also achieve pin unevenness suppression effects.

[0173] (Example 5, Reference Example 2, and Comparative Example 5: Preparation and Evaluation of Coating Compositions) Coating compositions were prepared in the same manner as in Example 1, using the copolymers shown in Table 3 below as the leveling agent. The resulting coating compositions were used to evaluate the leveling property and pin unevenness as described above. The results are shown in Table 3. Recoatability was also evaluated by the following method. The results are shown in Table 3.

[0174] (Recoatability) 3 ml of the obtained coating composition was dropped onto the center of a 10 cm x 10 cm chrome-plated glass substrate, spin-coated at a rotation speed of 1,000 rpm for 10 seconds, and then heated and dried at 100°C for 100 seconds to produce a laminate having a coating layer. 2 μL of propylene glycol monomethyl ether acetate (PGMEA) was dropped onto the coating layer of the obtained laminate, and the contact angle of the PGMEA over time 20 seconds after dropping was measured using a contact angle measuring device ("MODEL CA-W701" manufactured by Kyowa Interface Science Co., Ltd.) and evaluated according to the following criteria. The PGMEA contact angle indicates the wettability of the coating layer, with a smaller PGMEA contact angle indicating better recoatability. AA: PGMEA contact angle is 10 degrees or less. A: PGMEA contact angle is 10 degrees or more and less than 11 degrees. B: PGMEA contact angle is 11 degrees or more and less than 12 degrees. C: PGMEA contact angle is 12 degrees or more.

[0175]

[0176] The results in Table 3 show that recoatability is improved when the structure derived from the silicone monomer is an acrylate skeleton, the structure derived from the compatible monomer is also an acrylate skeleton, and the block copolymer is a block copolymer.

Claims

1. A leveling agent comprising, as at least polymerization components, a polymerizable monomer (a1), which is a compound represented by the following formula (a1-1), and a polymerizable monomer (a2), which is one or more types selected from the group consisting of a compound represented by the following formula (a2-1), a compound represented by the following formula (a2-2), a compound represented by the following formula (a2-3), and a compound represented by the following formula (a2-4): 【Chemistry 1】 (In the formula (a1-1), Each R is independently an alkyl group having 1 to 3 carbon atoms. L 1 is a divalent organic group or a single bond. 【Chemistry 2】 (In the formulas (a2-1), (a2-2), (a2-3) and (a2-4), R 21 is a hydrogen atom or a methyl group; R 22 is an alkyl group having 1 to 18 carbon atoms; R 23 is a hydrogen atom or a methyl group; R 24 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms; R 25 is a hydrogen atom or a methyl group; R 26 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms and an ether bond; R 27 is a hydrogen atom or a methyl group; R 28 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having an ether bond having 1 to 18 carbon atoms; L 2 is a divalent organic group or a single bond; n is an integer ranging from 1 to 4, m is the number of repetitions, p is an integer ranging from 1 to 10, and q is the number of repetitions.

2. R ２１ , R ２３ , R ２５ and R ２７ The leveling agent according to claim 1 , wherein each of the is a hydrogen atom.

3. 3. The leveling agent according to claim 1, wherein the content of the structural unit derived from the compound represented by formula (a1-1) is within a range of 20% by mass to 80% by mass of the total amount of the polymerization components.

4. 3. The leveling agent according to claim 1, wherein 50 mass % or more of the polymerization components other than the polymerizable monomer (a1) is a polymerizable monomer having an acryloyl group as a polymerizable unsaturated group.

5. 3. The leveling agent according to claim 1, which does not contain a fluorine atom.

6. 3. The leveling agent according to claim 1, which is a block copolymer having a polymer block of the polymerizable monomer (a1) and a polymer block of the polymerizable monomer (a2).

7. 3. The leveling agent according to claim 1, which has a number average molecular weight in the range of 1,000 to 500,000.

8. A coating composition comprising the leveling agent according to claim 1 or 2.

9. A coating of the coating composition of claim 8.

10. A resist composition comprising the leveling agent according to claim 1 or 2.

11. 11. The resist composition according to claim 10, further comprising an alkali-soluble resin, the content of said copolymer being 0.05 parts by mass or less per 100 parts by mass of said alkali-soluble resin.

12. A cured product obtained by curing the resist composition according to claim 10.

13. An article comprising the leveling agent according to claim 1 or 2.

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