Silicone-containing copolymer, leveling agent, coating composition, resist composition, color filter, and method for producing silicone-containing copolymer

Abstract

The present invention provides a silicone-containing copolymer which can reduce environmental burden and can impart an effect of suppressing the generation of foreign matter due to pigment sublimation on a coating film surface. Specifically, provided is a silicone-containing copolymer which contains, as polymerization components, at least a polymerizable monomer (A) having a group represented by general formula (a) and a polymerizable monomer (B) having a group containing a cyclic hydrocarbon skeleton. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a silicone-containing copolymer, a leveling agent, a coating composition, an etching resist composition, a color filter and a method for producing the silicone-containing copolymer. Background Art

[0002] Color filters used in color liquid crystal displays generally have a basic structure in which red (R), green (G), and blue (B) pixels are formed and a black matrix (BM) is formed therebetween for the purpose of improving display contrast.

[0003] The surfaces of the R, G, B pixels and BM in the color filter are required to have high smoothness. Therefore, when applying the color resist composition, it is necessary to apply it with a uniform film thickness without causing coating unevenness, depressions, and color unevenness.

[0004] A leveling agent is added to smoothen a coating film obtained by applying a coating composition such as a coating composition or a color resist composition. Specifically, by adding a leveling agent to a color resist composition, the smoothness of the obtained coating film can be improved, and the surfaces of red (R), green (G), and blue (B) pixels and the black matrix (BM) formed between these pixels show high smoothness, thereby making it possible to produce a color filter with less color unevenness.

[0005] In addition, the color filter requires the desired hue in each pixel of red, green, and blue. In the presence of such a requirement, for example, pigments such as Color Index (CI) Pigment Red 254 or CI Pigment Yellow 139 with excellent brightness have the property of being easily sublimated in the drying process of the coating film containing them, and easily growing as a crystallized product or agglomerate through its intermolecular interaction. Therefore, the pigment molecules sublimated from the inside of the coating film sometimes crystallize and / or agglomerate on the surface of the coating film to produce foreign matter. If foreign matter is produced on the surface of the coating film, light scattering will occur, so it is sometimes difficult to obtain the desired hue.

[0006] In addition, since foreign matter is generated on the coating surface due to sublimation of the pigment, the content ratio of the pigment changes from the coating surface to the inside, so it is sometimes difficult to obtain the desired hue. Thus, the generation of foreign matter such as crystallized matter or agglomerates generated on the coating surface due to sublimation of the pigment may cause color unevenness of pixels.

[0007] As a leveling agent for suppressing color unevenness of pixels, a leveling agent containing fluorine atoms has been proposed previously (Patent Document 1).

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: International Publication No. 2017 / 145771 Summary of the invention

[0011] Problems to be solved by the invention

[0012] Levelers containing fluorine atoms have a high environmental load, and a replacement technology corresponding to the recent strengthening of environmental regulations and further improvement of environmental awareness has been required.

[0013] An object of the present invention is to provide a silicone-containing copolymer which can reduce environmental load and impart an effect of suppressing the generation of foreign matter caused by sublimation of a pigment on the surface of a coating film.

[0014] Technical means of solving problems

[0015] The present inventors have conducted intensive studies to solve the above-mentioned problems and have found that, as a result, a silicone-containing copolymer containing at least a polymerizable monomer (A) represented by a specific group and a polymerizable monomer (B) having a group containing a cyclic hydrocarbon skeleton as polymerization components can obtain a silicone-containing copolymer that can reduce environmental load and can provide an effect of inhibiting the generation of foreign matter caused by sublimation of pigments on the surface of the coating film, thereby completing the present invention.

[0016] That is, the present invention relates to a silicone-containing copolymer comprising at least a polymerizable monomer (A) having a group represented by the following general formula (a) and a polymerizable monomer (B) having a group containing a cyclic hydrocarbon skeleton as polymerization components.

[0017] [Chemistry 1]

[0018]

[0019] (In the general formula (a),

[0020] R 11 are independently an alkyl group having 1 to 6 carbon atoms or -OSi(R 14 ) 3 The represented group (R 14 are each independently an alkyl group having 1 to 3 carbon atoms),

[0021] R 12 are each independently an alkyl group having 1 to 6 carbon atoms,

[0022] R 13 is an alkyl group having 1 to 6 carbon atoms,

[0023] x is the numerical average of the number of repetitions, which is an integer from 20 to 150)

[0024] In addition, the present invention relates to a leveling agent comprising the silicone copolymer.

[0025] In addition, the present invention relates to a coating composition comprising the silicone copolymer.

[0026] In addition, the present invention relates to a resist composition comprising the silicone copolymer and a colorant.

[0027] The present invention also relates to a color filter in which a coating layer of the resist composition is formed on a substrate.

[0028] The present invention also relates to a method for producing a silicone-containing copolymer by polymerizing a polymerizable monomer (A) having a group represented by the following general formula (a) and a polymerizable monomer (B) having a group containing a cyclic hydrocarbon skeleton.

[0029] [Chemistry 2]

[0030]

[0031] (In the general formula (a),

[0032] R 11 are independently an alkyl group having 1 to 6 carbon atoms or -OSi(R 14 ) 3 The represented group (R 14 are each independently an alkyl group having 1 to 3 carbon atoms),

[0033] R 12 are each independently an alkyl group having 1 to 6 carbon atoms,

[0034] R 13 is an alkyl group having 1 to 6 carbon atoms,

[0035] x is the numerical average of the number of repetitions, which is an integer from 20 to 150)

[0036] Effects of the Invention

[0037] The present invention provides a silicone-containing copolymer that can reduce environmental load and inhibit the generation of foreign matter caused by sublimation of pigment on the surface of a coating film. In addition, a leveling agent, a coating composition, a resist composition, and a color filter using the silicone-containing copolymer can be provided.

[0038] Furthermore, according to the present invention, a method for producing the silicone-containing copolymer can be provided. DETAILED DESCRIPTION

[0039] Hereinafter, an embodiment of the present invention will be described. The present invention is not limited to the following embodiment, and can be implemented by appropriately adding changes within a range that does not impair the effects of the present invention.

[0040] In the present specification, the term "(meth)acrylate" refers to one or both of acrylate and methacrylate.

[0041] [Silicone-containing copolymer]

[0042] The silicone-containing copolymer of the present invention (hereinafter, sometimes simply referred to as "the copolymer of the present invention") is a copolymer containing at least a polymerizable monomer (A) having a group represented by the following general formula (a) and a polymerizable monomer (B) having a group containing a cyclic hydrocarbon skeleton as polymerization components.

[0043] [Chemistry 3]

[0044]

[0045] (In the general formula (a),

[0046] R 11 are independently an alkyl group having 1 to 6 carbon atoms or -OSi(R 14 ) 3 The represented group (R 14 are each independently an alkyl group having 1 to 3 carbon atoms),

[0047] R 12 are each independently an alkyl group having 1 to 6 carbon atoms,

[0048] R 13 is an alkyl group having 1 to 6 carbon atoms,

[0049] x is the numerical average of the number of repetitions, which is an integer from 20 to 150)

[0050] In the copolymer of the present invention, the copolymer is made rigid by having a bulky group containing a cyclic hydrocarbon skeleton. Since the group represented by the general formula (a) is segregated on the surface (interface) of the coating film and the copolymer has a rigid structure, a rigid (dense) film can be formed at the interface. It is inferred that the sublimation of the colorant is physically prevented by the rigid film.

[0051] In the present invention, the term "polymerizable monomer" refers to a compound having a polymerizable unsaturated group, and examples of the polymerizable unsaturated group possessed by the polymerizable monomer (A) and the polymerizable monomer (B) include C=C-containing groups such as a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acryloylamino group, a vinyl ether group, an allyl group, a styryl group, and a maleimide group. Among these, a (meth)acryloyl group and a (meth)acryloyloxy group are preferred in terms of easy availability of raw materials and good polymerization reactivity.

[0052] The number of polymerizable unsaturated groups contained in the polymerizable monomer may be one or two or more.

[0053] In the present invention, the "polymerization component" refers to a component constituting a polymer, and does not include a solvent or a polymerization initiator that does not constitute a polymer.

[0054] In the general formula (a), R 11 Preferably, methyl or trimethylsilyl is 12 and R 13 Preferred is methyl.

[0055] In the general formula (a), x is 20 to 150. It is inferred that by setting the lower limit of the number average value of x in the polymer of the present invention to 20 or more, the copolymer of the present invention can exhibit a high surface tension reducing ability, and when it is prepared as a color resist composition or a coating composition, it is easy to be arranged on the surface (interface) of the composition, thereby suppressing the generation of foreign matter from the inside of the coating film to the surface due to the sublimation of the pigment molecules.

[0056] x is preferably in the range of 30-150, more preferably in the range of 50-130.

[0057] In the present invention, the "number average value of x" refers to the average number of repeating units of siloxane bonds per one type of polymerizable monomer (A) constituting the polymer of the present invention.

[0058] The number average value of x in the polymer of the present invention can be calculated from the number average molecular weight of the polymer of the present invention.

[0059] The polymerizable monomer (A) is preferably a compound represented by the following general formula (a-1).

[0060] [Chemistry 4]

[0061]

[0062] (In the general formula (a-1),

[0063] R 11 , R12 , R 13 and x are respectively the same as R 11 , R 12 , R 13 and x are the same,

[0064] R 15 is a hydrogen atom or a methyl group,

[0065] L 1 (divalent organic radical)

[0066] L 1 The divalent organic group is preferably a single bond, an alkylene group having 1 to 50 carbon atoms, or an alkyleneoxy group having 1 to 50 carbon atoms.

[0067] As L 1 The alkylene group having 1 to 50 carbon atoms includes methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene, n-dodecylene, isopropylene, 2-methylpropylene, 2-methylhexylene, tetramethylethylene and the like.

[0068] L 1 The alkylene group having 1 to 50 carbon atoms is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, further preferably a methylene group, an ethylene group, an n-propylene group or an isopropylene group.

[0069] L 1 The alkyleneoxy group having 1 to 50 carbon atoms is, for example, one of the alkylene groups -CH 2 - a group substituted by -O-.

[0070] L 1 The alkyleneoxy group having 1 to 50 carbon atoms is preferably an alkyleneoxy group having 1 to 15 carbon atoms, more preferably an alkyleneoxy group having 1 to 8 carbon atoms, further preferably a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, an oxytrimethylene group, a butyleneoxy group, an oxytetramethylene group, a pentyleneoxy group, a heptyleneoxy group or an octyleneoxy group.

[0071] In L 1 When the divalent organic group is an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms, the -CH 2 A part of - may be substituted with a carbonyl group (-C(=O)-), a phenylene group, an amide bond or a urethane bond, and a hydroxyl group or the like may be substituted with a carbon atom.

[0072] The polymerizable monomer (A) can be produced by a known method, or a commercially available product can be used.

[0073] The polymerizable monomer (B) having a group containing a cyclic hydrocarbon skeleton, which is a polymerization component of the silicone-containing copolymer of the present invention, has a function of, for example, making the copolymer rigid and also has a function of ensuring compatibility.

[0074] The polymerizable monomer (B) may be any polymerizable monomer having a group containing a cyclic hydrocarbon skeleton, and preferably includes a polymerizable monomer having a group containing a cyclic hydrocarbon skeleton having a bridged structure.

[0075] The polymerizable monomer (B) is preferably a compound represented by the following general formula (b-1). These compounds can impart compatibility when the copolymer of the present invention is used as a leveling agent.

[0076] [Chemistry 5]

[0077]

[0078] (In the general formula (b-1),

[0079] R b1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,

[0080] R b2 is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 18 carbon atoms, or a divalent linking group comprising a combination of two or more selected from an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 18 carbon atoms, and an ether bond (—O—),

[0081] R b3 is a group containing a cyclic hydrocarbon skeleton)

[0082] R b2 The alkylene group having 1 to 10 carbon atoms may be linear, branched, or cyclic.

[0083] R b2 The arylene group having 6 to 18 carbon atoms may be a monocyclic ring or a condensed ring. b2 Specific examples of the arylene group having 6 to 18 carbon atoms include phenylene and naphthylene.

[0084] R b2 The alkylene group and the arylene group may further have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogen atom, and the like.

[0085] In the general formula (b-1), R b3The base containing a cyclic hydrocarbon skeleton may be any one of a base containing a cyclic hydrocarbon skeleton having a bridged structure and a base containing a cyclic hydrocarbon skeleton without a bridged ring structure. As a specific example, a cyclohexane ring, an adamantane ring, a perhydroindene ring, a decahydronaphthalene ring, a perhydrofluorene ring, a perhydroanthracene ring, a perhydrophenanthrene ring, a dicyclopentane ring, a dicyclopentene ring, a perhydroacenaphthylene ring, a perhydrophenanthrene ring, a norbornane ring, an isobornane ring, a norbornene ring, etc. can be cited. Among them, in terms of suppressing the generation of foreign matter on the coating surface caused by the sublimation of the pigment, a cyclohexane ring, an adamantane ring, a dicyclopentane ring, a norbornane ring, and a norbornene ring are preferred.

[0086] Hereinafter, the polymerizable monomer having an adamantane ring and a polymerizable unsaturated group which can be preferably used as the polymerizable monomer (b-1) in the present invention will be described.

[0087] Examples of the polymerizable monomer having the adamantane ring and the (meth)acryloyl group include compounds represented by the following formula (b-1-1) and formula (b-1-2).

[0088] [Chemistry 6]

[0089]

[0090] (wherein, Z represents a reactive functional group, X and Y represent a divalent organic group or a single bond, R b1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

[0091] Examples of the reactive functional group include hydroxyl, isocyanate, epoxy, carboxyl, carboxylic acid halide, and anhydride. Among them, when the obtained copolymer is used to prepare a resist composition or a coating composition, a hydroxyl group is preferred in terms of obtaining a copolymer having good compatibility with the formulation components in the composition.

[0092] The organic group having the reactive functional group represented by -XZ in the general formula (b-1-1) and the bonding position of Y may be bonded to any carbon atom in the adamantane ring, and -XZ may have two or more groups. Furthermore, X and Y in the general formula (b-1-1) are divalent organic groups or single bonds, and examples of the divalent organic group include alkylene groups having 1 to 8 carbon atoms, such as methylene, propyl, and isopropylidene.

[0093] In the compound represented by the formula (b-1-2), the (meth)acryloyl group may be bonded to any carbon atom in the adamantane ring.

[0094] More specific examples of the polymerizable monomer represented by the general formula (b-1-1) include the following compounds.

[0095] [Chemistry 7]

[0096]

[0097] Moreover, as more specific examples of the polymerizable monomer represented by the general formula (b-1-2), for example, the compounds represented below can be cited.

[0098] [Chemistry 8]

[0099]

[0100] Among the polymerizable monomers having an adamantane ring and a (meth)acryloyl group, when using the obtained copolymer to manufacture an anti-etching composition, from the perspective of obtaining a random copolymer with good compatibility with the formulation components in the composition, the compound represented by the formula (b-1-2) is preferred, and the compound represented by the formula (b-1-2-1) is more preferred.

[0101] Hereinafter, the polymerizable monomer having a dicyclopentane ring and a polymerizable unsaturated group which can be preferably used as the polymerizable monomer (B) in the present invention will be described.

[0102] Examples of the polymerizable monomer having the dicyclopentane ring and the (meth)acryloyl group include compounds represented by the following formula (b-1-3).

[0103] [Chemistry 9]

[0104]

[0105] (Where R b1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

[0106] In the compound represented by the formula (b-1-3), the (meth)acryloyl group may be bonded to any carbon atom in the dicyclopentane ring.

[0107] More specific examples of the polymerizable monomer represented by the general formula (b-1-3) include the following compounds.

[0108] [Chemistry 10]

[0109]

[0110] Among the polymerizable monomers having a dicyclopentane ring and a (meth)acryloyl group, the compound represented by the formula (b-1-3-2) is preferred in that a resist composition capable of suppressing generation of foreign matter due to sublimation of a pigment can be obtained.

[0111] Hereinafter, the polymerizable monomer having a dicyclopentene ring and a polymerizable unsaturated group which can be preferably used as the polymerizable monomer (b-1) in the present invention will be described.

[0112] Examples of the polymerizable monomer having the dicyclopentene ring and the (meth)acryloyl group include compounds represented by the following formula (b-1-4).

[0113] [Chemistry 11]

[0114]

[0115] (Where R b1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

[0116] In the compound represented by the formula (b-1-4), the (meth)acryloyl group may be bonded to any carbon atom in the dicyclopentene ring.

[0117] More specific examples of the polymerizable monomer represented by the general formula (b-1-4) include the following compounds.

[0118] [Chemistry 12]

[0119]

[0120] Among the polymerizable monomers having a dicyclopentene ring and a (meth)acryloyl group, the compound represented by the formula (b-1-4-2) is preferred in that a resist composition capable of suppressing generation of foreign matter due to sublimation of the pigment can be obtained.

[0121] Hereinafter, the polymerizable monomer having a norbornane ring and a polymerizable unsaturated group which can be preferably used as the polymerizable monomer (b-1) in the present invention will be described.

[0122] Examples of the polymerizable monomer having the norbornane ring and the (meth)acryloyl group include compounds represented by the following formula (b-1-5).

[0123] [Chemistry 13]

[0124]

[0125] (Where R b1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

[0126] In the compound represented by the formula (b-1-5), the (meth)acryloyl group may be bonded to any carbon atom in the norbornane ring.

[0127] More specific examples of the polymerizable monomer represented by the general formula (b-1-5) include the following compounds.

[0128] [Chemistry 14]

[0129]

[0130] Among the polymerizable monomers having a norbornane ring and a (meth)acryloyl group, the compound represented by the formula (b-1-5-2) is preferred because a resist composition capable of suppressing generation of foreign matter due to sublimation of a pigment can be obtained.

[0131] Hereinafter, the polymerizable monomer having a norbornene ring and a polymerizable unsaturated group which can be preferably used as the polymerizable monomer (b-1) in the present invention will be described.

[0132] Examples of the polymerizable monomer having the norbornene ring and the (meth)acryloyl group include compounds represented by the following formula (b-1-6).

[0133] [Chemistry 15]

[0134]

[0135] (Where R b1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

[0136] In the compound represented by the formula (b-1-6), the (meth)acryloyl group may be bonded to any carbon atom in the norbornene ring.

[0137] More specific examples of the polymerizable monomer represented by the general formula (b-1-6) include the following compounds.

[0138] [Chemistry 16]

[0139]

[0140] Among the polymerizable monomers having a norbornene ring and a (meth)acryloyl group, the compound represented by the formula (b-1-6-2) is preferred because a resist composition capable of suppressing generation of foreign matter due to sublimation of a pigment can be obtained.

[0141] The polymerizable monomer (B) can be produced by a known method.

[0142] Moreover, a commercially available item can also be used as the polymerizable monomer (B).

[0143] The polymerizable monomer (B) constituting the silicone-containing copolymer of the present invention may be a single type or two or more types.

[0144] The polymerization form of the silicone-containing copolymer, which is a copolymer containing at least the polymerizable monomer (A) and the polymerizable monomer (B) as polymerization components, is not particularly limited, and may be a random copolymer of the polymerizable monomer (A) and the polymerizable monomer (B) or a block copolymer of the polymerizable monomer (A) and the polymerizable monomer (B).

[0145] The mass ratio of the polymerizable monomer (A) to the polymerizable monomer (B) in the silicone-containing copolymer is, for example, polymerizable monomer (A): polymerizable monomer (B) = 5:95 to 95:5, preferably polymerizable monomer (A): polymerizable monomer (B) = 5:95 to 80:20, more preferably polymerizable monomer (A): polymerizable monomer (B) = 5:95 to 60:40, further preferably 5:95 to 50:50, and particularly preferably polymerizable monomer (A): polymerizable monomer (B) = 5:95 to 30:70.

[0146] The silicone-containing copolymer of the present invention may be a copolymer of the polymerizable monomer (A) and the polymerizable monomer (B), and may contain structural units of polymerizable monomers other than the polymerizable monomer (A) and the polymerizable monomer (B) within a range not impairing the effects of the present invention.

[0147] The copolymer of the present invention is preferably a copolymer substantially composed of polymerizable monomers (A) and polymerizable monomers (B), and more preferably a copolymer containing only polymerizable monomers (A) and polymerizable monomers (B). Here, "substantially formed" means that the total content ratio of the polymerizable monomers (A) and the polymerizable monomers (B) in the copolymer of the present invention is 80% by mass or more, 90% by mass or more, 95% by mass or more, or 99% by mass or more.

[0148] The silicone-containing copolymer of the present invention preferably does not contain fluorine atoms. Since the silicone-containing copolymer of the present invention does not contain fluorine atoms, solvent resistance can be improved. In addition, since the silicone-containing copolymer of the present invention is a fluorine-free resin, the accumulation of the environment becomes low, thereby reducing the environmental load.

[0149] The weight average molecular weight (Mw) of the silicone-containing copolymer of the present invention is preferably in the range of 3,000 to 80,000, and more preferably in the range of 4,000 to 50,000.

[0150] The weight average molecular weight of the silicone-containing copolymer of the present invention is measured by the method described in Examples.

[0151] The ratio of the structure derived from the polymerizable monomer (A) in the silicone-containing copolymer of the present invention is, for example, in the range of 5 to 80 mass %, preferably 5 to 60 mass %, and more preferably 5 to 50 mass %.

[0152] The ratio of the structure derived from the polymerizable monomer (A) in the silicone-containing copolymer of the present invention is a value calculated from the mass ratio of the polymerizable monomer (A) relative to the total amount of the raw materials used.

[0153] The content of the silicone chain represented by the general formula (a) in the silicone-containing copolymer of the present invention is preferably in the range of 5 to 80 mass %, more preferably in the range of 5 to 60 mass %, and even more preferably in the range of 5 to 50 mass %.

[0154] The silicone chain content of the silicone-containing copolymer of the present invention is a value calculated from the mass ratio of the silicone chain relative to the total amount of the raw materials used.

[0155] [Method for producing silicone-containing copolymer]

[0156] The method for producing the copolymer of the present invention is not particularly limited, and the copolymer can be produced by a known method.

[0157] The copolymer of the present invention can be prepared by a polymerization mechanism such as free radical polymerization, cationic polymerization, anionic polymerization, etc., by solution polymerization, bulk polymerization, emulsion polymerization, etc. For example, in the case of free radical polymerization, the copolymer of the present invention can be prepared by placing the polymerization components in an organic solvent and adding a general free radical polymerization initiator.

[0158] The obtained copolymer is a random copolymer.

[0159] As the polymerization initiator, various polymerization initiators can be used, for example, acetyl peroxide, diacyl peroxide, cumyl peroxide, t-butyl peroxide, propionyl peroxide, benzoyl peroxide, 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, diisopropyl peroxycarbonate, tetralin hydroperoxide, t-butylperoxy-2-ethylhexanoate, 1-phenylene glycol, 1-hydroxy-2-thiophene carbonate ... Peroxides such as 2-methylpropyl-1-hydroperoxide, tert-butyl triphenylacetate, tert-butyl hydroperoxide, tert-butyl performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl per-2-ethylhexanoate, tert-butyl perphenylacetate, and tert-butyl per-4-methoxyacetate; 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo(methylethyl)diacetate, 2,2'-azobis(2-amidinopropane)nitrate, 2,2'-azobisisobutane, 2, 2'-azobisisobutylamide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobisisobutyric acid dimethyl ester, 2,2'-azobisisobutyric acid dimethyl ester, 2-(4-methylphenylazo)-2-methylmalononitrile, 4,4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-methylmalononitrile Nitrile, 1,1'-azobis-1-cyclohexanecarbonitrile, 1,1'-azobis-1-phenylethane, 1,1'-azobiscumene, ethyl 4-nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrotriphenylazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane and other azo compounds; azobisisobutyronitrile, dimethyl azobisisobutyrate, phenylazotriphenylmethane and other azo compounds; Mn(acac) 3 Metal chelate compounds, etc.

[0160] If necessary, chain transfer agents such as lauryl mercaptan, thioglycerol, 2-mercaptoethanol, ethylthioglycolic acid, octylthioglycolic acid, or thiol compounds having a coupling group such as γ-mercaptopropyltrimethoxysilane may be used as additives such as chain transfer agents.

[0161] As the organic solvent, ketones, esters, amides, sulfoxides, ethers, hydrocarbons, fluorine-based solvents, etc. are preferred. Specifically, for example, alcohols such as ethanol, isopropanol, n-butanol, isobutanol, and tert-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 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 Examples of the present invention include polar solvents such as diethyl ether, diisopropyl ether, 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; halogen solvents such as 1,1,1-trichloroethane and chloroform; ethers such as tetrahydrofuran and dioxane; aromatic solvents such as benzene, toluene, and xylene; fluorine solvents such as 1,3-bis(trifluoromethyl)benzene and 1,4-bis(trifluoromethyl)benzene; and fluorinated inert liquids such as perfluorooctane and perfluorotri-n-butylamine.

[0162] These organic solvents can be appropriately selected in consideration of boiling point, compatibility with raw materials or polymers, and polymerizability. The polymerizable monomer (A) has particularly excellent compatibility with organic solvents and is therefore soluble in most of the above-mentioned organic solvents.

[0163] These solvents may be used alone or in combination of two or more.

[0164] The copolymer of the present invention preferably starts with adding the polymerizable monomer (A) to the reaction system, and after starting the addition of the polymerizable monomer (A), the polymerizable monomer (B) and the polymerization initiator are added to the reaction system to start polymerization, and the addition of the polymerizable monomer (A) is completed before the addition of the polymerizable monomer (B) and the polymerization initiator.

[0165] This is because, by polymerizing the polymer of the present invention in this manner, unreacted silicone chains can be infinitely reduced, thereby suppressing coating film defects that may be caused by additives during coating.

[0166] The polymerizable monomer (A) may contain impurities such as compounds having a cyclic siloxane structure, and the compounds having a cyclic siloxane structure may be removed by distilling the polymerizable monomer (A) before adding it to the reaction system or by distilling the polymer after the reaction. The distillation may be carried out by a known method, for example, by thin film distillation.

[0167] The polymer of the present invention can also be produced by subjecting the polymerization components to living polymerization such as living radical polymerization and living anion polymerization.

[0168] In the living radical polymerization, a dormant species protected by an atom or an atomic group at the active polymerization end can reversibly generate a radical and react with a monomer to perform a growth reaction. Even if the first monomer is consumed, the growth end will not lose activity and react with the second monomer added successively to obtain a block polymer. Examples of such living radical polymerization include: atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT), nitroxide-mediated polymerization (NMP), and organic tellurium-mediated living radical polymerization (TERP). Among these methods, there is no particular restriction on which method is used, but ATRP is preferred in terms of ease of control. ATRP is a polymerization method in which an organic halide or a halogenated sulfonyl compound is used as a polymerization initiator and a metal complex containing a transition metal compound and a ligand is used as a catalyst.

[0169] Specific examples of the polymerization initiator that can be used in ATRP include 1-phenylethyl chloride, 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, α,α'-dichloroxylene, α,α'-dibromoxylene, hexa(α-bromomethyl)benzene, and alkyl esters of 2-halogenated carboxylic acids having 1 to 6 carbon atoms (e.g., 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, etc.).

[0170] More specific examples of the C1-6 alkyl ester of a C1-6 2-halogenated carboxylic acid include methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate, and ethyl 2-bromoisobutyrate.

[0171] The transition metal compounds that can be used in ATRP are M n+ X n The compound represented.

[0172] As M n+ X n The transition metal M of the transition metal compound represented by n+ , free Cu +, Cu 2+ , Fe 2+ , Fe 3+ 、Ru 2 + 、Ru 3+ Cr 2+ Cr 3+ 、Mo 0 、Mo + 、Mo 2+ 、Mo 3+ , W 2+ , W 3+ , Rh 3+ , Rh 4+ 、Co + 、Co 2+ 、Re 2+ 、Re 3+ 、Ni 0 、Ni + , Mn 3+ , Mn 4 + 、V 2+ 、V 3+ 、Zn + 、Zn 2+ 、Au + 、Au 2+ 、Ag + and Ag 2+ Select from the group you want to form.

[0173] M n+ X n X of the transition metal compound represented by the formula (a) may be a halogen atom, an alkoxy group having 1 to 6 carbon atoms, (SO 4 ) 1 / 2 ,(PO 4 ) 1 / 3 ,(HPO 4 ) 1 / 2 ,(H 2 PO 4 ), trifluoromethanesulfonate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate), SeR 11 , CN and R 12 Here, R 11 represents an aryl group, a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and R 12 It represents a hydrogen atom, and a linear or branched alkyl group having 1 to 6 carbon atoms (preferably a methyl group) which may be substituted 1 to 5 times by halogen (preferably substituted 1 to 3 times by fluorine or chlorine).

[0174] M n+ Xn In the transition metal compound represented by FIG. 1 , n represents the formal charge on the metal and is an integer of 0 to 7.

[0175] As ligand compounds capable of coordinating and bonding with the transition metal of the transition metal compound, there can be listed: compounds having ligands containing one or more nitrogen atoms, oxygen atoms, phosphorus atoms or sulfur atoms that can coordinate with the transition metal via a σ bond, compounds having ligands containing two or more carbon atoms that can coordinate with the transition metal via a π bond, and compounds having ligands that can coordinate with the transition metal via a μ bond or an η bond.

[0176] The transition metal complex is not particularly limited, and preferred ones include transition metal complexes of Group 7, Group 8, Group 9, Group 10, and Group 11. Further preferred ones include complexes of 0-valent copper, 1-valent copper, 2-valent ruthenium, 2-valent iron, or 2-valent nickel.

[0177] As specific examples of catalysts that can be used in ATRP, when the central metal is copper, there can be listed: complexes of ligands with polyamines such as 2,2'-bipyridine and its derivatives, 1,10-phenanthene and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexamethyltris(2-aminoethyl)amine. In addition, as divalent ruthenium complexes, there can be listed: dichlorotris(triphenylphosphine)ruthenium, dichlorotris(tributylphosphine)ruthenium, dichloro(cyclooctadiene)ruthenium, dichlorophenylruthenium, dichloro-p-isopropyltolueneruthenium, dichloro(norbornadiene)ruthenium, cis-dichlorobis(2,2'-bipyridine)ruthenium, dichlorotris(1,10-phenanthene)ruthenium, carbonyl chloride hydride tris(triphenylphosphine)ruthenium, etc. Further, as divalent iron complexes, there can be listed bistriphenylphosphine complexes and triazacyclononane complexes.

[0178] When the polymer of the present invention is produced by living polymerization, the polymerizable monomer (A) itself can be used as a polymerization initiator. The polymerizable monomer (A) that can be used as a polymerization initiator is a compound represented by the following general formula (a-2).

[0179] [Chemistry 17]

[0180]

[0181] (In the formula (a-2),

[0182] R 11 , R 12 , R 13 , L 1 and x and R of the general formula (a-1) 11 , R 12 , R 13 , L 1 and x are the same,

[0183] R X is a functional group with free radical generating ability)

[0184] In the formula (a-2), R X The functional group having a radical generating ability is, for example, a functional group having a halogen atom, and is preferably a functional group represented by the following formula (X-1).

[0185] [Chemistry 18]

[0186]

[0187] (In the formula (X-1),

[0188] R HAL is a halogen atom,

[0189] R 14 and R 15 are each independently an alkyl group having 1 to 6 carbon atoms,

[0190] Q is an oxygen atom or a sulfur atom)

[0191] In the living radical polymerization, it is preferred to use a solvent.

[0192] Examples of the solvent used in the living radical polymerization include ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ether solvents such as diisopropyl ether, dimethoxyethane, and diethylene glycol dimethyl ether; halogen solvents such as dichloromethane and dichloroethane; aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, and isopropanol; and aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide.

[0193] The above solvents may be used alone or in combination of two or more.

[0194] When the polymer of the present invention is produced by living polymerization, for example, it can be produced by any one of the following methods 1 to 3.

[0195] Method 1: A method in which a polymerizable monomer (A) and a polymerizable monomer (B) 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 coordinately bonding with the transition metal, and a solvent.

[0196] Method 2: In the presence of a polymerization initiator, a transition metal compound, a ligand compound capable of coordinately bonding with the transition metal, and a solvent, a polymerizable monomer (A) is subjected to living free radical polymerization (preferably atom transfer radical polymerization) to obtain a polymer block of the polymerizable monomer (A), and then a polymerizable monomer (B) is added to the reaction system to further subject the polymerizable monomer (B) and the polymer block of the polymerizable monomer (A) to living free radical polymerization (preferably atom transfer radical polymerization).

[0197] Method 3: In the presence of a polymerization initiator, a transition metal compound, a ligand compound capable of coordinately bonding with the transition metal, and a solvent, a polymerizable monomer (B) is subjected to living radical polymerization (preferably atom transfer radical polymerization) to obtain a polymer block of the polymerizable monomer (B), and then a polymerizable monomer (A) is added to the reaction system to further subject the polymerizable monomer (A) and the polymer block of the polymerizable monomer (B) to living radical polymerization (preferably atom transfer radical polymerization).

[0198] The polymerization temperature during the living radical polymerization is preferably in the range of room temperature to 120°C.

[0199] When the polymer of the present invention is produced by living radical polymerization, metal derived from the transition metal compound used in the polymerization may remain in the obtained polymer. The metal remaining in the obtained polymer can be removed using activated alumina or the like after the polymerization is completed.

[0200] [Coating composition]

[0201] The polymer of the present invention can be preferably used as a leveling agent for a coating composition, and the coating composition of the present invention contains the polymer of the present invention. The polymer of the present invention can be used as a leveling agent without fluorine atoms, and thus is a leveling agent with low environmental accumulation and low environmental load.

[0202] The content of the copolymer of the present invention contained in the coating composition of the present invention varies depending on the type of base resin, coating method, target film thickness, etc., but is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 5 parts by mass, and further preferably 0.01 to 2 parts by mass relative to 100 parts by mass of the solid content (e.g., base resin) of the coating composition. If the content of the copolymer of the present invention is within the above range, the surface tension can be sufficiently reduced, the target leveling property can be obtained, and the occurrence of undesirable conditions such as blistering during coating can be suppressed.

[0203] The application of the coating composition of the present invention is not particularly limited, and can be used for any application as long as leveling properties are required. The coating composition of the present invention can be used, for example, as various coating compositions or photosensitive resin compositions.

[0204] When the coating composition of the present invention is used as a coating composition, examples of the coating composition include coatings using natural resins such as petroleum resin coatings, shellac coatings, rosin-based coatings, cellulose-based coatings, rubber-based coatings, lacquer coatings, cashew resin coatings, and oily liquid coatings; and coatings using synthetic resins such as phenolic resin coatings, alkyd resin coatings, unsaturated polyester resin coatings, amino resin coatings, epoxy resin coatings, vinyl resin coatings, acrylic resin coatings, polyurethane resin coatings, and silicone resin coatings.

[0205] By adding the polymer of the present invention to the coating composition, smoothness can be imparted to the obtained coating film.

[0206] The coating composition may contain colorants such as pigments, dyes, and carbon; inorganic powders such as silicon dioxide, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, and calcium carbonate; organic fine powders such as higher fatty acids, polyacrylic resins, and polyethylene; and various additives such as light resistance enhancers, weather resistance enhancers, heat resistance enhancers, antioxidants, thickeners, and anti-settling agents.

[0207] Regarding the coating method of the coating composition of the present invention, any method can be used as long as it is a known and publicly available coating method, for example, slit coater, slit & spin coater, spin coater, roll coater, electrostatic coating, rod coater, gravure coater, die coater, knife coater, inkjet, dip coating, spray coating, shower coating, screen printing, gravure printing, lithographic printing, reverse coating and the like methods can be listed.

[0208] When a photosensitive resin composition is irradiated with light such as visible light or ultraviolet light, the physical properties of the resin such as solubility, viscosity, transparency, refractive index, conductivity, and ion permeability change.

[0209] In the photosensitive resin composition, the resist composition (photoresist composition, color resist composition for color filter, etc.) requires a high degree of leveling. Usually, the resist composition is applied by spin coating, and is coated on a silicon wafer or a glass substrate on which various metals have been evaporated in a manner of about 1 μm to 2 μm in thickness. At this time, if the coating film thickness deviates or uneven coating occurs, the linearity or reproducibility of the pattern is reduced, resulting in a problem that a resist pattern with target accuracy cannot be obtained. In addition, in addition to these problems, there are also various problems related to leveling, such as drip marks, overall unevenness, and bead phenomenon in which the edge portion is thickened compared to the center portion.

[0210] The coating composition of the present invention can form a uniform coating film (cured product) by exerting a high leveling property of the polymer of the present invention. Therefore, when used as a resist composition, the above-mentioned problems can be solved.

[0211] When the coating composition of the present invention is used as a photoresist composition, the photoresist composition contains an alkali-soluble resin, a radiation-sensitive substance (photosensitive substance), a solvent, and the like in addition to the polymer of the present invention.

[0212] The alkali-soluble resin contained in the photoresist composition refers to a resin that is soluble in an alkaline solution as a developer used when patterning a resist.

[0213] Examples of the alkali-soluble resin include: novolac resins obtained by condensing aromatic hydroxy compound derivatives such as phenol, cresol, xylenol, resorcinol, phloroglucinol, and hydroquinone with aldehyde compounds such as formaldehyde, acetaldehyde, and benzaldehyde; polymers or copolymers of vinyl phenol compound derivatives such as o-vinylphenol, m-vinylphenol, p-vinylphenol, and α-methylvinylphenol; (meth)acrylic acid polymers or copolymers such as acrylic acid, methacrylic acid, and hydroxyethyl (meth)acrylate; polyvinyl alcohol; modified resins having a radioactive radiation-sensitive group such as a quinonediazide group, a naphthoquinoneazide group, an aromatic azide group, or an aromatic cinnamoyl group introduced through a part of the hydroxyl groups of the above various resins; and carbamate resins containing an acidic group such as a carboxylic acid or a sulfonic acid in the molecule.

[0214] These alkali-soluble resins may be used alone or in combination of two or more.

[0215] The radiation-sensitive substance contained in the photoresist composition refers to a substance that changes the solubility of the alkali-soluble resin in the developer by irradiation with energy rays such as ultraviolet rays, extreme ultraviolet rays, excimer laser light, X-rays, electron beams, ion beams, molecular beams, and gamma rays.

[0216] Examples of radiation-sensitive substances include quinonediazide compounds, diazo compounds, azide compounds, onium salt compounds, halogenated organic compounds, mixtures of halogenated organic compounds and organic metal compounds, organic acid ester compounds, organic acid amide compounds, organic acid imide compounds, and poly(olefin sulfone) compounds.

[0217] Examples of the quinonediazide compound include 1,2-benzoquinone azide-4-sulfonate, 1,2-naphthoquinonediazide-4-sulfonate, 1,2-naphthoquinonediazide-5-sulfonate, 2,1-naphthoquinonediazide-4-sulfonate, 2,1-naphthoquinonediazide-5-sulfonate, and other sulfonyl chlorides of quinonediazide derivatives such as 1,2-benzoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 2,1-naphthoquinonediazide-4-sulfonyl chloride, and 2,1-naphthoquinonediazide-5-sulfonyl chloride.

[0218] Examples of the diazo compounds include salts of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde, inorganic diazo resin salts which are reactive species of hexafluorophosphate, tetrafluoroborate, perchlorate or periodate with the condensates, and organic diazo resin salts which are reaction products of the condensates with sulfonates as described in USP 3, 300, and 309.

[0219] Examples of the azide compounds include azidochalcone acid, diazidobenzylidenemethylcyclohexanones, azidobenzylideneacetophenones, aromatic azide compounds, and aromatic diazide compounds.

[0220] Examples of the halogenated organic compound include halogen-containing oxadiazole compounds, halogen-containing triazine compounds, halogen-containing acetophenone compounds, halogen-containing benzophenone compounds, halogen-containing sulfoxide compounds, halogen-containing sulfone compounds, halogen-containing thiazole compounds, halogen-containing oxazole compounds, halogen-containing triazole compounds, halogen-containing 2-pyrone compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, halogen-containing heterocyclic compounds, and sulfinyl halide compounds.

[0221] In addition to the above, compounds used as halogen flame retardants such as tris(2,3-dibromopropyl)phosphate, tris(2,3-dibromo-3-chloropropyl)phosphate, chlorotetrabromomethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenyl allyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis(bromoethyl ether)tetrabromobisphenol A, bis(chloroethyl ether)tetrachlorobisphenol A, tris(2,3-dibromopropyl)isocyanurate, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, and 2,2-bis(4-hydroxyethoxy-3,5-dibromophenyl)propane, and compounds used as organochlorine pesticides such as dichlorophenyltrichloroethane are also exemplified as halogenated organic compounds.

[0222] Examples of the organic acid ester include carboxylic acid ester and sulfonic acid ester. Examples of the organic acid amide include carboxylic acid amide and sulfonic acid amide. Examples of the organic acid imide include carboxylic acid imide and sulfonic acid imide.

[0223] The radiation sensitive substances may be used alone or in combination of two or more.

[0224] In the photoresist composition, the content of the radiation sensitive substance is preferably in the range of 10 to 200 parts by mass, more preferably 50 to 150 parts by mass, based on 100 parts by mass of the alkali-soluble resin.

[0225] Examples of the solvent for the photoresist composition include ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, and butyrolactone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, amyl alcohol, 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, ethyl butyrate, butyl butyrate, propyl butyrate, ethyl lactate, lactate Esters such as butyl 2-oxopropionate; monocarboxylic acid esters such as methyl 2-oxopropionate, ethyl 2-oxopropionate, propyl 2-oxopropionate, butyl 2-oxopropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate; cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; propylene glycols such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether; trichloroethylene, chlorofluorocarbon solvents, hydrochlorofluorocarbons (Hydrochloro Halogenated hydrocarbons such as fluorocarbon (HCFC) and hydrofluorocarbon (HFC); fully fluorinated solvents such as perfluorooctane; aromatic solvents such as toluene and xylene; polar solvents such as dimethylacetamide, dimethylformamide, N-methylacetamide, and N-methylpyrrolidone.

[0226] These solvents may be used alone or in combination of two or more.

[0227] When the coating composition of the present invention is used as a color resist composition, the color resist composition contains an alkali-soluble resin, a polymerizable compound, a colorant, and the like in addition to the polymer of the present invention.

[0228] As the alkali-soluble resin contained in the color resist, the same alkali-soluble resin as that contained in the above-mentioned photoresist composition can be used.

[0229] The polymerizable compound contained in the color resist composition refers to a compound having a photopolymerizable functional group that can be polymerized or cross-linked by irradiation with active energy rays such as ultraviolet rays, for example.

[0230] 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, and 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 aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds; polymerizable compounds having a carbamate skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl-containing hydroxy compound, and polymerizable compounds having an acid group.

[0231] The polymerizable compound may be used alone or in combination of two or more.

[0232] Examples of the esters of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include (meth)acrylates such as ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and glycerol (meth)acrylate.

[0233] In addition, examples include itaconate esters in which a portion of the (meth)acrylic acid in these acrylates is substituted with itaconic acid, crotonate esters in which a portion is substituted with crotonic acid, or maleate esters in which a portion is substituted with maleic acid.

[0234] Examples of the esters of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone di(meth)acrylate, resorcinol di(meth)acrylate, and gallol tri(meth)acrylate.

[0235] The ester obtained by the esterification reaction of unsaturated carboxylic acid, polycarboxylic acid and polyhydroxy compound may be a single substance or a mixture. Examples of such esters include: esters obtained from (meth)acrylic acid, phthalic acid and ethylene glycol; esters obtained from (meth)acrylic acid, maleic acid and diethylene glycol; esters obtained from (meth)acrylic acid, terephthalic acid and pentaerythritol; esters obtained from (meth)acrylic acid, adipic acid, butanediol and glycerol, etc.

[0236] Examples of the polymerizable compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a hydroxy compound containing a (meth)acryloyl group include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; and reaction products of aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate with hydroxy compounds having a (meth)acryloyl group such as 2-hydroxyethyl (meth)acrylate and 3-hydroxy〔1,1,1-tri(meth)acryloyloxymethyl〕propane.

[0237] The polymerizable compound having an acid group is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, preferably a polyfunctional polymerizable compound having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound. The aliphatic polyhydroxy compound used in the preparation of the polyfunctional polymerizable compound is preferably pentaerythritol or dipentaerythritol.

[0238] In terms of improving developability, curability, etc., the acid value of the polyfunctional polymerizable compound is preferably in the range of 0.1 to 40, and more preferably in the range of 5 to 30. When two or more polyfunctional polymerizable compounds having an acid group are used in combination, and when a polyfunctional polymerizable compound having an acid group and a polyfunctional polymerizable compound having no acid group are used in combination, it is preferred that the acid value of the mixture of polymerizable compounds be within the above range.

[0239] Specific examples of the polymerizable compound having an acid group include a mixture containing dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinate of dipentaerythritol pentaacrylate as main components. The mixture is commercially available as ARONIX TO-1382 (manufactured by Toagosei Co., Ltd.).

[0240] Examples of polymerizable compounds other than those described above include (meth)acrylamide such as ethylenebis(meth)acrylamide; allyl esters such as diallyl phthalate; and compounds having a vinyl group such as divinyl phthalate.

[0241] The content of the polymerizable compound in the color resist composition is preferably in the range of 5 to 80 mass %, more preferably 10 to 70 mass %, and further preferably 20 to 50 mass % based on the total solid content of the color resist composition.

[0242] The colorant of the color resist composition is not particularly limited as long as it is a colorant that can color the composition, and for example, a pigment or a dye may be used.

[0243] Any of organic pigments and inorganic pigments can be used as the pigment. As the organic pigment, various hue pigments such as red pigment, green pigment, blue pigment, yellow pigment, purple pigment, orange pigment, and brown pigment can be used. In addition, as the chemical structure of the organic pigment, for example, azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene can be listed. In addition, as the inorganic pigment, for example, barium sulfate, lead sulfate, titanium oxide, yellow lead, iron oxide, and chromium oxide can be listed.

[0244] In addition, "CI" mentioned below means color index.

[0245] Examples of the red pigment include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:4 :3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 1 49, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232 , 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, etc. Among these, CI Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242 or 254 is preferred, and CI Pigment Red 177, 209, 224 or 254 is more preferred.

[0246] Examples of the green pigment include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, and 58. Among these, CI Pigment Green 7, 36, or 58 is preferred.

[0247] Examples of the blue pigment include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 is preferred, and CI Pigment Blue 15:6 is more preferred.

[0248] Examples of the yellow pigment include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136 , 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, etc. Among these, CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185 is preferred, and CI Pigment Yellow 83, 138, 139, 150 or 180 is more preferred.

[0249] Examples of the violet pigment include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, CI Pigment Violet 19 or 23 is preferred, and CI Pigment Violet 23 is more preferred.

[0250] Examples of the orange pigment include CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79. Among these, CI Pigment Orange 38 or 71 is preferred.

[0251] Since the pixels of the three primary colors of the color filters used in liquid crystal display devices and organic electroluminescent (EL) display devices are red (R), green (G), and blue (B), the red pigment, green pigment, and blue pigment can be used as main components, and organic pigments of colors such as yellow, purple, and orange can be used for hue adjustment for the purpose of improving color reproducibility.

[0252] In order to improve the brightness of color liquid crystal display devices and organic EL display devices, the average particle size of the organic pigment is preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.3 μm or less. To achieve these average particle sizes, the organic pigment is preferably used after dispersion treatment.

[0253] The average primary particle size of the organic pigment is preferably 100 nm or less, more preferably 50 nm or less, further preferably 40 nm or less, and particularly preferably in the range of 10 nm to 30 nm.

[0254] The average particle size of the organic pigment is measured using a dynamic light scattering particle size distribution analyzer, for example, Nanotrac particle size distribution analyzers "UPA-EX150" and "UPA-EX250" manufactured by Nikkiso Co., Ltd. can be used for measurement.

[0255] The colorant used for forming a black matrix (BM) in a color resist composition is not particularly limited as long as it is black, and examples thereof include carbon black, lamp black, acetylene black, bone black, thermal black, channel black, furnace black, graphite, iron black, titanium black, etc. Among these, carbon black and titanium black are preferred from the viewpoint of light shielding rate and image characteristics.

[0256] Alternatively, two or more organic pigments may be mixed to form a black color.

[0257] Examples of commercially available carbon black include MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, and #960 manufactured by Mitsubishi Chemical Corporation. 0, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B, etc., can be listed: Evonik Degussa (Evonik Printex 3, Printex 3OP, Printex 30, Printex 30OP, Printex 40, Printex 45, Printex 55, Printex 60, Printex 75, Printex 80, Printex 85, Printex 90, Printex A, Printex 90 manufactured by Degussa Japan Co., Ltd. ex)L, Printex G, Printex P, Printex U, Printex V, Printex G, Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170, etc.,Examples include: Monarch 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 1500, Monarch 1600, Monarch 1700, Monarch 1800, Monarch 1900, Monarch 2000, Monarch 2100, Monarch 2200, Monarch 2300, Monarch 2400, Monarch 2500, Monarch 2600, Monarch 2700, Monarch 2800, Monarch 2800, Monarch 2900, Monarch 3000, Monarch 3100, Monarch 3200, Monarch 3300, Monarch 3400, Monarch 3500, Monarch 3600, Monarch 3700, Monarch 3800, Monarch 3900, Monarch 4000, Monarch 4100, Monarch 4100, Monarch 4200, Monarch 4300, Monarch 4400, Monarch 4500, Monarch 4600, Monarch 4700, Monarch 4800, Monarch 4900, Monarch 5000, Monarch 5100, Monarch 5100, Monarch 5100, Monarch 5100, Monarch 5100 h) 1400, Monarch 4630, REGAL 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R, BLACK PEARLS 480, PEARLS 130, VULCAN XC72R, ELFTEX-8, etc., Columbia Black (Columbian RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAV made by Carbon) company EN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000, etc. ,

[0258] Among the above carbon blacks, carbon black coated with a resin is preferred as it has high optical density and high surface resistivity required for a black matrix of a color filter.

[0259] Examples of commercially available products of the titanium black include titanium black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.

[0260] As a colorant used in forming the black matrix (BM), two or more organic pigments may be mixed to form black by mixing the colors. Examples of the colorant include a black pigment obtained by mixing three color pigments: red, green, and blue.

[0261] Examples of color materials that can be mixed for preparing black pigments include Victoria Pure Blue (CI42595), Auramine O (CI41000), Cathilon Brilliant Flavine (Basic 13), Rhodamine 6GCP (CI45160), Rhodamine B (CI45170), Safranin OK70:100 (CI50240), Erioglaucin X (CI42080), No. 120 / LIONOL Yellow (CI21090), LIONLO Yellow GRO (CI21090), SYMULER FAST Yellow 8GF (CI21105), Benzidine Yellow (CI21106), and Benzidine Yellow (CI21107). Yellow) 4T-564D (CI21095), SYMULER FAST Red 4015 (CI12355), LIONOL Red 7B4401 (CI15850), Fastogen Blue TGR-L (CI74160), LIONOL Blue SM (CI26150), LIONOL Blue ES (CI Pigment Blue 15:6), LIONOGEN Red GD (CI Pigment Red 168), LIONOL Green 2YS (CI Pigment Green 36), etc.

[0262] As other color materials that can be mixed for preparing the black pigment, for example, CI yellow pigment 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, CI orange pigment 36, 43, 51, 55, 59, 61, CI red pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, CI violet pigment 19, 23, 29, 30, 37, 40, 50, CI blue pigment 15, 15:1, 15:4, 22, 60, 64, CI green pigment 7, CI brown pigment 23, 25, 26, etc. are listed.

[0263] 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 μm to 0.08 μm, and more preferably in the range of 0.02 μm to 0.05 μm in terms of good developability.

[0264] The particle shape of carbon black is different from that of organic pigments, etc., and exists in a state of a structure formed by mutual fusion of primary particles, and sometimes fine pores are formed on the particle surface by post-treatment. Therefore, in order to express the particle shape of carbon black, it is usually preferred to measure the dibutylphthalate (DBP) absorption (Japanese Industrial Standards (JIS) K6221) and the specific surface area (JIS K6217) obtained by the Brunauer-Emmett-Teller (BET) method as an index of the structure or pore amount in addition to the average particle size of the primary particles obtained by the same method as the organic pigment.

[0265] The dibutyl phthalate (hereinafter referred to as "DBP") absorption of carbon black is preferably 40 cm 3 / 100g~100cm 3 The range of 50 cm / 100 g is more preferable in terms of good dispersibility and developability. 3 / 100g~80cm 3 The specific surface area of ​​carbon black measured by the BET method is preferably 50 m 2 / g~120m 2 The range of 60 m / g is more preferable in terms of good dispersion stability. 2 / g~95m 2 / g range.

[0266] Examples of the dye used as a colorant in the color resist composition include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

[0267] Examples of the azo dye include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, and CI Mordant Black 7.

[0268] Examples of the anthraquinone dye include CI Vat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Disperse Blue 60.

[0269] Examples of the phthalocyanine dye include CI Vat Blue 5, examples of the quinoneimine dye include CI Basic Blue 3, CI Basic Blue 9, etc., examples of the quinoline dye include CI Solvent Yellow 33, CI Acid Yellow 3, CI Disperse Yellow 64, and examples of the nitro dye include CI Acid Yellow 1, CI Acid Orange 3, CI Disperse Yellow 42, etc.

[0270] The colorant of the color resist composition is preferably a pigment from the viewpoint of excellent light resistance, weather resistance, and durability of the obtained coating film. However, a dye may be used in combination with the pigment as necessary for adjusting the hue.

[0271] The content of the colorant in the color resist composition is preferably 1% by mass or more, more preferably 5% by mass to 80% by mass, and even more preferably 5% by mass to 70% by mass, based on the total solid content of the color resist composition.

[0272] When the color resist composition is used to form each pixel of red (R), green (G), and blue (B) of a color filter, the content of the colorant in the color resist composition is preferably in the range of 5% by mass to 60% by mass, and more preferably in the range of 10% by mass to 50% by mass, based on the total solid content of the color resist composition.

[0273] 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 %, more preferably in the range of 30 to 70 mass %, based on the total solid content of the color resist composition.

[0274] In the color resist composition, when the colorant is a pigment, it is preferably used as a pigment dispersion prepared by dispersing the pigment in an organic solvent using a dispersant.

[0275] Examples of the dispersant include surfactants, intermediates or derivatives of pigments, intermediates or derivatives of dyes, resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins. Among these, preferred are graft copolymers having nitrogen atoms, acrylic block copolymers having nitrogen atoms, and urethane resin dispersants. Since these dispersants have nitrogen atoms, the nitrogen atoms have affinity for the pigment surface, and the affinity of the portion other than the nitrogen atoms for the medium is increased, thereby improving dispersion stability.

[0276] These dispersants may be used alone or in combination of two or more.

[0277] Commercially available products of the dispersant include: "EFKA" series (such as "EFKA46") manufactured by BASF; "Disperbyk" series and "BYK" series (such as "BYK-160", "BYK-161", and "BYK-2001") manufactured by BYK-Chemie Japan Co., Ltd.; "Solsperse" series manufactured by Lubrizol Japan Co., Ltd.; "KP" series manufactured by Shin-Etsu Chemical Co., Ltd., and "Polyflow" series manufactured by Kyoeisha Chemical Co., Ltd.; "DISPARLON" series manufactured by Kusumoto Chemical Co., Ltd.; and "AJISPER" series (such as "AJISPER PB-814") manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0278] Examples of the organic solvent used in preparing the pigment dispersion include acetate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxypropionate; aromatic solvents such as toluene, xylene, and methoxybenzene; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, and diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; nitrogen compound solvents such as N,N-dimethylformamide, γ-butyrolactam, and N-methyl-2-pyrrolidone; lactone solvents such as γ-butyrolactone; carbamates, etc.

[0279] These solvents may be used alone or in combination of two or more.

[0280] The method for preparing the pigment dispersion includes a method of mixing and dispersing the colorant and a micro-dispersing step, a method of only using a micro-dispersing step, etc. In the mixing and dispersing step, the colorant, a part of the alkali-soluble resin, and the dispersant as required are mixed and kneaded. The colorant can be dispersed by using a kneader while applying a strong shear force.

[0281] Examples of the machine used for kneading include a two-roll mill, a three-roll mill, a ball mill, a trommel, a disperser, a kneader, a bidirectional kneader, a homogenizer, a mixer, and a single-screw or double-screw extruder.

[0282] The colorant is preferably reduced to a fine particle size by a salt milling method or the like before the kneading.

[0283] In the micro-dispersion step, a substance obtained by adding a solvent to the composition containing the colorant obtained in the kneading and dispersing step, or a substance obtained by mixing a colorant, an alkali-soluble resin, a solvent and the dispersant as needed, is mixed and dispersed together with a dispersion medium for fine particles of glass, zirconia, or ceramics using a disperser, so that the particles of the colorant can be dispersed to a state of being microscopic close to primary particles.

[0284] From the viewpoint of improving the transmittance and contrast of the color filter, the average particle size of the primary particles of the colorant is preferably 10 nm to 100 nm, and more preferably 10 nm to 60 nm. In addition, the average particle size of the colorant is measured using a dynamic light scattering particle size distribution meter, for example, Nanotrac particle size distribution measuring device "UPA-EX150", "UPA-EX250" manufactured by Nikkiso Co., Ltd. can be used for measurement.

[0285] As the coating composition, a coating composition, a photoresist composition, and a color resist composition are exemplified above, but the coating composition is not limited to these.

[0286] Specific examples of the use of the coating composition of the present invention include: coating materials for various display screens such as liquid crystal displays (hereinafter referred to as "LCD (Liquid Crystal Display)"), plasma displays (hereinafter referred to as "PDP (Plasma Display Panel)"), organic EL displays (hereinafter referred to as "OLED (Organic Light-Emitting Diode)"), and quantum dot displays (hereinafter referred to as "QDD (Quantum Dot Display)"), namely, anti-glare (AG: anti-glare) hard coating materials, anti-reflection (LR) coating materials, low refractive index layer coating materials, high refractive index layer coating materials, transparent hard coating materials, and polymerizable liquid crystal coating materials; color filters (hereinafter referred to as "CF") such as LCDs for forming red, green, and blue (RedGreen) Color resists, inkjet inks, printing inks or coatings for each pixel such as blue, RGB); black matrix, black columnar spacer, black resist, inkjet ink, printing ink or coating for forming black photo spacer of CF such as LCD; transparent protective film coating for protecting CF surface used in CF such as LCD; LCD liquid crystal material, columnar spacer, resin composition for photo spacer; resin composition for pixel partition of LCD, PDP, OLED, QDD, etc., positive photoresist for electrode formation, protective film, insulating film, plastic frame, coating for plastic frame, window (frame) ink; prism sheet and light diffusion film as LCD backlight component; organic insulating film coating for liquid crystal thin film transistor (TFT) array of LCD; surface protective coating material for internal polarizer of LCD; PDP phosphor; OLED organic EL material, sealing material (protective film, gas barrier); QDD quantum dot ink, sealing material, protective film; micro (mini) light emitting diode (Light Emitting Diode) Diode, LED) display high refractive index lens, low refractive index seal, LED pixel; positive photoresist, chemical amplification photoresist, anti-reflective film, multilayer material (SOC, SOG), lower film, buffer coating, developer, rinse, pattern dumping prevention agent, polymer residue removal solution, detergent and other liquid, nanoimprint release agent used in semiconductor manufacturing; resin composition for semiconductor post-process or printed wiring board (epoxy resin, phenol resin, polyphenylene ether resin, liquid crystal polymer, polyimide resin, bismaleimide resin, bisallyl nadimide resin, benzoxazine resin and other resin composition), copper clad laminate, copper foil with resin, build-up film, passivation film, interlayer insulation film, flexible copper clad laminate, dry film resist; color resist for image sensor; liquid repellent for hot welding solvent; dispersant, coating, green sheet for laminated ceramic capacitor; positive electrode material, negative electrode material, diaphragm, electrolyte for lithium ion battery;Exterior coatings, rubber, elastomers, glass, vapor deposition anchor coatings, lighting lenses, solid lubricating coatings, heat dissipating substrates, interior coatings, and repair coatings for automobiles; wallpapers, flooring materials, kitchen components, and bathroom-toilet components for residential equipment; inkjet inks for printed materials, offset printing inks, gravure printing inks, screen printing inks, photoresists for printing plate manufacturing processes, photosensitive materials for lithographic printing plates (PS plates), encapsulating adhesives, and ballpoint pen inks; primers for easy adhesion of plastic films; hydrophobic agents for fibers; non-diffusing agents for grease; cleaning liquids for cleaning the surfaces of various products or parts; hard coating materials for optical recording media such as compact discs (CDs), digital versatile discs (DVDs), and blue-ray discs; coatings or hard coating materials for frames or screens for smartphones or mobile phones; embedded molding (in-mold decoration (In-Mold Decoration, IMD), In-Mold Forming (IMF) transfer film hard coating material; mold release film; coating or coating material for various plastic molded products such as home appliance frames; printing ink or coating material for various building materials such as decorative panels; coating material for window glass of houses; woodworking coatings such as furniture; coating material for artificial / synthetic leather; coating material for rubber rollers for office automation (OA) equipment such as copiers and printers; coating material for glass of reading parts of OA equipment such as copiers and scanners; optical lenses or coating materials such as cameras, camcorders, glasses, contact lenses; coating materials for windshields and glass of watches and clocks; coating materials for windows of various vehicles such as automobiles and railway vehicles; coating material for anti-reflective film of glass cover or film for solar cells; coating or coating material for fiberglass reinforced plastic (FRP) bath; pre-coated metal sheet (PCM) for metal building materials or home appliances; single-layer or multi-layer coating composition for photosensitive etching process, etc.;

[0287] Since the copolymer of the present invention has excellent surface tension reduction ability, it is not only possible to expect leveling, but also possible to expect various functions of wettability, permeability, cleanability, hydrophobicity, oleophobicity, antifouling, lubricity, anti-adhesion, and demoulding. In addition, if the polymer of the present invention is deployed in the coating or coating agent containing microparticles, the dispersibility of the microparticles is improved, and it is not only possible to expect leveling, but also possible to expect the function of the dispersant as microparticles. In addition, the polymer of the present invention is also added to the adhesive composition for adhesive tapes, etc., except being added to the coating composition, and it is not only possible to expect leveling, but also possible to expect the reduction of peeling force, the suppression of peeling force variation, and the suppression of stripping charge.

[0288] [Example]

[0289] Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples.

[0290] In addition, the present invention is not limited to the following examples.

[0291] The measurement conditions of gel permeation chromatography (GPC) of the silicone-containing copolymers obtained in the following Examples and Comparative Examples are as follows.

[0292] [GPC measurement conditions]

[0293] Measuring device: "HLC-8220GPC" manufactured by Tosoh Corporation

[0294] Column: Protection column "HHR-H" manufactured by Tosoh Corporation (6.0 mm I.D. × 4 cm)

[0295] + "TSK-GEL GMHHR-N" manufactured by TOSOH Corporation (7.8mm I.D.×30cm)

[0296] + "TSK-GEL GMHHR-N" manufactured by TOSOH Corporation (7.8mm I.D.×30cm)

[0297] + "TSK-GEL GMHHR-N" manufactured by TOSOH Corporation (7.8mm I.D.×30cm)

[0298] + "TSK-GEL GMHHR-N" manufactured by TOSOH Corporation (7.8mm I.D.×30cm)

[0299] Detector: Evaporative light scattering detector (ELSD2000 manufactured by Alltech Japan Co., Ltd.)

[0300] Data processing: "GPC-8020 Model II Data Analysis Version 4.30" manufactured by TOSOH Corporation

[0301] Measurement conditions: column temperature 40°C

[0302] Development solvent: Tetrahydrofuran (THF)

[0303] Flow rate 1.0ml / min

[0304] Sample: A tetrahydrofuran solution having a solid content of 1.0% by mass was filtered through a microfilter (5 μl).

[0305] Standard sample: According to the measurement manual of "GPC-8020 Model II Data Analysis Version 4.30", the following monodisperse polystyrene having a known molecular weight was used.

[0306] (monodisperse polystyrene)

[0307] "A-500" manufactured by TOSOH Co., Ltd.

[0308] "A-1000" manufactured by TOSOH Co., Ltd.

[0309] "A-2500" manufactured by TOSOH Co., Ltd.

[0310] "A-5000" manufactured by TOSOH Co., Ltd.

[0311] "F-1" manufactured by Tosoh Corporation

[0312] "F-2" manufactured by Tosoh Corporation

[0313] "F-4" manufactured by Tosoh Corporation

[0314] The F-10 manufactured by Tosoh Corporation

[0315] The F-20 manufactured by Tosoh Corporation

[0316] The F-40 manufactured by Tosoh Corporation

[0317] "F-80" manufactured by Tosoh Corporation

[0318] The F-128 manufactured by Tosoh Corporation

[0319] "F-288" manufactured by Tosoh Corporation

[0320] "F-550" manufactured by TOSOH Co., Ltd.

[0321] Example 1: Synthesis of silicone-containing copolymer (1)

[0322] A mixed solution A1 was prepared by mixing 180.0 g of commercially available adamantyl methacrylate and 70.0 g of butyl acetate as a solvent; a mixed solution B1 was prepared by mixing 3.0 g of tert-butyl peroxy-2-ethylhexanoate as a polymerization initiator and 10.0 g of butyl acetate as a solvent; and a mixed solution C1 was prepared by mixing 20.0 g of a commercially available monomethacrylate compound having a polysiloxane bond represented by the following formula and 20.0 g of butyl acetate as a solvent.

[0323] [Chemistry 19]

[0324]

[0325] (The average value of x1 is 65)

[0326] In a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, 200.0 g of butyl acetate as a solvent was placed, and the temperature was raised to 90° C. while stirring under a nitrogen flow.

[0327] Mixed solution A1 at 95° C. was dripped into the flask over 135 minutes. Mixed solution B1 and mixed solution C1 at 95° C. were dripped 5 minutes after the dripping of mixed solution A1 was started. The dripping of mixed solution C1 was stopped 120 minutes after the dripping of mixed solution C1, and the dripping of mixed solution A1 and mixed solution B1 was stopped 10 minutes after the dripping of mixed solution C1 (135 minutes after the dripping of mixed solution A1). After the dripping was completed, stirring was performed at 95° C. for 10 hours. After the reaction was completed, 500 g of butyl acetate was added to obtain a butyl acetate solution containing 20% ​​by mass of the silicone-containing copolymer (1).

[0328] The molecular weight of the obtained silicone-containing copolymer (1) was measured by GPC, and the weight average molecular weight (Mw) was 26,000.

[0329] In addition, based on the raw material charging ratio, the content ratio of the polymerizable unsaturated monomer having a silicone chain in the reaction mixture was 10 mass %.

[0330] Comparative Example 1: Synthesis of Silicone-Containing Copolymer (2)

[0331] A mixed solution A1' was prepared by mixing 180.0 g of commercially available polypropylene glycol-polybutylene glycol-monomethacrylate (the average repeating number of propylene glycol is 1, and the average repeating number of butylene glycol is 6) and 70.0 g of butyl acetate as a solvent; a mixed solution B1' was prepared by mixing 3.0 g of tert-butyl peroxy-2-ethylhexanoate as a polymerization initiator and 10.0 g of butyl acetate as a solvent; and a mixed solution C1' was prepared by mixing 20.0 g of the monomethacrylate compound having a polysiloxane bond as the same as in Synthesis Example 1 and 20.0 g of butyl acetate as a solvent.

[0332] In a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, 200.0 g of butyl acetate as a solvent was placed, and the temperature was raised to 90° C. while stirring under a nitrogen flow.

[0333] Mixed solution A1' at 90°C was added dropwise to the flask. Mixed solution B1' and mixed solution C1' at 90°C were added dropwise 5 minutes after the addition of mixed solution A1' was started. The addition of mixed solution C1' was stopped 120 minutes after the addition of mixed solution C1', and the addition of mixed solution A1' and mixed solution B1' was stopped 10 minutes after the addition of mixed solution C1' (135 minutes after the addition of mixed solution A1' was started). After the addition of mixed solution A1', the mixture was stirred at 90°C for 10 hours. After the reaction was completed, the solvent was distilled off to obtain a silicone-containing copolymer (2).

[0334] The molecular weight of the obtained silicone-containing copolymer (2) was measured by GPC, and the weight average molecular weight (Mw) was 38,000.

[0335] In addition, the content ratio of the polymerizable unsaturated monomer having a silicone chain in the silicone-containing copolymer (2) was 10% by mass based on the raw material charging ratio.

[0336] The molecular weight of the obtained silicone-containing copolymer (2) was measured by GPC, and the weight average molecular weight (Mw) was 17,000.

[0337] In addition, based on the raw material charging ratio, the content ratio of the polymerizable unsaturated monomer having a silicone chain in the silicone-containing copolymer (2) was 67% by mass.

[0338] Comparative Example 2: Synthesis of Silicone-Containing Copolymer (3)

[0339] A mixed solution A2' was prepared by mixing 45.0 g of 1-adamantyl methacrylate, 55.0 g of a commercially available monomethacrylate compound having a polysiloxane bond represented by the following formula, and 70.0 g of butyl acetate as a solvent, and a mixed solution B2' was prepared by mixing 3.0 g of tert-butylperoxy-2-ethylhexanoate as a polymerization initiator and 63.3 g of butyl acetate as a solvent.

[0340] [Chemistry 20]

[0341]

[0342] (The average value of x3 is 10)

[0343] In a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, 100.0 g of butyl acetate as a solvent was placed, and the temperature was raised to 90° C. while stirring under a nitrogen flow.

[0344] Mixed solution A2' at 90°C was added dropwise to the flask over 120 minutes, and mixed solution B2' at 90°C was added dropwise over 140 minutes. After the addition, the mixture was stirred at 90°C for 5 hours. After the reaction, 166.7 g of butyl acetate was added to obtain a butyl acetate solution containing 20% ​​by mass of the silicone-containing copolymer (3).

[0345] The molecular weight of the obtained silicone-containing copolymer (3) was measured by GPC, and the weight average molecular weight (Mw) was 15,000.

[0346] In addition, the content ratio of the polymerizable unsaturated monomer having a silicone chain in the silicone-containing copolymer (3) was 55% by mass based on the raw material charging ratio.

[0347] [Film formation and evaluation of coating films]

[0348] The silicone-containing copolymers (1) to (3) synthesized in Examples and Comparative Examples were formed into coating films, and their leveling properties and pigment sublimation foreign matter inhibition properties were evaluated.

[0349] (1) Leveling

[0350] Using the silicone-containing copolymer synthesized in each example, a coating film was formed in the following manner.

[0351] A resist composition was prepared by mixing 3.0 g of a binder resin (ACRYDIC ZL-295, manufactured by DIC Corporation), 1.2 g of Aronix M-402 (manufactured by Toagosei Chemical Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), 0.002 g of a silicone-containing copolymer synthesized in each example, and 8.1 g of propylene glycol monomethyl ether acetate (PGMEA) in terms of solid content.

[0352] 3 ml of the obtained resist composition was dropped onto the center of a 10 cm×10 cm chrome-plated glass substrate, and spin-coated at 500 rpm for 30 seconds, followed by heating and drying at 110° C. for 2 minutes using a hot plate to form a coating film.

[0353] The coating films prepared above were visually observed and evaluated based on the following criteria.

[0354] ○: Almost no coating unevenness was observed.

[0355] △: Unevenness of the coating film was partially observed.

[0356] ×: Uneven coating was observed throughout.

[0357] (2) Inhibition of foreign matter on the coating surface caused by pigment sublimation

[0358] Using the silicone-containing copolymer produced in each example, a coating film containing a pigment was formed in the following manner.

[0359] 10 g of CI Pigment Red 254 ("IRGAPHOR RED BT-CF" manufactured by BASF) as a red pigment is placed in a plastic bottle, and 44 g of PGMEA, 12 g of DISPERBYK LPN21116 (manufactured by BYK-Chemie Co., Ltd.) and SEPR beads with a diameter of 0.3 mm to 0.4 mm are added, and dispersed for 2 hours using a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) to obtain a red pigment dispersion.

[0360] Next, to 5.9 g of the red pigment dispersion, 1.5 g of a binder resin (UNIDIC RS20-160, manufactured by DIC Corporation), 0.6 g of Aronix M-402 (manufactured by Toagosei Chemical Co., Ltd.) as a photopolymerizable monomer, 0.05 g of Irgacure #369 (manufactured by BASF JAPAN Co., Ltd.) as a photopolymerization initiator, 0.0014 g of each silicone-containing copolymer calculated as a solid content, and 2.2 g of PGMEA were added and mixed to prepare a color resist composition.

[0361] The obtained color resist composition was spin-coated on a 7 cm x 7 cm square glass plate at a rotation speed of 1000 rpm for 10 seconds, and then dried at 80°C for 3 minutes. After drying, a high pressure mercury lamp was used to irradiate the glass plate at 50 mJ / cm 2 The coating film was formed by exposure. Thereafter, the coating film was heated at 270° C. for 1 hour, and then observed using a digital microscope VHX-900 (manufactured by Keyence Corporation) and evaluated based on the following criteria. The evaluation results are shown in Table 1.

[0362] ◯: One or less foreign matter due to sublimation of the pigment was confirmed in a 1 cm×1 cm square of the coating film.

[0363] △: On average, 2 to 9 foreign matters due to sublimation of the pigment were observed in a 1 cm×1 cm square of the coating film.

[0364] ×: On average, 10 or more foreign matters due to sublimation of the pigment were confirmed in a 1 cm×1 cm square of the coating film.

[0365] [Table 1]

[0366]

[0367] It is known that the coating film of Example 1 containing the silicone-containing copolymer of the present invention as a leveling agent has excellent coating properties and no foreign matter is generated on the surface of the coating film due to sublimation of the pigment. On the other hand, in Comparative Example 1, in which the weight average molecular weight of the silicone-containing copolymer is larger than that of Example 1 and the polymerizable monomer does not have a group containing a cyclic hydrocarbon skeleton, foreign matter is generated on the surface of the coating film due to sublimation of the pigment in the coating film. Similarly, in Comparative Example 2, foreign matter is generated on the surface of the coating film due to sublimation of the pigment in the coating film.

Claims

1. A silicone-containing copolymer comprising at least a polymerizable monomer (A) having a group represented by the following general formula (a) and a polymerizable monomer (B) having a group containing a cyclic hydrocarbon skeleton as polymerization components. [Chemistry 1] (In the general formula (a), R 11 are independently an alkyl group having 1 to 6 carbon atoms or -OSi(R 14 )3 represented by the group (R 14 are each independently an alkyl group having 1 to 3 carbon atoms), R 12 are each independently an alkyl group having 1 to 6 carbon atoms, R 13 is an alkyl group having 1 to 6 carbon atoms, x represents the numerical mean of the number of repetitions, which is an integer from 20 to 150.) 2. The silicone-containing copolymer according to claim 1, wherein The polymerizable monomer (A) is a compound represented by the following general formula (a-1). [Chemistry 2] (In the general formula (a-1), R 11 , R 12 , R 13 and x are respectively the same as R 11 , R 12 , R 13 and x are the same, R 15 is a hydrogen atom or a methyl group, L 1 It is a divalent organic radical.) 3. The silicone-containing copolymer according to claim 1 or 2, wherein The polymerizable monomer (B) is a polymerizable monomer represented by the following general formula (b-1). [Chemistry 3] (In the general formula (b-1), R b1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R b2 is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 18 carbon atoms, or a divalent linking group comprising a combination of two or more selected from an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 18 carbon atoms, and an ether bond (—O—), R b3 is a group containing a cyclic hydrocarbon skeleton. ) 4. The silicone-containing copolymer according to any one of claims 1 to 3, wherein The group including a cyclic hydrocarbon skeleton has a bridged ring structure.

5. The silicone-containing copolymer according to claim 4, wherein The group containing a cyclic hydrocarbon skeleton structure having the bridged ring structure is an adamantane ring, a dicyclopentane ring, a dicyclopentene ring, a norbornane ring, a norbornene ring, a cyclohexane ring or an isobornane ring.

6. The silicone-containing copolymer according to any one of claims 1 to 5 [1 or 2], wherein The weight average molecular weight (Mw) is 3,000 to 80,000.

7. The silicone-containing copolymer according to any one of claims 1 to 6, wherein Contains no fluorine atoms.

8. A leveling agent comprising the silicone-containing copolymer according to any one of claims 1 to 7.

9. A coating composition comprising the silicone-containing copolymer according to any one of claims 1 to 7. 10 . A resist composition comprising the silicone-containing copolymer according to claim 1 and a colorant.

11. A color filter, wherein: A coating layer of the resist composition according to claim 10 is formed on a substrate.

12. A method for producing a silicone-containing copolymer, comprising polymerizing a polymerizable monomer (A) having a group represented by the following general formula (a) and a polymerizable monomer (B) having a group containing a cyclic hydrocarbon skeleton. [Chemistry 4] (In the general formula (a), R 11 are independently an alkyl group having 1 to 6 carbon atoms or -OSi(R 14 )3 represented by the group (R 14 are each independently an alkyl group having 1 to 3 carbon atoms), R 12 are each independently an alkyl group having 1 to 6 carbon atoms, R 13 is an alkyl group having 1 to 6 carbon atoms, x represents the numerical mean of the number of repetitions, which is an integer from 20 to 150.) 13. The method for producing a silicone-containing copolymer according to claim 12, wherein: The polymerizable monomer (A) is a compound represented by the following general formula (a-1). [Chemistry 5] (In the general formula (a-1), R 11 , R 12 , R 13 and x are respectively the same as R 11 , R 12 , R 13 and x are the same, R 15 is a hydrogen atom or a methyl group, L 1 It is a divalent organic radical.) 14. The method for producing a silicone-containing copolymer according to claim 12 or 13, wherein: The polymerizable monomer (B) is a polymerizable monomer represented by the following general formula (b-1). [Chemistry 6] (In the general formula (b-1), R b1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R b2 is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 18 carbon atoms, or a divalent linking group comprising a combination of two or more selected from an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 18 carbon atoms, and an ether bond (—O—), R b3 is a group containing a cyclic hydrocarbon skeleton. ) 15. The method for producing a silicone-containing copolymer according to any one of claims 12 to 14, wherein The group including a cyclic hydrocarbon skeleton has a bridged ring structure.

16. The silicone-containing copolymer according to any one of claims 12 to 15, wherein The group containing a cyclic hydrocarbon skeleton having the bridged ring structure is an adamantane ring, a dicyclopentane ring, a dicyclopentene ring, a norbornane ring, a norbornene ring, a cyclohexane ring or an isobornane ring.

17. The method for producing a silicone-containing copolymer according to any one of claims 12 to 16, wherein The polymer components are copolymerized by a random copolymerization method or a living copolymerization method.

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