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

Abstract

To provide a silicone-containing copolymer which can reduce an environmental load and gives an effect of suppressing the generation of a foreign matter caused by sublimation of a pigment on the surface of a coating film.SOLUTION: There is provided a silicone-containing copolymer which contains 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 at least a polymerization component. (In the general formula (a), R11 each independently is an alkyl group having 1 to 6 carbon atoms or a group represented by -OSi(R14)3 (R14 each independently is an alkyl group having 1 to 3 carbon atoms), R12 each independently is an alkyl group having 1 to 6 carbon atoms, R13 is an alkyl group having 1 to 6 carbon atoms, x is a number average value showing a repeating number and is an integer of 1 to 5.)SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Color filters used in color liquid crystal displays and the like generally have a basic structure of red (R), green (G), and blue (B) pixels with a black matrix (BM) formed between them for the purpose of improving the display contrast, etc. The surfaces of these R, G, and B pixels and BM in a color filter are required to be highly smooth. To achieve this, when applying a color resist composition, it is necessary to apply the composition with a uniform film thickness, without uneven application or repelling, and without causing color unevenness.

[0003] The leveling agent is added to smooth the coating film obtained by applying a coating composition such as a paint composition, a color resist composition, etc. Specifically, by adding a leveling agent to a color resist composition, the smoothness of the resulting coating film is improved, and the surfaces of the red (R), green (G), and blue (B) pixels and the black matrix (BM) formed between these pixels can exhibit high smoothness, resulting in a color filter with little color unevenness.

[0004] In addition, color filters are required to have a desired hue in each pixel of red, green, and blue. In light of this demand, for example, pigments such as CI Pigment Red 254 and CI Pigment Yellow 139, which have excellent brightness, tend to sublimate during the drying process of a coating film containing them, and tend to grow as crystallized products or aggregates due to their intermolecular interactions. Therefore, pigment molecules sublimated from inside the coating film may crystallize and / or aggregate on the surface of the coating film, resulting in the generation of foreign matter. If foreign matter occurs on the surface of the coating film, light scattering occurs, making it difficult to obtain a desired hue.

[0005] In addition, the occurrence of foreign matter on the coating surface due to sublimation of the pigment causes a change in the pigment content ratio from the surface to the inside of the coating, which can make it difficult to obtain the desired hue. Thus, the occurrence of foreign matter such as crystallized matter and aggregates due to sublimation of the pigment on the coating surface may cause color unevenness in pixels. As a leveling agent for suppressing color unevenness in pixels, a leveling agent containing a fluorine atom has been proposed (Patent Document 1). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2017 / 145771 Summary of the Invention [Problem to be solved by the invention]

[0007] Leveling agents that contain fluorine atoms have a high environmental impact, and alternative technologies are required in response to the strengthening of environmental regulations and the further increase in environmental awareness in recent years. The problem that the present invention aims to solve is to provide a silicone-containing copolymer that can reduce the environmental impact and also has the effect of suppressing the generation of foreign matter caused by sublimation of pigments on the coating film surface. [Means for solving the problem]

[0008] The present inventors have conducted intensive research to solve the above problems, and as a result have discovered that a silicone-containing copolymer can be obtained that is environmentally friendly and also has the effect of suppressing the generation of foreign matter caused by sublimation of the pigment on the coating film surface by 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, thereby completing the present invention.

[0009] 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: [ka] (In the general formula (a), R 11 each independently represents an alkyl group having 1 to 6 carbon atoms or -OSi(R 14 A group represented by (R 14 are each independently an alkyl group having 1 to 3 carbon atoms, R 12 are each independently an alkyl group having 1 to 6 carbon atoms, R 13 is an alkyl group having 1 to 6 carbon atoms, x is a number average value indicating the number of repetitions and is an integer of 1 to 5.

[0010] The present invention also relates to a leveling agent comprising the above silicone-containing copolymer. The present invention also relates to a coating composition comprising the above silicone-containing copolymer. The present invention also relates to a resist composition containing the above silicone-containing copolymer and a colorant. The present invention also relates to a color filter comprising a coating layer of the above resist composition formed on a substrate.

[0011] The present invention also relates to a method for producing a silicone-containing copolymer, comprising polymerizing a polymerizable monomer (A) having a group represented by general formula (a) below, and a polymerizable monomer (B) having a group containing a cyclic hydrocarbon skeleton: [ka] (In the general formula (a), R 11 each independently represents an alkyl group having 1 to 6 carbon atoms or -OSi(R 14 A group represented by (R 14are 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 is a number average value indicating the number of repetitions and is an integer of 1 to 5. Effect of the Invention

[0012] According to the present invention, it is possible to provide a silicone-containing copolymer that can reduce the environmental load and also has the effect of suppressing the generation of foreign matter caused by sublimation of a pigment on the coating film surface. It is also possible to provide a leveling agent, a coating composition, a resist composition, and a color filter that use the silicone-containing copolymer. The present invention also provides a method for producing the silicone-containing copolymer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] An embodiment of the present invention will be described below. The present invention is not limited to the following embodiment, and can be implemented by making appropriate modifications within the scope that does not impair the effects of the present invention. In this specification, the term "(meth)acrylate" refers to either or both of an acrylate and a methacrylate.

[0014] [Silicone-containing copolymer] The silicone-containing copolymer of the present invention (hereinafter sometimes simply referred to as "the copolymer of the present invention") is a copolymer having, as at least polymerization components, 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:

[0015] [ka] (In the general formula (a), R 11each independently represents an alkyl group having 1 to 6 carbon atoms or -OSi(R 14 A group represented by (R 14 are each independently an alkyl group having 1 to 3 carbon atoms, R 12 are each independently an alkyl group having 1 to 6 carbon atoms, R 13 is an alkyl group having 1 to 6 carbon atoms, x is a number average value indicating the number of repetitions and is an integer of 1 to 5.

[0016] The copolymer of the present invention has a group containing a bulky cyclic hydrocarbon skeleton, which makes the copolymer rigid. The group represented by general formula (a) segregates to the surface (interface) of the coating film, and the copolymer has a rigid structure, which allows a rigid (dense) thin film to be formed at the interface. It can be assumed that the rigid thin film physically blocks the sublimation of the colorant.

[0017] In the present invention, the term "polymerizable monomer" means a compound having a polymerizable unsaturated group, and examples of the polymerizable unsaturated group possessed by the polymerizable monomer (A) and the polymerizable monomer (B) include C=C-containing groups such as (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamino group, vinyl ether group, allyl group, styryl group, maleimide group, etc. Among these, (meth)acryloyl group and (meth)acryloyloxy group are preferred because of the availability of raw materials and good polymerization reactivity. The number of polymerizable unsaturated groups contained in the polymerizable monomer may be one or two or more.

[0018] In the present invention, the term "polymerization component" refers to a component that constitutes a polymer, and does not include a solvent, a polymerization initiator, and the like that do not constitute a polymer.

[0019] In the general formula (a), R 11 is preferably a methyl group or a trimethylsiloxy group, R 12 and R 13 is preferably a methyl group.

[0020] In the general formula (a), by making x an integer of 1 to 5, the copolymer of the present invention can exhibit high surface tension reducing ability, and when made into a resist composition or a coating composition, it is presumed that the copolymer is likely to be unevenly distributed on the surface (interface) of the composition, thereby making it possible to suppress the generation of foreign matter from the inside of the coating film to the surface due to sublimation of pigment molecules. In the present invention, the "number average value of x" means the average number of repeating units of siloxane bonds per polymerizable monomer (A) constituting the polymer of the present invention. 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.

[0021] The polymerizable monomer (A) is preferably a compound represented by the following general formula (a-1).

[0022] [ka] (In the general formula (a-1), R 11 , R 12 , R 13 and x are each R in the general formula (a). 11 , R 12 , R 13 and x, R 15 is a hydrogen atom or a methyl group, L 1 is a divalent organic group.

[0023] 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.

[0024] L 1Examples of the alkylene group having 1 to 50 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, an n-decylene group, an n-dodecylene group, an isopropylene group, a 2-methylpropylene group, a 2-methylhexylene group, and a tetramethylethylene group.

[0025] L 1 The alkylene group having 1 to 50 carbon atoms is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and further preferably a methylene group, an ethylene group, an n-propylene group or an isopropylene group.

[0026] L 1 The alkyleneoxy group having 1 to 50 carbon atoms is, for example, a group in which one -CH2- in the alkylene group is replaced with -O-. L 1 The alkyleneoxy group having 1 to 50 carbon atoms is preferably an alkyleneoxy group having 1 to 15 carbon atoms, more preferably an alkyleneoxy group having 1 to 8 carbon atoms, and even more preferably a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, an oxytrimethylene group, a butyleneoxy group, an oxytetramethylene group, a pentyleneoxy group, a heptyleneoxy group, or an octyleneoxy group.

[0027] 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, in these divalent organic groups, a part of the -CH2- may be replaced by a carbonyl group (-C(=O)-), a phenylene group, an amide bond or a urethane bond, and further, a hydroxyl group or the like may be substituted on the carbon atom.

[0028] The length of the silicone chain possessed by the compound represented by the general formula (a-1) is preferably 3 or less, and more preferably 1. Specifically, the compound represented by the general formula (a-1) is preferably a compound represented by the following general formula (a-1-1).

[0029] [ka] (In the general formula (a-1-1), Each of the multiple R's is independently an alkyl group having 1 to 3 carbon atoms; R 15 is a hydrogen atom or a methyl group, L 1 is the same as the general formula (a-1) above.

[0030] The polymerizable monomer (A) may be a compound represented by the following general formula (a-2).

[0031] [ka] (In the general formula (a-2), R 11 , R 12 , R 13 and x are each R in the general formula (a). 11 , R 12 , R 13 and x is the same as L 1 is the same as the general formula (a-1) above. R 15 is a hydrogen atom or a methyl group.

[0032] With regard to the length of the silicone chain possessed by the compound represented by the general formula (a-2), the above-mentioned x is preferably 3 or less, and the above-mentioned x is more preferably 1.

[0033] The polymerizable monomer (A) can be produced by a known method, and a commercially available product may be used. Specific examples of the polymerizable monomer (A) include α-(3-methacryloyloxy)propylpolydimethylsiloxane, 3-(methacryloyloxy)propyltris(trimethylsiloxy)silane, and the like.

[0034] 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 the function of, for example, making the copolymer rigid and also has the function of ensuring compatibility.

[0035] The polymerizable monomer (B) may be any polymerizable monomer having a group containing a cyclic hydrocarbon skeleton, and preferably contains a polymerizable monomer having a group containing a cyclic hydrocarbon skeleton having a crosslinked structure.

[0036] 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.

[0037] [ka] (In the general formula (b-1), R b1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R b2 represents a divalent linking group consisting of 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.

[0038] R b2 The alkylene group having 1 to 10 carbon atoms may be linear, branched, or cyclic. R b2 The arylene group having 6 to 18 carbon atoms may be a single ring or a condensed ring. b2Specific examples of the arylene group having 6 to 18 carbon atoms include a phenylene group, a naphthylene group, and the like. R b2 The alkylene group and 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, and a halogen atom.

[0039] In the general formula (b-1), R b3 The group containing a cyclic hydrocarbon skeleton may be either a group containing a cyclic hydrocarbon skeleton having a bridged structure or a group containing a cyclic hydrocarbon skeleton not having a bridged ring structure. Specific examples of the cyclic hydrocarbon skeleton include a cyclohexane ring, an adamantane ring, a perhydroindene ring, a decalin ring, a perhydrofluorene ring, a perhydroanthracene ring, a perhydrophenanthrene ring, a dicyclopentane ring, a dicyclopentene ring, a perhydroacenaphthene ring, a perhydrophenalene ring, a norbornane ring, an isobornane ring, and a norbornene ring. Among these, a cyclohexane ring, an adamantane ring, a dicyclopentane ring, a norbornane ring, and a norbornene ring are preferred because they can suppress the generation of foreign matter on the coating film surface due to sublimation of the pigment.

[0040] 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.

[0041] Examples of the polymerizable monomer having an adamantane ring and a (meth)acryloyl group include compounds represented by the following formulas (b-1-1) and (b-1-2).

[0042] [ka] (In the formula, 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.

[0043] Examples of the reactive functional group include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, an acid anhydride group, etc. Among them, a hydroxyl group is preferred because, when a resist composition or a coating composition is produced using the resulting copolymer, a copolymer having good compatibility with the components contained in the composition can be obtained.

[0044] The binding positions of the organic group having the reactive functional group represented by -XZ in the above general formula (b-1-1) and Y may be any carbon atom in the adamantane ring, and there may be two or more -XZ. Furthermore, X and Y in the above 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 a methylene group, a propyl group, and an isopropylidene group.

[0045] 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.

[0046] More specific examples of the polymerizable monomer represented by the general formula (b-1-1) include the compounds represented below.

[0047] [ka]

[0048] More specific examples of the polymerizable monomer represented by general formula (b-1-2) include the compounds represented by the following formulas.

[0049] [ka]

[0050] Among the polymerizable monomers having an adamantane ring and a (meth)acryloyl group, 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, because when the resulting copolymer is used to produce a resist composition, a random copolymer having good compatibility with the components contained in the composition is obtained.

[0051] 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.

[0052] Examples of the polymerizable monomer having a dicyclopentane ring and a (meth)acryloyl group include compounds represented by the following formula (b-1-3).

[0053] [ka] (In the formula, R b1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0054] 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.

[0055] More specific examples of the polymerizable monomer represented by the general formula (b-1-3) include the compounds represented below.

[0056] [ka]

[0057] Among the polymerizable monomers having a dicyclopentane ring and a (meth)acryloyl group, the compound represented by formula (b-1-3-2) is preferred because it gives a resist composition that can suppress the generation of foreign matter due to sublimation of the pigment.

[0058] 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.

[0059] Examples of the polymerizable monomer having a dicyclopentene ring and a (meth)acryloyl group include compounds represented by the following formula (b-1-4).

[0060] [ka] (In the formula, R b1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0061] 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.

[0062] More specific examples of the polymerizable monomer represented by the general formula (b-1-4) include the compounds represented below.

[0063] [ka]

[0064] Among the polymerizable monomers having a dicyclopentene ring and a (meth)acryloyl group, the compound represented by formula (b-1-4-2) is preferred because it gives a resist composition that can suppress the generation of foreign matter due to sublimation of the pigment.

[0065] 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.

[0066] Examples of the polymerizable monomer having a norbornane ring and a (meth)acryloyl group include compounds represented by the following formula (b-1-5).

[0067] [ka] (In the formula, R b1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0068] 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.

[0069] More specific examples of the polymerizable monomer represented by the general formula (b-1-5) include the compounds represented below.

[0070] [ka]

[0071] Among the polymerizable monomers having a norbornane ring and a (meth)acryloyl group, the compound represented by formula (b-1-5-2) is preferred because it gives a resist composition that can suppress the generation of foreign matter due to sublimation of the pigment.

[0072] 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.

[0073] Examples of the polymerizable monomer having a norbornene ring and a (meth)acryloyl group include compounds represented by the following formula (b-1-6).

[0074] [ka] (In the formula, R b1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0075] In the compound represented by formula (b-1-6), the (meth)acryloyl group may be bonded to any carbon atom in the norbornene ring.

[0076] More specific examples of the polymerizable monomer represented by the general formula (b-1-6) include the compounds represented below.

[0077] [ka]

[0078] Among the polymerizable monomers having a norbornene ring and a (meth)acryloyl group, the compound represented by formula (b-1-6-2) is preferred because it gives a resist composition that can suppress the generation of foreign matter due to sublimation of the pigment.

[0079] The polymerizable monomer (B) can be produced by a known method. Moreover, the polymerizable monomer (B) may be a commercially available product.

[0080] The polymerizable monomer (B) constituting the silicone-containing copolymer of the present invention may be one type alone, or two or more types may be used.

[0081] The polymerization form of the silicone-containing copolymer, which is a copolymer having at least polymerizable monomer (A) and polymerizable monomer (B) as polymerization components, is not particularly limited, and may be a random copolymer of polymerizable monomer (A) and polymerizable monomer (B), or a block copolymer of polymerizable monomer (A) and polymerizable monomer (B).

[0082] 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)=10:90 to 90:10, preferably polymerizable monomer (A):polymerizable monomer (B)=10:90 to 80:20, more preferably polymerizable monomer (A):polymerizable monomer (B)=20:80 to 80:20, even more preferably 30:70 to 80:20, and particularly preferably polymerizable monomer (A):polymerizable monomer (B)=51:49 to 80:20.

[0083] The silicone-containing copolymer of the present invention may be a copolymer of polymerizable monomer (A) and polymerizable monomer (B), and may contain structural units of polymerizable monomers other than the polymerizable monomer (A) and the polymerizable monomer (B) as long as the effects of the present invention are not impaired. The copolymer of the present invention is preferably a copolymer substantially composed of polymerizable monomer (A) and polymerizable monomer (B), and more preferably a copolymer composed only of polymerizable monomer (A) and polymerizable monomer (B). Here, "substantially composed" refers to a case where the total content of polymerizable monomer (A) and polymerizable monomer (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.

[0084] The silicone-containing copolymer of the present invention is preferably free of fluorine atoms. When the silicone-containing copolymer of the present invention does not contain fluorine atoms, it can enhance the solvent resistance. In addition, when the silicone-containing copolymer of the present invention is a fluorine atom-free resin, it has low environmental accumulation and can reduce the environmental load.

[0085] 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. The weight average molecular weight of the silicone-containing copolymer of the present invention is measured by the method described in the Examples.

[0086] The proportion of structures derived from the polymerizable monomer (A) in the silicone-containing copolymer of the present invention is, for example, in the range of 10 to 80 mass %, preferably in the range of 20 to 80 mass %, and more preferably in the range of 30 to 80 mass %. The proportion of structures 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) to the total amount of the raw materials used.

[0087] The content of silicone chains represented by general formula (a) in the silicone-containing copolymer of the present invention is preferably in the range of 10 to 80 mass %, more preferably in the range of 20 to 80 mass %, and even more preferably in the range of 30 to 80 mass %. 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 to the total amount of the raw materials used.

[0088] [Method of manufacturing silicone-containing copolymer] The method for producing the copolymer of the present invention is not particularly limited, and the copolymer can be produced by a known method. The copolymer of the present invention can be produced based on a polymerization mechanism such as radical polymerization, cationic polymerization, anionic polymerization, etc., by subjecting the polymerization components to solution polymerization, bulk polymerization, emulsion polymerization, etc. For example, in the case of radical polymerization, the copolymer of the present invention can be produced by charging the polymerization components in an organic solvent and adding a general-purpose radical polymerization initiator. The copolymer obtained above is a random copolymer.

[0089] As the polymerization initiator, various types of 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-phenyl-2-methylperoxide ... -Methylpropyl-1-hydroperoxide, t-butyl perphenylacetate, t-butyl hydroperoxide, t-butyl performate, t-butyl peracetate, t-butyl perbenzoate, t-butyl per-2-ethylhexanoate, t-butyl perphenylacetate, t-butyl per-4-methoxyacetate and other peroxides; 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo(methylethyl) diacetate, 2,2'-azobis(2-amidinopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyrate amide, 2,2'-azobisisobutyronitrile, methyl 2,2'-azobis-2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, dimethyl 2,2'-azobisisobutyrate, 2-(4-methylphenylazo)-2-methylmalonodinitrile, 4,4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-methylmalonodinitrile, 1,1'-azobis-1-cyclohexyl Examples of the azo compounds include xanthanecarbonitrile, 1,1'-azobis-1-phenylethane, 1,1'-azobiscumene, 4-nitrophenylazobenzyl ethyl cyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrotriphenylazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane, etc.; azo compounds such as azobisisobutyronitrile, dimethyl azobisisobutyrate, phenylazotriphenylmethane, etc.; and metal chelate compounds such as Mn(acac)3. If necessary, a chain transfer agent such as lauryl mercaptan, thioglycerol, 2-mercaptoethanol, ethyl thioglycolic acid, or octyl thioglycolic acid, or a thiol compound having a coupling group such as γ-mercaptopropyltrimethoxysilane may be used as an additive such as a chain transfer agent.

[0090] The organic solvent is preferably a ketone, an ester, an amide, a sulfoxide, an ether, a hydrocarbon, a fluorine-based solvent, or the like. Specific examples of the organic solvent include alcohols such as ethanol, isopropyl alcohol, n-butanol, iso-butanol, and tert-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 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, dimethylsulfoxide, dimethylacetamide, N-methyl Examples of the solvent include polar solvents such as ethyl pyrrolidone, ethers 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-based solvents such as 1,1,1-trichloroethane and chloroform, ethers such as tetrahydrofuran and dioxane, aromatics such as benzene, toluene, and xylene, fluorine-based 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. The organic solvent is appropriately selected in consideration of the boiling point, compatibility with the raw material or polymer, and polymerizability. The polymerizable monomer (A) is particularly compatible with organic solvents, and can be almost dissolved in the above organic solvents. These solvents can be used alone or in combination of two or more.

[0091] In the copolymer of the present invention, preferably, addition of the polymerizable monomer (A) to a reaction system is started, and after the start of addition of the polymerizable monomer (A), the polymerizable monomer (B) and a 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. By polymerizing the polymer of the present invention in this manner, it is possible to minimize the amount of unreacted silicone chains, thereby making it possible to suppress coating film defects that are a concern due to additives during coating.

[0092] The polymerizable monomer (A) may contain impurities of compounds having a cyclic siloxane structure, and it is advisable to remove the compounds having a cyclic siloxane structure by distilling the polymerizable monomer (A) before adding it to the reaction system, or by distilling the polymer after the reaction, etc. The distillation can be carried out by a known method, for example, thin-film distillation.

[0093] The polymer of the present invention can also be produced by subjecting the polymerization components to living polymerization such as living radical polymerization or living anionic polymerization.

[0094] In the living radical polymerization, a dormant species whose active polymerization terminal is protected by an atom or an atomic group reversibly generates a radical and reacts with a monomer, so that a propagation reaction proceeds. Even if the first monomer is consumed, the propagation terminal does not lose activity, and reacts with the second monomer that is added sequentially to obtain a block polymer. Examples of such living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-fragmentation radical polymerization (RAFT), nitroxide-mediated radical polymerization (NMP), and radical polymerization using organotellurium (TERP). Of these, there is no particular restriction on which method is used, but ATRP is preferred because of ease of control. In ATRP, polymerization is carried out using an organic halide or a sulfonyl halide compound as a polymerization initiator and a metal complex consisting of a transition metal compound and a ligand as a catalyst.

[0095] Specific examples of polymerization initiators that can be used in ATRP include 1-phenylethyl chloride, 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, α,α'-dichloroxylene, α,α'-dibromoxylene, hexakis(α-bromomethyl)benzene, and alkyl esters having 1 to 6 carbon atoms 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.). More specific examples of the alkyl ester having 1 to 6 carbon atoms of a 2-halogenated carboxylic acid having 1 to 6 carbon atoms include methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate, and ethyl 2-bromoisobutyrate.

[0096] The transition metal compounds that can be used in ATRP are M n+ X n It is expressed as follows. M n+ X n The transition metal M of the transition metal compound represented by n+ As for the + , Cu 2+ , Fe 2+ , Fe3+ , 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+ The compound may be selected from the group consisting of: M n+ X n X in the transition metal compound represented by the formula (1) is a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, (SO4) 1 / 2 , (PO4) 1 / 3 , (HPO4) 1 / 2 , (H2PO4), triflate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate), SeR 11 , CN and R 12 COO, where R 11 represents an aryl group or a linear or branched alkyl group having 1 to 20 carbon atoms (preferably having 1 to 10 carbon atoms); R 12 represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms (preferably a methyl group) which may be substituted 1 to 5 times with halogen (preferably 1 to 3 times with fluorine or chlorine). M n+ X n In the transition metal compound represented by the formula (I), n represents a formal charge on the metal and is an integer of 0 to 7.

[0097] Examples of the ligand compound capable of forming a coordinate bond with the transition metal of the above-mentioned transition metal compound include a compound having a ligand containing one or more nitrogen atoms, oxygen atoms, phosphorus atoms, or sulfur atoms capable of coordinating with the transition metal via a σ bond, a compound having a ligand containing two or more carbon atoms capable of coordinating with the transition metal via a π bond, and a compound having a ligand capable of coordinating with the transition metal via a μ bond or η bond.

[0098] The transition metal complex is not particularly limited, but preferred examples include complexes of transition metals of Groups 7, 8, 9, 10, and 11, and more preferred examples include complexes of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel.

[0099] Specific examples of catalysts that can be used in ATRP include complexes with ligands such as 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, and polyamines such as tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexamethyltris(2-aminoethyl)amine when the central metal is copper. Examples of divalent ruthenium complexes include dichlorotris(triphenylphosphine)ruthenium, dichlorotris(tributylphosphine)ruthenium, dichloro(cyclooctadiene)ruthenium, dichlorobenzeneruthenium, dichlorop-cymeneruthenium, dichloro(norbornadiene)ruthenium, cis-dichlorobis(2,2'-bipyridine)ruthenium, dichlorotris(1,10-phenanthroline)ruthenium, and carbonylchlorohydridotris(triphenylphosphine)ruthenium. Examples of divalent iron complexes include bistriphenylphosphine complexes and triazacyclononane complexes.

[0100] In the living radical polymerization, it is preferable to use a solvent. Examples of solvents used in living radical polymerization include ester-based solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ether-based solvents such as diisopropyl ether, dimethoxyethane, and diethylene glycol dimethyl ether; halogen-based solvents such as dichloromethane and dichloroethane; aromatic solvents such as toluene and xylene; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol-based solvents such as methanol, ethanol, and isopropanol; and aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide. The above solvents may be used alone or in combination of two or more kinds.

[0101] When the polymer of the present invention is produced as a silicone-containing living copolymer by living polymerization, it can be produced, for example, by any one of Methods 1 to 3 shown below. 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 forming a coordinate bond with the transition metal, and a solvent. Method 2: A method in which polymerizable monomer (A) is subjected to living radical polymerization (preferably atom transfer radical polymerization) in the presence of a polymerization initiator, a transition metal compound, a ligand compound capable of forming a coordinate bond with the transition metal, and a solvent to obtain a polymer block of polymerizable monomer (A), and then polymerizable monomer (B) is added to the reaction system to further subject polymerizable monomer (B) to living radical polymerization (preferably atom transfer radical polymerization) on the polymer block of polymerizable monomer (A). Method 3: A method in which polymerizable monomer (B) is subjected to living radical polymerization (preferably atom transfer radical polymerization) in the presence of a polymerization initiator, a transition metal compound, a ligand compound capable of forming a coordinate bond with the transition metal, and a solvent to obtain a polymer block of polymerizable monomer (B), and then polymerizable monomer (A) is added to the reaction system to further subject polymerizable monomer (A) to living radical polymerization (preferably atom transfer radical polymerization) to the polymer block of polymerizable monomer (B).

[0102] The polymerization temperature during the living radical polymerization is preferably in the range of room temperature to 120°C.

[0103] When the polymer of the present invention is produced by living radical polymerization, the resulting polymer may contain residual metals resulting from the transition metal compound used in the polymerization. The residual metals in the resulting polymer may be removed using activated alumina or the like after the polymerization is completed.

[0104] [Coating composition] The polymer of the present invention can be suitably used as a leveling agent for a coating composition, and the coating composition of the present invention contains the polymer of the present invention. The polymer of the present invention can be used as a fluorine atom-free leveling agent that does not contain fluorine atoms, and therefore is a leveling agent that has low environmental accumulation and low environmental load.

[0105] 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, the coating method, the desired film thickness, etc., but is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 5 parts by mass, and even more preferably 0.01 to 2 parts by mass, relative to 100 parts by mass of the solid content of the coating composition (e.g., base resin). If the content of the copolymer of the present invention is within this range, the surface tension can be sufficiently reduced, the desired leveling property can be obtained, and the occurrence of defects such as foaming during coating can be suppressed.

[0106] The application of the coating composition of the present invention is not particularly limited, and it can be used for any application that requires leveling property. For example, the coating composition of the present invention can be used as various paint compositions or photosensitive resin compositions.

[0107] When the coating composition of the present invention is used as a paint composition, examples of the paint composition include paints using natural resins such as petroleum resin paints, shellac paints, rosin-based paints, cellulose-based paints, rubber-based paints, lacquer paints, cashew resin paints, and oil-based vehicle paints; and paints using synthetic resins such as phenolic resin paints, alkyd resin paints, unsaturated polyester resin paints, amino resin paints, epoxy resin paints, vinyl resin paints, acrylic resin paints, polyurethane resin paints, and silicone resin paints. By adding the polymer of the present invention to the above coating composition, smoothness can be imparted to the resulting coating film.

[0108] Various additives may be added to the coating composition as needed, such as colorants such as pigments, dyes, and carbon; inorganic powders such as silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, and calcium carbonate; organic fine powders such as higher fatty acids, polyacrylic resins, and polyethylene; and light resistance improvers, weather resistance improvers, heat resistance improvers, antioxidants, thickeners, and anti-settling agents.

[0109] Regarding the coating method of the coating composition of the present invention, any method can be used so long as it is a publicly known and publicly used coating method, and examples thereof include methods such as a slit coater, a slit & spin coater, a spin coater, a roll coater, electrostatic coating, a bar coater, a gravure coater, a die coater, a knife coater, an inkjet, dipping coating, spray coating, shower coating, screen printing, gravure printing, offset printing, and reverse coating.

[0110] The photosensitive resin composition changes its physical properties, such as solubility, viscosity, transparency, refractive index, conductivity, and ion permeability, when irradiated with light such as visible light or ultraviolet light. Among photosensitive resin compositions, resist compositions (photoresist compositions, color resist compositions for color filters, etc.) are required to have high leveling properties. The resist composition is usually applied by spin coating to a thickness of about 1 to 2 μm on a silicon wafer or a glass substrate on which various metals are deposited. In this case, if the applied film thickness fluctuates or uneven application occurs, the linearity and reproducibility of the pattern decreases, and a problem occurs in which a resist pattern with the desired accuracy cannot be obtained. In addition to these problems, there are various leveling-related problems such as drip marks, overall unevenness, and a bead phenomenon in which the film thickness is thicker at the edge compared to the center. The coating composition of the present invention can solve the above problems when used as a resist composition because the polymer of the present invention exhibits high leveling properties and can form a uniform coating film (cured product).

[0111] 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.

[0112] The alkali-soluble resin contained in the photoresist composition is a resin that is soluble in an alkaline solution, which is the developer used when patterning the resist. Examples of the alkali-soluble resin include novolak resins obtained by condensing an aromatic hydroxy compound derivative such as phenol, cresol, xylenol, resorcinol, phloroglucinol, or hydroquinone with an aldehyde compound such as formaldehyde, acetaldehyde, or benzaldehyde; polymers or copolymers of vinylphenol compound derivatives such as o-vinylphenol, m-vinylphenol, p-vinylphenol, or α-methylvinylphenol; (meth)acrylic acid-based polymers or copolymers such as acrylic acid, methacrylic acid, or hydroxyethyl (meth)acrylate; polyvinyl alcohol; modified resins in which a radioactive ray-sensitive group such as a quinone diazide group, a naphthoquinone azide group, an aromatic azide group, or an aromatic cinnamoyl group has been introduced via a portion of the hydroxyl groups of these various resins; and urethane resins containing an acidic group such as a carboxylic acid or sulfonic acid in the molecule. These alkali-soluble resins may be used alone or in combination of two or more.

[0113] The radiation-sensitive substance contained in the photoresist composition is a substance that changes the solubility of an alkali-soluble resin in a developer when irradiated with energy rays such as ultraviolet rays, far ultraviolet rays, excimer laser light, X-rays, electron beams, ion beams, molecular beams, and gamma rays. Examples of radiation-sensitive substances include quinone diazide compounds, diazo compounds, azide compounds, onium salt compounds, halogenated organic compounds, mixtures of halogenated organic compounds and organometallic compounds, organic acid ester compounds, organic acid amide compounds, organic acid imide compounds, and poly(olefin sulfone) compounds.

[0114] Examples of the quinone diazide compounds include 1,2-benzoquinone azide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,1-naphthoquinone diazide-4-sulfonic acid ester, 2,1-naphthoquinone diazide-5-sulfonic acid ester, and sulfonic acid chlorides of quinone diazide derivatives such as 1,2-benzoquinone azide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 2,1-naphthoquinone diazide-4-sulfonic acid chloride, and 2,1-naphthoquinone diazide-5-sulfonic acid chloride.

[0115] Examples of the diazo-based compound include salts of condensates of p-diazodiphenylamine with formaldehyde or acetaldehyde, inorganic diazo resin salts which are reaction products of the above-mentioned condensates with hexafluorophosphates, tetrafluoroborates, perchlorates or periodates, and organic diazo resin salts which are reaction products of the above-mentioned condensates with sulfonic acids as described in USP 3,300,309.

[0116] Examples of the azide-based compounds include azidochalconic acid, diazidobenzalmethylcyclohexanones, azidocinnamylideneacetophenones, aromatic azide compounds, and aromatic diazide compounds.

[0117] Examples of the halogenated organic compound include halogen-containing oxadiazole-based compounds, halogen-containing triazine-based compounds, halogen-containing acetophenone-based compounds, halogen-containing benzophenone-based compounds, halogen-containing sulfoxide-based compounds, halogen-containing sulfone-based compounds, halogen-containing thiazole-based compounds, halogen-containing oxazole-based compounds, halogen-containing trizole-based compounds, halogen-containing 2-pyrone-based compounds, halogen-containing aliphatic hydrocarbon-based compounds, halogen-containing aromatic hydrocarbon-based compounds, halogen-containing heterocyclic compounds, and sulfenyl halide-based compounds. In addition to the above, compounds used as halogen-based flame retardants such as tris(2,3-dibromopropyl)phosphate, tris(2,3-dibromo-3-chloropropyl)phosphate, chlorotetrabromomethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenyl allyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis(bromoethyl ether)tetrabromobisphenol A, bis(chloroethyl ether)tetrachlorobisphenol A, tris(2,3-dibromopropyl)isocyanurate, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, and 2,2-bis(4-hydroxyethoxy-3,5-dibromophenyl)propane, and compounds used as organic chloro-based pesticides such as dichlorophenyltrichloroethane are also exemplified as halogenated organic compounds.

[0118] Examples of the organic acid ester include carboxylate ester and sulfonate ester. Examples of the organic acid amide include carboxylate amide and sulfonate amide. Examples of the organic acid imide include carboxylate imide and sulfonate imide. The radiation sensitive substance may be used alone or in combination of two or more kinds.

[0119] In the photoresist composition, the content of the radiation-sensitive substance is preferably in the range of 10 to 200 parts by mass, and more preferably in the range of 50 to 150 parts by mass, per 100 parts by mass of the alkali-soluble resin.

[0120] 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-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, pentanol, heptanol, octanol, nonanol, and decanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dioxane; alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether; ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, butyl esters such as ethyl butyrate, butyl butyrate, propyl butyrate, ethyl lactate, butyl lactate, etc.; monocarboxylic acid esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, etc.; cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate. cellosolve esters such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and other propylene glycols; diethylene glycols such as diethylyl glycol monomethyl ether, diethylyl glycol monoethyl ether, diethylyl glycol dimethyl ether, diethylyl glycol diethyl ether, and diethylyl glycol methyl ethyl ether;Examples of such solvents include halogenated hydrocarbons such as trichloroethylene, fluorocarbon solvents, HCFCs, and HFCs; fully fluorinated solvents such as perfluorooctane, aromatics such as toluene and xylene; and polar solvents such as dimethylacetamide, dimethylformamide, N-methylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.

[0121] 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.

[0122] The alkali-soluble resin contained in the color resist can be the same as the alkali-soluble resin contained in the above-mentioned photoresist composition.

[0123] The polymerizable compound contained in the color resist composition is, for example, a compound having a photopolymerizable functional group that can undergo a polymerization or crosslinking reaction when irradiated with active energy rays such as ultraviolet rays. Examples of the polymerizable compound include unsaturated carboxylic acids such as (meth)acrylic acid, esters of monohydroxy compounds and unsaturated carboxylic acids, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, esters obtained by esterification reactions of unsaturated carboxylic acids with polyvalent carboxylic acids and polyvalent hydroxy compounds such as the above-mentioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, polymerizable compounds having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound, and polymerizable compounds having an acid group. The polymerizable compounds may be used alone or in combination of two or more kinds.

[0124] Examples of the esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and glycerol (meth)acrylate. In addition, examples of the (meth)acrylic acid portion of these acrylates include itaconic acid esters in which itaconic acid is substituted, crotonic acid esters in which crotonic acid is substituted, and maleic acid esters in which maleic acid is substituted.

[0125] Examples of the esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone di(meth)acrylate, resorcinol di(meth)acrylate, and pyrogallol tri(meth)acrylate. The ester obtained by the esterification reaction of the unsaturated carboxylic acid, the polycarboxylic acid, and the polyhydroxy compound may be a single substance or a mixture. Examples of such esters include esters obtained from (meth)acrylic acid, phthalic acid, and ethylene glycol, esters obtained from (meth)acrylic acid, maleic acid, and diethylene glycol, esters obtained from (meth)acrylic acid, terephthalic acid, and pentaerythritol, and esters obtained from (meth)acrylic acid, adipic acid, butanediol, and glycerin.

[0126] Examples of the polymerizable compound having a urethane skeleton obtained by reacting the polyisocyanate compound with a hydroxy compound containing a (meth)acryloyl group include reaction products of aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; and aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, with a hydroxy compound having a (meth)acryloyl group, such as 2-hydroxyethyl (meth)acrylate and 3-hydroxy[1,1,1-tri(meth)acryloyloxymethyl]propane.

[0127] The polymerizable compound having an acid group is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a polyfunctional polymerizable compound having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride is preferable. The aliphatic polyhydroxy compound used for preparing the polyfunctional polymerizable compound is preferably pentaerythritol or dipentaerythritol. The acid value of the polyfunctional polymerizable compound is preferably in the range of 0.1 to 40, and more preferably in the range of 5 to 30, in order to improve developability, curability, etc. When two or more polyfunctional polymerizable compounds having an acid group are used in combination, or when a polyfunctional polymerizable compound having an acid group and a polyfunctional polymerizable compound not having an acid group are used in combination, it is preferable that the acid value of the mixture of polymerizable compounds is adjusted to be within the above range.

[0128] Specific examples of the polymerizable compound having an acid group include a mixture mainly composed of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and a succinic acid ester of dipentaerythritol pentaacrylate, and the mixture is commercially available as ARONIX TO-1382 (manufactured by Toagosei Co., Ltd.).

[0129] Examples of polymerizable compounds other than those mentioned above include (meth)acrylamides such as ethylene bis(meth)acrylamide; allyl esters such as diallyl phthalate; and compounds having a vinyl group such as divinyl phthalate.

[0130] In the color resist composition, the content of the polymerizable compound is preferably in the range of 5 to 80 mass % of the total solid content of the color resist composition, more preferably in the range of 10 to 70 mass %, and even more preferably in the range of 20 to 50 mass %.

[0131] The colorant for the color resist composition is not particularly limited as long as it is capable of imparting color, and may be, for example, a pigment or a dye. Either organic or inorganic pigments can be used as the pigment. As the organic pigment, pigments of various hues such as red pigments, green pigments, blue pigments, yellow pigments, purple pigments, orange pigments, and brown pigments can be used. In addition, examples of the chemical structure of the organic pigment include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments. In addition, examples of the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide. In addition, "CI" below stands for color index.

[0132] Examples of the red pigment include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, and 53:2. , 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 1 49, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 23 3, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, etc. Among these, CI Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242 or 254 is preferable, and CI Pigment Red 177, 209, 224 or 254 is more preferable.

[0133] 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.

[0134] 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.

[0135] 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 preferable, and CI Pigment Yellow 83, 138, 139, 150 or 180 is more preferable.

[0136] Examples of the purple pigment include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, CI Pigment Violet 19 or 23 is preferable, and CI Pigment Violet 23 is more preferable.

[0137] 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.

[0138] The three primary color pixels of color filters used in liquid crystal display devices and organic EL display devices are red (R), green (G), and blue (B). Therefore, the red, green, and blue pigments are used as the main components, and organic pigments of colors such as yellow, purple, and orange may be used for hue adjustment in order to improve color reproducibility.

[0139] The average particle size of the organic pigment is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less, in order to increase the brightness of color liquid crystal displays and organic EL displays. The organic pigment is preferably used after being subjected to a dispersion treatment so as to have such an average particle size. The average primary particle size of the organic pigment is preferably 100 nm or less, more preferably 50 nm or less, even more preferably 40 nm or less, and particularly preferably in the range of 10 to 30 nm. The average particle size of the organic pigment is measured using a dynamic light scattering particle size distribution analyzer, and can be measured using, for example, Nanotrac particle size distribution analyzers "UPA-EX150" and "UPA-EX250" manufactured by Nikkiso Co., Ltd.

[0140] When the color resist composition is used to form a black matrix (BM), the colorant is not particularly limited as long as it is black, and examples thereof include carbon black, lamp black, acetylene black, bone black, thermal black, channel black, furnace black, graphite, iron black, titanium black, etc. Among these, carbon black and titanium black are preferred from the viewpoints of light shielding rate and image characteristics. In addition, two or more organic pigments may be mixed to produce a black color.

[0141] Examples of commercially available carbon blacks include MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150, # 3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B, and the like. Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Print ex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack 350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170, and the like, and Monarch 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R, BLACK manufactured by Cabot Japan Co., Ltd.PEARLS480, PEARLS130, VULCAN XC72R, ELFTEX-8, etc. are included, and RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN 1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000, and the like.

[0142] Among the above carbon blacks, resin-coated carbon black is preferred because it has the high optical density and high surface resistivity required for the black matrix of a color filter.

[0143] Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.

[0144] As a colorant used in forming a black matrix (BM), two or more kinds of organic pigments may be mixed to produce a black color, and examples of the black pigment include a mixture of three color pigments, red, green, and blue. The colorants that can be mixed to prepare black pigments include Victoria Pure Blue (CI 42595), Auramine O (CI 41000), Catilone Brilliant Flavin (Basic 13), Rhodamine 6GCP (CI 45160), Rhodamine B (CI 45170), Safranin OK 70:100 (CI 50240), Erioglaucine X (CI 42080), No. 120 / Leonol Yellow (CI 21090), Leonol Yellow GRO (CI 21090), and Shimla First Yellow. -8GF (CI21105), Benzidine Yellow 4T-564D (CI21095), Shimla First Red 4015 (CI12355), Lionor Red 7B4401 (CI15850), Firstgen Blue TGR-L (CI74160), Lionor Blue SM (CI26150), Lionor Blue ES (CI Pigment Blue 15:6), Lionor Red GD (CI Pigment Red 168), Lionor Green 2YS (CI Pigment Green 36), etc.

[0145] Other colorants that can be mixed and used to prepare a black pigment include, for example, CI Yellow Pigment 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, CI Orange Pigment 36, 43, 51, 55, 59, 61, CI Red Pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, CI Violet Pigment 19, 23, 29, 30, 37, 40, 50, CI Blue Pigment 15, 15:1, 15:4, 22, 60, 64, CI Green Pigment 7, CI Brown Pigment 23, 25, 26, and the like.

[0146] When carbon black is used as the black pigment, the average primary particle size of the carbon black is preferably in the range of 0.01 to 0.08 μm, and more preferably in the range of 0.02 to 0.05 μm because of its good developability.

[0147] Carbon black has a particle shape different from organic pigments, etc., and exists in a state called a structure in which primary particles are fused to each other, and fine pores may be formed on the particle surface by post-treatment. Therefore, in order to express the particle shape of carbon black, it is generally preferable to measure the DBP absorption amount (JIS K6221) and the specific surface area by the BET method (JIS K6217) in addition to the average particle size of the primary particles, which is obtained by the same method as the organic pigments, and use these as indicators of the structure and pore amount. The dibutyl phthalate (DBP) absorption of carbon black is 40-100 cm 3 / 100g is preferable, and 50 to 80 cm is preferable because of its good dispersibility and developability. 3 The specific surface area of ​​carbon black by the BET method is preferably in the range of 50 to 120 m 2 The range of 60 to 95 m / g is preferable because of good dispersion stability. 2 / g range is more preferred.

[0148] Examples of dyes that can be used as colorants in the color resist composition include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

[0149] Examples of the azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, and CI Mordant Black 7.

[0150] Examples of the anthraquinone dyes include CI Vat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Disperse Blue 60.

[0151] Examples of the phthalocyanine dyes include CI Pad Blue 5, and the like. Examples of the quinoneimine dyes include CI Basic Blue 3 and CI Basic Blue 9, and the like. Examples of the quinoline dyes include CI Solvent Yellow 33, CI Acid Yellow 3 and CI Disperse Yellow 64, and the like. Examples of the nitro dyes include CI Acid Yellow 1, CI Acid Orange 3 and CI Disperse Yellow 42, and the like.

[0152] It is preferable to use a pigment as the colorant for the color resist composition, since the resulting coating film is excellent in light resistance, weather resistance, and fastness. However, in order to adjust the hue, a dye may be used in combination with the pigment as necessary.

[0153] In the color resist composition, the content of the colorant is preferably 1 mass % or more, more preferably in the range of 5 to 80 mass %, and even more preferably in the range of 5 to 70 mass %, of the total solid content of the color resist composition.

[0154] When the color resist composition is used to form red (R), green (G), and blue (B) pixels of a color filter, the content of the colorant in the color resist composition is preferably in the range of 5 to 60 mass % of the total solid content of the color resist composition, and more preferably in the range of 10 to 50 mass %.

[0155] When the color resist composition is used to form a black matrix of a color filter, the content of the colorant in the color resist composition is preferably in the range of 20 to 80 mass % of the total solid content of the color resist composition, and more preferably in the range of 30 to 70 mass %.

[0156] In the color resist composition, when the colorant is a pigment, it is preferable to use the pigment as a pigment dispersion prepared by dispersing the pigment in an organic solvent using a dispersant. Examples of the dispersant include surfactants, pigment intermediates or derivatives, dye intermediates or derivatives, and resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins. Among these, graft copolymers having nitrogen atoms, acrylic block copolymers having nitrogen atoms, and urethane resin dispersants are preferred. Since these dispersants have nitrogen atoms, the nitrogen atoms have affinity for the pigment surface, and the portions other than the nitrogen atoms increase the affinity for the medium, thereby improving the dispersion stability. These dispersants may be used alone or in combination of two or more.

[0157] Commercially available dispersants include the "EFKA" series (such as "EFKA 46") manufactured by BASF; the "Disperbyk" series and "BYK" series (such as "BYK-160", "BYK-161", and "BYK-2001") manufactured by BYK Japan Co., Ltd.; the "Solsperse" series manufactured by Lubrizol Japan Co., Ltd.; the "KP" series manufactured by Shin-Etsu Chemical Co., Ltd., the "Polyflow" series manufactured by Kyoeisha Chemical Co., Ltd.; the "Disparlon" series manufactured by Kusumoto Chemical Co., Ltd.; and the "Ajisper" series (such as "Ajisper PB-814") manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0158] Examples of organic solvents used in preparing the pigment dispersion include acetate-based solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate-based solvents such as ethoxypropionate; aromatic solvents such as toluene, xylene, and methoxybenzene; ether-based solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, and diethylene glycol dimethyl ether; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon-based solvents such as hexane; nitrogen compound-based solvents such as N,N-dimethylformamide, γ-butyrolactam, and N-methyl-2-pyrrolidone; lactone-based solvents such as γ-butyrolactone; and carbamic acid esters. These solvents may be used alone or in combination of two or more.

[0159] The method for preparing the pigment dispersion liquid includes a method that includes a colorant kneading / dispersing step and a fine-dispersing step, and a method that includes only the fine-dispersing step. In the kneading / dispersing step, the colorant, a part of the alkali-soluble resin, and optionally the dispersant are mixed and kneaded. The colorant can be dispersed by dispersing while applying a strong shearing force using a kneader. Examples of machines used for kneading include two-roll machines, three-roll machines, ball mills, tron ​​mills, dispersers, kneaders, co-kneaders, homogenizers, blenders, and single- or twin-screw extruders. It is preferable that the colorant be reduced in particle size by a salt milling method or the like before the above kneading is carried out.

[0160] In the fine dispersion step, a solvent is added to the composition containing the colorant obtained in the kneading and dispersion step, or a mixture of a colorant, an alkali-soluble resin, a solvent, and, if necessary, the dispersant is mixed together with a dispersion medium such as fine particles of glass, zirconia, or ceramic, using a dispersing machine, thereby dispersing the colorant particles to a fine state close to primary particles.

[0161] From the viewpoint of improving the transmittance, contrast, etc. of the color filter, the average particle size of the primary particles of the colorant is preferably 10 to 100 nm, and more preferably 10 to 60 nm. The average particle size of the colorant is measured by a dynamic light scattering type particle size distribution analyzer, and can be measured by, for example, Nanotrac particle size distribution analyzers "UPA-EX150" and "UPA-EX250" manufactured by Nikkiso Co., Ltd.

[0162] As the coating composition, a paint composition, a photoresist composition, and a color resist composition have been exemplified above, but the coating composition is not limited to these.

[0163] Specific examples of applications of the coating composition of the present invention include anti-glare (AG: anti-glare) hard coat materials, anti-reflection (LR) coat materials, low refractive index layer coat materials, high refractive index layer coat materials, clear hard coat materials, and polymerizable liquid crystal coat materials, which are coating materials for various display screens such as liquid crystal displays (hereinafter abbreviated as "LCD"), plasma displays (hereinafter abbreviated as "PDP"), organic electroluminescent displays (hereinafter abbreviated as "OLED"), and quantum dot displays (hereinafter abbreviated as "QDD"); color resists, inkjet inks, printing inks, or paints for forming each pixel such as RGB of color filters (hereinafter abbreviated as "CF") of LCDs, etc.; black resists, inkjet inks, printing inks, or paints for forming black matrices, black column spacers, and black photospacers of CFs of LCDs, etc.; transparent protective film paints for protecting the CF surface used in CFs of LCDs, etc.; resin compositions for liquid crystal materials, column spacers, and photospacers of LCDs; resin compositions for pixel partition walls of LCDs, PDPs, OLEDs, QDDs, etc., positive photoresists for forming electrodes, protective Films, insulating films, plastic housings, paints for plastic housings, bezel (frame) inks; prism sheets and light diffusion films used as backlight components for LCDs; paints for organic insulating films in LCD liquid crystal TFT arrays; surface protective coating materials for LCD internal polarizers; phosphors for PDPs; organic EL materials and encapsulants (protective films, gas barriers) for OLEDs; quantum dot inks, encapsulants, and protective films for QDDs; high refractive index lenses, low refractive index encapsulants, and LED pixels for micro (mini) LED displays; positive photoresists, chemically amplified photoresists, anti-reflective films, and multilayers used in semiconductor manufacturing Materials (SOC, SOG), underlayer films, buffer coats, developers, rinsing solutions, pattern collapse prevention agents, polymer residue removal solutions, cleaning agents and other chemicals, nanoimprint release agents; resin compositions for semiconductor post-processing or printed wiring boards (resin compositions such as epoxy resins, phenolic resins, polyphenylene ether resins, liquid crystal polymers, polyimide resins, bismaleimide resins, bisallylnadimide resins, and benzoxazine resins), copper-clad laminates, resin-coated copper foils, build-up films, passivation films, interlayer insulating films, flexible copper-clad laminates, and dry film resists;Color resist for image sensors; Liquid repellents for solder flux; Dispersants, paints, green sheets for multilayer ceramic capacitors; Cathode materials, anode materials, separators, electrolytes for lithium-ion batteries; Automotive exterior paints, rubber, elastomers, glass, deposition anchor coats, headlamp lenses, solid lubricant paints, heat dissipation substrates, interior paints, repair paints; Wallpaper, flooring, kitchen materials, bathroom and toilet materials for housing facilities; Inkjet inks for printed matter, offset printing inks, gravure printing inks, screen printing inks, photoresists for the printing plate manufacturing process, photosensitive materials for lithographic printing plates (PS plates), packaging adhesives, ballpoint pen inks; Primers for easy adhesion of plastic films, etc.; Water repellents for textiles; Non-diffusion agents for greases; Cleaning fluids for cleaning the surfaces of various products or parts; Hard coat materials for optical recording media such as CDs, DVDs, and Blu-ray discs; Smartphones or Paints or hard coat materials for the housing or screen of a mobile phone; hard coat materials for transfer films for insert molds (IMD, IMF); release films; paints or coating materials for various plastic molded products such as the housing of home appliances; printing inks or paints for various building materials such as decorative panels; coating materials for window glass in houses; paints for woodworking such as furniture; coating materials for artificial and synthetic leather; coating materials for rubber rollers for office equipment such as copy machines and printers; coating materials for glass in the reading parts of office equipment such as copy machines and scanners; optical lenses or coating materials for cameras, video cameras, glasses, contact lenses, etc.; coating materials for windshields and glass for watches such as wristwatches; coating materials for windows of various vehicles such as automobiles and railway cars; paints for anti-reflection films for cover glass or films for solar cells; paints or coating materials for FRP bathtubs; PCM for metal building materials or home appliances; single-layer or multi-layer coating compositions for photofabrication processes, etc.;

[0164] The copolymer of the present invention has excellent surface tension reducing ability, so that it can be expected to have not only leveling properties but also wettability, permeability, cleanability, water repellency, oil repellency, antifouling properties, lubricity, antiblocking properties, and releasability.In addition, when the polymer of the present invention is blended into a paint or coating agent containing fine particles, it can be expected to improve the dispersibility of the fine particles, and can be expected to function as a dispersant for the fine particles as well as leveling properties.In addition to the above coating composition, the polymer of the present invention can be added to an adhesive composition used for adhesive tapes, etc., and can be expected to have not only leveling properties but also the functions of reducing peeling force, suppressing peeling force fluctuation, and suppressing peeling electrification. EXAMPLES

[0165] The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

[0166] The GPC measurement conditions for the silicone-containing copolymers obtained in the following Examples and Comparative Examples are as follows. [GPC measurement conditions] Measurement equipment: Tosoh Corporation "HLC-8220 GPC" Column: Tosoh Corporation guard column "HHR-H" (6.0 mm I.D. x 4 cm) + Tosoh Corporation "TSK-GEL GMHHR-N" (7.8mm I.D. x 30cm) + Tosoh Corporation "TSK-GEL GMHHR-N" (7.8mm I.D. x 30cm) + Tosoh Corporation "TSK-GEL GMHHR-N" (7.8mm I.D. x 30cm) + Tosoh Corporation "TSK-GEL GMHHR-N" (7.8mm I.D. x 30cm) Detector: Evaporative light scattering detector ("ELSD2000" manufactured by Ortech Japan Co., Ltd.) Data processing: Tosoh Corporation "GPC-8020 Model II Data Analysis Version 4.30" Measurement conditions: Column temperature 40℃ Developing solvent: Tetrahydrofuran (THF) Flow rate 1.0ml / min Sample: A 1.0% by mass solids solution in tetrahydrofuran filtered through a microfilter (5 μl). Standard sample: In accordance with the measurement manual for the aforementioned "GPC-8020 Model II Data Analysis Version 4.30," the following monodisperse polystyrene with known molecular weight was used.

[0167] (monodisperse polystyrene) "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation "F-128" manufactured by Tosoh Corporation "F-288" manufactured by Tosoh Corporation "F-550" manufactured by Tosoh Corporation

[0168] Example 1: Synthesis of Silicone-Containing Copolymer (1) Mixed solution A1 was prepared by dissolving 67.0 g of a commercially available monomethacrylate compound having a polysiloxane bond (3-methacryloyloxypropyltris(trimethylsiloxy)silane) and 33.0 g of commercially available 1-adamantyl methacrylate in 70.0 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and mixed solution B1 was prepared by mixing 5.0 g of t-butylperoxy-2-ethylhexanoate as a polymerization initiator and 42.5 g of PGMEA as a solvent.

[0169] A flask purged with nitrogen was charged with 100.0 g of PGMEA as a solvent, and the temperature was raised to 95°C while stirring under a nitrogen stream. Mixtures A1 and B1 were added dropwise at 95°C over 120 minutes. After the dropwise addition was completed, the mixture was stirred at 95°C for 5 hours, and then at 110°C for 1 hour. After the reaction was completed, 187.5 g of PGMEA was added to obtain a PGMEA solution containing 20% ​​by mass of silicone-containing copolymer (1).

[0170] The molecular weight of the obtained silicone-containing copolymer (1) was measured by GPC, and as a result, the weight average molecular weight (Mw) was 9300. Furthermore, based on the raw material charging ratio, the content of functional groups represented by -Si[OSi(CH3)3]3 in the silicone-containing copolymer (1) was 50 mass%.

[0171] Example 2: Synthesis of Silicone-Containing Copolymer (2) Mixed solution A2 was prepared by dissolving 35.0 g of a commercially available monomethacrylate compound having a polysiloxane bond (3-methacryloyloxypropyltris(trimethylsiloxy)silane) and 65.0 g of commercially available 1-adamantyl methacrylate in 97.5 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and mixed solution B2 was prepared by mixing 5.0 g of t-butylperoxy-2-ethylhexanoate as a polymerization initiator and 15.0 g of PGMEA as a solvent.

[0172] A flask purged with nitrogen was charged with 100.0 g of PGMEA as a solvent, and the temperature was raised to 95°C while stirring under a nitrogen stream. Mixtures A2 and B2 were added dropwise at 95°C over 120 minutes. After the dropwise addition was completed, the mixture was stirred at 95°C for 5 hours, and then at 110°C for 1 hour. After the reaction was completed, 20.8 g of PGMEA was added to obtain a PGMEA solution containing 30% by mass of silicone-containing copolymer (2).

[0173] The molecular weight of the obtained silicone-containing copolymer (2) was measured by GPC, and as a result, the weight average molecular weight (Mw) was 11,000. Furthermore, based on the raw material charging ratio, the content of functional groups represented by -Si[OSi(CH3)3]3 in the silicone-containing copolymer (1) was 26 mass%.

[0174] Example 3: Synthesis of Silicone-Containing Copolymer (3) Mixed solution A3 was prepared by dissolving 67.0 g of a commercially available monomethacrylate compound having a polysiloxane bond (3-methacryloyloxypropyltris(trimethylsiloxy)silane) and 33.0 g of commercially available 1-adamantyl methacrylate in 97.5 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and mixed solution B3 was prepared by mixing 10.0 g of t-butylperoxy-2-ethylhexanoate as a polymerization initiator and 15.0 g of PGMEA as a solvent.

[0175] A flask purged with nitrogen was charged with 100.0 g of PGMEA as a solvent, and the temperature was raised to 105°C while stirring under a nitrogen stream. Mixture A3 was added dropwise over 120 minutes, and B3 was added dropwise over 180 minutes. After the dropwise addition was completed, the mixture was stirred at 105°C for 5 hours, and after the reaction was completed, 20.8 g of PGMEA was added to obtain a PGMEA solution containing 30% by mass of silicone-containing copolymer (3).

[0176] The molecular weight of the obtained silicone-containing copolymer (3) was measured by GPC, and as a result, the weight average molecular weight (Mw) was 6,100. Furthermore, based on the raw material charging ratio, the content of functional groups represented by -Si[OSi(CH3)3]3 in the silicone-containing copolymer (3) was 50 mass%.

[0177] Example 4: Synthesis of Silicone-Containing Copolymer (4) Mixed solution A4 was prepared by dissolving 20.0 g of a commercially available monomethacrylate compound having a polysiloxane bond (3-methacryloyloxypropyltris(trimethylsiloxy)silane) and 80.0 g of commercially available 1-adamantyl methacrylate in 97.5 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and mixed solution B4 was prepared by mixing 15.0 g of t-butylperoxy-2-ethylhexanoate as a polymerization initiator and 15.0 g of PGMEA as a solvent.

[0178] A flask purged with nitrogen was charged with 100.0 g of PGMEA as a solvent, and the temperature was raised to 105°C while stirring under a nitrogen stream. Mixture A4 was added dropwise over 120 minutes, and B4 was added dropwise over 180 minutes. After the dropwise addition was completed, the mixture was stirred at 105°C for 5 hours, and after the reaction was completed, 20.8 g of PGMEA was added to obtain a PGMEA solution containing 30% by mass of silicone-containing copolymer (4).

[0179] The molecular weight of the obtained silicone-containing copolymer (4) was measured by GPC, and as a result, the weight average molecular weight (Mw) was 4000. Furthermore, based on the raw material charging ratio, the content of the functional group represented by -Si[OSi(CH3)3]3 in the silicone-containing copolymer (4) was 15% by mass.

[0180] Example 5: Synthesis of Silicone-Containing Copolymer (5) Mixed solution A5 was prepared by dissolving 10.0 g of a commercially available monomethacrylate compound having a polysiloxane bond (3-methacryloyloxypropyltris(trimethylsiloxy)silane) and 90.0 g of commercially available 1-adamantyl methacrylate in 97.5 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and mixed solution B5 was prepared by mixing 15.0 g of t-butylperoxy-2-ethylhexanoate as a polymerization initiator and 15.0 g of PGMEA as a solvent.

[0181] A flask purged with nitrogen was charged with 100.0 g of PGMEA as a solvent, and the temperature was raised to 105°C while stirring under a nitrogen stream. Mixture A5 was added dropwise over 120 minutes, and B5 was added dropwise over 180 minutes. After the dropwise addition was completed, the mixture was stirred at 105°C for 5 hours, and after the reaction was completed, 20.8 g of PGMEA was added to obtain a PGMEA solution containing 30% by mass of silicone-containing copolymer (5).

[0182] The molecular weight of the obtained silicone-containing copolymer (5) was measured by GPC, and as a result, the weight average molecular weight (Mw) was 3800. Furthermore, based on the raw material charging ratio, the content of the functional group represented by -Si[OSi(CH3)3]3 in the silicone-containing copolymer (5) was 15% by mass.

[0183] Comparative Example 1: Synthesis of Silicone-Containing Copolymer (1') Mixture A1' was prepared by mixing 67.0 g of a monomethacrylate compound having the same polysiloxane bond as in Example 1 (3-methacryloyloxypropyltris(trimethylsiloxy)silane), 33.0 g of a commercially available polypropylene glycol-polybutylene glycol-monomethacrylate (average repeat number of propylene glycol: 1, average repeat number of butylene glycol: 6), and 70.0 g of butyl acetate as a solvent. Mixture B1' was prepared by mixing 3.0 g of t-butylperoxy-2-ethylhexanoate as a polymerization initiator and 63.3 g of butyl acetate as a solvent.

[0184] Into a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 100.0 g of butyl acetate was placed as a solvent, and the temperature was raised to 90° C. with stirring under a nitrogen stream. Mixtures A1' and B1' were added dropwise to this flask over 120 minutes at 90° C. After the addition was complete, the mixture was stirred at 90° C. for 5 hours, and then stirred at 110° C. for 1 hour. After the reaction was complete, the solvent was distilled off to obtain a silicone-containing copolymer (1').

[0185] The molecular weight of the resulting silicone-containing copolymer (1') was measured by GPC, and the weight average molecular weight (Mw) was found to be 17,000. Furthermore, based on the raw material charging ratio, the content of the polymerizable unsaturated monomer having a silicone chain in the silicone-containing copolymer (1') was 50 mass %.

[0186] Comparative Example 2: Synthesis of Silicone-Containing Copolymer (2') A mixed solution A2' was prepared by mixing 55.0 g of a commercially available monomethacrylate compound having a polysiloxane bond represented by the following formula, 45.0 g of commercially available adamantyl methacrylate, and 70.0 g of butyl acetate as a solvent, and a mixed solution B2' was prepared by mixing 3.0 g of t-butylperoxy-2-ethylhexanoate as a polymerization initiator and 63.3 g of butyl acetate as a solvent.

[0187] [ka] (The average value of x3 is 10)

[0188] Into a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 100.0 g of butyl acetate was placed as a solvent, and the temperature was raised to 90° C. with stirring under a nitrogen stream. 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 dropwise addition was completed, the mixture was stirred at 90° C. for 5 hours, and then stirred at 110° C. for 1 hour. After the reaction was completed, 166.7 g of butyl acetate was added to obtain a butyl acetate solution containing 20 mass % of silicone-containing copolymer (2').

[0189] The molecular weight of the resulting silicone-containing copolymer (2') was measured by GPC, and the weight average molecular weight (Mw) was found to be 15,000. Furthermore, based on the raw material charging ratio, the content of the polymerizable unsaturated monomer having a silicone chain in the silicone-containing copolymer (2') was 50 mass %.

[0190] [Coating film formation and evaluation] For the silicone-containing copolymers (1) to (5), (1') and (2') synthesized in the examples and comparative examples, coating films were formed and the leveling properties and the ability to inhibit pigment sublimation foreign matter were evaluated.

[0191] (1) Leveling ability Using the silicone-containing copolymer synthesized in each example, a coating film was formed as follows. A resist composition was prepared by mixing 3.0 g of binder resin (UNIDIC RS20-160, manufactured by DIC Corporation), 1.2 g of ARONIX M-402 (manufactured by Toagosei Chemical Industry Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), 0.002 g (calculated as solid content) of the silicone-containing copolymer synthesized in each example, and 8.1 g of PGMEA. 3 ml of the obtained resist composition was dropped onto the center of a 10 cm x 10 cm chrome-plated glass substrate and spin-coated at a rotation speed of 500 rpm for 30 seconds. The substrate was then heated and dried at 110°C for 2 minutes using a hot plate to produce a coating film. The coating film prepared above was visually observed and evaluated according to the following criteria. The results are shown in Table 1. ◯: Almost no coating unevenness was observed. △: Coating unevenness was observed in some areas. ×: Coating unevenness was observed throughout the entire surface.

[0192] (2) Suppression of the generation of foreign matter on the coating surface caused by sublimation of pigments Using the silicone-containing copolymer produced in each example, a pigmented coating film was formed as follows. 10 g of red pigment CI Pigment Red 254 (BASF "IRGAPHOR RED BT-CF") was placed in a plastic bottle, 44 g of PGMEA, 12 g of DISPERBYK LPN21116 (BYK-Chemie Co., Ltd.), and Seprubeads with a diameter of 0.3 to 0.4 mm were added, and the mixture was dispersed for 2 hours using a Paint Conditioner (Toyo Seiki Co., Ltd.) to obtain a red pigment dispersion.

[0193] Next, 1.5 g of binder resin (UNIDIC RS20-160, manufactured by DIC Corporation), 0.6 g of ARONIX M-402 (manufactured by Toagosei Chemical Industry Co., Ltd.) as a photopolymerizable monomer, 0.05 g of IRGACURE #369 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator, 0.0014 g of the silicone-containing copolymer of each example in terms of solid content, and 2.2 g of PGMEA were added and mixed to 5.9 g of the above red pigment dispersion to prepare a color resist composition.

[0194] 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 a rotation time of 10 seconds, and then dried at 80°C for 3 minutes. After drying, a high-pressure mercury lamp was used to apply 50 mJ / cm 2The coating film was then heated at 270°C for 1 hour, and then observed with a digital microscope VHX-900 (manufactured by Keyence Corporation) and evaluated according to the following criteria. The evaluation results are shown in Table 1.

[0195] ○: One or less foreign matter resulting from sublimation of pigment can be confirmed in a coating film of 1 cm x 1 cm square. △: An average of 2 to 9 foreign objects caused by sublimation of pigments were found in a 1 cm x 1 cm square coating film. ×: An average of 10 or more foreign objects due to sublimation of pigments can be confirmed in a coating film of 1 cm × 1 cm square.

[0196] [Table 1]

[0197] It can be seen that the coating film of Example 1 containing the silicone-containing copolymer of the present invention as a leveling agent has excellent coatability and does not generate foreign matter on the coating film surface 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 generated on the coating film surface due to sublimation of the pigment. Similarly, in Comparative Example 2, in which the weight average molecular weight of the silicone-containing copolymer is larger than that of Example 1 and the amount of the polymerizable monomer having a group represented by general formula (a) is larger than that of the polymerizable monomer having a group containing a cyclic hydrocarbon skeleton, foreign matter generated on the coating film surface due to sublimation of the pigment.

Claims

1. A silicone-containing copolymer comprising, as polymerization components, 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: 【Chemistry 1】 (In the general formula (a), R １１ each independently represents an alkyl group having 1 to 6 carbon atoms or —OSi(R １４ ) ３ A group represented by R １４ each independently represents 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 is a number average value indicating the number of repetitions and is an integer from 1 to 5.

2. 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 each R in the general formula (a). １１ , R １２ , R １３ and x, R １５ is a hydrogen atom or a methyl group, L １ is a divalent organic group.

3. 3. The silicone-containing copolymer according to claim 1, 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 a divalent linking group consisting of 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 containing a cyclic hydrocarbon skeleton has a bridged ring structure.

5. 5. The silicone-containing copolymer according to claim 4, wherein the group containing a cyclic hydrocarbon skeleton structure having a 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, having a weight average molecular weight (Mw) of 3,000 to 80,000.

7. The silicone-containing copolymer according to any one of claims 1 to 6, which does not contain 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 any one of claims 1 to 7 and a colorant.

11. A color filter, comprising a coating layer of the resist composition according to claim 10 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 each independently represents an alkyl group having 1 to 6 carbon atoms or —OSi(R １４ ) ３ A group represented by R １４ each independently represents 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 is a number average value indicating the number of repetitions and is an integer from 1 to 5.

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 each R in the general formula (a). １１ , R １２ , R １３ and x, R １５ is a hydrogen atom or a methyl group, L １ is a divalent organic group.

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 a divalent linking group consisting of 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 containing 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 a 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 polymerization components are copolymerized by a random copolymerization method or a living copolymerization method.

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