Composition, film using the same, optical filter, solid-state imaging sensing device, image display device, and infrared sensor

Abstract

To provide a composition that is excellent in coating properties even after storage and can form a film in which color mixture is suppressed.SOLUTION: A composition includes a pigment (A), resin (B), a leveling agent (C), and a solvent (D). The leveling agent (C) includes a block copolymer (C1) having an A block formed from a monomer unit (c1) represented by the following general formula (1), and a B block formed from a monomer unit (c2) other than the monomer unit (c1) represented by general formula (1). The solvent (D) includes a solvent (D1) in which the hydrogen bond term of the Hansen solubility parameter is 10 MPa1 / 2 or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a composition and its use. [Background technology]

[0002] In recent years, color filters, which are a type of optical filter used in liquid crystal displays, smartphones, infrared sensors, and the like, are produced, for example, through the following steps: a step of applying a composition used in the production of a color filter to a substrate such as glass, and removing the solvent from the coating film by drying; a step of irradiating and curing this coating film with ultraviolet light through a photomask having a desired pattern shape (hereinafter referred to as exposure); a step of washing and removing the unexposed parts of this coating film with a developer (hereinafter referred to as development); and a step of performing a heat treatment (hereinafter referred to as post-baking) to sufficiently cure the film to obtain a pattern of the first color. Then, the same operation is performed using compositions of different colors to sequentially form patterns of the second and subsequent colors to produce a color filter.

[0003] Therefore, it is necessary to suppress the adhesion of development residues of other colors on the previously formed pattern (hereinafter, suppression of color mixing). In particular, when post-baking is performed at a low temperature, there is a tendency for color mixing to occur, and improvement is required. Furthermore, the quality of a color filter is significantly reduced if there are pinholes or unevenness. Therefore, a composition used in the manufacture of a color filter is required to have excellent coatability. And, the coatability must be the same immediately after the composition is manufactured and when it is stored and used for the manufacture of a color filter. Furthermore, in recent years, from an environmental standpoint, there has been a demand to reduce the use of fluorine-based compounds in the components used in the compositions used in the production of color filters.

[0004] For example, Patent Document 1 discloses a colored radiation-sensitive composition capable of suppressing color mixing, which contains a dye, a photopolymerizable compound, a photopolymerization initiator, and a nonionic surfactant having a specific structure with a weight-average molecular weight of 2500 or less and an HLB value of 9.2 to 15.5 according to the Griffin method. In addition, as a composition capable of suppressing color mixing, a composition containing a silicone surfactant A having a surface tension of 26 mN / m or more in a 1000 ppm by mass propylene glycol monomethyl ether acetate solution, a curable compound, and a solvent is disclosed. In addition, Patent Document 3 discloses a colored composition capable of producing a film in which the occurrence of coating unevenness and striations is suppressed, which contains a colorant, a resin, a curable compound, a surfactant, and a solvent, and has a contact angle of more than 0 degrees and less than 5.5 degrees according to a specific measurement method. Furthermore, Patent Document 4 discloses a resin composition capable of forming a colored layer with low surface roughness, the resin composition containing a polymer, a polymerizable compound, a polymerization initiator, a colorant, and a compound having a fluorocarbon group and a crosslinked cyclic aliphatic group. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2014-199436 A [Patent Document 2] International Publication No. 2023 / 022120 [Patent Document 3] JP 2018-54918 A [Patent Document 4] International Publication No. 2017 / 169951 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the compositions described in Patent Documents 1 to 4 could not simultaneously satisfy high levels of coatability after storage and inhibition of color mixing.

[0007] An object of the present invention is to provide a composition capable of forming a film which has excellent coatability even after storage and in which color mixing is suppressed. [Means for solving the problem]

[0008] The present invention relates to a composition comprising a pigment (A), a resin (B), a leveling agent (C), and a solvent (D), The leveling agent (C) includes a block copolymer (C1) having an A block formed from a monomer unit (c1) represented by the following general formula (1) and a B block formed from a monomer unit (c2) other than the monomer unit (c1) represented by the general formula (1), The solvent (D) has a hydrogen bond term of the Hansen solubility parameter of 10 MPa. 1 / 2 The present invention relates to a composition containing the above-mentioned solvent (D1). General formula (1) [ka]

[0009] In general formula (1), R1's are each independently an alkyl group having 1 to 6 carbon atoms, or a group represented by -OSi(R5)3 (R5's are each independently an alkyl group having 1 to 3 carbon atoms). Each R2 is independently an alkyl group having 1 to 6 carbon atoms. R3 is an alkyl group having 1 to 6 carbon atoms. R4 is a hydrogen atom or a methyl group. L1 is a divalent organic group or a single bond. n is an integer from 1 to 70. Effect of the Invention

[0010] According to the present invention, there is provided a composition capable of forming a film having excellent coatability even after storage and suppressed color mixing. The present invention also provides a film, an optical filter, a solid-state imaging device, an image display device, and an infrared sensor using the composition. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic cross-sectional view of an infrared sensor having an optical filter of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, the embodiment of the composition of the present invention will be described in detail. Note that the present invention is not limited to the following embodiment, and can be modified within the scope of the problem that can be solved.

[0013] In this specification, unless otherwise specified, "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" respectively mean "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide". In addition, "CI" means Color Index (CI; published by The Society of Dyers and Colourists). In this specification, a polymerizable unsaturated group is an ethylenically unsaturated double bond. As used herein, a monomer is a compound that will polymerize to form a resin. A monomer is in an unreacted state, and a monomer unit is a monomer that has been polymerized to form a polymer. In this specification, for low molecular weight compounds whose molecular weight can be specified, the molecular weight is a calculated value or measured by ESI-MS (electrospray ionization mass spectrometry), and for compounds having a molecular weight distribution, the molecular weight is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0014] <Composition> A composition according to one embodiment of the present invention is a composition comprising a pigment (A), a resin (B), a leveling agent (C), and a solvent (D), The leveling agent (C) includes a block copolymer (C1) having an A block formed from a monomer unit (c1) represented by the following general formula (1) and a B block formed from a monomer unit (c2) other than the monomer unit (c1) represented by the general formula (1), The solvent (D) has a hydrogen bond term of the Hansen solubility parameter of 10 MPa. 1 / 2 The solvent (D1) is as described above. General formula (1) [ka]

[0015] In general formula (1), R1's are each independently an alkyl group having 1 to 6 carbon atoms, or a group represented by -OSi(R5)3 (R5's are each independently an alkyl group having 1 to 3 carbon atoms). Each R2 is independently an alkyl group having 1 to 6 carbon atoms. R3 is an alkyl group having 1 to 6 carbon atoms. R4 is a hydrogen atom or a methyl group. L1 is a divalent organic group or a single bond. n is an integer from 1 to 70.

[0016] The mechanism by which the composition having the above-mentioned configuration can solve the problems of the present invention is not clear, but is speculated as follows.

[0017] Generally, a smooth film is obtained by orienting the leveling agent (C) on the surface, but the leveling agent (C) may be adsorbed to or dissolved in other components contained in the composition, such as the pigment (A) or resin (B), during storage, and may not be effective enough during coating. However, a block copolymer (C1) (hereinafter, also referred to simply as block copolymer (C1)) having an A block formed from a monomer unit (c1) represented by general formula (1) and a B block formed from a monomer unit (c2) other than the monomer unit (c1) represented by general formula (1), and a copolymer having a hydrogen bond term of the Hansen solubility parameter of 10 MPa 1 / 2 It is believed that by using the above-mentioned solvent (D1) (hereinafter also simply referred to as solvent (D1)) in combination, it is possible to control the interaction between the block copolymer (C1) and other components, and to obtain excellent coatability even after storage. In addition, since the block copolymer (C1) has silicone chains in the side chains, it is presumed that the silicone chains are easily oriented on the film surface, thereby suppressing the adhesion of development residues and the like.

[0018] Components that are or may be included in the composition of one embodiment will be described in detail below.

[0019] Pigment The composition of the present invention contains a pigment (A).

[0020] The pigment (A) is not particularly limited, and a known compound can be used. For example, a chromatic pigment, a white pigment, a black pigment, and a near infrared absorbing pigment can be mentioned. The pigment (A) may be colorless. In the present invention, the solubility of the pigment (A) in 100 g of propylene glycol monomethyl ether acetate at 25° C. is preferably less than 2 g, more preferably less than 1 g, and particularly preferably 0.5 g or less.

[0021] When the composition of the present invention is used for a color filter, the pigment (A) is preferably a chromatic pigment. The chromatic pigment may be used alone or in combination of two or more. When the composition of the present invention is used for a near-infrared cut filter, the pigment is preferably a near-infrared absorbing pigment. The near-infrared absorbing pigment may be used alone or in combination of two or more. When used for a near-infrared transmission filter, it is preferable to use a black pigment or two or more chromatic pigments in combination to produce black. Furthermore, a near-infrared absorbing pigment may be used in combination.

[0022] (chromatic pigments) The chromatic pigment is not particularly limited, and any known chromatic pigment can be used, for example, a compound classified as a pigment in the Color Index.

[0023] Chromatic pigments include, for example, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179,1 81,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259,260, Nos. 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, JP 2014-134712 A, and the pigments described in Japanese Patent No. 6368844.

[0024] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0025] CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 1 No. 27,128,129,138,139,147,150,151,152, 153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,192,193,194,196,198,199,213,214,231,233, and JP-A-2012-226110.

[0026] Further, examples of yellow pigments include metal azo pigments containing one or more anions selected from the group consisting of azo compounds represented by the following general formula (4) and mono-, di-, tri-, and tetraanions of azo compounds having a tautomeric structure thereof, at least two metal ions selected from Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, and a compound represented by the following general formula (5).

[0027] General formula (4) [ka]

[0028] In general formula (4), R1's each independently represent -OH, -NH2, -NH-CN, an acylamino group, an alkylamino group, or an arylamino group, and R2's each independently represent -OH or -NH2.

[0029] General formula (5) [ka]

[0030] In formula (5), each R3 independently represents a hydrogen atom or an alkyl group.

[0031] Examples of the metal azo pigment include those described in JP-A-2014-12838, JP-A-2017-171912, JP-A-2017-171913, JP-A-2017-171914, JP-A-2017-171915, and JP-A-2022-61494.

[0032] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, 64, 65, and 66.

[0033] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, 80, 87, and 88.

[0034] Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.

[0035] The chromatic pigments can be used alone or in combination of two or more kinds. For example, in the case of black, in addition to using the black pigment described later, two or more chromatic pigments selected from the group consisting of red pigments, yellow pigments, green pigments, blue pigments, and purple pigments can be used (combined) to obtain the color. Examples of the combination include the following modes. (1) Contains yellow and purple pigments. (2) Contains red, yellow, and purple pigments. (3) Contains red, yellow, and blue pigments. (4) Contains red, yellow, and green pigments. (5) Contains yellow pigment, blue pigment, and purple pigment. (6) Contains red pigment, yellow pigment, blue pigment, and purple pigment. (7) Contains yellow pigment, blue pigment, green pigment, and purple pigment.

[0036] An example of the above embodiment (1) is an embodiment in which the yellow pigment contains one or more selected from CI Pigment Yellow 139, 185, 231, and 233, and the purple pigment contains CI Pigment Violet 23. An example of the above embodiment (2) is an embodiment in which the red pigment is one or more selected from CI Pigment Red 177, 254, 291, 295, and 296; the yellow pigment is one or more selected from CI Pigment Yellow 139, 185, 231, and 233; and the purple pigment is CI Pigment Violet 23. An example of the above embodiment (3) is an embodiment containing one or more red pigments selected from CI Pigment Red 177, 254, 291, 295, and 296, one or more yellow pigments selected from CI Pigment Yellow 139, 185, 231, and 233, and one or more blue pigments selected from CI Pigment Blue 15:3, 15:4, and 15:6. An example of the above embodiment (4) is an embodiment containing one or more red pigments selected from CI Pigment Red 177, 254, 291, 295, and 296, one or more yellow pigments selected from CI Pigment Yellow 139, 185, 231, and 233, and one or more green pigments selected from CI Pigment Green 7, 36, 58, 59, and 63. An example of the above embodiment (5) is an embodiment in which the yellow pigment contains one or more selected from CI Pigment Yellow 139, 185, 231, and 233; the blue pigment contains one or more selected from CI Pigment Blue 15:3, 15:4, and 15:6; and the purple pigment contains CI Pigment Violet 23. An example of the above embodiment (6) is an embodiment in which the red pigment contains one or more selected from CI Pigment Red 177, 254, 291, 295, and 296; the yellow pigment contains one or more selected from CI Pigment Yellow 139, 185, 231, and 233; the blue pigment contains one or more selected from CI Pigment Blue 15:3, 15:4, and 15:6; and the purple pigment contains CI Pigment Violet 23. An example of the above embodiment (7) is an embodiment in which the yellow pigment contains one or more selected from CI Pigment Yellow 139, 185, 231, and 233; the blue pigment contains one or more selected from CI Pigment Blue 15:3, 15:4, and 15:6; the green pigment contains one or more selected from CI Pigment Green 7, 36, 58, 59, and 63; and the purple pigment contains CI Pigment Violet 23.

[0037] Table 1 shows the preferred mass ratios (mass %) of each chromatic pigment in each embodiment.

[0038] [Table 1]

[0039] The above combinations of chromatic pigments (1) to (7) are preferred when the composition of the present invention is used for a near-infrared transmission filter.

[0040] (White pigment) The white pigment is not particularly limited, and any known white pigment can be used. Examples of the white pigment include titanium oxide, magnesium oxide, zirconium oxide, aluminum oxide, antimony oxide, barium sulfate, calcium carbonate, silica, zinc oxide, mica, talc, kaolin, clay, strontium titanate, barium tungstate, zinc phosphate, aluminum hydroxide, aluminum silicate, hollow resin particles, and compounds described in JP2011-075786A, WO2013 / 061621A, JP2015-047520A, and JP2015-164881A. Further, examples of compounds classified as pigments in the Color Index include CI Pigment White 1, 2, 3, 4, 5, 6, 6:1, 7, 8, 10, 11, 12, 13, 14, 15, 16, 17, 18, 18:1, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 30, 32, and 33.

[0041] (Black pigment) The black pigment is not particularly limited, and known black pigments can be used, such as carbon black, titanium black, acetylene black, lamp black, graphite, aniline black, cyanine black, perylene black, and compounds described in JP-A-1-170601, JP-A-2-34664, JP-A-2007-302836, JP-T-2010-534726, and JP-T-2012-515233. Further, examples of compounds classified as pigments in the Color Index include CI Pigment Black 1, 6, 7, 12, 20, and 31.

[0042] (Near infrared absorbing pigment) The near-infrared absorbing pigment is a compound having a maximum absorption in the wavelength range of 700 to 2,000 nm, and may be either an organic pigment (also called a near-infrared absorbing organic pigment) or an inorganic pigment (also called a near-infrared absorbing inorganic pigment). In addition, a near-infrared absorbing organic pigment and a near-infrared absorbing inorganic pigment may be used in combination.

[0043] The near infrared absorbing organic pigment is not particularly limited, and known near infrared absorbing organic pigments can be used. For example, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, croconium compounds, porphyrin compounds, etc. can be mentioned. Among these, from the viewpoint of near infrared absorbing property and heat resistance, naphthalocyanine compounds, pyrrolopyrrole compounds, squarylium compounds, and indigo compounds are preferred, and naphthalocyanine compounds, squarylium compounds, and indigo compounds are more preferred.

[0044] Cyanine compounds are disclosed in WO 2006 / 006573, WO 2010 / 073857, JP 2013-241598, JP 2016-113501, JP 2016-113504, etc.; phthalocyanine compounds are disclosed in JP 4-23868, JP 06-192584, JP 2000-63691, WO 2014 / 208514, JP 2022-022070, etc. , JP 2022-110262 A, etc.; naphthalocyanine compounds are described in JP 11-152414 A, JP 2000-86919 A, JP 2009-29955 A, WO 2018 / 186490 A, JP 2022-123689 A, JP 2022-091099 A, etc.; indigo compounds are described in JP 2013-230412 A, etc.; immonium compounds are described in JP 2005-336150 A, JP Anthraquinone compounds are described in JP-A-62-903 and JP-A-1-172458, etc. Pyrrolopyrrole compounds are described in JP-A-2009-263614, JP-A-2010-90313, JP-A-2011-068731, and WO 2021 / 039205; squarylium compounds are described in JP-A-2011-132361 and JP-A-2016 -142891, WO 2017 / 135359, WO 2018 / 225837, JP 2019-001987, WO 2020 / 054718, WO 2020 / 189459, etc.; croconium compounds are described in WO 2019 / 021767; porphyrin compounds are described in JP 2006-209059, WO 2022 / 131191, etc.

[0045] The near infrared absorbing inorganic pigment is not particularly limited, and any known near infrared absorbing inorganic pigment can be used, such as indium tin oxide, antimony tin oxide, zinc oxide, aluminum-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, cesium tungsten oxide, lanthanum boride, copper, nickel, silver, gold, or other metal oxide particles or metal particles.

[0046] The pigment (A) can be used alone or in combination of two or more kinds.

[0047] The content of the pigment (A) is preferably from 0.5 to 60 mass %, and more preferably from 1 to 50 mass %, based on 100 mass % of the nonvolatile content of the composition.

[0048] The pigment (A) is preferably used in a finely divided state. The method of finely dividing is not particularly limited, and examples thereof include wet grinding, dry grinding, and solution precipitation. Among these, salt milling treatment by a kneader method, which is a type of wet grinding, is preferred. The average primary particle diameter of the finely divided pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. From the viewpoint of dispersibility, the average primary particle diameter is more preferably 10 to 70 nm.

[0049] In the salt milling treatment, a resin may be added as necessary. By adding a resin, the pigment (A) is coated with the resin, and the stability, light resistance, etc. are improved. The type of the resin is not particularly limited, and examples thereof include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferable that the resin is solid at room temperature, insoluble in water, and partially soluble in an organic solvent. The amount of the resin added is preferably 2 to 200 parts by mass relative to 100 parts by mass of the pigment (A).

[0050] [Resin (B)] The composition of the present invention contains a resin (B).

[0051] Resin (B) used mainly to disperse pigment (A) is also called dispersing resin, and resin (B) used mainly to impart film resistance is also called binder resin. One type of resin (B) may have both the functions of dispersing resin and binder resin. Such use of resin (B) is just one example, and resin (B) can also be used for other purposes. However, resin (B) is a resin that does not contain monomer unit (c1) represented by general formula (1).

[0052] The resin (B) is not particularly limited, and a known compound can be used, such as (meth)acrylic resin, styrene resin, styrene / (meth)acrylic resin, epoxy resin, urethane resin, urethane acrylic resin, polycarbonate resin, polyester resin, polyether resin, polyimide resin, polyamideimide resin, and cyclic olefin resin.

[0053] The weight average molecular weight of the resin (B) is preferably from 3,000 to 200,000, and more preferably from 4,000 to 150,000.

[0054] The resin (B) can be used alone or in combination of two or more kinds.

[0055] The content of the resin (B) is preferably from 1 to 60 mass %, and more preferably from 5 to 60 mass %, based on 100 mass % of the nonvolatile content of the composition.

[0056] (Resin (B1)) From the viewpoint of storage stability, the resin (B) preferably contains the resin (B1) as a dispersing resin. By containing the resin (B1) as a dispersing resin, the coatability is also improved.

[0057] The resin (B1) is preferably a resin having an adsorptive group having a high affinity for the pigment (A). The adsorptive group preferably has at least one type of basic group and acidic group.

[0058] Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a group containing a nitrogen atom such as a nitrogen-containing heterocycle.

[0059] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0060] Examples of the resin type of resin (B1) include urethane resins, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylates, modified products thereof, amides formed by the reaction of poly(lower alkyleneimines) with polyesters having free carboxyl groups and salts thereof, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphates.

[0061] Examples of the structure of the resin (B1) include a random structure, a block structure, a graft structure, a comb structure, and a star structure, etc. Among these, from the viewpoint of storage stability, the graft structure, the block structure, and the comb structure are preferred.

[0062] The resin (B1) is, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, Anti-Terra-U203, 204, BYK-P104, P104S, 220S, Lactimon, Lactimon-WS, Bykumen, SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, etc. manufactured by Lubrizol Japan 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, etc. manufactured by BASF Japan Co., Ltd. 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Aji Super PA111, PB711, PB821, PB822, manufactured by Ajinomoto Fine-Techno Co., Ltd.PB824, etc., JP 2008-029901 A, JP 2009-155406 A, JP 2010-185934 A, JP 2011-157416 A, International Publication No. 2008 / 007776, JP 2008-029901 A, JP 2009-155406 A, JP 2010-185 Examples of the resins include those described in JP-A-934, JP-A-2011-157416, JP-A-2012-255128, JP-A-2009-251481, JP-A-2007-23195, JP-A-1996-143651, JP-A-2017-206689, and JP-A-2019-095548.

[0063] The content of the resin (B1) is preferably from 1 to 50 mass % in 100 mass % of the resin (B).

[0064] From the viewpoint of developability, the resin (B1) preferably contains a resin having a main chain based on an aromatic carboxylic acid ester moiety having an ester bond, which is a reaction product site between an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and a side chain based on a vinyl polymer moiety.

[0065] The aromatic carboxylate moiety in the main chain is obtained by a ring-opening reaction between an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and an aromatic carboxyl group is generated at the same time as the ester bond is generated. The aromatic carboxyl group acts as an adsorption site for the pigment (A) and a dissolution site in the developer.

[0066] The vinyl polymer moiety in the side chain acts as a steric repulsion site and suppresses the association and aggregation of the pigment (A). The vinyl polymer moiety in the side chain can be obtained, for example, by the following two methods. The first method is a method of copolymerizing a monomer in the presence of a compound having two or more hydroxyl groups. The compound having two or more hydroxyl groups is preferably a compound having two hydroxyl groups and one thiol group in the molecule. The second method is a method in which a monomer is copolymerized in the presence of a reaction product between an aromatic compound having two or more acid anhydride groups and a hydroxyl group of a compound having two or more hydroxyl groups. The difference between the above two methods is whether the vinyl polymer moiety is introduced first or later by copolymerizing the monomer. The molecular weight may differ slightly depending on various conditions, but in theory, the same compound can be synthesized if the raw materials and reaction conditions are the same.

[0067] The main chain and the side chain will be described in detail below.

[0068] [Main Chain] The aromatic carboxylate moiety can be obtained by a ring-opening reaction between an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups.

[0069] Examples of aromatic compounds having two or more acid anhydride groups include compounds represented by the following general formulas (6) and (7).

[0070] [ka]

[0071] In formula (6), n represents 1 or 2. In general formula (7), Q represents a direct bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, a group represented by the following general formula (8), or a group represented by the following general formula (9).

[0072] [ka]

[0073] Specific examples of aromatic compounds having two or more acid anhydride groups include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, and 2,3,6,7-naphthalene tetracarboxylic dianhydride. 3,3',4,4'-Dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3',4,4'-Tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-Furanetetracarboxylic dianhydride, 4,4'-Bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4,4'-Bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride Anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether tert-butyl dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride, etc. Among these, aromatic tetracarboxylic acid dianhydrides are preferred, and pyromellitic dianhydride is more preferred.

[0074] As described above, the compound having two or more hydroxyl groups is preferably a compound having two hydroxyl groups and one thiol group in the molecule.

[0075] Examples of compounds having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[0076] The aromatic carboxylate moiety is preferably a reaction product site of 0.9 to 1.5 moles of an aromatic compound having two or more acid anhydride groups per mole of a compound having two or more hydroxyl groups. More preferably, it is a reaction product site of 1.0 to 1.3 moles of an aromatic compound having two or more acid anhydride groups per mole of a compound having two or more hydroxyl groups. By increasing the proportion of aromatic carboxyl groups, which are adsorption sites to the pigment (A), the storage stability is improved. Theoretically, when the aromatic compound having two or more acid anhydride groups exceeds 1 mole, the terminal becomes an acid anhydride group.

[0077] In addition, the acid anhydride group present at the end of the aromatic carboxylate moiety may be reacted with a monoalcohol. That is, the acid anhydride group is ring-opened with the monoalcohol to generate an alcohol ester and a carboxyl group. This improves the solubility in a developer and improves the developability.

[0078] Examples of the monoalcohol include monoalcohols such as methanol, ethanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, isopentyl alcohol, tert-pentyl alcohol, cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, isononyl alcohol, 1-nonyl alcohol, amyl alcohol, lauryl alcohol, n-butyl alcohol, isobutyl alcohol, cyclohexanol, benzyl alcohol, and methylcyclohexanol; monoalcohols having an ether group, such as 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, and propylene glycol monomethyl ether; Examples of the lactate include monoalcohols having a carbonyl group, such as methyl lactate, ethyl lactate, and diacetone alcohol. Among these, from the viewpoint of developability, compounds having an ether group or a carbonyl group are preferred, and 3-methoxybutanol, propylene glycol monomethyl ether, and diacetone alcohol are more preferred. The monoalcohols may be used alone or in combination of two or more kinds.

[0079] The amount of monoalcohol used relative to the acid anhydride group is preferably 1 to 30 equivalents, more preferably 1.5 to 20 equivalents, relative to 1 equivalent of the acid anhydride group in the main chain.

[0080] [Side Chain] As described above, the vinyl polymer segment can be synthesized by a method of copolymerizing a monomer in the presence of a compound having two or more hydroxyl groups, or a method of copolymerizing a monomer in the presence of a reaction product between an aromatic compound having two or more acid anhydride groups and hydroxyl groups of a compound having two or more hydroxyl groups.

[0081] Examples of the monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cetyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, and the like. ) acrylate, tridecyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, or isostearyl (meth)acrylate, methoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolytetramethylene glycol (meth)acrylate, or methoxypolyethylene glycol polypropylene glycol (meth)acrylate, or other linear or branched alkyl (meth)acrylates; cyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, tertiary butyl cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, or isobornyl (meth)acrylate; Fluoroalkyl (meth)acrylates such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, or tetrafluoropropyl (meth)acrylate; (Meth)acryloxy-modified polydimethylsiloxanes (silicone macromers); (meth)acrylates having a heterocycle, such as tetrahydrofurfuryl (meth)acrylate or 3-methyl-3-oxetanyl (meth)acrylate; (meth)acrylates having an aromatic ring, such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, paracumylphenoxyethyl (meth)acrylate, paracumylphenoxypolyethylene glycol (meth)acrylate, or nonylphenoxypolyethylene glycol (meth)acrylate; (meth)acrylates having a carboxyl group, such as (meth)acrylic acid, acrylic acid dimer, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth)acrylate, β-carboxyethyl (meth)acrylate, or ω-carboxypolycaprolactone (meth)acrylate; Vinyl such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth)acrylate, or allyl (meth)acrylate; N-substituted (meth)acrylamide such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine; Amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate or N,N-diethylaminoethyl (meth)acrylate; Nitriles such as (meth)acrylonitrile; styrenes such as styrene and α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; vinyl acetate, vinyl propionate and other vinyl fatty acids; Examples of the monomer include acidic group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

[0082] From the viewpoint of film resistance after low-temperature post-baking, the vinyl polymer portion preferably has a thermally crosslinkable group and / or a polymerizable unsaturated group. Examples of the thermally crosslinkable group include a hydroxyl group, an epoxy group, an oxetanyl group, a tert-butyl group, and a blocked isocyanate group. A thermally crosslinkable group can be introduced by using a monomer having a hydroxyl group, an epoxy group, an oxetanyl group, a tert-butyl group, a blocked isocyanate group, or the like. The polymerizable unsaturated group can be introduced, for example, by reacting a hydroxyl group present in the vinyl polymer moiety with an isocyanate group of a monomer having an isocyanate group.

[0083] A preferred synthesis method is, for example, to radically polymerize a monomer in the presence of a compound (a) having two hydroxyl groups and one thiol group at one end, which is a compound having two or more hydroxyl groups, to generate a vinyl polymer having two hydroxyl groups at one end, and then react the resulting polymer with a tetracarboxylic dianhydride (b), which is an aromatic compound having two or more acid anhydride groups. Furthermore, when the end of the resin is an acid anhydride group, a blocking moiety derived from the monoalcohol can be introduced by reacting the resin with a monoalcohol.

[0084] [ka]

[0085] In (c), X is the reaction residue after the tetracarboxylic dianhydride (b) reacts with a hydroxyl group, Z is the reaction residue after a compound having two hydroxyl groups reacts with an acid anhydride group, and R is the residue of a monoalcohol.

[0086] The polymerization temperature of the vinyl polymer portion is preferably 40 to 150° C., more preferably 50 to 110° C. If it is 40° C. or higher, the polymerization proceeds easily, and if it is 150° C. or lower, it becomes easy to control the molecular weight.

[0087] When polymerizing the vinyl polymer portion, 0.001 to 5% by mass of a polymerization initiator can be used based on the total monomer mass of the monomers. Examples of the polymerization initiator include azo compounds and organic peroxides.

[0088] Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]. Examples of organic peroxides include benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, t-butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, and diacetyl peroxide. The polymerization initiators can be used alone or in combination of two or more.

[0089] The vinyl polymer portion is preferably synthesized by bulk polymerization or solution polymerization. Examples of the polymerization solvent for solution polymerization include, but are not limited to, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate. The polymerization solvent can be used alone or in combination of two or more kinds.

[0090] A reaction catalyst can be used for the synthesis of the aromatic carboxylate moiety. The reaction catalyst is preferably a tertiary amine compound. Examples of the tertiary amine compound include triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-undecene, and 1,5-diazabicyclo-[4.3.0]-5-nonene.

[0091] For the synthesis of the aromatic carboxylate moiety, solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile, and propylene glycol monomethyl ether acetate can be used.

[0092] The synthesis temperature for the aromatic carboxylate moiety is preferably from 50 to 180°C, more preferably from 80 to 140°C.

[0093] The acid value of a resin having a main chain based on an aromatic carboxylate moiety having an ester bond, which is a reaction product site of an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and a side chain based on a vinyl polymer moiety, is preferably 20 to 250 mgKOH / g, and more preferably 30 to 200 mgKOH / g.

[0094] The weight average molecular weight of the resin having a main chain based on an aromatic carboxylic acid ester moiety having an ester bond, which is a reaction product site of an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and a side chain based on a vinyl polymer moiety, is preferably 2,000 to 40,000, and more preferably 4,000 to 30,000.

[0095] The resin having a main chain based on an aromatic carboxylic acid ester moiety having an ester bond, which is a reaction product site of an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and a side chain based on a vinyl polymer moiety, can be used alone or in combination of two or more kinds.

[0096] From the viewpoint of storage stability, the resin having a main chain based on an aromatic carboxylic acid ester moiety having an ester bond, which is a reaction product site of an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and a side chain based on a vinyl polymer moiety, is preferably contained in an amount of 1 to 60 mass%, and more preferably 5 to 50 mass%, in 100 mass% of the resin (B1).

[0097] (Resin (B2)) From the viewpoint of suppressing color mixing during low-temperature post-baking, the resin (B) preferably contains a resin (B2) (hereinafter, simply referred to as resin (B2)) having a thermally crosslinkable group-containing monomer unit (b1) as a binder resin. The thermally crosslinkable group is a group that undergoes a crosslinking reaction by heating and crosslinks. Examples of the thermally crosslinkable group include a cyclic ether group, a methylol group, an isocyanate group, a blocked isocyanate group, an acetoacetoxy group, an alkoxysilyl group, and a tertiary alkyl group. Examples of the resin (B2) include a monomer that forms a thermally crosslinkable group-containing monomer unit (b1), and a copolymer optionally containing another copolymerizable monomer.

[0098] [Thermal crosslinkable group-containing monomer unit (b1)] From the viewpoint of suppressing color mixing during low-temperature post-baking, the thermally crosslinkable group-containing monomer unit (b1) is preferably formed from a monomer represented by the following general formulas (10) to (14).

[0099] General formula (10) [ka]

[0100] In general formula (10), R 1 represents a hydrogen atom or a methyl group.

[0101] In general formula (10), R 2 and R 3 each independently represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isoamyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, and decyl groups. Among these, methyl, ethyl, and n-propyl groups are preferred.

[0102] In general formula (10), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bonds. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, and n-propylene are preferred.

[0103] In general formula (10), L 2 represents a single bond or an oxygen atom.

[0104] In general formula (10), L3 and L 4 each independently represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, and n-propylene are preferred.

[0105] The method for producing the monomer represented by the general formula (10) is not particularly limited, and a known method can be used. For example, the methods described in JP-A-10-316643 and WO 2022 / 145298 can be mentioned.

[0106] Specific examples of the monomer represented by general formula (10) include compounds represented by formulas (10-1) to (10-10), although the present invention is not limited thereto.

[0107] [ka]

[0108] The monomer represented by general formula (10) is preferably at least one selected from the compounds of formulae (10-1), (10-2), (10-3), (10-4), (10-9), and (10-10) above, from the viewpoint of suppressing color mixing during low-temperature post-baking.

[0109] The monomer represented by the general formula (10) can be used alone or in combination of two or more kinds.

[0110] General formula (11) [ka]

[0111] In general formula (11), R 1 represents a hydrogen atom or a methyl group.

[0112] In general formula (11), R 4 ~R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isoamyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, and decyl groups. Among these, R 4 and R 5 is preferably a hydrogen atom, R 6 is preferably a methyl group, an ethyl group, or an n-propyl group.

[0113] In general formula (11), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bonds. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, and n-propylene are preferred.

[0114] The method for producing the monomer represented by the general formula (11) is not particularly limited, and a known method can be used. For example, the method described in International Publication No. 2022 / 145298 can be mentioned.

[0115] Specific examples of the monomer represented by formula (11) include compounds represented by formulas (11-1) to (11-6), although the present invention is not limited thereto.

[0116] [ka]

[0117] The monomer represented by the general formula (11) can be used alone or in combination of two or more kinds.

[0118] General formula (12) [ka]

[0119] In general formula (12), R 1 represents a hydrogen atom or a methyl group.

[0120] In general formula (12), R 7 represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isoamyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, and decyl groups. Among these, methyl, ethyl, and n-propyl groups are preferred.

[0121] In general formula (12), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bonds. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, and n-propylene are preferred.

[0122] The method for producing the monomer represented by the general formula (12) is not particularly limited, and a known method can be used, for example, the method described in Coatings Technology, Vol. 62, by Witzeman, JS, and Dell Rector, FJ.

[0123] Specific examples of the monomer represented by formula (12) include compounds represented by formulas (12-1) to (12-4), although the present invention is not limited thereto.

[0124] [ka]

[0125] The monomer represented by the general formula (12) can be used alone or in combination of two or more kinds.

[0126] General formula (13) [ka]

[0127] In general formula (13), R 1 represents a hydrogen atom or a methyl group.

[0128] In general formula (13), R 8 ~R 10 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. 8 ~R 10At least one of them is an alkoxy group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a butyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an isopropyl group, and an isobutyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, etc. Among these, a methoxy group and an ethoxy group are preferable. In general formula (13), R 8 ~R 10 At least two of them are preferably alkoxy groups having 1 to 6 carbon atoms.

[0129] In general formula (13), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bonds. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, and n-propylene are preferred.

[0130] Specific examples of the monomer represented by formula (13) include compounds represented by formulas (13-1) to (13-6), although the present invention is not limited thereto.

[0131] [ka]

[0132] Commercially available products of the monomer represented by the general formula (13) include, for example, KBM-502, 503, 5103, 5803, KBE-502, 503, and the like manufactured by Shin-Etsu Silicones.

[0133] The monomer represented by formula (13) can be used alone or in combination of two or more kinds.

[0134] General formula (14) [ka]

[0135] In general formula (14), R 1 represents a hydrogen atom or a methyl group.

[0136] In general formula (14), R 11 ~R 13 each independently represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isoamyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, and decyl groups. Among these, the methyl group is preferred.

[0137] In general formula (14), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, a group having --NH--, or a combination thereof. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, and n-propylene are preferred.

[0138] Specific examples of the monomer represented by formula (14) include compounds represented by formulas (14-1) to (14-6), although the present invention is not limited thereto.

[0139] [ka]

[0140] The monomer represented by formula (14) can be used alone or in combination of two or more kinds.

[0141] From the viewpoint of suppressing color mixing during low-temperature post-baking, the thermally crosslinkable group-containing monomer unit (b1) is more preferably a monomer unit formed from one or more of the monomers represented by general formula (10) and the monomers represented by general formula (11).

[0142] The thermally crosslinkable group-containing monomer unit (b1) can be formed by using the monomers represented by the general formulae (10) to (14) alone or in combination of two or more kinds.

[0143] The thermally crosslinkable group-containing monomer unit (b1) can be a combination of a monomer unit formed of a monomer represented by any one of the general formulae (10) to (14) and a monomer unit formed of a monomer other than the monomer represented by any one of the general formulae (10) to (14).

[0144] Examples of the monomer other than the monomers represented by the general formulas (10) to (14) include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 ]Decan-8-yl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-9-yl (meth)acrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl (meth)acrylate, and the like.

[0145] The content of the thermally crosslinkable group-containing monomer unit (b1) is preferably 1 to 80 mol %, more preferably 5 to 70 mol %, of all monomer units in the resin (B2) from the viewpoint of suppressing color mixing during low-temperature post-baking.

[0146] The resin (B2) can contain, in addition to the thermally crosslinkable group-containing monomer unit (b1), for example, an acidic group-containing monomer unit (b2), a hydroxyl group-containing monomer unit (b3), a polycyclic alicyclic hydrocarbon group-containing monomer unit (b4), a polymerizable unsaturated group-containing monomer unit (b5), and other monomer units (b6).

[0147] [Acidic group-containing monomer unit (b2)] Examples of the acidic group-containing monomer include (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethylhexyl hydrophthalic acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and 2-(meth)acryloyloxyethyl acid phosphate. The acidic group-containing monomers can be used alone or in combination of two or more kinds.

[0148] The content of the acidic group-containing monomer unit (b2) in all the structural units of the resin (B2) is preferably from 1 to 40 mol %, and more preferably from 5 to 30 mol %.

[0149] In addition, the method of introducing the acidic group-containing monomer unit (b2) into the resin (B2) may be a method of adding an acid anhydride (modifying compound) to the hydroxyl group contained in the resin (precursor) other than a method of copolymerizing a thermally crosslinkable group-containing monomer and an acidic group-containing monomer. Examples of the acid anhydride include succinic anhydride, phthalic anhydride, and 1,2,3,6-tetrahydrophthalic anhydride.

[0150] [Hydroxyl group-containing monomer unit (b3)] Examples of hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-acryloyloxyethyl-2-hydroxyethyl phthalate. The hydroxyl group-containing monomers can be used alone or in combination of two or more kinds.

[0151] The content of the hydroxyl group-containing monomer unit (b3) is preferably from 1 to 60 mol %, more preferably from 5 to 50 mol %, of all the monomer units in the resin (B2).

[0152] The method for introducing the hydroxyl group-containing monomer unit (b3) into the resin (B2) may include, other than copolymerizing a thermally crosslinkable group-containing monomer with a hydroxyl group-containing monomer, a method for adding a compound having a carboxyl group (modifying compound) to an epoxy group contained in the resin (precursor), or a method for adding a compound having an epoxy group (modifying compound) to a carboxyl group contained in the resin (precursor).

[0153] [Polycyclic alicyclic hydrocarbon group-containing monomer unit (b4)] Examples of the polycyclic alicyclic hydrocarbon group-containing monomer unit include isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, etc. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred. The polycyclic alicyclic hydrocarbon group-containing monomer units can be used alone or in combination of two or more kinds.

[0154] [Polymerizable unsaturated group-containing monomer unit (b5)] Examples of the method for incorporating the polymerizable unsaturated group-containing monomer unit (b5) into the resin (B2) include the following methods (i) to (iii).

[0155] <Method (i)> In the method (i), for example, a precursor having an epoxy group is first synthesized, and then an acidic group-containing monomer in which the acidic group is a carboxyl group is added to the epoxy group of the precursor.

[0156] The site where a monomer having a carboxyl group is added to the epoxy group of the precursor can be further reacted with an acid anhydride.

[0157] Examples of the acid anhydride include 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

[0158] <Method (ii)> In the method (ii), for example, a precursor having an acidic group-containing monomer unit (b2) in which the acidic group is a carboxyl group is first synthesized, and then an epoxy group-containing monomer (modifying compound) is added to the carboxyl group of the precursor.

[0159] Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate.

[0160] <Method (iii)> In the method (iii), for example, first, a precursor having a hydroxyl group-containing monomer (b3) is synthesized, and then the hydroxyl group of the precursor is reacted with the isocyanate group of an isocyanate group-containing monomer (modifying compound).

[0161] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0162] [Other monomer units (b6)] Examples of other monomers include acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, EO-modified (meth)acrylate of phenol, EO- or PO-modified (meth)acrylate of nonylphenol, EO- or PO-modified (meth)acrylate of paracumylphenol, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate; Aromatic vinyl compounds such as styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, and vinylnaphthalene; (Meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; vinyl acetate or vinyl propionate or other vinyl fatty acids; Phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N- N-substituted maleimides such as (4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine; Examples of such dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate include diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, and di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate. The other monomers can be used alone or in combination of two or more.

[0163] The weight average molecular weight of the resin (B2) is preferably from 3,000 to 50,000, and more preferably from 3,000 to 20,000.

[0164] The molecular weight distribution (weight average molecular weight / number average molecular weight) of the resin (B2) is preferably from 1.2 to 3.0, more preferably from 1.3 to 2.8.

[0165] The acid value of the resin (B2) is preferably from 20 to 200 mgKOH / g, more preferably from 30 to 180 mgKOH / g.

[0166] The resin (B2) can be used alone or in combination of two or more kinds.

[0167] The content of the resin (B2) is preferably from 1 to 80 mass % in 100 mass % of the resin (B).

[0168] [Leveling agent (C)] The composition of the present invention contains a leveling agent (C).

[0169] The leveling agent (C) is not particularly limited, and any known compound can be used, such as a silicone-based leveling agent, a fluorine-based leveling agent, an acrylic-based leveling agent, or an acetylene diol-based leveling agent.

[0170] Examples of commercially available silicone leveling agents include BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, and 3570 manufactured by BYK-Chemie Co., Ltd., and FZ-7002, 2110, 2122, 2123, 2191, and 5609 manufactured by Dow Corning Toray Co., Ltd. Examples of such silicone rubbers include X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, and KP-341 manufactured by Shin-Etsu Silicones Co., Ltd., and TegoGlide 432, 440, and 450, TegoWet 250, 260, 265, 270, and 280 manufactured by Evonik Corporation.

[0171] Examples of commercially available fluorine-based leveling agents include Surflon S-242, 243, 420, 611, 651, and 386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, and 576, R-40-LM, R-41, RS-72-K, and DS-21 manufactured by DIC Corporation; FC-4430 and 4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; and Futergent 602A manufactured by Neos Corporation.

[0172] Commercially available acrylic leveling agents include, for example, BYK-350, 352, 354, 355, 358, 380, 381, 392, and 394 manufactured by BYK-Chemie Co., Ltd., and Polyflow 57, 77, and 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0173] Commercially available acetylene diol leveling agents include, for example, Surfynol 420, 440, 465, 485, SE, DF110D, DE85, and Olfine E1004 and 1010 manufactured by Nissin Chemical Industry Co., Ltd.

[0174] The leveling agent (C) can be used alone or in combination of two or more kinds.

[0175] The content of the leveling agent (C) is preferably from 0.01 to 2.0 mass %, and more preferably from 0.05 to 1.0 mass %, based on 100 mass % of the nonvolatile content of the composition.

[0176] (Block copolymer (C1)) The composition of the present invention contains, as a leveling agent (C), a block copolymer (C1) having an A block formed from monomer units (c1) represented by general formula (1) and a B block formed from monomer units (c2) other than the monomer units (c1) represented by general formula (1) (hereinafter, also simply referred to as other monomer units (c2)).

[0177] General formula (1) [ka]

[0178] In general formula (1), R1's are each independently an alkyl group having 1 to 6 carbon atoms, or a group represented by -OSi(R5)3 (R5's are each independently an alkyl group having 1 to 3 carbon atoms). Each R2 is independently an alkyl group having 1 to 6 carbon atoms. R3 is an alkyl group having 1 to 6 carbon atoms. R4 is a hydrogen atom or a methyl group. L1 is a divalent organic group or a single bond. n is an integer from 1 to 70.

[0179] [Monomer unit (c1) represented by general formula (1)] The monomer represented by the general formula (1) will be explained.

[0180] In general formula (1), R1's are each independently an alkyl group having 1 to 6 carbon atoms, or a group represented by -OSi(R5)3 (R5's are each independently an alkyl group having 1 to 3 carbon atoms). The alkyl group having 1 to 6 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methyl, ethyl, butyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, and isobutyl groups. Among these, R1 is preferably a methyl group or a trimethylsiloxy group from the viewpoints of coatability and suppression of color mixing.

[0181] In general formula (1), R2's are each independently an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methyl, ethyl, butyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, and isobutyl groups. Among these, R2 is preferably a methyl group.

[0182] In the general formula (1), R3 is an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methyl, ethyl, butyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, and isobutyl groups. Among these, R3 is preferably an alkyl group having 1 to 4 carbon atoms.

[0183] In general formula (1), R4 is a hydrogen atom or a methyl group.

[0184] In the general formula (1), L1 is a divalent organic group or a single bond. Among these, L1 is preferably a divalent organic group, more preferably an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms. The alkylene group having 1 to 50 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene groups. Among these, methylene, ethylene, n-propylene, and isopropylene groups are preferred. Examples of the alkyleneoxy group having 1 to 50 carbon atoms include a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, an oxytrimethylene group, a butyleneoxy group, an oxytetramethylene group, a pentyleneoxy group, and a heptyleneoxy group.

[0185] A part of -CH2- in the alkylene group having 1 to 50 carbon atoms or the alkyleneoxy group having 1 to 50 carbon atoms may be substituted with a carbonyl group, 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.

[0186] In the general formula (1), n ​​is an integer of 1 to 70. From the viewpoints of coatability and suppression of color mixing, n is preferably an integer of 1 to 50, and more preferably an integer of 1 to 30.

[0187] Examples of the monomer represented by the general formula (1) include 3-(methacryloyloxy)propyltris(trimethylsiloxy)silane, α-(3-methacryloyloxy)propylpolydimethylsiloxane, etc. Commercially available products include Silaplane FM-0711, FM-0721, FM-0725, and FM-0701T manufactured by JNC Corporation, and X-22-174ASX, X-22-174BX, X-22-2426, and X-22-2404 manufactured by Shin-Etsu Chemical Co., Ltd.

[0188] The monomer represented by formula (1) can be used alone or in combination of two or more kinds.

[0189] The A block is a portion formed from the monomer unit (c1) represented by the general formula (1). The A block may contain monomer units (c2) other than the monomer units (c1) represented by general formula (1) as long as the effects of the present invention are not impaired.

[0190] The content of the monomer unit (c1) represented by general formula (1) is preferably from 90 to 100 mass %, and more preferably from 95 to 100 mass %, in 100 mass % of the A block, from the viewpoints of coatability and suppression of color mixing.

[0191] The content of the A block is preferably from 20 to 95 mass %, and more preferably from 30 to 85 mass %, in 100 mass % of the block copolymer (C1), from the viewpoints of coatability and suppression of color mixing.

[0192] [Other monomer units (c2)] From the viewpoint of coatability and suppression of color mixing, the other monomer unit (c2) preferably contains at least one selected from the group consisting of a monomer unit (c2-1) represented by the following general formula (2) and a monomer unit (c2-2) represented by the following general formula (3). This makes it possible to control the compatibility with other components contained in the composition, and to maintain coatability and suppression of color mixing even after storage.

[0193] General formula (2) [ka]

[0194] In the general formula (2), R6 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. R7 is a hydrogen atom or a methyl group. m is an integer from 1 to 4. o is an integer from 2 to 200.

[0195] General formula (3) [ka]

[0196] In the general formula (3), R8 is an alicyclic hydrocarbon group having 3 to 20 carbon atoms. R9 is a hydrogen atom or a methyl group.

[0197] <<Monomer unit (c2-1) represented by general formula (2)>> The monomer represented by the general formula (2) will be explained.

[0198] In the general formula (2), R6 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. The alkyl group having 1 to 18 carbon atoms may be any of linear, branched, cyclic, and combinations thereof. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups. Among these, R6 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom.

[0199] In general formula (2), R9 is a hydrogen atom or a methyl group.

[0200] In the general formula (2), m is an integer of 1 to 4. From the viewpoints of coatability and suppression of color mixing, m is preferably 3 or 4.

[0201] In the general formula (2), o is an integer of 2 to 200. From the viewpoints of coatability and suppression of color mixing, o is preferably an integer of 3 to 50.

[0202] Examples of the monomer represented by the general formula (2) include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polytrimethylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, poly(ethylene glycol·propylene glycol) mono(meth)acrylate, polyethylene glycol·polypropylene glycol mono(meth)acrylate, poly(ethylene glycol·tetramethylene glycol) mono(meth)acrylate, polyethylene glycol·polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol·tetramethylene glycol) mono(meth)acrylate, polypropylene glycol·polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol·1,2-butylene glycol) mono(meth)acrylate, polypropylene glycol·poly1,2-butylene glycol mono(meth)acrylate, poly(ethylene glycol·1,2-butylene glycol) mono(meth)acrylate, Poly(ethylene glycol·poly 1,2-butylene glycol) mono(meth)acrylate, Poly(tetramethylene glycol·1,2-butylene glycol) mono(meth)acrylate, Polytetraethylene glycol·poly 1,2-butylene glycol mono(meth)acrylate, Poly 1,2-butylene glycol mono(meth)acrylate, Poly(ethylene glycol·trimethylene glycol) mono(meth)acrylate, Polyethylene glycol·polytrimethylene glycol mono(meth)acrylate, poly(propylene glycol·trimethylene glycol) mono(meth)acrylate, poly(1,2-butylene glycol·trimethylene glycol) mono(meth)acrylate, poly 1,2-butylene glycol·polytrimethylene glycol mono(meth)acrylate, poly(1,2-butylene glycol·tetramethylene glycol) mono(meth)acrylate, poly 1,2-butylene glycol·polytetramethylene glycol mono(meth)acrylate, etc.The above "poly(ethylene glycol-propylene glycol)" refers to a random copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol-polyethylene glycol" refers to a block copolymer of ethylene glycol and propylene glycol. Commercially available products include NK Ester M-20G, M-40G, M-90G, M-130G, M-230G, AM-90G, AM-130G, and AM-230G manufactured by Shin-Nakamura Chemical Co., Ltd., and Blenmar PE-90, PE-200, PE-350, PP-500, PP-800, PP-1000, 50PEP-300, 55PET-800, 10PPB-500B, AE-200, AE-400, and AP-400 manufactured by NOF Corporation.

[0203] The monomer represented by formula (2) can be used alone or in combination of two or more kinds.

[0204] <<Monomer unit (c2-1) represented by general formula (3)>> The monomer represented by the general formula (3) will be explained.

[0205] In the general formula (3), R8 is an alicyclic hydrocarbon group having 3 to 20 carbon atoms. The alicyclic hydrocarbon group having 3 to 20 carbon atoms may have a substituent, such as an alkyl group, a hydroxyl group, a nitro group, an amino group, an alkoxy group, a halogen atom, or a combination thereof. Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include monocyclic and polycyclic alicyclic hydrocarbon groups. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include an isobornyl group, a norbornyl group, an adamantyl group, a tricyclodecyl group, a dicyclopentanyl group, a dicyclopentenyl group, a tricyclopentenyl group, a tricyclopentadiene group, and a dicyclopentadiene group. Among these, polycyclic alicyclic hydrocarbon groups are preferred, with an isobornyl group, a dicyclopentanyl group and an adamantyl group being more preferred, and an adamantyl group being even more preferred.

[0206] In general formula (3), R9 is a hydrogen atom or a methyl group.

[0207] Examples of the monomer represented by general formula (3) include cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 2-isopropyl-2-adamantyl (meth)acrylate, and dimethyladamantyl (meth)acrylate.

[0208] The monomer represented by formula (3) can be used alone or in combination of two or more kinds.

[0209] From the viewpoints of coatability and suppression of color mixing, the total content of the monomer units (c2-1) represented by general formula (2) and the monomer unit (c2-2) represented by general formula (3) is preferably 90 to 100 mass%, and more preferably 95 to 100 mass%, in 100 mass% of the B block.

[0210] The B block is a portion formed from the other monomer unit (c2). The B block may contain vinyl monomer units other than the monomer unit (c2-1) represented by general formula (2) and the monomer unit (c2-2) represented by general formula (3) within the range that does not impair the effects of the present invention.

[0211] The content of the B block is preferably from 5 to 80 mass %, and more preferably from 15 to 70 mass %, in 100 mass % of the block copolymer (C1) from the viewpoints of coatability and suppression of color mixing.

[0212] The vinyl monomer is not particularly limited, and known monomers can be used. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, benzyl (meth)acrylate, acrylate, 2-phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, acroylmorpholine, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, etc. These can be used alone or in combination of two or more.

[0213] The method for producing the block copolymer (C1) is not particularly limited, and any known method can be used, for example, living polymerization methods such as living radical polymerization and living anionic polymerization. Living radical polymerization is described, for example, in JP-A-9-62002 and JP-A-2002-31713, and in P. Lutz, P. Masson et al., Polym. Bull. 12, 79 (1984), BC Anderson, GD Andrews et al., Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al. al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Migite, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Research Papers, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Soc, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Organic Synthesis Chemistry, 43, 300 (1985), DY Sogoh, WRHertler et al, Macromolecules, 20, 1473 (1987), etc. Among these, reversible addition-fragmentation chain transfer polymerization (hereinafter, RAFT), atom transfer radical polymerization (hereinafter, ATRP), living radical polymerization using an iodine compound, and living radical polymerization using an organotellurium compound (hereinafter, TERP) are preferred. Specifically, it can be synthesized by the methods described in, for example, WO 2021 / 131726, WO 2022 / 050062, WO 2022 / 244586, etc.

[0214] The number and arrangement of A blocks and B blocks of the block copolymer (C1) are not particularly limited. For example, the block copolymer (C1) may have an arrangement such as an AB block copolymer, an ABA block copolymer, or a BAB block copolymer. Furthermore, blocks other than the A block and the B block may be included as long as the effects of the present invention are not impaired.

[0215] The weight average molecular weight of the block copolymer (C1) is preferably from 5,000 to 40,000.

[0216] The number average molecular weight of the block copolymer (C1) is preferably 2,000 to 20,000.

[0217] The average molecular weight distribution (weight average molecular weight / number average molecular weight) of the block copolymer (C1) is preferably from 1.0 to 3.0.

[0218] The block copolymer (C1) can be used alone or in combination of two or more kinds.

[0219] The content of the block copolymer (C1) is preferably from 10 to 100 mass %, and more preferably from 30 to 100 mass %, in 100 mass % of the leveling agent (C).

[0220] (Leveling agent (C2) other than block copolymer (C1)) The composition of the present invention may contain a leveling agent (C2) other than the block copolymer (C1) (hereinafter, also simply referred to as other leveling agent (C2)). Examples of the other leveling agent (C2) include the leveling agents described above.

[0221] [Solvent (D)] The composition of the present invention comprises a solvent (D).

[0222] The solvent (D) is not particularly limited, and known compounds can be used. For example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, methyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3-ethoxyethyl propionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy -3-Methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, toluene, o-chlorotoluene, benzene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert- Butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone,Dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, water, etc.,

[0223] The solvent (D) can be used alone or in combination of two or more kinds.

[0224] The content of the solvent (D) is preferably an amount such that the nonvolatile content of the composition is 5 to 60 mass %.

[0225] (Hansen solubility parameter hydrogen bond term is 10MPa 1 / 2 or more (D1) The composition of the present invention is a solvent (D) having a hydrogen bond term of the Hansen solubility parameter of 10 MPa. 1 / 2 The solvent (D1) (hereinafter, simply referred to as solvent (D1)) is as described above.

[0226] Here, the Hansen solubility parameter is a solubility parameter introduced by Hildebrand, which is divided into three components, a dispersion term (hereinafter also referred to as δd), a polar term (hereinafter also referred to as δp), and a hydrogen bond term (hereinafter also referred to as δh), and expressed in three-dimensional space. The dispersion term indicates the effect due to dispersion forces, the polar term indicates the effect due to dipole-dipole forces, and the hydrogen bond term indicates the effect due to hydrogen bonding forces.

[0227] The definition and calculation of Hansen solubility parameters are described in "Hansen Solubility Parameters; A Users Handbook (CRC Press, 2007)" by Charles M. Hansen. In addition, the Hansen solubility parameters can be calculated from chemical structures using computer software "Hansen Solubility Parameters in Practice (HSPiP)". For the solvent (D1) of the present invention, the values ​​in Hansen Solubility Parameters; A Users Handbook, Second Edition are used, and for those not described, the values ​​calculated using "Hansen Solubility Parameters in Practice (HSPiP)" are used.

[0228] Examples of the solvent (D1) include dipropylene glycol monobutyl ether (δh=10.0), diethylene glycol hexyl ether (δh=10.0), butyl lactate (δh=10.2), propylene glycol monoethyl ether (δh=10.5), diethylene glycol monobutyl ether (δh=10.6), diacetone alcohol (δh=10.8), dipropylene glycol monopropyl ether (δh=11.0), dipropylene glycol monomethyl ether (δh=11.2), propylene glycol monomethyl ether (δh=11.6), diethylene glycol monoethyl ether (δh=12.2), and ethylene glycol monobutyl ether (δh=12.3). , 3-methyl-1-butanol (δh=13.3), ethyl lactate (δh=12.5), diethylene glycol monomethyl ether (δh=12.6), cyclohexanol (δh=13.5), 3-methoxy-1-butanol (δh=13.6), benzyl alcohol (δh=13.7), 2-methyl-1-butanol (δh=14.3), ethylene glycol monoethyl ether (δh=14.3), 2-butanol (δh=14.5), methyl lactate (δh=14.6), furfuryl alcohol (δh=15.1), 1-butanol (δh=15.8), ethylene glycol monomethyl ether (δh=16.4), ethanol (δh=19.4), water (δh=42.3), etc.

[0229] The hydrogen bond parameter of the solvent (D1) is 10 to 45 MPa from the viewpoints of coatability after storage and suppression of color mixing. 1 / 2 is preferred.

[0230] From the viewpoints of coatability after storage and suppression of color mixing, the solvent (D1) preferably contains at least one selected from the group consisting of propylene glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethyl lactate, cyclohexanol, 3-methoxy-1-butanol, ethylene glycol monoethyl ether, 1-butanol, methyl lactate, and water. More preferably, the liquid composition contains water and further contains at least one selected from the group consisting of propylene glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethyl lactate, cyclohexanol, 3-methoxy-1-butanol, ethylene glycol monoethyl ether, methyl lactate, and 1-butanol.

[0231] The content of the solvent (D1) is preferably from 0.01 to 20 mass %, more preferably from 0.05 to 15 mass %, in 100 mass % of the composition, from the viewpoints of coatability after storage and suppression of color mixing.

[0232] The water content is preferably from 0.01 to 2 mass %, and more preferably from 0.05 to 1 mass %, based on 100 mass % of the composition, from the viewpoint of coatability after storage.

[0233] (Solvent (D2) other than solvent (D1)) The composition of the present invention may contain, as the solvent (D), a solvent (D2) other than the solvent (D1) (hereinafter, also simply referred to as solvent (D2)).

[0234] The solvent (D2) is not particularly limited, and the above-mentioned solvents can be used.

[0235] The solvent (D2) preferably contains at least one selected from the group consisting of propylene glycol diacetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, ethyl 3-ethoxypropionate, cyclopentanone, methyl 3-methoxypropionate, propylene glycol monomethyl ether acetate, cyclohexanone, and butyl acetate.

[0236] From an environmental viewpoint, the composition of the present invention preferably does not substantially contain any aromatic hydrocarbon solvents (toluene, xylene, benzene, chlorobenzene, etc.) Substantially not containing means that the content of such solvents in the composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, and more preferably 10 ppm by mass or less.

[0237] [Polymerizable compound (E)] The composition of the present invention further comprises a polymerizable compound (E).

[0238] The polymerizable compound (E) is not particularly limited, and known compounds can be used. For example, a monomer or oligomer having a polymerizable unsaturated group can be used. Examples of the polymerizable unsaturated group include a vinyl group, (meth)allyl group, (meth)acryloyl group, and (meth)acryloyloxy group having an ethylenically unsaturated double bond.

[0239] Examples of the polymerizable compound (E) include lactone-modified polymerizable compounds, polymerizable compounds having an acidic group, polymerizable compounds having a hydroxyl group, polymerizable compounds having a urethane bond, polymerizable compounds having an amine structure, polymerizable compounds having a dendrimer structure or a hyperbranched structure, and other polymerizable compounds.

[0240] The polymerizable compound (E) can be used alone or in combination of two or more kinds.

[0241] The content of the polymerizable compound (E) is preferably from 1 to 80 mass %, more preferably from 5 to 70 mass %, based on 100 mass % of the nonvolatile content of the composition.

[0242] (Lactone-modified polymerizable compound) The lactone-modified polymerizable compound is a compound having a structure modified with lactone in the molecule. The lactone-modified polymerizable compound can be obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethylthritol, tripentaerythritol, glycerin, diglycerol, or trimethylolmelamine with (meth)acrylic acid and ε-caprolactone or another lactone compound.

[0243] Commercially available lactone-modified polymerizable compounds include, for example, KAYARAD DPCA-20, DPCA-30, and DPCA-60 manufactured by Nippon Kayaku Co., Ltd.

[0244] (Polymerizable compound having an acidic group) Examples of the polymerizable compound having an acidic group include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; esters of polycarboxylic acids with monohydroxyalkyl (meth)acrylates; and the like.

[0245] Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0246] Examples of the dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like.

[0247] Examples of the polyvalent carboxylic acid include trimellitic acid and pyromellitic acid. Examples of monohydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, and 2-hydroxy-3-acryloyloxypropyl methacrylate.

[0248] Commercially available polymerizable compounds having an acidic group include Aronix M-5300, M-5400, M-510, M-520, and M-521 manufactured by Toagosei Co., Ltd., Light Acrylate HOA-MS(N), HOA-HH(N), HOA-MPE(N), and P-1A(N) manufactured by Kyoeisha Chemical Co., Ltd., and β-CEA manufactured by Daicel-Allnex Corporation.

[0249] (Polymerizable compound having a hydroxyl group) Examples of the polymerizable compound having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and the like. acrylates such as isocyanuric acid EO or PO modified (meth)acrylates, isocyanuric acid EO or PO modified di(meth)acrylates, pentaerythritol tri(meth)acrylates, dipentaerythritol penta(meth)acrylates, polypentaerythritol penta(meth)acrylates, dipentaerythritol EO or PO modified penta(meth)acrylates, and epoxy (meth)acrylates obtained by reacting the epoxy group of an epoxy compound with the carboxyl group of (meth)acrylic acid.

[0250] Examples of commercially available polymerizable compounds having a hydroxyl group include KAYARAD R-128H and R-167 manufactured by Nippon Kayaku Co., Ltd.; Blenmar GLM, GLM-R, GMR-M, GMR-R, GAM, GAM-R, and G-FA80 manufactured by NOF Corp.; Aronix M-5700 and M-920 manufactured by Toagosei Co., Ltd.; NK Ester 701A manufactured by Shin-Nakamura Chemical Co., Ltd.; Light Ester HOP(N), HOA(N), HOP-A(N), HOB(N), and G-201P, Epoxy Ester M-600A, 40EM, 70PA, 200PA, 80MFA, 3002M(N), 3002A(N), and 3000A manufactured by Kyoeisha Chemical Co., Ltd.; and OGSOL GA-5060P and GA-2800 manufactured by Osaka Gas Chemical Co., Ltd.

[0251] (Polymerizable compound having urethane bond) Examples of the polymerizable compound having a urethane bond include urethane (meth)acrylates obtained by reacting a hydroxyl group-containing (meth)acrylate with a polyfunctional isocyanate, and urethane (meth)acrylates obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and further reacting the polyhydric alcohol with a hydroxyl group-containing (meth)acrylate.

[0252] Examples of the hydroxyl group-containing (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide (EO)-modified penta(meth)acrylate, dipentaerythritol propylene oxide (PO)-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy(meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

[0253] Examples of the polyfunctional isocyanate include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate, aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, and alicyclic diisocyanate such as isophorone diisocyanate, as well as biuret forms, isocyanurate forms, and trimethylolpropane adducts thereof.

[0254] From the viewpoint of developability, the polymerizable compound having a urethane bond may further have an acidic group. Examples of the acidic group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Among these, the carboxyl group is preferred.

[0255] The method for introducing an acidic group into a polymerizable compound having a urethane bond can be, for example, by first reacting the hydroxyl group-containing (meth)acrylate with the polyfunctional isocyanate, and then adding a mercapto compound having a carboxyl group to the product.

[0256] Examples of the mercapto compound having a carboxyl group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

[0257] Commercially available polymerizable compounds having a urethane bond include, for example, AH-600, UA-306H, UA-306T, UA-306I, UA-510H, and UF-8001G manufactured by Kyoeisha Chemical Co., Ltd., UA-1100H, U-6LPA, UA-33H, U-10HA, and U-15HA manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL1290 and KRM8452 manufactured by Daicel-Allnex Corporation.

[0258] (Polymerizable compound having an amine structure) The amine structure of the polymerizable compound having an amine structure may be any of a primary amine, secondary amine, and tertiary amine structures, but is preferably a secondary or tertiary amine structure, provided that the amine structure of the polymerizable compound having an amine structure does not include an amide structure, an imide structure, or a urethane structure in which a carbonyl group is directly bonded to a nitrogen atom.

[0259] Examples of the polymerizable compound having an amine structure include tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, and a Michael addition reaction product of a (meth)acrylate compound (X) and an amine compound (Y).

[0260] Examples of the (meth)acrylate compound (X) include glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, penta ...hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, Examples of the alkylene oxide-modified tetra(meth)acrylate include phosphorus tri(meth)acrylate, diglycerol tetra(meth)acrylate, trimethylolpropane alkylene oxide-modified tri(meth)acrylate, ditrimethylolpropane alkylene oxide-modified tri- and tetra(meth)acrylate, pentaerythritol alkylene oxide-modified tri- and tetra(meth)acrylate, diglycerol alkylene oxide-modified tri- and tetra(meth)acrylate, and dipentaerythritol alkylene oxide-modified tetra-, penta- and hexa(meth)acrylate. Examples of the alkylene oxide unit in the alkylene oxide modification include ethylene oxide, propylene oxide, and butylene oxide. The (meth)acrylate compound (X) also includes a (meth)acrylate compound having an acidic group.

[0261] The (meth)acrylate compounds (X) can be used alone or in combination of two or more.

[0262] Examples of the amine compound (Y) include primary amines such as n-propylamine, n-butylamine, n-hexylamine, benzylamine, aminocaproic acid, monoethanolamine, 2-(2-aminoethoxy)ethanol, o-aminophenol, m-aminophenol, and p-aminophenol; Examples of the secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, morpholine, piperidine, 1-methylpiperazine, proline, N-merylethanolamine, N-acetylethanolamine, diethanolamine, 3-anilinephenol, and 4-anilinephenol.

[0263] The amine compound (Y) can be used alone or in combination of two or more kinds.

[0264] The method for producing the Michael addition reaction product of the (meth)acrylate compound (X) and the amine compound (Y) is not particularly limited, and a known method can be used. For example, the methods described in International Publication No. 2006 / 075754, JP-A-2008-545859, JP-A-2017-066347, etc. can be mentioned.

[0265] The polymerizable compound having an amine structure may have an acidic group and / or a hydroxyl group. Examples of a method for introducing an acidic group and / or a hydroxyl group include a method of using a compound having an acidic group and / or a hydroxyl group in a (meth)acrylate compound (X) or an amine compound (Y), and a method of adding an acid anhydride after a Michael addition reaction.

[0266] Examples of commercially available polymerizable compounds having an amine structure include Aronix MT-3041 and 3042 manufactured by Toagosei Co., Ltd., EBECRYL80 and 7100 manufactured by Daicel-Allnex Corporation, and CN371NS, 372, 374, 383, and 386 manufactured by Arkema.

[0267] The polymerizable compound having an amine structure may further have a urethane bond. This forms a chemical crosslinked structure by polymerization as well as a physical crosslinked structure by intermolecular hydrogen bonds between the urethane bonds and between the urethane bonds and the functional groups of the substrate. The molecular cohesive energy of the intermolecular hydrogen bonds of the urethane bonds is greater than the cohesive energy of other organic structures such as ether bonds. Therefore, it is presumed that the film becomes flexible and strong due to the interaction between the urethane bonds, improving its resistance.

[0268] The urethane bond can be introduced, for example, by a urethane reaction between a Michael addition reaction product (precursor) of the above-mentioned (meth)acrylate compound (X) and the above-mentioned amine compound (Y) having a hydroxyl group, and a polyisocyanate compound (Z).

[0269] Examples of the polyisocyanate compound (Z) include polyisocyanate compounds having an aliphatic structure, such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; Polyisocyanate compounds having an alicyclic structure, such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatemethyl)cyclohexane; Examples of the polyisocyanate compound include polyisocyanate compounds having an aromatic structure, such as 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyl diphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethyl xylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyl diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanate methyl)benzene. Further, biuret, isocyanurate, adduct and allophanate forms of these compounds are also included.

[0270] The polyisocyanate compounds (Z) can be used alone or in combination of two or more kinds.

[0271] The method of the urethane reaction between the precursor and the polyisocyanate compound (Z) is not particularly limited, and a known method can be used. For example, the method described in JP-A-2018-517797 can be mentioned.

[0272] (Polymerizable compound having a dendrimer structure or a hyperbranched structure) A polymerizable compound having a dendrimer structure has a chemical structure in which the core-constituting chemical structure (hereinafter also referred to as the core portion) is regularly branched outward, and a polymerizable unsaturated group is bonded to the end of the branch, and has a highly controlled spherical chemical structure and molecular weight. The hyperbranched structure has a chemical structure similar to that of the dendrimer structure.

[0273] Commercially available polymerizable compounds having a dendrimer structure or a hyperbranched structure include, for example, Viscoat #1000LT (dendrimer structure, average number of acryloyl groups: 14) manufactured by Osaka Organic Chemical Industry Co., Ltd., Miramer SP-1106 (dendrimer structure, average number of acryloyl groups: 18) and Miramer SP-1108 (dendrimer structure, average number of acryloyl groups: 13) manufactured by Miwon Specialty Chemical Co., Ltd., CN2301 (hyperbranched structure, average number of acryloyl groups: 9), CN2302 (hyperbranched structure, average number of acryloyl groups: 16), CN2303 (hyperbranched structure, average number of acryloyl groups: 6), CN2304 (hyperbranched structure, average number of acryloyl groups: 18), and Eternal Examples of such copolymers include Etercure 6361-100 (hyperbranched structure, average number of acryloyl groups: 8), Etercure 6362-100 (hyperbranched structure, average number of acryloyl groups: 12), Etercure 6363 (hyperbranched structure, average number of acryloyl groups: 16), and Etercure DR-E522 (hyperbranched structure, average number of acryloyl groups: 15), all of which are manufactured by Materials.

[0274] (Other polymerizable compounds) Other polymerizable compounds include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, glycerol tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO- or PO-modified tri(meth)acrylate, and the like. Examples of the acrylic acid ester include various acrylic acid esters and methacrylic acid esters such as isocyanuric acid EO- or PO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol EO- or PO-modified hexa(meth)acrylate, tricyclodecanyl (meth)acrylate, and (meth)acrylic acid esters of methylolated melamine, as well as styrene, vinyl acetate, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

[0275] Other commercially available polymerizable compounds include, for example, KAYARAD NPGDA, PEG400DA, FM-400, HX-200, HX-620, R-551, R-712, R-604, R-684, GPOD-303, TMPTA, T-1420(T), RP-1040, DPEA-12, and D-310 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-101A, M-102, M-111, M-113, M-120, M-140, M-208, and M-211B manufactured by Toagosei Co., Ltd. M-220, M-225, M-270, M-240, M-309, M-310, M-321, M-350, M-360, M-408, M-460, M-930, Viscoat #150, #155, #160, #192, #MTG, #200, #196, #195, #230, #260, #310, #700HV, #295 manufactured by Osaka Organic Chemical Industry Co., Ltd., OGSOL manufactured by Osaka Gas Chemical Co., Ltd. Examples of such esters include EA-0200, EA-0300, Miramer HR6060, 6100, and 6200 manufactured by Miwon Specialty Chemical Co., Ltd., and NK Ester A-HD-N, A-NPG, A-200, A-400, APG-200, APG-400, A-DCP, ABE-300, A-BPE-4, A-BPE-10, A-TMPT, A-TMPT-9EO, A-GLY-3E, A-GLY-9E, A-TMMT, ATM-35E, and AD-TMP manufactured by Shin-Nakamura Chemical Co., Ltd.

[0276] Further, polymerizable compounds having a hydroxyl group and an acidic group, and polymerizable compounds having a hydroxyl group and a urethane bond are also included.

[0277] The polymerizable compound (E) preferably contains at least one selected from the group consisting of polymerizable compounds having an amine structure, polymerizable compounds having a hydroxyl group, and polymerizable compounds having a dendrimer structure or a hyperbranched structure.

[0278] The total content of the polymerizable compound having an amine structure, the polymerizable compound having a hydroxyl group, and the polymerizable compound having a dendrimer structure or a hyperbranched structure is preferably from 10 to 100 mass%, and more preferably from 20 to 100 mass%, in 100 mass% of the polymerizable compound (E).

[0279] [Polymerization initiator (F)] The composition of the present invention further comprises a polymerization initiator (F).

[0280] The polymerization initiator (F) is not particularly limited, and any known compound can be used. For example, a compound that generates radicals by the action of light or heat to initiate or promote a radical polymerization reaction can be used. The polymerization initiator that generates radicals by light (hereinafter, also simply referred to as a photopolymerization initiator) is preferably a compound that generates radicals by light rays in the ultraviolet to visible light range. The polymerization initiator that generates radicals by heat (hereinafter, also simply referred to as a thermal polymerization initiator) may be a compound that generates radicals by the action of heat and light.

[0281] Examples of the photopolymerization initiator include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; triazine-based compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, and 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; Oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Examples of the compound include quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate-based compounds; and carbazole-based compounds.

[0282] Commercially available products include acetophenone compounds such as Omnirad 907, 369E, 379EG, 127, 184, 1173, and 2959 manufactured by IGM Resins, acylphosphine compounds such as Omnirad 819 and TPO manufactured by IGM Resins, oxime ester compounds such as IRGACURE OXE-01, 02, 03, 04, and 05 manufactured by BASF Japan, ADEKA Arcles N-1919, NCI-730, 831E, and 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, and 3057 manufactured by Changzhou Strong New Materials Co., Ltd., and IGM Examples of such adhesives include Omnirad 1312, 1314, and 1316 manufactured by Resins, SPI-02, 03, 04, 05, 06, and 07 manufactured by Samyang Corporation, and DFI-020, 306, and EOX-01 manufactured by Daito Chemistrys. In addition, compounds described in JP 2007-210991 A, JP 2009-179619 A, JP 2010-037223 A, JP 2010-215575 A, JP 2011-020998 A, WO 2015 / 036910 A, JP 2019-507108 A, JP 2019-528331 A, WO 2021 / 175855 A, JP 2022-5115524 A, WO 2023 / 085056 A, WO 2023 / 085072 A, etc. are also included. Among these, oxime ester compounds are preferred. As the oxime ester compound, a compound having two or more oxime ester groups is more preferred.

[0283] Specific examples of the oxime ester compound are shown below, but the present invention is not limited thereto.

[0284] [ka]

[0285] [ka]

[0286] [ka]

[0287] Examples of the thermal polymerization initiator include benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetra(4-methoxyphenyl)ethane, and 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane. pinacol compounds such as 1,2-bis(triethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(tert-butyldimethylsiloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, and 1-hydroxy-2-tert-butyldimethylsiloxy-1,1,2,2-tetraphenylethane; azo compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-(2-propenyl)2-methylpropionamide], 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); Examples of the organic peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, succinic peroxide, and benzoyl peroxide.

[0288] The polymerization initiator (F) can be used alone or in combination of two or more kinds.

[0289] The content of the polymerization initiator (F) is preferably from 0.1 to 20 mass%, more preferably from 0.5 to 10 mass%, based on 100 mass% of the nonvolatile content of the composition.

[0290] [Thermal crosslinkable compound (G)] The composition of the present invention preferably contains a thermally crosslinkable compound (G). This allows the thermally crosslinkable compound (G) to crosslink by heating, improving the resistance of the film. In this specification, the thermally crosslinkable compound (G) is not included in the resin (B) or the polymerizable compound (E).

[0291] The thermal crosslinking compound (G) is not particularly limited as long as it is a compound having a thermal crosslinking group, and a known compound can be used. For example, a compound having an epoxy group, a compound having a blocked isocyanate group, a compound having an oxetanyl group, a compound having a methylol group, a compound having a phenol group, a compound having an alkoxyalkyl group, etc. can be mentioned. Among these, it is preferable to include at least one selected from the group consisting of a compound having an epoxy group and a compound having a blocked isocyanate group.

[0292] The thermally crosslinkable compound (G) can be used alone or in combination of two or more kinds.

[0293] The content of the thermally crosslinkable compound (G) is preferably from 0.5 to 40 mass %, more preferably from 1 to 30 mass %, based on 100 mass % of the nonvolatile content of the composition.

[0294] (Compound (G1) having an epoxy group) The thermally crosslinkable compound (G) preferably contains a compound (G1) having an epoxy group, whereby the epoxy group is crosslinked by heating, thereby further improving resistance.

[0295] The epoxy group is a group having a three-membered cyclic ether structure, including an alicyclic epoxy group. Examples of compounds having an epoxy group include polyglycidyl ether compounds of bisphenols, such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol F diglycidyl ether; Polyglycidyl ether compounds of polyhydric alcohols, such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether; Polyglycidyl ether compounds of polyether polyols obtained by adding alkylene oxides to polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl compounds having two or more 3,4-epoxycyclohexyl groups in the molecule, such as bis(3,4-epoxycyclohexylmethyl)-5,5-spiro-3,4-epoxy)cyclohexane-metadioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylene bis(3,4-epoxycyclohexane), ethylene bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, butanetetracarboxylate tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone; Examples include an adduct of 2,2-bis(hydroxymethyl)-1-butanol with 1,2-epoxy-4-(2-oxiranyl)cyclohexane.

[0296] Commercially available products of the compound (G1) having an epoxy group include, for example, Epicoat 807, 815, 825, 827, 828, 190P, and 191P manufactured by Yuka Shell Epoxy Co., Ltd., and TECHMORE manufactured by Mitsui Chemicals, Inc. VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd., Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 manufactured by Japan Epoxy Resins Co., Ltd., Celloxide 2021, EHPE-3150, Epolead GT401 manufactured by Daicel Chemical Industries, Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Nagase ChemteX Corporation, TEPIC-L, H, S manufactured by Nissan Chemical Industries, and EPICLON manufactured by DIC Corporation Examples include 830, 840, 850, 860, 1050, 3050, 4050, N-660, N-670, N-740, N-770, N865, HP-7200, HP-4700, HP-4770, HP-5000, HP-6000, and HP-9500.

[0297] The compound (G1) having an epoxy group is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0298] The epoxy equivalent of the compound (G1) having an epoxy group is preferably 50 to 400 g / eq, more preferably 100 to 200 g / eq. The epoxy equivalent is defined as the mass of an epoxy compound containing one equivalent of an epoxy group.

[0299] The compound (G1) having an epoxy group more preferably includes a compound represented by the following general formula (15).

[0300] General formula (15) [ka]

[0301] In formula (15), R represents a group obtained by removing m hydroxyl groups from an m-hydric alcohol, m represents an integer of 1 to 6, and n represents an integer of 1 to 30.

[0302] R represents a group obtained by removing m hydroxyl groups from an m-hydric alcohol. The group obtained by removing m hydroxyl groups from the m-hydric alcohol is preferably an alkyl group having 2 to 20 carbon atoms, and may be linear, branched, or cyclic, or a group in which they are combined. Examples of the alkyl group having 2 to 20 carbon atoms include an ethyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a 2,2-dimethylpropyl group, a butyl group, an isobutyl group, a tert-butyl group, a 3,3-dimethylbutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a hexadecyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylmethyl group. Among these, a branched alkyl group having 3 to 12 carbon atoms is more preferable. m represents an integer of 1 to 6, and n represents an integer of 1 to 30. When m is 2 or more, n in each group in parentheses in general formula (15) may be the same or different.

[0303] The compound represented by the general formula (15) is, for example, a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol. Commercially available products include EHPE-3150 and EHPE-3150CE manufactured by Daicel Corporation.

[0304] The acid value of the compound (G1) having an epoxy group is preferably 10 mgKOH / g or less.

[0305] The compound (G1) having an epoxy group can be used alone or in combination of two or more kinds.

[0306] The content of the compound (G1) having an epoxy group is preferably from 0.5 to 20 mass %, and more preferably from 1 to 15 mass %, in 100 mass % of the thermally crosslinkable compound (G).

[0307] (Compound (G2) having a blocked isocyanate group) The thermally crosslinkable compound (G) preferably contains a compound (G2) having a blocked isocyanate group.

[0308] The compound (G2) having a blocked isocyanate group is a compound in which the isocyanate group of a compound having an isocyanate group is protected with a blocking agent. The desorption temperature of the blocking agent of the blocked isocyanate group is preferably 60 to 160°C, more preferably 70 to 130°C, and particularly preferably 80 to 100°C.

[0309] The compound (G2) having a blocked isocyanate group is synthesized by reacting a compound having an isocyanate group with a blocking agent by a known method, such as the methods described in JP-A-52-116420, JP-A-60-149572, JP-A-7-31953, JP-A-10-306136, and JP-A-2012-012567.

[0310] The blocking agent is preferably one or more selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds, more preferably oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds, and from the viewpoint of film resistance after low-temperature post-baking, active methylene compounds are particularly preferable. The desorption temperature of the active methylene compound or the temperature of the ester exchange reaction is low at 80 to 110°C, and the reaction is sufficient even at low temperatures, improving resistance. Examples of the active methylene compound include dimethyl malonate, diethyl malonate, dibutyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone, with diethyl malonate and dibutyl malonate being preferred.

[0311] Examples of the compound having an isocyanate group include compounds having an aliphatic structure, such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; Compounds having an alicyclic structure, such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatemethyl)cyclohexane; Examples of the aromatic compounds include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyl diphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethyl xylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyl diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanate methyl)benzene. Further examples include biuret forms, isocyanurate forms, adduct forms, allophanate forms, and reaction products of these compounds with polyols.

[0312] The compound having an isocyanate group is preferably a biuret, isocyanurate, adduct or allophanate of a compound having an aliphatic structure or a compound having an alicyclic structure.

[0313] Examples of the compound (G2) having a blocked isocyanate group include the following compounds: In the following structural formula, X represents a blocked isocyanate group, but the present invention is not limited thereto.

[0314] [ka]

[0315] Examples of X (blocked isocyanate group) in the above compound include the structures shown in (X-1) to (X-6) below. In the following structures, * represents a bond. However, the present invention is not limited to these.

[0316] [ka]

[0317] Examples of commercially available compounds (G2) having a blocked isocyanate group and having an aliphatic structure include Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G manufactured by Asahi Kasei Corporation, Takenate B-882 manufactured by Mitsui Chemicals, Inc., and BI7960, BI7961, BI7982, BI7991, and BI7992 manufactured by Baxenden Chemical Co., Ltd.; Examples of compounds having an alicyclic structure include Takenate B-846N manufactured by Mitsui Chemicals, Inc., Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation, and BI7950, BI7951, and BI7990 manufactured by Baxenden Chemical Co., Ltd.; Examples of compounds having an aromatic structure include Takenate B-830 and B-815N manufactured by Mitsui Chemicals.

[0318] The compound (G2) having a blocked isocyanate group preferably has 1 to 20 blocked isocyanate groups, and more preferably has 2 to 15 blocked isocyanate groups.

[0319] The weight average molecular weight of the compound (G2) having a blocked isocyanate group is preferably from 300 to 5,000, and more preferably from 500 to 3,000.

[0320] The acid value of the compound (G2) having a blocked isocyanate group is preferably 10 mgKOH / g or less.

[0321] The compound (G2) having a blocked isocyanate group can be used alone or in combination of two or more kinds.

[0322] The content of the compound (G2) having a blocked isocyanate group is preferably from 0.5 to 20 mass %, and more preferably from 1 to 15 mass %, in 100 mass % of the thermally crosslinkable compound (G).

[0323] [Silane coupling agent (H)] The composition of the present invention preferably contains a silane coupling agent (H), which reacts with functional groups on the substrate surface and functional groups of other components contained in the composition to improve film resistance.

[0324] The silane coupling agent (H) is a compound having a hydrolyzable group and other functional groups. The hydrolyzable group is a group that is directly bonded to a silicon atom and generates a siloxane bond by at least one of hydrolysis and condensation reactions. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group. Among these, an alkoxy group is preferred. From the viewpoint of reactivity, the alkoxy group is preferably a methoxy group or an ethoxy group. Examples of the other functional groups include an epoxy group, an amino group, a vinyl group, a (meth)acryloyl group, an isocyanate group, an isocyanurate group, a mercapto group, an oxetanyl group, a styryl group, and a ureido group. In this specification, the silane coupling agent (H) is not included in the resin (B) and the polymerizable compound (E).

[0325] Examples of the silane coupling agent (H) include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane. hydrochloride, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, 3-ureidopropyltrialkoxysilane, and the like.

[0326] Commercially available products of the silane coupling agent (H) include, for example, KBM-302, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803, KBM-602, KBM-603, KBM-903, KBE-9103P, KBM-573, KBM-6803, KBM-1003, and KBE -1003, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5803, X-12-1048, X-12-1050, KBE-9007N, KBM-9659, KBM-802, KBM-803, KBM-1043, KBE-585A, X-12-1048, X-12-50, etc.

[0327] The silane coupling agent (H) may be a polymer type, such as a polysiloxane type or an organic polymer type.

[0328] The polysiloxane type is a compound in which the hydrolyzable group and the other functional groups are bonded to a polymer having a polysiloxane skeleton in the main chain. Commercially available polysiloxane type products include KR-513, KR-516, KR-517, X-41-1805, and X-41-1810 manufactured by Shin-Etsu Silicone Co., Ltd.

[0329] The organic polymer type is a silane coupling agent (H) in which the hydrolyzable group and the other functional groups are bonded to an organic polymer whose main chain is an organic structure. Commercially available organic polymer type products include X-12-9815, X-12-9845, X-12-1154, X-12-972F, and X-12-1159L manufactured by Shin-Etsu Silicone Co., Ltd.

[0330] The silane coupling agent (H) preferably contains a compound represented by the following general formula (16). The compound represented by general formula (16) has a urethane bond, and therefore forms hydrogen bonds between the urethane bonds and with functional groups of other components contained in the photosensitive composition, forming a strong film. In addition, since the urethane bond has flexibility, it is presumed that the film is strong yet flexible.

[0331] General formula (16) [ka]

[0332] In general formula (16), three R1s each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R2 represents an alkylene group having 1 to 8 carbon atoms, Q represents a group represented by any one of the following general formulae (Q-1) to (Q-4), and n represents an integer of 1 to 10.

[0333] [ka]

[0334] In the general formula (Q-1), R3 represents an alkylene group having 1 to 8 carbon atoms. In the general formulae (Q-1) to (Q-4), R4 each independently represents a hydrogen atom or a methyl group. * represents a bond to an oxygen atom.

[0335] In the general formula (16), the three R1's are preferably methyl groups.

[0336] In the general formula (16), Q is preferably any of the general formulae (Q-1) to (Q-3).

[0337] The molecular weight (formula weight) or weight average molecular weight of the silane coupling agent (H) is preferably from 100 to 3,000, and more preferably from 150 to 1,500.

[0338] The acid value of the silane coupling agent (H) is preferably 10 mgKOH / g or less.

[0339] The silane coupling agent (H) can be used alone or in combination of two or more kinds.

[0340] The content of the silane coupling agent (H) is preferably 0.1 to 10 mass % in 100 mass % of the nonvolatile content of the composition.

[0341] [Thiol-based chain transfer agents (I)] The composition of the present invention preferably contains a thiol-based chain transfer agent (I), which is presumably responsible for the generation of thiyl radicals that are less susceptible to polymerization inhibition by oxygen during the exposure step, and thus for the advancement and improvement of photocuring.

[0342] Examples of the thiol chain transfer agent (I) include monofunctional thiol compounds such as thiophenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-benzimidazole, butanethiol, octanethiol, 1-dodecanethiol, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, and 2-ethylhexyl 3-mercaptopropionate; Monofunctional thiol compounds having a hydroxyl group or an acidic group, such as 2-mercaptoethanol, 1-thioglycerol, thioglycolic acid, 2-mercaptobenzoic acid, 3-mercaptobenzoic acid, 4-mercaptonicotinic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 4-mercaptobutanoic acid, octyl thioglycolate, mercaptosuccinic acid, 11-mercaptoundecanoic acid, and 2-mercaptoethanesulfonic acid; Examples of polyfunctional thiol compounds include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis thioglycolate, pentaerythritol tetrakis(3-mercaptopropionate), trimercaptopropionic acid tris(2-hydroxyethyl)isocyanate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine.

[0343] The thiol chain transfer agent (I) can be used alone or in combination of two or more kinds.

[0344] The content of the thiol chain transfer agent (I) is preferably 0.5 to 10 mass % in 100 mass % of the nonvolatile content of the composition.

[0345] [Dye (J)] The composition of the present invention may contain a dye (J).

[0346] The dye (J) is not particularly limited, and known compounds can be used. Examples include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. In addition, derivatives, lake compounds, salt-forming compounds, and polymers thereof can also be used.

[0347] The acid dye preferably has an acid group such as sulfonic acid or carboxylic acid. In addition, a salt-forming compound which is a salt of an acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound is preferable. In addition, a salt-forming compound which is a salt of a resin component having such a functional group and an acid dye is also preferable. In addition, the salt-forming compound is easily modified into a sulfonamide compound to obtain a photosensitive composition with excellent resistance. In addition, a salt-forming compound of an acid dye and a compound having an onium salt group is also preferable because it has excellent durability. The compound having an onium salt group is preferably a resin having a cationic group.

[0348] Although the basic dye can be used as it is, a salt-forming compound that forms a salt with an organic acid, perchloric acid or a metal salt thereof is preferred. The salt-forming compound of the basic dye is preferred because it has excellent resistance and affinity with the pigment. In addition, the anion component acting as a counter ion in the salt-forming compound of the basic dye is preferably an organic sulfonic acid, an organic sulfuric acid, a fluorine group-containing phosphorus anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt-forming compound formed with an acid dye. The resistance of the salt-forming compound is further improved when the salt-forming compound contains a polymerizable unsaturated group in the molecule.

[0349] The chemical structure of the dye (J) may be, for example, an azo dye, a disazo dye, an azomethine dye (such as indoaniline dyes and indophenol dyes), a dipyrromethene dye, a quinone dye (such as benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, and anthrapyridone dyes), a carbonium dye (such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, and acridine dyes), a quinoneimine dye (such as oxazine dyes and thiazine dyes), an azine dye, Examples of the dye structure include those derived from dyes selected from polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, naphthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

[0350] Among these, from the viewpoint of color properties such as hue, color separation, and color unevenness, a dye structure derived from a dye selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, naphthalocyanine dyes, and subphthalocyanine dyes is preferred, and a dye structure derived from a dye selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes is more preferred.

[0351] The dye (J) can be used alone or in combination of two or more kinds.

[0352] The content of the dye (J) is preferably from 0.5 to 60 mass %, and more preferably from 1 to 50 mass %, based on 100 mass % of the nonvolatile content of the composition.

[0353] [Pigment derivatives (K)] The composition of the present invention may contain a pigment derivative (K). Use of the pigment derivative (K) enables the pigment (A) to be stably dispersed.

[0354] The pigment derivative (K) is not particularly limited, and known compounds can be used. For example, compounds having a structure in which a part of the pigment is substituted with an acidic group, a basic group, a neutral group, etc. can be mentioned. Specifically, compounds having acidic substituents such as sulfo groups, carboxy groups, and phosphoric acid groups, and amine salts thereof, compounds having basic substituents such as sulfonamide groups or tertiary amino groups at the terminals, and compounds having neutral substituents such as phenyl groups and phthalimidoalkyl groups can be mentioned. Examples of pigments include diketopyrrolopyrrole compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, perinone compounds, perylene compounds, thiazine indigo compounds, triazine compounds, benzimidazolone compounds, benzoisoindole compounds, isoindoline compounds, isoindolinone compounds, quinophthalone compounds, naphthol compounds, squarylium compounds, threne compounds, and naphthalocyanine compounds.

[0355] The pigment derivative (K) is preferably added during the above-mentioned micronization of the pigment (A) or during the dispersion treatment of the pigment (A) described below. The average primary particle size of the pigment derivative (K) is preferably 5 to 200 nm.

[0356] The pigment derivative (K) can be used alone or in combination of two or more kinds.

[0357] The content of the pigment derivative (K) is preferably from 1 to 50 parts by mass, and more preferably from 2 to 40 parts by mass, based on 100 parts by mass of the pigment (A).

[0358] [Ultraviolet absorber (L)] The photosensitive composition of the present invention may contain an ultraviolet absorber (L).

[0359] The ultraviolet absorber (L) is not particularly limited, and any known compound can be used, such as a benzophenone compound, a benzotriazole compound, a triazine compound, a conjugated diene compound, a methyldibenzoyl compound, a coumarin compound, an acrylnitrile compound, a benzothiazole compound, or a salicylate compound.

[0360] Examples of the benzophenone compound include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, 2-hydroxy-4-octyloxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, diethylaminohydroxybenzoyl hexyl benzoate, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 2-aminobenzophenone. Examples of commercially available products include Uvinal A, 3049, 3050, and UVA-935LH manufactured by BASF Japan, and Adeka STAB 1413 manufactured by ADEKA. Among these, 2,2',4,4'-tetrahydroxybenzophenone and 4,4'-bis(diethylamino)benzophenone are preferred.

[0361] Benzotriazole compounds include, for example, 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole, ester compounds of benzenepropanoic acid and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy (C7-9 side chain and straight chain alkyl), 2-[5-chloro-(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, and 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol. , 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, etc. Commercially available products include, for example, Tinuvin PS, 99-2, 326, 384-2, 900, 928, 970, 1130, UVA-903KT manufactured by BASF Japan, and Adeka STAB LA-31RG, LA-31G, etc. manufactured by ADEKA Corporation.

[0362] Examples of the triazine compound include a reaction product of 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hydroxyphenyl with [(C10-C16 (mainly C12-C13) alkyloxy)methyl]oxirane, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4- Examples of the bis-[{4-(4-ethylhexyloxy)-4-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]-phenol, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, etc. Examples of commercially available products include Tinuvin 400, 405, 406, 477, and 479 manufactured by BASF Japan, and Adeka STAB LA-46 and LA-F70 manufactured by ADEKA.

[0363] An example of the conjugated diene compound is UV503 manufactured by Daito Chemical Co., Ltd.

[0364] Examples of the methyldibenzoyl compound include 1,3-diphenyl-1,3-propanedione, 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)-1,3-propanedione, and 1,3-bis(4-methoxyphenyl)-1,3-propanedione.

[0365] Examples of the coumarin compound include 4-hydroxycoumarin and 7-hydroxycoumarin.

[0366] The ultraviolet absorbents (L) can be used alone or in combination of two or more kinds.

[0367] The content of the ultraviolet absorber (L) is preferably 0.1 to 5 mass % in 100 mass % of the nonvolatile content of the composition.

[0368] [Other ingredients (M)] The composition of the present invention may contain components other than those described above (hereinafter, also referred to as other components (M)). Examples of other components (M) include polymerization inhibitors, antioxidants, storage stabilizers, sensitizers, acid generators, salt generators, curing accelerators, curing catalysts, semiconductor nanocrystals, semiconductor materials, organic electroluminescent materials, and insulating materials. The content of other components (M) may be appropriately set within a range that does not impair the effects of the present invention.

[0369] [Specific metal element content] The composition of the present invention preferably contains Li, Na, K, Mg, Ca, Fe, and Cr (hereinafter also referred to as specific metal elements) in a total amount of 500 ppm by mass or less.

[0370] When the total amount of the specific metal elements is within the above range, the composition has excellent dispersion stability even after storage over time. The content of the specific metal elements can be measured by inductively coupled plasma emission spectrometry (ICP).

[0371] [Method of producing the composition] The composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the composition, the components may be mixed at once, or each component may be dissolved or dispersed in the solvent (D) or the polymerizable compound (E) and then mixed successively. For example, a dispersion is produced by adding a pigment (A), a resin (B), a solvent (D), etc., and carrying out a dispersion treatment. Then, a leveling agent (C), a polymerizable compound (E), a polymerization initiator (F), etc. are added to the dispersion and mixed to produce the dispersion. The timing of mixing each material is arbitrary. The dispersion process can also be carried out multiple times.

[0372] Examples of dispersing machines for carrying out the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor.

[0373] The average dispersed particle size (secondary particle size) of the pigment (A) in the composition is preferably from 30 to 200 nm, more preferably from 40 to 200 nm.

[0374] The average dispersed particle size (secondary particle size) is measured, for example, using Nikkiso Microtrack UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), with particle permeability set to absorption mode, particle shape set to non-spherical, and D50 particle size set to average size. The dilution solvent used for measurement is the organic solvent used for dispersion, and it is preferable to measure samples treated with ultrasonic waves immediately after sample preparation, as this tends to provide results with less variation.

[0375] The composition is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation, filtration with a sintered filter or membrane filter, etc. The composition of the present invention is preferably substantially free of particles of 0.5 μm or more, and more preferably free of particles of 0.3 μm or less.

[0376] <Membrane> The film of the present invention is formed using the composition described above. The film is preferably a patterned film, but can also be used as a planar film.

[0377] [Membrane manufacturing method] The method for producing the film is not particularly limited, and known methods can be used. From the viewpoint of the environment, the film of the present invention is preferably a film formed at 150°C or less, more preferably 130°C or less. In addition, by performing heating at 150°C or less, when an organic EL element is used as a light emitting source of an image display device, when a photoelectric conversion film of an image sensor is made of an organic material, when a heat-sensitive base material such as a plastic film is used, and the like, these performances can be maintained. In addition, the heating temperature is preferably 50°C or more.

[0378] [Coating process] Examples of the substrate include substrates made of materials such as glass, resin, and silicone. The glass may be colorless and transparent, or colored glass such as blue glass may be used depending on the application. Examples of the resin include polyester-based resins such as polyester terephthalate, polyolefin-based resins such as polypropylene and polyethylene, polycarbonate resins, and epoxy resins. The thickness of the substrate is preferably 0.01 to 10 mm. An organic light-emitting layer may be formed on these substrates. Also, an imaging element such as a CCD or a CMOS may be formed on the substrate. Also, an undercoat layer may be provided on the substrate as necessary to improve adhesion with the upper layer, prevent diffusion of substances, and flatten the surface.

[0379] The coating method may be a known method, such as a dropping method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, an inkjet method, flexographic printing, screen printing, gravure printing, or offset printing.

[0380] The thickness of the membrane can be appropriately adjusted depending on the purpose, and is preferably 0.05 to 20.0 μm, more preferably 0.3 to 10.0 μm.

[0381] [Drying process] The method for drying the film applied to the substrate is not particularly limited, and a known method can be used. For example, a reduced pressure drying method using a vacuum drying device, a hot plate, an IR oven, a convection oven, etc. Examples of the drying method include a heating and drying method using an oven or a combination of these.

[0382] The drying temperature and time can be appropriately adjusted. The drying temperature is preferably about 50 to 130° C., and the drying time is preferably about 10 seconds to 5 minutes.

[0383] Next, a pattern is formed. The method for forming the pattern includes photolithography and dry etching, and photolithography is preferred. When the film is used as a flat film, the step of forming a pattern is not necessary, and after coating, the film is dried or exposed to light on the entire surface as necessary.

[0384] The method for forming the pattern will now be described in detail.

[0385] When forming a pattern by photolithography, a layer formed by applying the composition of the present invention onto a substrate is dried and then exposed to light in a pattern through a mask (exposure step), and the unexposed parts are removed by alkaline development (development step), after which the pattern is heat-treated (post-bake step).

[0386] [Exposure process] In the exposure step, the layer formed by coating is exposed to a specific pattern through a mask using an exposure device such as a stepper. This allows the exposed portion to be cured. Examples of active energy rays used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm). When using light with a specific wavelength, an optical filter can also be used. In addition, the exposure may be performed by continuous irradiation with light, or by repeating irradiation and pause of light in a short cycle (for example, on the order of milliseconds or less) (pulse exposure). In addition, a plurality of active energy rays may be used in combination, or exposure may be performed in a plurality of steps.

[0387] [Development process] Next, an alkali development process is carried out, whereby the unexposed portions of the layer are dissolved in an aqueous alkali solution, and only the hardened portions remain, yielding a patterned film. Examples of the alkaline aqueous solution include aqueous solutions containing alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene, etc. Two or more of these alkaline compounds can be used in combination. The concentration of the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, it suppresses roughening and peeling of the pattern and improves the remaining film rate after development. The alkaline aqueous solution may contain a surfactant and an organic solvent in addition to the alkaline compound and water. Examples of the developing method include a dipping method, a spraying method, a puddle method, etc. The developing temperature is preferably 15 to 40° C. After the alkaline development, it is preferable to wash with pure water.

[0388] [Post-bake process] After development, a heat treatment (post-baking) is performed, which improves the resistance of the film. The heating temperature is preferably equal to or lower than 150° C., more preferably equal to or lower than 130° C. The heating time is preferably about 2 minutes to 2 hours.

[0389] <Optical filters> The optical filter of the present invention has the above-mentioned film. The optical filter is used, for example, in a color filter, a black matrix, a light-shielding filter, an anti-reflection filter, an infrared cut filter, an infrared transmission filter, a microlens, etc. The optical filter of the present invention can be manufactured by the same method as the above-mentioned film.

[0390] <Solid-state imaging element> The solid-state imaging device of the present invention has the above optical filter. The solid-state imaging device is not particularly limited as long as it includes the optical filter of the present invention and functions as a solid-state imaging device. For example, the following configurations can be mentioned.

[0391] The substrate has a plurality of photodiodes constituting a light receiving area of ​​a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon or the like, a light shielding film with only the light receiving part of the photodiode open on the photodiode and the transfer electrode, a device protection film made of silicon nitride or the like formed on the light shielding film so as to cover the entire light shielding film and the light receiving part of the photodiode, and the optical filter (color filter) of the present invention on the device protection film. Furthermore, the device protection film may have a light collecting means (e.g., a microlens, etc., the same below) on the device protection film and below the optical filter (the side closer to the substrate), or a light collecting means on the optical filter. The filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned by partitions, for example, in a lattice shape. In this case, the partitions preferably have a low refractive index with respect to each color pixel. An imaging device including a solid-state imaging element of the present invention can be used for various purposes, such as digital cameras, electronic devices with imaging functions (such as mobile phones and smartphones), vehicle-mounted cameras, and surveillance cameras.

[0392] <Image display device> The image display device of the present invention includes the above optical filter. Examples of the image display device include a liquid crystal display and an organic EL display. The form used for the image display device is not particularly limited as long as it functions as an image display device. For example, the configuration described in "Next Generation Liquid Crystal Display Technology" (by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994) can be mentioned. The definition of image display devices and details of each image display device are described, for example, in "Electronic Display Devices" (written by Sasaki Akio, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Ibuki Yoshiaki, published by Sangyo Tosho Co., Ltd. in 1989).

[0393] <Infrared sensor> The infrared sensor of the present invention has the above optical filter. The form of the infrared sensor used is not particularly limited as long as it is provided with the optical filter of the present invention and functions as an infrared sensor, and examples thereof include the following configurations.

[0394] A substrate has a plurality of photodiodes constituting a light receiving area of ​​a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon or the like. A light shielding film with only the light receiving portion of the photodiodes open is provided on the photodiodes and the transfer electrodes. A device protection film is provided on this light shielding film, and the optical filter of the present invention is provided on this device protection film. Furthermore, the device protection film may have a light collecting means (e.g., a microlens, etc., the same applies below) below the optical filter (the side closer to the substrate) on the device protection film, or the light collecting means may be provided on the optical filter.

[0395] 1 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor equipped with an optical filter of the present invention. The infrared sensor shown in FIG.

[0396] The imaging area provided on the solid-state imaging element 110 is configured by combining an infrared cut filter 111 and a color filter 112 .

[0397] The infrared cut filter 111 transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared region (for example, light with a wavelength of 800 to 1,300 nm).

[0398] The color filter 112 is a color filter having pixels formed therein that transmit and absorb light of specific wavelengths in the visible light region, and for example, a color filter having red (R), green (G), and blue (B) pixels formed therein is used.

[0399] Between the infrared transmission filter 113 and the solid-state imaging element 110, a resin film 114 that is capable of transmitting light of a wavelength that has passed through the infrared transmission filter 113 is disposed.

[0400] The infrared transmission filter 113 is a filter that has a visible light blocking property and transmits infrared rays of a specific wavelength. The infrared transmission filter 113 preferably blocks light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1,300 nm, for example.

[0401] A microlens 115 is disposed on the incident light h side of the color filter 112 and the infrared transmission filter 113. A planarization film 116 is formed so as to cover the microlens 115.

[0402] In the embodiment shown in FIG. 1, the resin film 114 is disposed, but instead of the resin film 114, an infrared transmission filter 113 may be formed.

[0403] This infrared sensor can simultaneously capture image information, making it possible to perform motion sensing that recognizes the object whose movement is to be detected. In addition, this infrared sensor can obtain distance information, making it possible to capture images that include 3D information. Furthermore, this infrared sensor can also be used as a biometric authentication sensor. EXAMPLES

[0404] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. In addition, "parts" means "parts by mass" and "%" means "% by mass". In addition, in the present invention, the non-volatile content or non-volatile content concentration refers to the mass residue after standing in an oven at 110°C for 3 hours.

[0405] Before describing the examples, each measurement method will be described.

[0406] (Average molecular weight of resin) The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (manufactured by Tosoh Corporation), with two separation columns connected in series, and both packings were "TSK-GEL SUPER HZM-N" connected in series. The oven temperature was 40°C, a tetrahydrofuran (THF) solution was used as the eluent, and the flow rate was 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters were injected. The molecular weight is a polystyrene equivalent value.

[0407] (Acid value of resin) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of the resin solution, and the solution was stirred to dissolve uniformly. The solution was titrated with an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) using a 0.1 mol / L KOH aqueous solution as the titrant to measure the acid value (mgKOH / g). The acid value per unit of non-volatile content of the resin was calculated from the acid value of the resin solution and the concentration of the non-volatile content of the resin solution.

[0408] (Amine value of resin) The amine value of the resin is the total amine value (mgKOH / g) measured according to the method of ASTM D 2074 and converted into non-volatile content.

[0409] (Water content measurement) The water content of the composition was measured using a Karl Fischer titrator (volumetric water content measuring device KF-06, manufactured by Mitsubishi Chemical Corporation).

[0410] <Production of Pigment (A)> (Near infrared absorbing pigment (A-13)) 400 parts of toluene were mixed with 40.0 parts of 1,8-diaminonaphthalene, 32.2 parts of 3,5-dimethylcyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 3 hours to react. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol. Next, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, heated and stirred in a nitrogen gas atmosphere, and refluxed for 8 hours to react. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the solvent was distilled, and 200 parts of hexane was added while stirring the resulting reaction mixture. The resulting black-brown precipitate was filtered off, washed with hexane, ethanol, and acetone, and dried under reduced pressure to obtain a near-infrared absorbing pigment (A-13) represented by the following chemical formula (17). 50 parts of the obtained near-infrared absorbing pigment (A-13), 500 parts of sodium chloride, and 60 parts of diethylene glycol were charged into a stainless steel gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 ° C for 12 hours. Next, the kneaded mixture was poured into hot water, heated to about 80 ° C and stirred for 1 hour to form a slurry, filtered, and washed with ion-exchanged water several times, then dried overnight at 80 ° C and pulverized to obtain a finely divided near-infrared absorbing pigment (A-13).

[0411] Chemical formula (17) [ka]

[0412] (Near infrared absorbing pigment (A-14)) In a reaction vessel, 26 parts of phthalonitrile, 143 parts of 2,3-dicyanonaphthalene, 890 parts of n-amyl alcohol, 137 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene), and 34 parts of aluminum trichloride were mixed and stirred, and after heating, the mixture was refluxed at 136°C for 5 hours to react. The reaction solution was cooled to 30°C while stirring, and poured into a mixed solvent consisting of 5,000 parts of methanol and 10,000 parts of ion-exchanged water while stirring, to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2,000 parts of methanol and 4,000 parts of ion-exchanged water, and dried to obtain compound a. Next, in a reaction vessel, 140 parts of compound a were added to 1,500 parts of concentrated sulfuric acid in an ice bath, and the mixture was stirred for 1 hour to react. Subsequently, this sulfuric acid solution was poured into 1,000 parts of cold water at 3°C, and the resulting precipitate was filtered, washed with water, washed with a 2.5% aqueous sodium hydroxide solution, washed with water, and dried to obtain compound b. 5 parts of diphenyl phosphate was added to 200 parts of N-methylpyrrolidone, thoroughly mixed and heated to 50°C. 10 parts of compound b was gradually added to this solution, and the solution was stirred at 90°C for 120 minutes to react. The end point of the reaction was confirmed, for example, by dropping the reaction solution onto filter paper and waiting until no bleeding occurred. Subsequently, this reaction solution was poured into 2,000 parts of ion-exchanged water, and the resulting precipitate was filtered and washed with ion-exchanged water several times, and then dried to obtain a near-infrared absorbing pigment (A-14) which is a mixture of compounds represented by the following chemical formula (18) (mass ratio: n1:n2:n3:n4=7:19:59:15). Next, it was finely divided by the same method as for the near-infrared absorbing pigment (A-13).

[0413] Chemical formula (18) [ka]

[0414] (Near infrared absorbing pigment (A-15)) According to the description of WO 2019 / 058882, a near infrared absorbing pigment (A-15) represented by the following chemical formula (19) was obtained. The near infrared absorbing pigment (A-15) was then micronized in the same manner as for the near infrared absorbing pigment (A-13). In the chemical formula (19), Ph represents a phenyl group.

[0415] Chemical formula (19) [ka]

[0416] (Near infrared absorbing pigment (A-16)) 10.7 parts of aniline, 120 parts of bromobenzene, and 25.7 parts of diazabicyclooctane were added to a reaction vessel and stirred. Then, 95.2 parts of a 1 mol / l toluene solution of titanium tetrachloride was added dropwise. After the dropwise addition, 10.0 parts of indigo were added and refluxed for 10 hours. After the reaction was completed, methanol was added and filtered to obtain a green powder. This was separated with dichloromethane and water, and the organic layer was concentrated to obtain 14.6 parts of compound c. In a reaction vessel, 13.5 parts of compound c, 9.0 parts of bis(2,4-pentanedionato)zinc(II), and 120 parts of tetrahydrofuran were mixed and stirred, and the mixture was heated and stirred at 40°C for 5 hours. The reaction solution was cooled to 30°C while stirring, and poured into 500 parts of methanol while stirring to obtain a blue slurry. This slurry was filtered, washed with 500 parts of methanol, washed several times with 500 parts of ion-exchanged water, and dried to obtain a near-infrared absorbing pigment (A-16) which is a mixture of compounds represented by the following chemical formula (20) (mass ratio of dimer: trimer: tetramer = 81:17:2). Next, it was pulverized in the same manner as the near-infrared absorbing pigment (A-13).

[0417] Chemical formula (20) [ka]

[0418] <Production of Resin (B)> (Resin (B1-1) solution) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMAc), and 0.2 parts of monobutyltin oxide as a catalyst were charged, and after replacing with nitrogen gas, the reaction was carried out at 120°C for 5 hours (first step). It was confirmed by measuring the acid value that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step, calculated as non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of tert-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, and the inside of the reaction vessel was heated to 80°C, and 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) were added and reacted for 12 hours (second step). It was confirmed that 95% or more of the monomer had reacted by measuring the non-volatile content. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate, and 0.1 parts of hydroquinone were charged and reacted. IR showed that the 2,270 cm -1 The reaction was continued until the disappearance of the peak was confirmed (third step). After cooling, PGMAc was added so that the non-volatile content was 30 mass %, to obtain a resin (B1-1) solution. The acid value was 68 mgKOH / g, and the weight average molecular weight was 13,000.

[0419] (Resin (B1-2) solution) A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of iso-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc, and substituted with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile and 90 parts of PGMAc was added and reacted for 7 hours. It was confirmed that the monomer had reacted at 95% or more by measuring the non-volatile content. Next, 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added to the reaction vessel, and the reaction was carried out at 100°C for 7 hours. The reaction was terminated when it was confirmed by measuring the acid value that 98% or more of the acid anhydride had been half-esterified. After cooling, PGMAc was added so that the non-volatile content was 30% by mass, and a resin (B1-2) solution was obtained. The acid value was 70 mgKOH / g and the weight average molecular weight was 8,500.

[0420] (Resin (B1-3) solution) In a reaction vessel equipped with a gas inlet tube, a condenser, an agitator, and a thermometer, 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the atmosphere in the reaction vessel was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 100 parts of PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to initiate polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content. Next, 50 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were charged into the reaction vessel, and the reaction was continued by stirring while maintaining 110°C under a nitrogen atmosphere. Two hours after the addition, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more based on the non-volatile content. After cooling, PGMAc was added so that the non-volatile content was 30% by mass, and a resin (B1-3) solution was prepared. The amine value was 169.8 mg KOH / g.

[0421] (Resin (B1-4) solution) According to Example A3 of WO 2022 / 172607, resin (B1-4) was synthesized, and PGMAc was added so that the non-volatile content was 30% by mass. The amine value was 67 mgKOH / g and the weight average molecular weight was 5,600.

[0422] (Resin (B2-1) solution) A reaction vessel equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube was charged with 100 parts of PGMAc, which was then stirred while replacing with nitrogen and heated to 78°C. Next, a mixture of 25.2 parts of Karenz MOI-DEM (2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl ester of malonic acid manufactured by Showa Denko K.K., 31.2 parts of 2-hydroxyethyl methacrylate, 37.5 parts of dicyclopentanyl methacrylate, 20.7 parts of methacrylic acid and 27.0 parts of methyl methacrylate, and 12.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) dissolved in 50 parts of PGMAc were dropped into the reaction vessel from the dropping funnel. After the dropwise addition, the mixture was stirred at 78°C for 3 hours to react. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, to prepare a resin (B2-1) solution. The acid value was 74 mgKOH / g, and the weight average molecular weight was 8,000.

[0423] (Resin (B2-2) solution) In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 190.2 parts of diethyl malate, 0.17 parts of 2,6-di-tert-butyl-4-methylphenol, and 0.33 parts of dibutyltin dilaurate were added and stirred, and cooled to 15 to 20°C. Then, the temperature was maintained at 15 to 20°C, and 141.1 parts of 2-acryloyloxyethyl isocyanate was added dropwise from the dropping funnel while stirring. After the dropwise addition, the mixture was stirred and reacted at 25°C for 13 hours to obtain compound a. Next, 150 parts of PGMAc was put into a reaction vessel equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, and the mixture was stirred while replacing with nitrogen and heated to 78 ° C. 148.8 parts of compound a, Karenz MOI-BP (2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate manufactured by Showa Denko K.K.) 24.7 parts, 2-hydroxyethyl methacrylate 25.5 parts, 2-ethylhexyl acrylate 8.6 parts, and 17.4 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (polymerization initiator) were mixed and dropped into the reaction vessel from the dropping funnel. After the dropwise addition, the mixture was stirred and reacted at 78 ° C for 3 hours, and then 0.2 parts of 1,8-diazabicyclo [5.4.0] -undecene-7 was added and further stirred at 78 ° C for 30 minutes. Next, 9.9 parts of succinic anhydride and 0.5 parts of lithium naphthenate (catalyst) were added, and the mixture was stirred at 78° C. for 1 hour. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, to prepare a resin (B2-2) solution. The acid value was 44 mgKOH / g, and the weight average molecular weight was 12,500.

[0424] (Resin (B2-3) solution) 100 parts of PGMAc was placed in a reaction vessel equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, and the mixture was stirred while replacing with nitrogen and heated to 90°C. Next, a mixture of 20.7 parts of 2-(acetoacetoxy)ethyl methacrylate, 26.7 parts of methacrylic acid and 52.6 parts of dicyclopentanyl methacrylate, and 5.0 parts of 2,2'-azobis(isobutyric acid)dimethyl dissolved in 30 parts of PGMAc were dropped into the reaction vessel from the dropping funnel. After the dropwise addition, the mixture was stirred at 90°C for 6 hours to react. The mixture was then cooled to 40°C, and 0.12 parts of 4-methoxyphenol, 17.6 parts of 3,4-epoxycyclohexylmethyl acrylate, and 4.7 parts of triphenylphosphine were added, and the temperature was raised to 110°C, followed by stirring for 10 hours to carry out the reaction. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, to prepare a resin (B2-3) solution. The acid value was 103 mgKOH / g, and the weight average molecular weight was 14,300.

[0425] (Resin (B2-4) solution) 200 parts of PGMAc was added to a reaction vessel equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, and the mixture was stirred while replacing with nitrogen and heated to 105°C. Next, a mixture of 106.9 parts of 3-methacryloyloxypropyltrimethoxysilane, 40.8 parts of methacrylic acid and 125 parts of methyl methacrylate, and 27.3 parts of dimethyl 2,2'-azobis(isobutyrate) was added dropwise from the dropping funnel to the reaction vessel. After the dropwise addition, the mixture was reacted for 2 hours while stirring at 105°C. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, and a resin (B2-4) solution was prepared. The acid value was 99 mgKOH / g, and the weight average molecular weight was 7,100.

[0426] (Resin (B2-5) solution) A reaction vessel equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube was charged with 100 parts of PGMAc, which was then stirred while being replaced with nitrogen, and heated to 90°C. Next, a mixture of 35 parts of tert-butyl methacrylate, 5 parts of 2-(acetoacetoxy)ethyl methacrylate, 10 parts of N-benzylmaleimide, 20 parts of 2-hydroxyethyl methacrylate, 17.1 parts of methacrylic acid, and 2 parts of t-butylperoxy-2-ethylhexanoate (polymerization initiator), and a mixture of 0.6 parts of n-dodecyl mercaptan and 20 parts of PGMAc were dropped into the reaction vessel from the dropping funnel. After the dropwise addition, the mixture was kept at 90°C for 30 minutes, then heated to 115°C, and reacted with stirring for 90 minutes. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, and a resin (B2-5) solution was prepared. The acid value was 98 mgKOH / g, and the weight average molecular weight was 19,500.

[0427] (Resin (B3-1) solution) A thermometer, a cooling tube, a nitrogen gas inlet tube, and a reaction vessel equipped with a stirrer were charged with 100 parts of PGMAc, and the vessel was heated to 120 ° C while injecting nitrogen gas into it. At the same temperature, a mixture of 56.86 parts of glycidyl methacrylate, 66.09 parts of dicyclopentanyl methacrylate, and 31.25 parts of styrene was added dropwise from the dropping tube over 2.5 hours, and azobisisobutyronitrile was dissolved in 5.0 parts of PGMAc as a polymerization initiator. After the dropwise addition was completed, the mixture was stirred at 120 ° C for another 2 hours to cause the reaction. Next, the inside of the reaction vessel was replaced with air, and 28.82 parts of AA, 0.3 parts of trisdimethylaminomethylphenol, and 0.3 parts of hydroquinone were added, and the mixture was stirred at 120 ° C for 5 hours to cause the reaction. Further, 48.68 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were added, and the mixture was reacted at 120° C. for 4 hours with stirring. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, to prepare a resin (B3-1) solution. The acid value was 77 mgKOH / g, and the weight average molecular weight was 10,000.

[0428] <Production of Leveling Agent (C)> (Block copolymer (C1-1) solution) In a nitrogen-substituted reaction vessel, 15.0 parts of 3-methacryloyloxypropyltris(trimethylsiloxy)silane and 79.0 parts of methyl ethyl ketone were charged, and the temperature was raised to 50°C while stirring under a nitrogen stream. Next, 4.2 parts of 2,2'-bipyridyl and 1.5 parts of cuprous chloride were charged, and the mixture was stirred at 50°C for 30 minutes. Then, 2.7 parts of ethyl 2-bromoisobutyrate were added, and the mixture was reacted at 50°C for 3 hours under a nitrogen stream to synthesize the A block portion, which is a polymer of 3-methacryloyloxypropyltris(trimethylsiloxy)silane. Next, 35.0 parts of polypropylene glycol monomethacrylate (average repeat number of propylene glycol: 4-6) was added to the reaction system containing the A block, which was a polymer of 3-methacryloyloxypropyltris(trimethylsiloxy)silane, and the reaction was carried out at 50°C for 18 hours to synthesize the B block, which was a polymer of polypropylene glycol monomethacrylate (average repeat number of propylene glycol: 4-6). Then, 30 parts of activated alumina was added and stirred. After filtration, the mixture was distilled under reduced pressure to obtain a block copolymer (C1-1). Thereafter, PGMAc was added so that the non-volatile content became 1% by mass, to obtain a solution of a block copolymer (C1-1). The weight average molecular weight was 10,300 and the number average molecular weight was 9,200.

[0429] (Block copolymer (C1-2)~(C1-12) solution) Block copolymers (C1-2) to (C1-12) were synthesized in the same manner as for block copolymer (C1-1) by changing the type and amount of monomer so as to obtain the composition and structure shown in Table 2, and PGMAc was added to adjust the non-volatile content to 1 mass%.

[0430] [Table 2]

[0431] The components listed in Table 2 are as follows:

[0432] Chemical formula (21) [ka]

[0433] Chemical formula (22) [ka]

[0434] Chemical formula (23) [ka]

[0435] <Production of Silane Coupling Agent (H)> (Silane coupling agent (H)) In a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 116 parts of hydroxyethyl acrylate was charged and heated to 80°C. 205 parts of 3-isocyanatepropyltrimethoxysilane was added dropwise thereto and stirred at 80°C for 4 hours to react. After that, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material had completely disappeared and instead an absorption peak derived from a urethane bond had been generated, and a silane coupling agent (H) whose main component is represented by the following chemical formula (24) was obtained. In addition, as a secondary component, a dimer to decamer which is a condensation product of the chemical formula (24) was included.

[0436] Chemical formula (24) [ka]

[0437] <Production of dye (J)> (Dye (J-1)) A reaction vessel equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75°C under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 6.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and 25.1 parts of methyl ethyl ketone were mixed uniformly, then charged into a dropping funnel, attached to a four-neck separable reaction vessel, and reacted while dropping for 2 hours. The reaction was continued for 2 hours after the end of the dropping. After that, it was confirmed from the non-volatile content that the polymerization yield was 98% or more and the weight average molecular weight was 6,830, and the mixture was cooled to 50°C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, and the mixture was reacted at 50° C. for 2 hours, then heated to 80° C. over 1 hour, reacted for 2 hours, and cooled to obtain resin 1. Next, 30 parts of resin 1 in terms of non-volatile content were added to 2,000 parts of water, and the mixture was thoroughly stirred and mixed, and then heated to 60°C. Meanwhile, an aqueous solution was prepared by dissolving 10 parts of CI Acid Red 52 in 90 parts of water, and the solution was gradually added to the resin 1 solution. After the dropwise addition, the reaction was carried out while stirring at 60°C for 120 minutes. To confirm the end point of the reaction, the reaction solution was dropped onto a filter paper, and the end point was determined to be when no bleeding occurred, and the salt-forming compound was obtained. After cooling to room temperature while stirring, suction filtration was performed, and the salt-forming compound remaining on the filter paper was dried by removing moisture in a dryer, to obtain dye (J-1), which is a salt-forming compound of 32 parts of CI Acid Red 52 and resin 1. At this time, the content of the component derived from CI Acid Red 52 in dye (J-1) was 25% by mass.

[0438] (Dye (J-2)) According to Example 30 of JP-A-05-345861, a compound represented by the following chemical formula (25) was obtained: In the chemical formula (25), Et represents an ethyl group.

[0439] Chemical formula (25) [ka]

[0440] <Preparation of Dispersion> (Dispersion 1) The following raw materials were mixed and stirred until uniform, and then dispersed in an Eiger mill (Eiger Japan Co., Ltd., "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a filter with a pore size of 1.0 μm to produce Dispersion 1. The non-volatile content was 21.1% by mass. Pigment (A-1): 15.0 parts Pigment derivative (K-1): 1.0 part Resin (B1-1) solution: 8.5 parts Resin (B1-2) solution: 8.5 parts Solvent (D2-1): 67.0 parts

[0441] (Dispersion 2~16) Dispersions 2 to 16 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts thereof were changed as shown in Tables 3-1 and 3-2.

[0442] [Table 3-1]

[0443] [Table 3-2]

[0444] The components listed in Tables 3-1 and 3-2 are as follows.

[0445] Pigment A-1: CI Pigment Blue 15:3 A-2: CI Pigment Blue 15:6 A-3: CI Pigment Violet 23 A-4: CI Pigment Green 58 A-5: CI Pigment Green 36 A-6: CI Pigment Green 62 A-7: CI Pigment Red 177 A-8: CI Pigment Yellow 138 A-9: CI Pigment Yellow 139 A-10: CI Pigment Yellow 150 A-11: CI Pigment Red 264 A-12: CI Pigment Red 254

[0446] Each of the pigments (A-1) to (A-12) was pulverized by salt milling, thoroughly washed with ion-exchanged water so as to have the specific metal content described above, and thoroughly dried before use.

[0447] [Pigment derivatives (K)] [ka]

[0448] [Solvent (D)] (Solvent (D2)) D2-1:PGMAc

[0449] <Production of Composition> [Example 1] The following raw materials were put into a container that had been replaced with sufficiently dry air, and stirred under a dry air stream. Then, the amount of water (solvent D1-10) was adjusted so that the water content in the composition was 0.1 mass%, and solvent D2-1 was added so that the total amount of the composition was 100 parts, and the mixture was stirred, and then filtered through a filter with a pore size of 1.0 μm to obtain composition 1. The non-volatile content was 15.0 mass%. In Table 4, the dispersion was decomposed into each raw material, and the solvent contained in each raw material was entered as solvent (D). Dispersion 2: 1.00 parts Dispersion 5: 21.00 parts Dispersion 9: 3.00 parts Resin (B2-1) solution: 9.77 parts Resin (B3-1) solution: 7.33 parts Block copolymer (C1-1) solution: 1.00 parts Block copolymer (C1-8) solution: 1.00 parts Solvent (D1-1): 3.00 parts Solvent (D1-9): 0.30 parts Solvent (D2-1): 28.00 parts Solvent (D2-2): 8.00 parts Solvent (D2-3): 8.00 parts Solvent (D2-4): 0.30 parts Polymerizable compound (E-1): 0.50 part Polymerizable compound (E-2): 2.00 parts Polymerization initiator (F-1): 0.10 parts Polymerization initiator (F-2): 0.05 parts Compound having an epoxy group (G1-1): 0.40 parts Silane coupling agent (H): 0.35 parts Thiol chain transfer agent (I): 0.30 parts UV absorber (L): 0.30 parts

[0450] [Examples 2 to 54 and Comparative Examples 1 and 2] (Photosensitive composition 2-56) Compositions 2 to 56 were prepared in the same manner as in Example 1 using the raw materials and amounts shown in Tables 4-1 to 4-5.

[0451] [Table 4-1]

[0452] [Table 4-2]

[0453] [Table 4-3]

[0454] [Table 4-4]

[0455] [Table 4-5]

[0456] [Table 4-6] The respective raw materials listed in Tables 4-1 to 4-6 are as follows.

[0457] [Leveling agent (C)] (Other leveling agents (C2)) C2-1: 1% PGMAc solution of the compound with the following structure (hydroxyl value 80 mgKOH / g)

[0458] [ka]

[0459] C2-2: 1% PGMAc solution of BYK-330 (manufactured by BYK-Chemie) (not included in the block copolymer (C1))

[0460] [Solvent (D)] (Solvent (D1)) D1-1: Propylene glycol monomethyl ether (δh=11.6) D1-2: Propylene glycol monoethyl ether (δh=10.5) D1-3: Ethylene glycol monobutyl ether (δh=12.3) D1-4: Ethyl lactate (δh=12.5) D1-5: Cyclohexanol (δh=13.5) D1-6: 3-methoxy-1-butanol (δh=13.6) D1-7: Ethylene glycol monoethyl ether (δh=14.3) D1-8: Methyl lactate (δh=14.6) D1-9: 1-butanol (δh=15.8) D1-10: Water (δh=42.3)

[0461] (Other solvents (D2)) D2-1:PGMAc D2-2: Cyclohexanone D2-3: Ethyl 3-ethoxypropionate D2-4: Butyl acetate

[0462] [Polymerizable compound (E)] E-1: CN9906 (Arkema, multifunctional acrylate with an amine structure) E-2: Aronix M-306 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate) E-3: Miramer SP-1106 (Miwon Specialty Chemical Co., Ltd., a compound having a dendrimer structure with an average number of 18 acryloyl groups) E-4: Dipentaerythritol EO modified hexaacrylate

[0463] [Polymerization initiator (F)] F-1: Compound (F-1) described above F-2: Compound (F-2) described above F-3: Compound (F-3) described above F-4: Compound having the following structure

[0464] [ka]

[0465] [Thermal crosslinkable compound (G)] (Compound (G1) having an epoxy group) E1-1: EHPE-3150 (manufactured by Daicel Corporation, a compound represented by general formula (15), with an average of 15 epoxy groups and an epoxy equivalent of 170 to 190 g / eq)

[0466] (Compound (G2) having a blocked isocyanate group) E2-1: Duranate MF-K60B (Asahi Kasei Corporation, a compound blocked with an active methylene compound)

[0467] [Thiol chain transfer (I)] A mixture of mercaptosuccinic acid and pentaerythritol tetrakis(3-mercaptopropionate) in a mass ratio of 5:5

[0468] [Ultraviolet absorber (L)] A 5:5 mixture of 4,4'-bis(diethylamino)benzophenone and 2,2',4,4'-tetrahydroxybenzophenone by mass ratio.

[0469] <Production of Composition for Color Mixing Evaluation> 24.0 parts of Dispersion 4, 12.0 parts of Dispersion 8, 10.5 parts of resin (B2-1) solution, 2.5 parts of polymerizable compound (E-1), 0.15 parts of polymerization initiator (F-1), 0.3 parts of thiol chain transfer agent (I), 0.3 parts of silane coupling agent (H), 0.4 parts of compound (G1) having an epoxy group, 0.3 parts of ultraviolet absorber (L), 2.0 parts of 1% PGMAc solution of BYK-333 (a silicone-based leveling agent manufactured by BYK-Chemie), and 47.55 parts of PGMAc were added, mixed and stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a composition for color mixing evaluation. BYK-333 is not included in the block copolymer (C1).

[0470] <Evaluation of Composition> The following evaluations were carried out on the obtained compositions 1 to 56 immediately after production. These evaluations were taken as evaluations before storage. The evaluation results are shown in Table 5.

[0471] [Evaluation of coating properties before storage (1)] The obtained composition was applied by spin coating onto a 100 mm long x 100 mm wide x 0.7 mm glass substrate (Corning Eagle 2000) at a rotation speed of 1000 rpm for a rotation time of 10 seconds, and dried on a hot plate at 90°C for 2 minutes. The coating was irradiated with a sodium lamp and the condition of the coating was visually observed. The evaluation criteria are as follows, with a rating of 3 or higher being considered practical. 5: No wavy coating unevenness was observed. 4: Slight wavy coating unevenness was observed only on the edge surface of the substrate. 3: Slight wavy coating unevenness was observed. 2: Wavy coating unevenness was clearly observed only on the edge surface of the substrate. 1: Wavy coating unevenness was clearly observed.

[0472] [Evaluation of coating properties before storage (2)] The obtained composition was applied by spin coating onto a 100 mm long x 100 mm wide x 0.7 mm glass substrate (Corning Eagle 2000) at a rotation speed of 200 rpm for a rotation time of 10 seconds, and dried on a hot plate at 90°C for 2 minutes. The occurrence of cissing was observed using an optical microscope. Cissing is a phenomenon in which circular dents or holes appear on the coating surface after the composition is applied to a glass substrate and dried. The evaluation criteria are as follows, with a rating of 3 or higher being considered practical. 5: The number of repellings was less than 3. 4: The number of repellings was 3 or more but less than 5. 3: The number of repellings was 5 or more and less than 15. 2: The number of repellings was 15 or more and less than 30. 1: The number of repellings was 30 or more.

[0473] [Color mixing evaluation before storage (1): 230℃ post-bake] The obtained composition was applied by spin coating onto a glass substrate (Corning Eagle 2000) measuring 100 mm length x 100 mm width x 0.7 mm so that the film thickness after drying would be 2.5 μm, and then dried on a hot plate at 90° C. for 2 minutes. Next, after cooling the substrate to room temperature, an ultra-high pressure mercury lamp was used to illuminate the substrate through a photomask with a stripe pattern of 100 μm width at an illumination intensity of 30 mW / cm. 2 , 100mJ / cm 2 The substrate was spray-developed using an aqueous developer containing 0.12% by mass of a non-ionic leveling agent and 0.04% by mass of potassium hydroxide at 23°C, then washed with ion-exchanged water and air-dried. It was then post-baked in a clean oven at 230°C for 30 minutes to form a one-color pattern. Using a scanning electron microscope at a magnification of 20,000 times, it was confirmed that there was no development residue on the first-color pattern. Next, a pattern of a second color was formed between the patterns of the first color (areas without patterns) using the composition for evaluating color mixing in the same manner as in the formation of the pattern of the first color. The amount of development residue on the first color pattern was measured using a scanning electron microscope at a magnification of 20,000 times. The evaluation criteria are as follows, with 3 or more being considered usable. 5: No residue was observed within a 1.0 μm square area. 4: One to three residues were observed in an area of ​​1.0 μm square. 3: Four to seven residues were observed in an area of ​​1.0 μm square. 2: Seven to ten residues were observed in an area of ​​1.0 μm square. 1: More than 10 residues were observed in a 1.0 μm square area.

[0474] [Color mixing evaluation before storage (2): 130℃ post-bake] The post-bake temperature was changed to 130° C., and the evaluation was performed in the same manner as in the evaluation of color mixing before storage (1).

[0475] [Evaluation of coating properties after storage and color mixing evaluation] The obtained composition was placed in a separate sealed container, left at 40°C for 12 hours, and then left at -10°C for 12 hours, repeating this temperature increase and decrease cycle for 10 cycles. Next, the coating property and color mixing evaluation of the composition after storage were performed in the same manner as before storage. This is the evaluation after storage. The evaluation results are shown in Table 5.

[0476] [Table 5]

Claims

1. A composition comprising a pigment (A), a resin (B), a leveling agent (C), and a solvent (D), The leveling agent (C) includes a block copolymer (C1) having an A block formed from a monomer unit (c1) represented by the following general formula (1) and a B block formed from a monomer unit (c2) other than the monomer unit (c1) represented by the general formula (1), The solvent (D) has a hydrogen bond term of the Hansen solubility parameter of 10 MPa. １／２ A composition comprising the above solvent (D1). General formula (1) 【Chemistry 1】 (In general formula (1), R １ are each independently an alkyl group having 1 to 6 carbon atoms, or —OSi(R ５ ) ３ A group represented by (R ５ are each independently an alkyl group having 1 to 3 carbon atoms. R ２ are each independently an alkyl group having 1 to 6 carbon atoms. R ３ is an alkyl group having 1 to 6 carbon atoms. R ４ is a hydrogen atom or a methyl group. L １ is a divalent organic group or a single bond. n is an integer from 1 to 70.

2. The composition according to claim 1, wherein the monomer unit (c2) other than the monomer unit (c1) represented by the general formula (1) includes at least one selected from the group consisting of a monomer unit (c2-1) represented by the following general formula (2) and a monomer unit (c2-2) represented by the following general formula (3): General formula (2) 【Chemistry 2】 (In general formula (2), R ６ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. R ７ is a hydrogen atom or a methyl group. m is an integer from 1 to 4. o is an integer from 2 to 200. General formula (3) 【Chemistry 43】 (In general formula (3), R ８ is an alicyclic hydrocarbon group having 3 to 20 carbon atoms. R ９ is a hydrogen atom or a methyl group.

3. The composition according to claim 1, wherein the content of the solvent (D1) is 0.01 to 20 mass% in 100 mass% of the composition.

4. The composition according to claim 1, wherein the solvent (D1) comprises at least one selected from the group consisting of propylene glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethyl lactate, cyclohexanol, 3-methoxy-1-butanol, ethylene glycol monoethyl ether, 1-butanol, methyl lactate, and water.

5. The composition according to claim 1 , further comprising a polymerizable compound (E) and a polymerization initiator (F).

6. A film formed from the composition according to any one of claims 1 to 5.

7. An optical filter comprising the film according to claim 6.

8. A solid-state imaging device comprising the optical filter according to claim 7.

9. An image display device comprising the optical filter according to claim 7.

10. An infrared sensor comprising the optical filter according to claim 7.

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