Resin composition, cured product and laminate

Abstract

To provide a resin composition comprising perylene black pigment that transmits near-infrared (NIR) radiation without absorbing LiDAR signals, wherein the pigment has good dispersibility in the resin and excellent hiding power due to black color development, and a paint comprising the resin composition has excellent ultraviolet (UV) curability (short-time curability) after application and drying thereof.SOLUTION: There is provided a resin composition comprising an inorganic fine particle composite (M) and perylene black pigment. The inorganic fine particle composite (M) comprises a composite resin (A) and inorganic fine particles (m). The composite resin (A) comprises: a polysiloxane segment (a1) having a group with a polymerizable double bond or an epoxy group; and a vinylic polymer segment (a2). The polysiloxane segment (a1) has a structural unit represented by general formula (1) and / or general formula (2) and a silanol group and / or a hydrolyzable silyl group. In the inorganic fine particle composite (M), the polysiloxane segment (a1) and the vinylic polymer segment (a2) are bonded via siloxane bonds, and the composite resin (A) and the inorganic fine particles (m) are bonded by a bond represented by the following general formula (4). (Descriptions in the formula are as set forth in this specification)SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition, a cured product of the resin composition, and a laminate having a coating film of the cured product.

Background Art

[0002] Black pigments are generally used to color paints, printing inks, plastics, glass, leather, or other materials black. As black pigments, carbon black, aniline black, iron oxide black, chromium oxide black, or a tricolor colorant mixture is known. Since these black pigments generally have the property of absorbing light having wavelengths from ultraviolet rays to far-infrared rays, that is, the infrared rays and thermal radiation of the sun, there is a problem that they are greatly heated by sunlight irradiation.

[0003] Being heated greatly as described above becomes a major problem such as affecting the cooling efficiency in the automotive field, such as vehicle body paints, especially in electric vehicles where energy conservation is emphasized. Further, in automobiles, in recent years, a laser beam has been used to measure the distance to a vehicle traveling ahead and to detect obstacles with high precision by a so-called LiDAR sensor. However, since the black pigment also absorbs the LiDAR signals (905 nm and 1550 nm), there is concern that the LiDAR sensor, which is also called the eye of an autonomous vehicle, may not function sufficiently.

[0004] Under the above circumstances, as a black pigment used for vehicle bodies in the automotive field and the like, a perylene black pigment that transmits near-infrared (NIR) light, which is difficult to absorb LiDAR signals (905 nm and 1550 nm), is used. However, the perylene black pigment has problems with dispersibility in resins. For example, in Patent Document 1 below, a black perylene pigment containing a mixture of two isomers is used. In Patent Document 2 below, as coloring pigments that reflect and / or transmit infrared light, organic pigments such as azo pigments, aniline black, and perylene black, and composite oxide pigments are used. In Patent Document 3 below, a black pigment having a core containing at least one organic black pigment selected from the group consisting of benzodifuranone-based black pigments, perylene-based black pigments, azo-based black pigments, and their isomers, and a coating layer containing silica, metal oxides, and / or metal hydroxides is used.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] When the present inventors examined the black pigments using perylene black of Patent Documents 1-3 above, they found that the dispersibility of the black pigments in resins was poor. They also found that there were problems with the hiding power due to black coloring and the ultraviolet (UV) curability after paint application and drying.

[0007] Accordingly, the problem to be solved by the present invention is to provide a resin composition that uses a perylene black pigment that transmits near-infrared rays (NIR) without absorbing LiDAR signals, has good dispersibility in resins, excellent black color development, and excellent ultraviolet (UV) curability (short-time curability) after paint application and drying.

Means for Solving the Problem

[0008] As a result of intensive research to solve the above problems, the present inventors have found that by using a specific inorganic fine particle composite composed of polysiloxane / colloidal silica / acrylic resin having an unsaturated double bond as a dispersing resin, the perylene black pigment can be stably dispersed without using a special dispersant, and it is excellent in concealability by color development and short-time curability, thus completing the present invention.

[0009] That is, the present invention relates to the following inventions. [1] A resin composition containing an inorganic fine particle composite (M) and a perylene black pigment, wherein the inorganic fine particle composite (M) is composed of a composite resin (A) and inorganic fine particles (m), the composite resin (A) contains a polysiloxane segment (a1) having a polymerizable double bond or an epoxy group and a vinyl-based polymer segment (a2), and the polysiloxane segment (a1) has a structural unit represented by General Formula (1) and / or General Formula (2), a silanol group, and / or a hydrolyzable silyl group.

Chemical Formula

Chemical Formula

[0010] Since the resin composition of the present invention uses a perylene black pigment, it can transmit near-infrared (NIR) without absorbing LiDAR signals. In addition, because a specific MFG resin is used, the dispersibility is good, and it is excellent in black color development and ultraviolet (UV) curability (short-time curability) after paint application and drying. [Embodiments for Carrying Out the Invention]

[0011] [Resin Composition] The resin composition of the present invention is a resin composition containing an inorganic fine particle composite (M) and a perylene black pigment, wherein the inorganic fine particle composite (M) is composed of a composite resin (A) and inorganic fine particles (m), the composite resin (A) contains a polysiloxane segment (a1) having a polymerizable double bond or an epoxy group and a vinyl-based polymer segment (a2), and the polysiloxane segment (a1) has a structural unit represented by the general formula (1) and / or the general formula (2) and a silanol group and / or a hydrolyzable silyl group. [Chemical formula] [Chemical formula] (In the general formulas (1) and (2), R 1 , R 2 and R 3 are each independently a group having a polymerizable double bond selected from the group consisting of -R 4 -CH=CH2, -R 4 -C(CH3)=CH2, -R 4 -O-CO-C(CH3)=CH2, and -R 4 -O-CO-CH=CH2, or a group represented by the following formula (3) (wherein R 4 represents a single bond or an alkylene group having 1 to 6 carbon atoms). [Chemical formula] (In the general formula (3), n1 is an integer represented by 1 to 5, and the structure Q represents either -CH=CH2 or -C(CH3)=CH2). In the inorganic fine particle composite (M), the polysiloxane segment (a1) is bonded via a siloxane bond. The composite resin (A) and the inorganic fine particles (m) are bonded by a bond represented by the following general formula (4). [Chemical formula] (In general formula (4), the carbon atom constitutes a part of the vinyl polymer segment (a2), and the silicon atom bonded only to the oxygen atom constitutes a part of the polysiloxane segment (a1).)

[0012] The inorganic particle composite (M) in the present invention is the above-described specific inorganic particle composite, and is an inorganic-organic hybrid resin in which a polysiloxane mainly composed of a hydrolysis condensate of alkoxysilane and an acrylic resin are chemically bonded. It acts as a dispersant for enhancing the dispersibility of the black pigment and also acts as a matrix resin for dispersing the pigment. In the resin composition of the present invention, a resin other than the inorganic particle composite (M) (for example, vinyl chloride acetate) may be used in combination.

[0013] (Perylene black pigment) As the perylene black pigment, known black organic pigments having a perylene structure can be used. For example, perylene black such as those shown in C.I. Pigment Black 31 and C.I. Pigment Black 32 can be used. Such perylene black may be used alone or in combination of two or more. Also, commercially available products of perylene black can be used. For example, Lumogen (registered trademark) Black FK4280 (manufactured by BASF), Paliogen (registered trademark) Black S0084 (BASF / C.I. Pigment Black 31), Spectrasense (registered trademark) Black L 0086, 0087, EH8082 (L0082), K0087, K0088, S0084, IR765 (manufactured by Sankyo Chemical Co., Ltd.), etc. can be used. The perylene black pigment can be used singly or in combination of two or more.

[0014] The above-mentioned perylene black pigment is preferably a black pigment represented by the following formula (I), (II), or (III), a black perylene-based pigment obtained by firing a diimide derivative of perylene tetracarboxylic acid or a diimide derivative of perylenediiminodicarboxylic acid, or a black pigment containing one isomer represented by the following formula (VI) or a mixture of two isomers of (V).

Chemical formula

Chemical formula

[0015] Examples of R 5 and R 6 in the compound represented by formula (I) include a butyl group, a phenylethyl group, a methoxyethyl group, and a 4-methoxyphenylmethyl group. Preferred examples of R 3 and R 4is a phenylene group, 3-methoxyphenylene group, 4-methoxyphenylene group, 4-ethoxyphenylene group, C1-C3 alkylphenylene group, hydroxyphenylene group, 4,6-dimethylphenylene group, 3,5-dimethylphenylene group, 3-chlorophenylene group, 4-chlorophenylene group, 5-chlorophenylene group, 3-bromophenylene group, 4-bromophenylene group, 5-bromophenylene group, 3-fluorophenylene group, 4-fluorophenylene group, 5-fluorophenylene group, 2,3-pyridinediyl group, 3,4-pyridinediyl group, 4-methyl-2,3-pyridinediyl group, 5-methyl-2,3-pyridinediyl group, 6-methyl-2,3-pyridinediyl group, 5-methyl-3,4-pyridinediyl group, 4-methoxy-2,3-pyridinediyl group, 4-chloro-2,3-pyridinediyl group and naphthalenediyl group. More preferred R 7 and R 8 are a phenylene group, 2,3-pyridinediyl group, 3,4-pyridinediyl group. The method for producing the perylene black pigment represented by the above formulas (I), (II), and (III) will be described. One compound selected from the group of compounds is calcined in a vacuum or an inert gas atmosphere at a temperature of usually 200 to 600 °C, preferably 450 to 550 °C, for usually 0.5 to 2 hours, preferably 1 to 2 hours. Examples of the inert gas used include helium and argon. The obtained calcined product is subjected to a normal finishing treatment such as grinding treatment to obtain a perylene black pigment.

[0016] The perylene black pigment obtained by heating and reacting 2-methyl-2,4-pentanediol and nitric acid represented by the above formulas (I), (II), and (III) can be produced by the method described in JP-A-2006-328238.

[0017] In addition, the perylene black pigment in the present invention contains one or a mixture of two isomers represented by the above formula (IV) or (V) and has a black value of 210 or more in an alkyd / melamine baking paint. This perylene black pigment can be produced by the method described in JP-A-2007-522297.

[0018] The average particle diameter (cumulant average particle diameter) of the perylene black pigment is preferably 200 nm or less, more preferably 170 nm or less. This is because if the average particle diameter is 200 nm or less, the perylene black pigment has excellent dispersibility. However, even if the average particle diameter is 170 nm or less, it is necessary that the pigment does not aggregate over time (dispersion stability). From the viewpoints of dispersion stability and light shielding property, etc., the average particle diameter is preferably 50 nm or more.

[0019] The content of the perylene black pigment is preferably 2% by mass or more and 25% by mass or less, more preferably 3% by mass or more and 15% by mass or less, based on the total mass of the resin composition. If it is less than 2% by mass, the coloring may be insufficient due to the low pigment concentration. If it exceeds 25% by mass, the viscosity becomes high, and problems such as poor handleability are likely to occur. Also, the content of the perylene black pigment is preferably 3 parts by mass or more and 30 parts by mass or less, more preferably 4 parts by mass or more and 25 parts by mass or less, based on 100 parts by mass of the inorganic fine particle composite (M).

[0020] Other pigments other than the perylene black pigment may be used as long as the property of transmitting near-infrared rays (NIR) without absorbing the LiDAR signal is not impaired. Examples of other pigments include various black pigments (such as carbon black), red pigments, blue pigments, purple pigments, and yellow pigments. The ratio of the inorganic fine particle composite (M) in the total pigments is, for example, 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more.

[0021] [Inorganic fine particle composite (M)] The above composite resin (A) is characterized in that it is a composite resin (A) in which a polysiloxane segment (a1) (hereinafter simply referred to as the polysiloxane segment (a1)) having a structural unit represented by the general formula (1) and / or the general formula (2) and a silanol group and / or a hydrolyzable silyl group is bonded to a vinyl-based polymer segment (a2) by a bond represented by the general formula (4). The inorganic fine particle composite (M) can be used alone or in combination of two or more.

[0022] The polysiloxane segment (a1) is a segment obtained by condensing a silane compound having a silanol group and / or a hydrolyzable silyl group, and has a structural unit represented by the general formula (1) and / or the general formula (2), and a silanol group and / or a hydrolyzable silyl group. The content of the polysiloxane segment (a1) is preferably 10 to 90% by weight based on the total solid content of the composite resin (A) because it facilitates bonding with the inorganic fine particles (m) described below.

[0023] It has a structural unit represented by the following general formulas (1) and (2) and a silanol group and / or a hydrolyzable silyl group.

Chemical formula

Chemical formula

[0024] R in the above general formulas (1) and (2) 1 , R 2 and R 3 are each independently a polymerizable double bond-containing group selected from the group consisting of -R 4 -CH=CH2, -R 4 -C(CH3)=CH2, -R 4 -O-CO-C(CH3)=CH2, and -R 4 -O-CO-CH=CH2, or a group represented by the following formula (3) (wherein R 4 represents a single bond or an alkylene group having 1 to 6 carbon atoms), an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, an aralkyl group having 7 to 12 carbon atoms, or an epoxy group.

Chemical formula

[0025] The structural unit represented by the general formula (1) and / or the general formula (2) is a three-dimensional network polysiloxane structural unit in which two or three of the silicon bonds are involved in crosslinking. Since it does not form a dense network structure while forming a three-dimensional network structure, it does not cause gelation or the like and has good storage stability.

[0026] R in the general formulas (1) and (2) 1 , R 2 and R 3 In, R 4 Examples of the alkylene group having 1 to 6 carbon atoms in R include methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, pentylene group, isopentylene group, neopentylene group, tert-pentylene group, 1-methylbutylene group, 2-methylbutylene group, 1,2-dimethylpropylene group, 1-ethylpropylene group, hexylene group, isohexylene group, 1-methylpentylene group, 2-methylpentylene group, 3-methylpentylene group, 1,1-dimethylbutylene group, 1,2-dimethylbutylene group, 2,2-dimethylbutylene group, 1-ethylbutylene group, 1,1,2-trimethylpropylene group, 1,2,2-trimethylpropylene group, 1-ethyl-2-methylpropylene group, 1-ethyl-1-methylpropylene group, etc. Among them, R 4 is preferably a single bond or an alkylene group having 2 to 4 carbon atoms from the viewpoint of easy availability of raw materials.

[0027] In addition, examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 1,2-dimethylpropyl group, a 1-ethylpropyl group, a hexyl group, an isohexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 1,1-dimethylbutyl group, a 1,2-dimethylbutyl group, a 2,2-dimethylbutyl group, a 1-ethylbutyl group, a 1,1,2-trimethylpropyl group, a 1,2,2-trimethylpropyl group, a 1-ethyl-2-methylpropyl group, a 1-ethyl-1-methylpropyl group, and the like.

[0028] In addition, examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.

[0029] In addition, examples of the aryl group include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-vinylphenyl group, a 3-isopropylphenyl group, and the like. Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, a diphenylmethyl group, a naphthylmethyl group, and the like.

[0030] R 1 、R 2 and R 3 If at least one of them has a polymerizable double bond, it can be cured by active energy rays or the like. Due to the two curing mechanisms of active energy rays and the condensation reaction of silanol groups and / or hydrolyzable silyl groups, the crosslink density of the obtained cured product becomes high, and a cured product having more excellent abrasion resistance and low linear expansion can be formed. Groups having a conjugated double bond are preferably present in the polysiloxane segment (a1) in an amount of two or more, more preferably 3 to 200, still more preferably 3 to 50, and a molded article with lower linear expansion can be obtained. Specifically, if the content of the conjugated double bond in the polysiloxane segment (a1) is 3 to 35% by weight, the desired linear expansion rate can be obtained. Here, the conjugated double bond is a general term for groups capable of undergoing a growth reaction by free radicals among vinyl groups, vinylidene groups, or vinylene groups. Further, the content of the conjugated double bond indicates the weight percentage in the polysiloxane segment of the vinyl group, vinylidene group, or vinylene group. As the group having a conjugated double bond, all known functional groups containing the vinyl group, vinylidene group, or vinylene group can be used. Among them, -R 4 -C(CH3)=CH2 or -R 4 The (meth)acryloyl group represented by -O-CO-C(CH3)=CH2 is rich in reactivity during ultraviolet curing and has good compatibility with the vinyl polymer segment (a2) described later.

[0031] When the group having a conjugated double bond is a group represented by the above general formula (3), the structure Q in the formula indicates that a plurality of vinyl groups may be bonded to the aromatic ring. For example, when two Qs are bonded to the aromatic ring,

Chemical formula

[0032] Since the structure represented by the styryl group does not contain an oxygen atom, oxidative decomposition based on the oxygen atom hardly occurs and the thermal decomposition resistance is high, so it is suitable for applications requiring heat resistance. This is presumably because the reaction of being oxidized is inhibited by the bulky structure. Further, for improving the heat resistance, it is also preferable to have a group having a conjugated double bond selected from the group consisting of -R 4 -CH=CH2, -R 4 -C(CH3)=CH2.

[0033] In the polysiloxane segment (a1), in the formula, R 1 , R 2 and R 3 If at least one of them is an epoxy group, it can be cured by thermosetting or active energy ray curing. Due to the two curing mechanisms of the epoxy group and the condensation reaction of the silanol group and / or the hydrolyzable silyl group, the crosslink density of the resulting cured product becomes high, and a cured product having a more excellent low coefficient of linear expansion can be formed.

[0034] In the present invention, the silanol group is a silicon-containing group having a hydroxyl group directly bonded to a silicon atom. Specifically, the silanol group is preferably a silanol group formed by bonding a hydrogen atom to an oxygen atom having a bond in a structural unit represented by the general formula (1) and / or the general formula (2).

[0035] In the present invention, the hydrolyzable silyl group is a silicon-containing group having a hydrolyzable group directly bonded to a silicon atom, and specifically, for example, a group represented by the general formula (6) can be mentioned.

Chemical formula

[0036] R 11Among them, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 1,2-dimethylpropyl group, a 1-ethylpropyl group, a hexyl group, an isohexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 1,1-dimethylbutyl group, a 1,2-dimethylbutyl group, a 2,2-dimethylbutyl group, a 1-ethylbutyl group, a 1,1,2-trimethylpropyl group, a 1,2,2-trimethylpropyl group, a 1-ethyl-2-methylpropyl group, a 1-ethyl-1-methylpropyl group, and the like. Examples of the aryl group include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-vinylphenyl group, a 3-isopropylphenyl group, and the like. Examples of the aralkyl group include a benzyl group, a diphenylmethyl group, a naphthylmethyl group, and the like.

[0037] R 12 Among them, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group, and the like. Examples of the acyloxy group include formyloxy, acetoxy, propanoyloxy, butanoyloxy, pivaloyloxy, pentanoyloxy, phenylacetoxy, acetoacetoxy, benzoyloxy, naphthoyloxy, and the like. Examples of the aryloxy group include phenyloxy, naphthyloxy, and the like. Examples of the alkenyloxy group include a vinyloxy group, an allyloxy group, a 1-propenyloxy group, an isopropenyloxy group, a 2-butenyloxy group, a 3-butenyloxy group, a 2-pentenyloxy group, a 3-methyl-3-butenyloxy group, a 2-hexenyloxy group, and the like.

[0038] R 12 When the hydrolyzable group represented by is hydrolyzed, the hydrolyzable silyl group represented by the general formula (6) becomes a silanol group. Among them, a methoxy group and an ethoxy group are preferable because of their excellent hydrolyzability. Specifically, the hydrolyzable silyl group is preferably a hydrolyzable silyl group in which an oxygen atom having a bond in the structural unit represented by the general formula (1) and / or the general formula (2) is bonded or substituted with a hydrolyzable group.

[0039] Since a hydrolysis condensation reaction proceeds between the hydroxyl group in the silanol group and the hydrolyzable group in the hydrolyzable silyl group, the crosslinking density of the polysiloxane structure increases, and a cured product having excellent abrasion resistance and low linear expansion can be formed. It is used when bonding a polysiloxane segment (a1) containing a silanol group or a hydrolyzable silyl group and a vinyl polymer segment (a2) described later via a bond represented by the general formula (3).

[0040] The polysiloxane segment (a1) is not particularly limited as long as it has a structural unit represented by the general formula (1) and / or the general formula (2) and a silanol group and / or a hydrolyzable silyl group, and may contain other groups. For example, R in the general formula (1) 1 is a structural unit having a polymerizable double bond, and R in the general formula (1) 1 is a polysiloxane segment (a1) in which a structural unit having an alkyl group such as methyl coexists, or R in the general formula (1) 1 is a structural unit having a polymerizable double bond, and R in the general formula (1) 1 is a polysiloxane segment (a1) in which a structural unit having an alkyl group such as a methyl group coexists, and R in the general formula (2) 2 and R 3 is a polysiloxane segment (a1) in which a structural unit having an alkyl group such as a methyl group coexists, or R in the general formula (1) 1a structural unit having a polymerizable double bond and R in the general formula (2) 2 and R 3 It may be a polysiloxane segment (a1) in which a structural unit having an alkyl group such as a methyl group coexists, and there is no particular limitation.

[0041] The vinyl polymer segment (a2) in the present invention is a polymer segment obtained by polymerizing a vinyl group or a (meth)acrylic group-containing monomer, and examples thereof include a vinyl polymer segment, an acrylic polymer segment, and a vinyl / acrylic copolymer segment. These are preferably appropriately selected depending on the application. Since the inorganic fine particle composite (M) has a vinyl polymer segment (a2), it has excellent film-forming properties even when inorganic fine particles are blended.

[0042] For example, the acrylic polymer segment is obtained by polymerizing or copolymerizing a general-purpose (meth)acrylic monomer. There is no particular limitation on the (meth)acrylic monomer, and examples thereof include alkyl (meth)acrylates having an alkyl group with 1 to 22 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate; aralkyl (meth)acrylates such as benzyl (meth)acrylate and 2-phenylethyl (meth)acrylate; cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; ω-alkoxyalkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate and 4-methoxybutyl (meth)acrylate; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl pivalate, and vinyl benzoate; alkyl esters of crotonic acid such as methyl crotonate and ethyl crotonate; and dialkyl esters of unsaturated dibasic acids such as dimethyl maleate, di-n-butyl maleate, dimethyl fumarate, and dimethyl itaconate.

[0043] For example, specific examples of the vinyl polymer segment include an aromatic vinyl polymer segment, a polyolefin polymer, a fluoroolefin polymer, etc., and their copolymers may also be used. To obtain these vinyl polymers, vinyl group-containing monomers may be polymerized. Specifically, α-olefins such as ethylene, propylene, 1,3-butadiene, cyclopentylethylene; vinyl compounds having an aromatic ring such as styrene, 1-ethynyl-4-methylbenzene, divinylbenzene, 1-ethynyl-4-methylethylbenzene, benzonitrile, acrylonitrile, p-tert-butylstyrene, 4-vinylbiphenyl, 4-ethynylbenzyl alcohol, 2-ethynylnaphthalene, phenanthrene-9-ethynyl; fluoroolefins such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, etc. can be preferably used. More preferably, they are styrene and p-tert-butylstyrene which are vinyl compounds having an aromatic ring.

[0044] A vinyl / acrylic copolymer segment obtained by copolymerizing a (meth)acrylic monomer and a vinyl group-containing monomer may also be used.

[0045] There are no particular limitations on the polymerization method, solvent, or polymerization initiator when copolymerizing the monomers, and the vinyl polymer segment (a2) can be obtained by known methods. For example, the vinyl polymer segment (a2) can be obtained using polymerization initiators such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), tert-butyl peroxypivalate, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide, cumene hydroperoxide, diisopropyl peroxydicarbonate, etc. by various polymerization methods such as bulk radical polymerization method, solution radical polymerization method, non-aqueous dispersion radical polymerization method, etc.

[0046] The number average molecular weight of the vinyl polymer segment (a2) is preferably in the range of 500 to 200,000 in terms of the number average molecular weight (hereinafter abbreviated as Mn), which can prevent thickening and gelation during the production of the composite resin (A) and has excellent durability. Among them, the range of 700 to 100,000 is more preferable, and the range of 1,000 to 50,000 is even more preferable.

[0047] The vinyl polymer segment (a2) is a composite resin (A) bonded by a bond represented by the general formula (4) to the polysiloxane segment (a1). Therefore, in the vinyl polymer segment (a2), it has a silanol group directly bonded to a carbon atom and / or a hydrolyzable silyl group. Since these silanol groups and / or hydrolyzable silyl groups will form a bond represented by the general formula (4) in the composite resin (A), they hardly exist in the vinyl polymer segment (a2) in the final product composite resin (A). However, even if silanol groups and / or hydrolyzable silyl groups remain in the vinyl polymer segment (a2), there is no problem at all. When curing the inorganic particle composite (M) containing the present composite resin (A), a hydrolysis condensation reaction proceeds between the hydroxyl group in the silanol group and the hydrolyzable group in the hydrolyzable silyl group. Therefore, the crosslinking density of the polysiloxane structure of the obtained cured product increases, and a cured product excellent in heat resistance and wear resistance can be formed.

[0048] To introduce a silanol group directly bonded to a carbon atom and / or a hydrolyzable silyl group into the vinyl polymer segment (a2), specifically, when polymerizing the vinyl polymer segment (a2), a vinyl monomer and a (meth) acrylic monomer are used. A vinyl monomer containing a silanol group directly bonded to a carbon bond and / or a hydrolyzable silyl group may be used in combination. Examples of the vinyl monomer containing a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon atom include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyltri(2-methoxyethoxy)silane, vinyltriacetoxysilane, vinyltrichlorosilane, 2-trimethoxysilylethyl vinyl ether, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropyltrichlorosilane, and the like. Among them, vinyltrimethoxysilane and 3-(meth)acryloyloxypropyltrimethoxysilane are preferred because the hydrolysis reaction can proceed easily and the by-products after the reaction can be easily removed.

[0049] The vinyl polymer segment (a2) may have various functional groups. For example, it may have a group having a polymerizable double bond, an epoxy group, an alcoholic hydroxyl group, etc. To introduce them, a vinyl monomer having a corresponding functional group may be blended during polymerization.

[0050] Examples of the vinyl monomer having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, vinyl cyclohexene oxide, glycidyl vinyl ether, methyl glycidyl vinyl ether, or allyl glycidyl ether.

[0051] Examples of the vinyl monomer having an alcoholic hydroxyl group include various hydroxyalkyl esters of α,β-ethylenically unsaturated carboxylic acids such as (2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl monobutyl fumarate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, "Placcel FM or Placcel FA" [caprolactone-added monomer manufactured by Daicel Chemical Industries, Ltd.], or an adduct of these and ε-caprolactone.

[0052] The inorganic fine particles (m) used in the present invention are not particularly limited as long as the effects of the present invention are not impaired. However, since they are bonded via a siloxane bond to the polysiloxane segment (a1), they have a functional group capable of forming a siloxane bond. The functional group capable of forming a siloxane bond may be any functional group capable of forming a siloxane bond, such as a hydroxyl group, a silanol group, an alkoxysilyl group, etc. The inorganic fine particles (m) themselves may have the functional group capable of forming a siloxane bond, or the functional group may be introduced by modifying the inorganic fine particles (m). As a method for modifying the inorganic fine particles (m), a known and commonly used method may be used, such as a method of treating with a silane coupling agent or coating with a resin having a functional group capable of forming a siloxane bond.

[0053] Examples of the inorganic fine particles (m) include, for those with excellent heat resistance, alumina, magnesia, titania, zirconia, silica (quartz, fumed silica, precipitated silica, anhydrous silicic acid, fused silica, crystalline silica, ultrafine amorphous silica, etc.); for those with excellent thermal conductivity, boron nitride, aluminum nitride, aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, etc.; for those with excellent conductivity, a metal filler and / or a metal-coated filler using a simple metal or an alloy (e.g., iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.); for those with excellent barrier properties, minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, smectite, etc., and potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, magnesium hydroxide; for those with a high refractive index, barium titanate, zirconia oxide, titanium oxide, etc.; for those exhibiting photocatalytic properties, photocatalytic metals such as titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, tellurium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, lead, etc., composites of the above metals, their oxides, etc.; for those with excellent abrasion resistance, metals such as silica, alumina, zirconia, magnesium, etc., and their composites and oxides, etc.; for those with excellent conductivity, metals such as silver, copper, etc., tin oxide, indium oxide, etc.; for those with excellent insulation properties, silica, etc.; for those with excellent ultraviolet shielding properties, titanium oxide, zinc oxide, etc. These inorganic fine particles (m) may be appropriately selected according to the application and may be used alone or in combination of multiple types. In addition, since the above inorganic fine particles (m) have various properties other than those listed as examples, they may be selected according to the application in a timely manner.

[0054] For example, when using silica as the inorganic fine particles (m), there is no particular limitation, and known silica fine particles such as powdery silica and colloidal silica can be used. Examples of commercially available powdery silica fine particles include Aerosil 50, 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, H122 manufactured by Asahi Glass Co., Ltd., E220A, E220 manufactured by Nippon Silica Industry Co., Ltd., SYLYSIA 470 manufactured by Fuji Silysia Chemical Ltd., SG Flake manufactured by Nippon Sheet Glass Co., Ltd., and the like. Examples of commercially available colloidal silica include methanol silica sol, IPA-ST, PGM-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc. manufactured by Nissan Chemical Industries, Ltd.

[0055] Silica fine particles with surface modification may also be used. For example, those obtained by surface-treating silica fine particles with a reactive silane coupling agent having a hydrophobic group, or those modified with a compound having a (meth)acryloyl group can be mentioned. Examples of commercially available powdery silica modified with a compound having a (meth)acryloyl group include Aerosil RM50, R7200, R711, etc. manufactured by Nippon Aerosil Co., Ltd. Examples of commercially available colloidal silica modified with a compound having a (meth)acryloyl group include MIBK-SD, MEK-SD, etc. manufactured by Nissan Chemical Industries, Ltd. Examples of colloidal silica surface-treated with a reactive silane coupling agent having a hydrophobic group include MIBK-ST, MEK-ST, etc. manufactured by Nissan Chemical Industries, Ltd.

[0056] The shape of the silica fine particles is not particularly limited, and spherical, hollow, porous, rod-shaped, plate-shaped, fibrous, or irregularly shaped particles can be used. For example, as commercially available hollow silica fine particles, Silenax manufactured by Nippon Steel & Sumitomo Metal Corporation can be used.

[0057] As the titanium oxide fine particles, not only extender pigments but also ultraviolet light-responsive photocatalysts can be used. For example, anatase-type titanium oxide, rutile-type titanium oxide, brookite-type titanium oxide, etc. can be used. Furthermore, particles designed to respond to visible light by doping a heterogeneous element into the crystal structure of titanium oxide can also be used. As the element to be doped into titanium oxide, anion elements such as nitrogen, sulfur, carbon, fluorine, phosphorus, etc. and cation elements such as chromium, iron, cobalt, manganese, etc. are preferably used. Also, as the form, powders, sols or slurries dispersed in an organic solvent or water can be used. Examples of commercially available powdered titanium oxide fine particles include Aerosil P-25 manufactured by Nippon Aerosil Co., Ltd., ATM-100 manufactured by Tayca Corporation, etc. Examples of commercially available slurry-type titanium oxide fine particles include TKD-701 manufactured by Tayca Corporation, etc.

[0058] In the inorganic fine particles (m), the primary particle diameter is preferably in the range of 5 to 200 nm. When it is 5 nm or more, the inorganic fine particles (m) in the dispersion are well dispersed, and if the diameter is within 200 nm, the strength of the cured product is good. More preferably, it is 10 nm to 100 nm. Here, the "particle diameter" is measured using a scanning electron microscope (TEM) or the like.

[0059] The inorganic fine particle composite (M) can be produced by the method described in International Publication No. 2014 / 175369 through Step 1 of synthesizing a vinyl-based polymer segment (a2) having a silanol group, Step 2 of mixing an alkoxysilane and inorganic fine particles (m), and Step 3 of subjecting the alkoxysilane to a condensation reaction.

[0060] When the silanol groups and / or hydrolyzable silyl groups of the aforementioned polysiloxane segment (a1) and the silanol groups and / or hydrolyzable silyl groups of the aforementioned vinyl polymer segment (a2) undergo a dehydration condensation reaction, a bond represented by the general formula (4) is formed. Therefore, in the general formula (4), the carbon atoms constitute a part of the vinyl polymer segment (a2), and the silicon atom bonded only to the oxygen atom constitutes a part of the polysiloxane segment (a1). Also, by condensing in a state where a silanol group and / or hydrolyzable silyl group-containing silane compound and inorganic fine particles (m) are mixed, a siloxane bond is formed between the silanol group and / or hydrolyzable silyl group-containing silane compound and the inorganic fine particles (m), and the polysiloxane segment (a1) and the inorganic fine particles (m) are chemically bonded.

[0061] In the composite resin (A), the bonding position between the polysiloxane segment (a1) and the vinyl polymer segment (a2) is arbitrary. For example, a composite resin having a graft structure in which the polysiloxane segment (a1) is chemically bonded as a side chain of the polymer segment (a2), a composite resin having a block structure in which the polymer segment (a2) and the polysiloxane segment (a1) are chemically bonded, and the like can be mentioned.

[0062] As the silanol group and / or the silane compound containing a hydrolyzable silyl group, general-purpose silane compounds can be used. For example, various organotrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, iso-butyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane; various diorganodialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, methylcyclohexyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane; chlorosilanes such as methyltrichlorosilane, ethyltrichlorosilane, vinyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane or the like.

[0063] Tetrafunctional alkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane or tetra-n-propoxysilane, and partial hydrolysis condensates of the tetrafunctional alkoxysilane compounds can also be used in combination within a range not impairing the effects of the present invention. When using the tetrafunctional alkoxysilane compound or its partial hydrolysis condensate in combination, it is preferable to use it in such a range that the silicon atoms of the tetrafunctional alkoxysilane compound do not exceed 20 mol% with respect to all the silicon atoms constituting the polysiloxane segment (a1).

[0064] In the silane compound, metal alkoxide compounds other than silicon atoms such as boron, titanium, zirconium or aluminum can also be used in combination within a range not impairing the effects of the present invention. For example, it is preferable to use it in such a range that the metal atoms of the above metal alkoxide compounds do not exceed 25 mol% with respect to all the silicon atoms constituting the polysiloxane segment (a1).

[0065] Examples of the monoalkyltrialkoxysilane having an alkyl group with 1 to 4 carbon atoms include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, butyltriethoxysilane, etc., and methyltrimethoxysilane is preferred.

[0066] In addition, examples of the silane compound having both a group having a polymerizable double bond and a silanol group and / or a hydrolyzable silyl group, which is used when introducing a group having a polymerizable double bond, include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyltri(2-methoxyethoxy)silane, vinyltriacetoxysilane, vinyltrichlorosilane, 2-trimethoxysilylethyl vinyl ether, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropyltrichlorosilane, etc. Among them, vinyltrimethoxysilane and 3-(meth)acryloyloxypropyltrimethoxysilane are preferred because the hydrolysis reaction can proceed easily and the by-products after the reaction can be removed easily.

[0067] In addition, to introduce an epoxy group into the polysiloxane segment (a1), an epoxy group-containing silane compound may be used. Examples of the epoxy group-containing silane compound include those described in International Publication No. 2014 / 175369.

[0068] In addition, to introduce the group represented by the formula (3) into the polysiloxane segment (a1), a silane compound having the group represented by the formula (3) may be used. Specific examples of the silane compound having the group represented by the formula (3) include p-styryltrimethoxysilane and p-styryltriethoxysilane.

[0069] Part or all of the silanol group and / or hydrolyzable silyl group-containing silane compound to be mixed with the inorganic fine particles (m) may be hydrolytically condensed. Further, a dispersion medium may be used for the purpose of adjusting the solid content and viscosity. The dispersion medium may be any liquid medium that does not impair the effects of the present invention, and examples thereof include various organic solvents, water, liquid organic polymers, and monomers.

[0070] Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); cyclic ethers such as tetrahydrofuran (THF) and dioxolane; esters such as methyl acetate, ethyl acetate, and butyl acetate; aromatics such as toluene and xylene; and alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether, and normal propyl alcohol. These can be used alone or in combination.

[0071] Examples of the resin other than the inorganic fine particle composite (M) include thermoplastic resins and thermosetting resins, and a reactive compound may be appropriately contained in inks and paints. Examples of the thermoplastic resin include vinyl chloride, polyurethane, polyethylene, polypropylene, polyvinyl acetate, ABS, AS, and acrylic resins. Examples of the thermosetting resin include phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, and silicone resin.

[0072] When the above resin is included, the proportion of the inorganic fine particle composite (M) in the entire resin excluding the perylene pigment is, for example, 30 to 99% by mass, preferably 50 to 98% by mass, more preferably 60 to 97% by mass.

[0073] [Inks and Paints] The ink and paint of the present invention are not particularly limited as long as they contain a resin composition. Since the resin composition of the present invention has inorganic fine particles (m) strongly bonded to the resin and excellent dispersion stability, it can be suitably used as an ink and a paint. As the ink and paint, it is particularly preferable for automobile bodies because it transmits near-infrared (NIR) without absorbing LiDAR signals. The ink and paint may contain components such as a reactive compound, a curing accelerator, a dispersion medium, and a leveling agent in addition to the resin composition.

[0074] The reactive compound is a polymer or monomer having a reactive group that directly contributes to the curing reaction with the inorganic fine particle composite (M). When the inorganic fine particle composite (M) has a reactive group, a resin composition using a reactive compound having a group that reacts with the reactive group has no problems of bleed-out or plasticization from the cured product because the inorganic fine particle composite (M) and the reactive compound form a three-dimensional crosslink, and a cured product particularly excellent in weather resistance and abrasion resistance can be obtained.

[0075] When using polyisocyanate as the reactive compound, it is preferable that the vinyl polymer segment (a2) in the composite resin (A) has an alcoholic hydroxyl group. The polyisocyanate at that time is preferably contained in an amount of 5 to 50% by weight based on the total amount of the inorganic fine particle composite of the present invention. By containing polyisocyanate in this range, a cured product particularly excellent in long-term weather resistance (specifically, crack resistance) outdoors can be obtained. This is presumably because polyisocyanate reacts with the hydroxyl groups in the system (these are the hydroxyl groups in the vinyl polymer segment (a2) and the hydroxyl groups in the active energy ray curable monomer having an alcoholic hydroxyl group described later), and the urethane bond, which is a soft segment, is formed, which serves to relieve the stress concentration due to the curing of the polymerizable double bond.

[0076] The polyisocyanate to be used is not particularly limited and known ones can be used. However, polyisocyanates mainly composed of aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane-4,4'-diisocyanate, and aralkyl diisocyanates such as meta-xylylene diisocyanate and α,α,α',α'-tetramethyl-meta-xylylene diisocyanate have the problem that the cured coating film turns yellow upon long-term outdoor exposure, so it is preferable to minimize the amount used.

[0077] It is preferable that the isocyanate groups in the polyisocyanate be 3 to 30% by weight from the viewpoints of crack resistance and abrasion resistance of the cured coating film obtained when used as a paint. When the isocyanate groups in the polyisocyanate are more than 30%, the molecular weight of the polyisocyanate becomes small, and there is a possibility that the crack resistance due to stress relaxation may not be exhibited. The reaction between the polyisocyanate and the hydroxyl groups in the system (these are the hydroxyl groups in the vinyl polymer segment (a2) and the hydroxyl groups in the active energy ray-curable monomer having an alcoholic hydroxyl group described later) does not particularly require heating or the like, and the reaction proceeds gradually by leaving it at room temperature. Further, if necessary, heating may be performed at 80°C for several minutes to several hours (20 minutes to 4 hours) to accelerate the reaction between the alcoholic hydroxyl group and the isocyanate. In that case, a known urethanization catalyst may be used as necessary. The urethanization catalyst is appropriately selected according to the desired reaction temperature.

[0078] When using an active energy ray-curable monomer as the reactive compound, it is preferable to contain a polyfunctional vinyl-based monomer characterized by having a plurality of vinyl-based reaction groups. There are no particular limitations on the polyfunctional vinyl-based monomer, and known ones such as polyfunctional vinyl monomers and polyfunctional (meth)acrylic monomers can be used. For example, 1,2-ethanediol diacrylate, 1,2-propanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, tris(2-acryloyloxy) isocyanurate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, di(trimethylolpropane) tetraacrylate, di(pentaerythritol) pentaacrylate, di(pentaerythritol) hexaacrylate, and other polyfunctional (meth)acrylates having two or more polymerizable double bonds in one molecule can be mentioned. Also, urethane acrylate, polyester acrylate, epoxy acrylate, etc. can also be exemplified as polyfunctional acrylates. These may be used alone or in combination of two or more. For example, when using the aforementioned polyisocyanate in combination, acrylates having a hydroxyl group such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate are preferable. Also, in order to further increase the crosslinking density, it is also effective to use (meth)acrylates having a particularly high number of functional groups such as di(pentaerythritol) pentaacrylate and di(pentaerythritol) hexaacrylate. Also, for the purpose of improving abrasion resistance, it is preferable to use a polyvalent (meth)acrylate having an isocyanurate structure. Specifically, tris(2-acryloyloxyethyl) isocyanurate, ε-caprolactone-modified tris(2-acryloyloxyethyl) isocyanurate, isocyanuric acid EO-modified diacrylate, etc. can be mentioned.

[0079] A monofunctional vinyl monomer can also be used in combination. For example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, caprolactone-modified hydroxy (meth)acrylate (e.g., manufactured by Daicel Corporation, trade name "Placcel"), mono (meth)acrylate of polyester diol obtained from phthalic acid and propylene glycol, mono (meth)acrylate of polyester diol obtained from succinic acid and propylene glycol, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, pentaerythritol tri (meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, (meth)acrylic acid adducts of various epoxy esters, etc., hydroxyl group-containing (meth)acrylic acid esters; carboxyl group-containing vinyl monomers such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc.; sulfonic acid group-containing vinyl monomers such as vinyl sulfonic acid, styrene sulfonic acid, sulfoethyl (meth)acrylate, etc.; acidic phosphate ester-based vinyl monomers such as 2-(meth)acryloyloxyethyl acid phosphate, 2-(meth)acryloyloxypropyl acid phosphate, 2-(meth)acryloyloxy-3-chloro-propyl acid phosphate, 2-methacryloyloxyethyl phenyl phosphate, etc.; vinyl monomers having a methylol group such as N-methylol (meth)acrylamide, etc. These can be used alone or in combination of two or more.

[0080] As the reactive compound in the case of containing an epoxy group, known curing agents for epoxy resins can be used. For example, phenolic compounds such as phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zylok resin), naphthol aralkyl resin, trimethylolmethane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (a polyhydric phenol compound in which phenol nuclei are linked by bismethylene groups), biphenyl-modified naphthol resin (a polyhydric naphthol compound in which phenol nuclei are linked by bismethylene groups), aminotriazine-modified phenol resin (a polyhydric phenol compound in which phenol nuclei are linked by melamine, benzoguanamine, etc.), and alkoxy group-containing aromatic ring-modified novolak resin (a polyhydric phenol compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked by formaldehyde); acid anhydride compounds such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride; amide compounds such as dicyandiamide, polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine; amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivative, etc.

[0081] If necessary, a curing accelerator can also be appropriately used in combination with the above reactive compound. Various curing accelerators can be used. For example, phosphorus compounds, tertiary amines, imidazoles, metal organic salts, Lewis acids, amine complex salts, etc. can be mentioned. Particularly, from the viewpoints of excellent curability, heat resistance, electrical properties, moisture resistance reliability, etc., 2-ethyl-4-methylimidazole is preferred among imidazole compounds, triphenylphosphine is preferred among phosphorus compounds, and 1,8-diazabicyclo-[5.4.0]-undecene (DBU) is preferred among tertiary amines.

[0082] When using the reactive compound, the amount used is preferably 1 to 85% by weight, more preferably 5 to 80% by weight, based on the total solid content in the resin composition containing the inorganic fine particle composite (M). By using the reactive compound within the above range, physical properties such as the hardness of the obtained layer can be improved.

[0083] (Dispersion medium) The ink and paint of the present invention may use a dispersion medium for the purpose of adjusting the solid content and viscosity. The dispersion medium may be any liquid medium that does not impair the effects of the present invention, and various aqueous solvents, organic solvents, liquid organic polymers, etc. can be mentioned.

[0084] Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); cyclic ethers such as tetrahydrofuran (THF) and dioxolane; esters such as methyl acetate, ethyl acetate, and butyl acetate; aromatics such as toluene and xylene; and alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether, and normal propyl alcohol. These can be used alone or in combination, and among them, methyl ethyl ketone is preferred from the viewpoints of volatility during coating and solvent recovery.

[0085] A liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction. Examples include carboxyl group-containing polymer modifiers (Floren G-900, NC-500: Kyoeisha), acrylic polymers (Floren WK-20: Kyoeisha), amine salts of special modified phosphate esters (HIPLAAD ED-251: Enomoto Kasei), modified acrylic block copolymers (DISPERBYK 2000; BYK Chemie), and the like.

[0086] In addition to the above, the inks and paints of the present invention may contain leveling agents, polymerization initiators, coupling agents such as silane coupling agents, photosensitizers, polymerization inhibitors, defoamers, surface modifiers other than leveling agents, viscosity modifiers, light stabilizers, weather stabilizers, heat stabilizers, ultraviolet absorbers, antioxidants, organic pigments, inorganic pigments, pigment dispersants, and other additives; inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, and antimony pentoxide. These components can be used alone or in combination of two or more.

[0087] (Leveling Agent) A leveling agent is used to adjust the surface tension of the coating film and smooth the surface of the coating film. The presence of the leveling agent lowers the surface tension (surface energy) of the coating film and increases the water contact angle, resulting in less adhesion of dirt and the like, and imparting antifouling properties to the cured coating film.

[0088] Examples of leveling agents include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoroalkyl ethylene oxide derivatives, polyethylene glycol derivatives, alkyl ammonium salts, fluoroalkyl ammonium salts, and the like. Among them, fluorine compound-based leveling agents containing fluorine atoms, such as fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, fluoroalkyl ethylene oxide derivatives, and fluoroalkyl ammonium salts, are preferred.

[0089] As the leveling agent, commercially available products can also be used. Examples of commercially available products include those described in International Publication No. 2014 / 175369.

[0090] When using a leveling agent, the ratio of the leveling agent to the total solid content is preferably 0.0001 to 3 parts by mass, more preferably 0.0005 to 1 part by mass, and even more preferably 0.001 to 0.1 part by mass.

[0091] (Polymerization initiator) The ink and paint of the present invention can be made into a cured coating film by irradiating active energy rays after being applied on a substrate. This active energy ray refers to ionizing radiation such as ultraviolet rays, electron beams, α-rays, β-rays, γ-rays, etc., and ultraviolet rays are widely used industrially. The polymerization initiator is contained in the composition of the present invention to initiate the polymerization reaction of compound (A) in response to the irradiation of active energy rays, and compounds generally known as photopolymerization initiators can be used. Examples of the photopolymerization initiator include those described in International Publication No. 2014 / 175369. Commercially available products of the polymerization initiator can also be those described in International Publication No. 2014 / 175369.

[0092] The blending amount of the polymerization initiator component is preferably 0.05 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 15 parts by mass with respect to 100 parts by mass in total of the solid content of the inorganic fine particle composite (M) and the reactive compound in the ink or paint.

[0093] (Coupling agent) The ink and paint of the present invention may contain a coupling agent. The coupling agent is not particularly limited as long as it is a compound capable of bonding a plurality of materials, and a compound generally known as a coupling agent can be used. Among them, a silane coupling agent is preferable. Examples of the silane coupling agent include those described in WO 2014 / 175369. When the ink and paint of the present invention contain a coupling agent, the blending amount can be 0.001 to 10 parts by mass based on 100 parts by mass in total with the pigment.

[0094] The ink and paint of the present invention are suitable for applications that require infrared transmissivity, such as black matrices and column spacers in color filters of liquid crystals and organic EL displays, black bank materials for organic EL displays, optical windows for infrared camera lenses, applications for coloring the optical path black before reaching the heat fusion interface during heat adhesion of plastic parts with an infrared laser, and colorants for heat insulating paints by solar light reflection. The above infrared cameras are assumed to be those mounted on in-vehicle distance sensors such as LiDAR, iris authentication for biometric authentication, and sensors for vein authentication.

[0095] [Cured product] The cured product of the present invention is obtained by curing a resin composition-containing product. The resin composition of the present invention can be used as it is as a component of ink and paint, but can also be cured and used as a cured product. As the curing method, a known and commonly used curing method may be selected. The cured product of the present invention can also be used in the applications mentioned for the ink and paint of the present invention above.

[0096] When the polysiloxane segment (a1) of the inorganic fine particle composite (M) is cured via a silanol group and / or a hydrolyzable silyl group, heat curing may be performed. In heat curing, it is possible to heat and cure alone, but it is also possible to use a known curing catalyst as follows in combination. For example, inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate, and acetic acid; inorganic bases such as sodium hydroxide or potassium hydroxide; titanate esters such as tetraisopropyl titanate and tetrabutyl titanate; 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole, 1-methylimidazole and other compounds containing various basic nitrogen atoms; various quaternary ammonium salts such as tetramethylammonium salts, tetrabutylammonium salts, and dilauryl dimethylammonium salts, which are quaternary ammonium salts having chloride, bromide, carboxylate or hydroxide as a counter anion; tin carboxylates such as dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetylacetonate, tin octylate or tin stearate. The catalyst may be used alone or in combination of two or more.

[0097] In addition, when the vinyl polymer segment (a2) contains an alcoholic hydroxyl group and the composition further contains an isocyanate group-containing compound, a urethanization reaction can be caused by adding a catalyst. When the vinyl polymer segment (a2) or the polysiloxane segment (a1) has a group having a polymerizable double bond, it can be reacted by using a thermal polymerization initiator. When the vinyl polymer segment (a2) or the polysiloxane segment (a1) has an epoxy group, it can be reacted by blending a compound having an epoxy group, a hydroxyl group, a carboxyl group or an acid anhydride, or an amide group, and a general curing agent for epoxy resin can be used.

[0098] It is also possible to use a thermosetting resin in combination. Examples of the thermosetting resin include vinyl resins, unsaturated polyester resins, polyurethane resins, epoxy resins, epoxy ester resins, acrylic resins, phenolic resins, petroleum resins, ketone resins, silicone resins, or modified resins thereof.

[0099] In the inorganic fine particle composite (M), when the vinyl polymer segment (a2) or the polysiloxane segment (a1) has a polymerizable unsaturated group, it is possible to photocure by blending a photoinitiator into the heat-resistant material. As the photocuring, ultraviolet curing is preferable.

[0100] Known photoinitiators may be used. For example, one or more selected from the group consisting of acetophenones, benzyl ketals, and benzophenones can be preferably used. Examples of the acetophenones include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and the like. Examples of the benzyl ketals include 1-hydroxycyclohexyl-phenyl ketone, benzyldimethyl ketal, and the like. Examples of the benzophenones include benzophenone, methyl o-benzoylbenzoate, and the like. Examples of the benzoins and the like include benzoin, benzoin methyl ether, benzoin isopropyl ether, and the like. The photoinitiator may be used alone or in combination of two or more.

[0101] When performing ultraviolet curing, a polyfunctional (meth)acrylate may be blended as necessary, and since the curing density is improved, the heat resistance is improved. Also, a monofunctional (meth)acrylate may be used.

[0102] When performing ultraviolet curing, light sources such as low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, argon lasers, helium-cadmium lasers, and ultraviolet light-emitting diodes can be used.

[0103] [Laminate] The laminate of the present invention contains the above-mentioned cured product. By forming a coating film of the cured product of the present invention on a substrate constituting a vehicle body, a display, etc., a laminate can be obtained. The substrate is not particularly limited, and examples include plastics, glass, high-tensile steel sheets, aluminum, wood, inorganic substances, leather, and artificial leather. The substrate may have been coated or surface-treated, etc. Among the substrates, plastic substrates are particularly preferable because the inorganic fine particle composite (M) has a vinyl polymer segment (a2), and thus has excellent adhesion to the substrate.

[0104] Since the cured product of the laminate of the present invention is excellent in water resistance, weather resistance, abrasion resistance, light resistance, etc., it can also be used as a protective film with high hard coat properties. In particular, when the inorganic fine particle composite (M) has a group having a polymerizable double bond, photocuring is possible. Therefore, even a plastic that is relatively weak to heat can be easily coated, and since it has excellent light resistance, it can be suitably used for polycarbonate, etc. that are prone to yellowing.

[0105] The method for manufacturing the laminate is not particularly limited. The ink and paint of the present invention may be applied to a substrate and then cured, or the ink and paint may be cured into a sheet shape, etc., and then attached to the substrate. As the coating method, the sheet manufacturing method, etc., known and commonly used methods may be used. Examples of the laminate of the present invention include members that are black or require infrared transmissivity, such as color filters and column spacers of liquid crystals and organic EL displays, and organic EL displays.

Examples

[0106] Hereinafter, the present invention will be described more specifically by way of examples. Unless otherwise specified, “%” means “mass %” and “parts” means “parts by mass”.

[0107] Details of the compounds used in the examples and comparative examples are as shown in Tables 1 to 4 below.

[0108] [Table 1]

[0109] [Table 2]

[0110] [Table 3]

[0111] [Table 4]

[0112] (Synthesis Example 1) Preparation of Vinyl Polymer Segment (a2) Into a reaction vessel similar to that in Synthesis Example 1, 20.1 parts of PTMS as a silane compound, 24.4 parts of DMDMS, and 107.7 parts of MIBK as a solvent were charged. While purging with nitrogen gas and stirring, the temperature was raised to 95°C.

[0113] Next, a mixture containing 1.5 parts of AA, 1.5 parts of BA, 30.6 parts of MMA, 29.4 parts of BMA, 75 parts of CHMA, 7.5 parts of HEMA, 4.5 parts of MPTS, 6.8 parts of TBPEH, and 15 parts of MIBK was added dropwise into the reaction vessel at the same temperature with nitrogen gas flowing through while stirring over 4 hours. Then, it was further stirred at the same temperature for 2 hours to obtain a reaction solution containing a vinyl polymer with a number average molecular weight of 5800 and a hydroxyl value (OHv) of 64.7 mg KOH / g. A mixture of 0.06 part of "A-4" and 12.8 parts of deionized water was added dropwise into the reaction vessel over 5 minutes and stirred at the same temperature for 5 hours to promote the hydrolysis and condensation reaction of the silane compound. When the reaction product was analyzed by 1H-NMR, almost 100% of the trimethoxysilyl groups of the silane monomer in the reaction vessel had hydrolyzed. Then, by stirring at the same temperature for 10 hours, a vinyl polymer segment (a2) with a remaining amount of TBPEH of 0.1% or less was obtained.

[0114] (Preparation Example 1) Preparation of Dispersion of Inorganic Particles (m) 651.5 parts of MTMS, 1188.2 parts of MPTS, 1450.4 parts of Aerosil 200, 0.8 part of "A-4", 258.7 parts of deionized water, and 1450.4 parts of MIBK were blended and dispersed using an Ultra Apex Mill UAM015 manufactured by Kotobuki Industries Co., Ltd. In preparing the dispersion, 100-μm zirconia beads were filled as media in the mill at 70% of the mill volume, and the formulation was circulated and pulverized at a peripheral speed of 10 m / s and a flow rate of 1.5 liters per minute. The circulation and pulverization were carried out for 30 minutes to obtain a dispersion of inorganic particles (m) in which silica particles were dispersed in the mixture.

[0115] (Synthesis Example 2) Synthesis of Inorganic Fine Particle Composite (M) To 336.8 parts of the vinyl polymer segment (a2), 886.3 parts of the dispersion of inorganic particles (m) were added, and the mixture was stirred for 5 minutes. Then, 14.7 parts of deionized water was added, and the mixture was stirred at 80°C for 4 hours to carry out a hydrolysis condensation reaction between the vinyl polymer segment and the silane compound. The reaction product obtained was distilled for 2 hours under reduced pressure of 1 to 30 kPa at 40 to 60°C to remove the methanol and water produced, and then PGM was added to obtain an inorganic fine particle composite (M) (solid content 50.0%) in which the silica content was 33% by weight and the inorganic particles (m) were bonded.

[0116] Example 1 50 parts of the inorganic microparticle composite (M) obtained in Synthesis Example 2, 2.5 parts of Spectrasense Black L0086 (manufactured by Sun Chemical Co.), and 60 parts of zirconia particles having a diameter of 2 mm as a medium were dispersed in a paint conditioner, and the dispersion was terminated when the grind meter value (GM value), which is an index of the degree of dispersion, became less than 5 μm, thereby obtaining a resin composition (1). The obtained resin composition (1) was subjected to various evaluations, and the results are shown in Table 5 below.

[0117] [Evaluation of dispersibility of resin composition] (GM value) After starting dispersion of the resin composition (1), the GM value (the value in μm at which streaks occur) was measured every hour for a maximum of 3 hours, and a value of 5 μm or less was deemed to be acceptable. (Coatability) After the start of dispersion of the resin composition (1), the resin composition was applied to a stretched polymer film having a thickness of 75 μm every hour. The wet film thickness is 10 μm on polyethylene film (Toray Lumirror 75-U48). The coating was performed using a bar coater as shown in the figure, and the condition of the coated surface (streaks, hiding power, unevenness) was observed. . ◎: No abnormalities whatsoever. O: There is an abnormality in one of the items. △: Two or more are abnormal. ×: An abnormality occurred in all cases.

[0118] [Evaluation of the laminate] To 100 parts by solid content of the resin composition (1), 4 parts of a photoinitiator (Runtecure 1104, manufactured by Runtech Chemical) was added, and the mixture was uniformly stirred. The resulting mixture was applied onto a stretched polyethylene film (Lumirror 75-U48, manufactured by Toray Industries, Inc.) with a film thickness of 75 μm. After volatilizing the solvent, under a mercury lamp with a lamp output of 1 kW, at an irradiation dose of about 400 mJ / cm 2 , the laminate was obtained by irradiating with ultraviolet rays. (UV curability) Laminates were prepared so that the DRY film thicknesses were 7 μm and 12 μm, and the curability of the coated surface at each film thickness was observed by finger touch. ○: Finger-touch dry (tack-free) state. ×: Tack remains. (Total light transmittance) Using a haze meter NDH 5000 manufactured by Nippon Denshoku Industries Co., Ltd., the total light transmittance (%) was evaluated according to ASTM D 1003. ◎: 5% or less 〇: More than 5% and less than 10% ×: 10% or more (Transmittance at each wavelength) Using a spectrophotometer V-770DS manufactured by JASCO Corporation, the light transmittances at 365 nm, 905 nm, and 1550 nm were evaluated.

[0119] (Examples 2 to 4, Comparative Examples 2 and 3) Resin compositions (2) to (4), (6), and (7) were obtained in the same manner as the resin composition (1) except that the composition shown in Table 5 was changed. Each evaluation was carried out, and the results are described in Table 5.

[0120] (Comparative Example 1) 50 parts of vinyl chloride acetate (Solvaine A), 1.25 parts of Spectrasense Black EH8082 (manufactured by Sankyo Chemical Co., Ltd.), 4 parts of MEK, and 60 parts of zirconia particles with a diameter of 2 mm as a medium were dispersed for 3 hours using a paint conditioner to obtain a resin composition (5). The obtained resin composition (5) was applied onto a stretched polyethylene film (Lumirror 75-U48 manufactured by Toray Industries, Inc.) with a film thickness of 75 μm, and then heat-treated at 120°C for 30 seconds to obtain a laminate. Except for the evaluation of UV curability, each evaluation was performed in the same manner as in Example 1, and the results are shown in Table 5.

[0121]

Table 5

[0122] From the results of Examples 1 to 4 in Table 5 above, it was confirmed that the resin composition of the present invention is excellent in the dispersibility of perylene pigments in the resin and cures without impairing the UV curability even with a relatively thick film. Also, in the laminate, it was confirmed that the laminate transmits near-infrared rays (NIR) required for LiDAR signals (905 nm, 1550 nm). On the other hand, it was confirmed that Comparative Examples 1 to 3 are inferior in at least one of the characteristics.

Claims

1. A resin composition containing an inorganic fine particle composite (M) and a perylene black pigment, wherein the inorganic fine particle composite (M) is composed of a composite resin (A) and inorganic fine particles (m), the composite resin (A) includes a polysiloxane segment (a1) having a polymerizable double bond or an epoxy group and a vinyl-based polymer segment (a2), the polysiloxane segment (a1) has a structural unit represented by General Formula (1) and / or General Formula (2) and a silanol group and / or a hydrolyzable silyl group, 【Chemical Formula 1】 【Chemical Formula 2】 (In General Formulas (1) and (2), R 1 , R 2 and R 3 are each independently -R 4 -CH=CH 2 , -R 4 -C(CH 3 )=CH 2 , -R 4 -O-CO-C(CH 3 )=CH 2 , and -R 4 -O-CO-CH=CH 2 , or a group having a polymerizable double bond selected from the group consisting of the groups represented by the following formula (3) (wherein R 4 represents a single bond or an alkylene group having 1 to 6 carbon atoms)) 【Chemical Formula 3】 (In General Formula (3), n1 is an integer represented by 1 to 5, and the structure Q represents either -CH=CH 2 or -C(CH 3 )=CH 2 )) In the inorganic fine particle composite (M), the polysiloxane segment (a1) is bonded via a siloxane bond, A resin composition in which the composite resin (A) and the inorganic fine particles (m) are bonded by a bond represented by the following general formula (4). 【Chemical Formula 4】 (In general formula (4), the carbon atom constitutes a part of the vinyl polymer segment (a2), and the silicon atom bonded only to the oxygen atom constitutes a part of the polysiloxane segment (a1).)

2. The resin composition according to claim 1, wherein the inorganic fine particles (m) are silica.

3. The resin composition according to claim 1, wherein the perylene black pigment is a black pigment represented by the following formula (I), (II), or (III), a diimide derivative of perylene tetracarboxylic acid, a diimide derivative of perylene diiminodicarboxylic acid, a black perylene-based pigment obtained by firing treatment, or a black pigment containing one or a mixture of two isomers represented by the following formula (VI) or (V). 【Chemical Formula 5】 (In formula (I), R 5 and R 6 are each the same and each represents a butyl group, a phenylethyl group, a methoxyethyl group, a 4-methoxyphenylmethyl group, or a 3,5-dimethylphenyl group. In formulas (II) and (III), R 7 and R 8 may be the same or different and each represents a phenylene group, an alkylphenylene group, an alkoxyphenylene group, a hydroxyphenylene group, a halogenated phenylene group, a pyridinediyl group, an alkylpyridinediyl group, an alkoxypyridinediyl group, a halogenated pyridinediyl group, or a naphthalenediyl group, and are bonded at adjacent positions of the aromatic ring.) 【Chemical Formula 6】 (In formulas (IV) and (V), R 9 , R 10 are each independently phenylene, naphthylene, or pyridylene, and these may each be monosubstituted or polysubstituted by an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, nitro, and / or a halogen, X is a halogen, and n2 is an integer from 0 to 4.)

4. Inks and paints containing the resin composition according to any one of claims 1 to 3.

5. A cured product containing the resin composition according to any one of claims 1 to 3.

6. A laminate having a coating film of the cured product according to claim 5.

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