CN118234768A - Active energy ray-curable resin composition, cured coating film, and article - Google Patents

Active energy ray-curable resin composition, cured coating film, and article Download PDF

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CN118234768A
CN118234768A CN202280070665.2A CN202280070665A CN118234768A CN 118234768 A CN118234768 A CN 118234768A CN 202280070665 A CN202280070665 A CN 202280070665A CN 118234768 A CN118234768 A CN 118234768A
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acrylate
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active energy
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桐泽理惠
井上直人
向井隆
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DIC Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D155/00—Coating compositions based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09D123/00 - C09D153/00

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Abstract

The present invention provides an active energy ray-curable resin composition comprising a composite resin (A) wherein a polysiloxane segment (a 1) having a specific structural unit and a silanol group and/or a hydrolyzable silyl group is bonded to a vinyl polymer segment (a 2) by a specific bond, an acrylic (meth) acrylate resin (B) having a weight average molecular weight of 10,000 ～ 70,000, and a photopolymerization initiator (C). The active energy ray-curable resin composition can form a coating film excellent in appearance, adhesion, solvent resistance, scratch resistance, weather resistance, stain resistance and processability, and therefore can be used as a coating agent or an adhesive.

Description

Active energy ray-curable resin composition, cured coating film, and article
Technical Field
The present invention relates to an active energy ray-curable resin composition, a cured coating film, and an article.
Background
In recent years, thermoplastic resin materials represented by plastics have been widely used in the fields of construction, automobiles, and the like from the viewpoint of excellent lightweight, impact resistance, processability, and recyclability. However, since the weather resistance, stain resistance, heat resistance, solvent resistance, yellowing resistance and the like are poor, a coating layer is often provided to supplement the performance.
As such a coating layer, there has been proposed a uv-curable resin composition containing an inorganic-organic composite resin (for example, refer to patent document 1). The ultraviolet-curable resin composition contains a composite resin having a polysiloxane segment and a vinyl polymer segment, and is excellent in weather resistance, heat resistance, solvent resistance, scratch resistance, and the like, but has a problem that it is poor in substrate following property, and therefore cracks are generated during processing with high design properties and processing after coating.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2006-328354
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide an active energy ray-curable resin composition, a cured coating film and an article, wherein the active energy ray-curable resin composition can form a coating film with excellent appearance, adhesiveness, solvent resistance, scratch resistance, weather resistance, stain resistance and processability.
Means for solving the problems
The present inventors have made intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by using an active energy ray-curable resin composition comprising a specific composite resin, a specific acrylic (meth) acrylate resin and a photopolymerization initiator, and have completed the present invention.
Specifically, the present invention relates to an active energy ray-curable resin composition, a cured coating film, and an article, wherein the active energy ray-curable resin composition comprises a composite resin (A), an acrylic (meth) acrylate resin (B), and a photopolymerization initiator (C), wherein the composite resin (A) is formed by bonding a polysiloxane segment (a 1) and a vinyl polymer segment (a 2) through a bond represented by a general formula (3), and the polysiloxane segment (a 1) has a structural unit represented by a general formula (1) and/or a general formula (2), and a silanol group and/or a hydrolyzable silyl group, and the weight average molecular weight of the acrylic (meth) acrylate resin (B) is 10,000 ～ 70,000.
[ Chemical formula 1]
[ Chemical formula 2]
(In the general formulae (1) and (2), R 1、R2 and R 3 each independently represent 1 group having a polymerizable double bond (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, or an aralkyl group having 7 to 12 carbon atoms) selected from -R4-CH＝CH2、-R4-C(CH3)＝CH2、-R4-O-CO-C(CH3)＝CH2 and-R 4-O-CO-CH＝CH2
[ Chemical formula 3]
(In the general formula (3), a carbon atom forms part of the vinyl-based polymer segment (a 2), and a silicon atom bonded to only an oxygen atom forms part of the polysiloxane segment (a 1)
Effects of the invention
The active energy ray-curable resin composition of the present invention can form a cured coating film excellent in appearance, adhesion, solvent resistance, scratch resistance, weather resistance, stain resistance and processability of the coating film, and therefore can be used as a coating agent or an adhesive, and in particular, can be suitably used as a coating agent.
Detailed Description
The active energy ray-curable resin composition of the present invention comprises a composite resin (A) wherein a polysiloxane segment (a 1) and a vinyl polymer segment (a 2) are bonded by a bond represented by the general formula (3), an acrylic (meth) acrylate resin (B) having a silanol group and/or a hydrolyzable silyl group, and a weight average molecular weight of 10,000 ～ 70,000, and a photopolymerization initiator (C), wherein the polysiloxane segment (a 1) has a structural unit represented by the general formula (1) and/or the general formula (2).
The composite resin (a) is a composite resin in which a polysiloxane segment (a 1) 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 (hereinafter, simply referred to as a polysiloxane segment (a 1)) and a vinyl polymer segment (a 2) having an alcoholic hydroxyl group (hereinafter, simply referred to as a vinyl polymer segment (a 2)) are bonded by a bond represented by the general formula (3).
The silanol group and/or hydrolyzable silyl group of the polysiloxane segment (a 1) described later and the silanol group and/or hydrolyzable silyl group of the vinyl polymer segment (a 2) described later undergo dehydration condensation reaction to produce a bond represented by the general formula (3) described above. Therefore, in the general formula (3), the carbon atom forms a part of the vinyl-based polymer segment (a 2), and only the silicon atom bonded to the oxygen atom forms a part of the polysiloxane segment (a 1).
Examples of the form of the composite resin (a) include: a composite resin having a graft structure in which the polysiloxane segment (a 1) is chemically bonded to the side chain of the polymer segment (a 2), a composite resin having a block structure in which the polymer segment (a 2) is chemically bonded to the polysiloxane segment (a 1), and the like.
The polysiloxane segment (a 1) is a segment 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. The structural unit represented by the general formula (1) and/or the general formula (2) contains a group having a polymerizable double bond.
The structural unit represented by the general formula (1) and/or the general formula (2) contains a group having a polymerizable double bond as an essential component.
Specifically, R 1、R2 and R 3 in the general formulae (1) and (2) each independently represent 1 group having a polymerizable double bond (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, or an aralkyl group having 7 to 12 carbon atoms, selected from -R4-CH＝CH2、-R4-C(CH3)＝CH2、-R4-O-CO-C(CH3)＝CH2 and-R 4-O-CO-CH＝CH2, and at least 1 of R 1、R2 and R 3 is the group having a polymerizable double bond. Examples of the alkylene group having 1 to 6 carbon atoms in R 4 include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, sec-butylene, tert-butylene, pentylene, isopentylene, neopentylene, tert-pentylene, 1-methylbutylene, 2-methylbutylene, 1, 2-dimethylpropylene, 1-ethylpropylene, hexylene, isohexylene, 1-methylpentylene, 2-methylpentylene, 3-methylpentylene, 1-dimethylbutylene, 1, 2-dimethylbutylene, 2-dimethylbutylene, 1-ethylbutylene, 1, 2-trimethylpropylene, 1, 2-trimethylpropylene, 1-ethyl-2-methylpropylene, and 1-ethyl-1-methylpropylene. Among them, R 4 is preferably a single bond or an alkylene group having 2 to 4 carbon atoms, from the viewpoint of easiness in obtaining the raw material.
Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, 2-methylbutyl, 1, 2-dimethylpropyl, 1-ethylpropyl, hexyl, isohexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 2-dimethylbutyl, 1-ethylbutyl, 1, 2-trimethylpropyl, 1, 2-trimethylpropyl, 1-ethyl-2-methylpropyl, 1-ethyl-1-methylpropyl and the like.
Examples of the cycloalkyl group having 3 to 8 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of the aryl group include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-vinylphenyl, and 3-isopropylphenyl.
Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl, diphenylmethyl, naphthylmethyl and the like.
In addition, at least 1 of R 1、R2 and R 3 is the above group having a polymerizable double bond, specifically, R 1 is the above group having a polymerizable double bond when the polysiloxane segment (a 1) has only a structural unit represented by the general formula (1), R 2 and/or R 3 is the above group having a polymerizable double bond when the polysiloxane segment (a 1) has only a structural unit represented by the general formula (2), and at least 1 of R 1、R2 and R 3 is the group having a polymerizable double bond when the polysiloxane segment (a 1) has both structural units represented by the general formula (1) and the general formula (2).
The polymerizable double bond is preferably present in the polysiloxane segment (a 1) in an amount of 2 or more, more preferably 3 to 200, still more preferably 3 to 50, and a coating film excellent in durability can be obtained. Specifically, if the content of the polymerizable double bond in the polysiloxane segment (a 1) is 3 to 35% by weight, desired weather resistance and adhesion can be obtained. The polymerizable double bond herein refers to a group capable of undergoing a radical-based growth reaction in vinyl, vinylidenyl (Japanese-original: eugenol), or 1, 2-vinylidene (Japanese-original: eugenol). The content of the polymerizable double bond represents the weight% of the vinyl group, the vinylidene group, or the 1, 2-vinylidene group in the polysiloxane segment.
As the group having a polymerizable double bond, all known functional groups containing the vinyl group, the vinylidene group, and the 1, 2-vinylidene group can be used, and among them, the (meth) acryloyl group represented by-R 4-C(CH3)＝CH2、-R4-O-CO-C(CH3)＝CH2 is preferable in terms of reactivity at the time of ultraviolet curing, good compatibility with a vinyl-based polymer segment (a 2) described later, and excellent transparency, and a cured coating film can be obtained.
The structural units represented by the general formula (1) and/or the general formula (2) are three-dimensional network-like polysiloxane structural units obtained by crosslinking 2 or 3 of the silicon bond bonds. Since a three-dimensional network structure is formed but a dense network structure is not formed, gelation and the like do not occur at the time of manufacturing or forming a primer, and storage stability is also good.
In the present invention, silanol group means 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 an oxygen atom having a bond to a hydrogen atom of the structural unit represented by the general formula (1) and/or the general formula (2).
In the present invention, the hydrolyzable silyl group refers to a silicon-containing group having a hydrolyzable group directly bonded to a silicon atom, and specifically, examples thereof include groups represented by the general formula (4).
[ Chemical formula 4]
(In the general formula (4), R 5 is a 1-valent organic group such as an alkyl group, an aryl group, or an aralkyl group, and R 6 is a hydrolyzable group selected from a halogen atom, an alkoxy group, an acyloxy group, a phenoxy group, an aryloxy group, a mercapto group, an amino group, an amide group, an aminooxy group, an iminooxy group, and an alkenyloxy group.
And b is an integer of 0 to 2. )
Examples of the alkyl group for R 5 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, 2-methylbutyl, 1, 2-dimethylpropyl, 1-ethylpropyl, hexyl, isohexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 2-dimethylbutyl, 1-ethylbutyl, 1, 2-trimethylpropyl, 1, 2-trimethylpropyl, 1-ethyl-2-methylpropyl, 1-ethyl-1-methylpropyl and the like.
Examples of the aryl group include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-vinylphenyl, and 3-isopropylphenyl.
Examples of the aralkyl group include benzyl, diphenylmethyl, and naphthylmethyl.
Examples of the halogen atom in R 6 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy and the like.
Examples of the acyloxy group include formyloxy, acetoxy, propionyloxy, butyryloxy, pivaloyloxy, valeryloxy, phenylacetyloxy, acetoacetyloxy, benzoyloxy, and naphthoyloxy.
Examples of the aryloxy group include a phenoxy group and a naphthoxy group.
Examples of the alkenyloxy group include vinyloxy group, allyloxy group, 1-propenyloxy group, isopropenyloxy group, 2-butenyloxy group, 3-butenyloxy group, 2-pentenyloxy group, 3-methyl-3-butenyloxy group, and 2-hexenyloxy group.
The hydrolyzable group represented by R 6 is hydrolyzed, whereby the hydrolyzable silyl group represented by the general formula (4) becomes a silanol group. Among them, methoxy and ethoxy are preferable in view of excellent hydrolyzability.
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 to or substituted with the hydrolyzable group.
In the case of forming a coating film by a curing reaction of the silanol group and the hydrolyzable silyl group with the group having a polymerizable double bond, a hydrolytic condensation reaction occurs between the hydroxyl group in the silanol group and the hydrolyzable group in the hydrolyzable silyl group in parallel with the curing reaction, and thus the crosslinking density of the polysiloxane structure of the obtained coating film is increased, and a coating film excellent in solvent resistance and the like can be formed.
The present invention is also applicable to bonding a polysiloxane segment (a 1) containing the silanol group and the hydrolyzable silyl group to a vinyl polymer segment (a 2) described below via a bond represented by the general formula (3).
The polysiloxane segment (a 1) is not particularly limited, and may contain other groups, except for having structural units represented by the above general formula (1) and/or the above general formula (2) and silanol groups and/or hydrolyzable silyl groups. For example, the number of the cells to be processed,
A polysiloxane segment (a 1) in which a structural unit in which R 1 in the general formula (1) is the group having a polymerizable double bond and a structural unit in which R 1 in the general formula (1) is an alkyl group such as a methyl group coexist,
A polysiloxane segment (a 1) in which R 1 in the general formula (1) is a structural unit of the group having a polymerizable double bond, R 1 in the general formula (1) is a structural unit of an alkyl group such as a methyl group, and R 2 and R 3 in the general formula (2) are structural units of an alkyl group such as a methyl group,
The polysiloxane segment (a 1) may be one in which the structural unit in which R 1 in the general formula (1) is the group having a polymerizable double bond and the structural unit in which R 2 and R 3 in the general formula (2) are alkyl groups such as methyl groups coexist, and is not particularly limited.
Specifically, examples of the polysiloxane segment (a 1) include a segment having the following structure.
[ Chemical formula 5]
[ Chemical formula 6]
[ Chemical formula 7]
[ Chemical formula 8]
[ Chemical formula 9]
[ Chemical formula 10]
[ Chemical formula 11]
[ Chemical formula 12]
[ Chemical formula 13]
The vinyl polymer segment (a 2) is a vinyl polymer segment such as an acrylic polymer, a fluoroolefin polymer, a vinyl ester polymer, an aromatic vinyl polymer, or a polyolefin polymer, and among these, an acrylic polymer segment is preferable in view of excellent transparency and gloss of the obtained coating film.
The acrylic polymerizable segment is obtained by polymerizing or copolymerizing a general-purpose (meth) acrylic monomer. The (meth) acrylic monomer is not particularly limited, and a vinyl monomer may be copolymerized. Examples thereof include alkyl (meth) acrylates having an alkyl group having 1 to 22 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-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; omega-alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate and 4-methoxybutyl (meth) acrylate; aromatic vinyl monomers such as styrene, p-t-butylstyrene, α -methylstyrene, and vinyltoluene; vinyl esters of carboxylic acids such as vinyl acetate, vinyl propionate, vinyl pivalate, and vinyl benzoate; alkyl esters of crotonic acid such as methyl crotonate and ethyl crotonate; dialkyl esters of unsaturated dibasic acids such as dimethyl maleate, di-n-butyl maleate, dimethyl fumarate and dimethyl itaconate; alpha-olefins such as ethylene and propylene; fluoroolefins such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene; alkyl vinyl ethers such as ethyl vinyl ether and n-butyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether; and tertiary amide group-containing monomers such as N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidine and N-vinylpyrrolidone (Japanese text: 3-stage A/D group).
Further, from the viewpoint of improving adhesion to a plastic substrate, the vinyl polymer segment (a 2) is more preferably a (meth) acrylic repeating unit having a cyclic hydrocarbon group. The (meth) acrylic repeating unit having a cyclic hydrocarbon group may preferably be a (meth) acrylic ester having a cyclic hydrocarbon group such as cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecyl (meth) acrylate, tetracyclododecyl (meth) acrylate, dicyclopentanyl (meth) acrylate, or isobornyl acrylate. They may be used singly or in combination of 2 or more.
The polymerization method, solvent, or polymerization initiator used in copolymerizing the above monomers is not particularly limited, and the vinyl polymer segment (a 2) can be obtained by a known method. For example, the vinyl polymer segment (a 2) can be obtained by various polymerization methods such as a bulk radical polymerization method, a solution radical polymerization method, and a non-aqueous dispersion radical polymerization method, and using a polymerization initiator such as 2,2' -azobis (isobutyronitrile), 2' -azobis (2, 4-dimethylvaleronitrile), 2' -azobis (2-methylbutyronitrile), t-butyl peroxypivalate, t-butyl peroxybenzoate, t-butyl peroxy2-ethylhexanoate, di-t-butyl peroxide, cumene hydroperoxide, and diisopropyl peroxycarbonate.
The number average molecular weight of the vinyl polymer segment (a 2) is preferably 500 to 200,000 in terms of a number average molecular weight (hereinafter abbreviated as Mn), and thickening and gelation at the time of producing the composite resin (a) can be prevented, and the durability is excellent. Among them, mn is more preferably in the range of 700 to 100,000, and is more preferably 1,000 to 50,000 from the reasons of coating suitability and adhesion to a substrate, which will be described later.
In order to form the composite resin (a) by bonding the polysiloxane segment (a 1) to the bond represented by the general formula (3), the vinyl polymer segment (a 2) has a silanol group and/or a hydrolyzable silyl group directly bonded to a carbon bond in the vinyl polymer segment (a 2). Since these silanol groups and/or hydrolyzable silyl groups become bonds represented by the general formula (3) in the production of the composite resin (a) described later, they are hardly present in the vinyl polymer segment (a 2) in the composite resin (a) as a final product. However, even if silanol groups and/or hydrolyzable silyl groups remain in the vinyl-based polymer segment (a 2), there is no problem in that, in the formation of a coating film by the curing reaction of the above-mentioned group having a polymerizable double bond, in parallel with the curing reaction, a hydrolytic condensation reaction proceeds between hydroxyl groups in silanol groups and the above-mentioned hydrolyzable groups in hydrolyzable silyl groups, and therefore, the crosslinking density of the polysiloxane structure of the obtained coating film is improved, and a coating film excellent in durability can be formed.
Specifically, the vinyl polymer segment (a 2) having a silanol group and/or a hydrolyzable silyl group directly bonded to carbon is obtained by copolymerizing the above-mentioned general-purpose monomer and a vinyl monomer containing a silanol group and/or a hydrolyzable silyl group directly bonded to carbon.
Examples of the vinyl monomer containing a silanol group and/or a hydrolyzable silyl group bonded directly to a carbon bond include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriacetoxysilane, vinyltrichlorosilane, 2-trimethoxysilylethyl vinyl ether, 3- (meth) acryloxypropyl trimethoxysilane, 3- (meth) acryloxypropyl triethoxysilane, 3- (meth) acryloxypropyl methyldimethoxysilane, and 3- (meth) acryloxypropyl trichlorosilane. Among them, vinyltrimethoxysilane and 3- (meth) acryloxypropyl trimethoxysilane are preferable in that hydrolysis reaction can be easily performed and by-products after the reaction can be easily removed.
When the polyisocyanate to be described later is contained, the vinyl polymer segment (a 2) preferably has an alcoholic hydroxyl group. The vinyl polymer segment (a 2) having an alcoholic hydroxyl group can be obtained by copolymerizing a (meth) acrylic monomer having an alcoholic hydroxyl group. Specific examples of the (meth) acrylic monomer having an alcoholic hydroxyl group include various α, β -ethylenically unsaturated carboxylic acid hydroxyalkyl esters 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 addition monomer manufactured by Daicel chemical Co., ltd.), and adducts thereof with ε -caprolactone. Among them, 2-hydroxyethyl (meth) acrylate is preferred because it reacts easily.
The amount of the alcoholic hydroxyl group(s) is preferably appropriately determined by calculation from the amount of the polyisocyanate to be added.
In the present invention, as described later, an active energy ray-curable monomer having an alcoholic hydroxyl group is more preferably used in combination. Therefore, the amount of the alcoholic hydroxyl group(s) in the vinyl polymer segment (a 2) having an alcoholic hydroxyl group(s) can be determined in consideration of the amount of the active energy ray-curable monomer having an alcoholic hydroxyl group(s) used in combination. It is substantially preferably contained so that the hydroxyl value of the vinyl polymer segment (a 2) is in the range of 30 to 300.
Specifically, the composite resin (a) is produced by the following methods (method 1) to (method 3).
(Method 1) copolymerizing the general-purpose (meth) acrylic monomer and the like and the vinyl monomer containing a silanol group and/or a hydrolyzable silyl group directly bonded to carbon to obtain a vinyl polymer segment (a 2) containing a silanol group and/or a hydrolyzable silyl group directly bonded to carbon. A silane compound having a silanol group and/or a hydrolyzable silyl group and a polymerizable double bond, and if necessary, a general-purpose silane compound are mixed therewith, and a hydrolytic condensation reaction is performed.
In this method, a silanol group or a hydrolyzable silyl group of a silane compound having both a silanol group and/or a hydrolyzable silyl group and a polymerizable double bond, and a silanol group and/or a hydrolyzable silyl group of a vinyl polymer segment (a 2) having a silanol group and/or a hydrolyzable silyl group bonded directly to a carbon bond undergo a hydrolytic condensation reaction to form the polysiloxane segment (a 1), and a composite resin (a) is obtained in which the polysiloxane segment (a 1) and the vinyl polymer segment (a 2) are composited by a bond represented by the general formula (3).
(Method 2) in the same manner as in method 1, a vinyl polymer segment (a 2) containing a silanol group and/or a hydrolyzable silyl group directly bonded to a carbon bond is obtained.
On the other hand, a silane compound having both a silanol group and/or a hydrolyzable silyl group and a polymerizable double bond, and if necessary, a general-purpose silane compound are subjected to a hydrolytic condensation reaction to obtain a polysiloxane segment (a 1). Then, the silanol group and/or the hydrolyzable silyl group of the vinyl polymer segment (a 2) and the silanol group and/or the hydrolyzable silyl group of the polysiloxane segment (a 1) are subjected to a hydrolytic condensation reaction.
(Method 3) As in method 1, a vinyl polymer segment (a 2) containing a silanol group and/or a hydrolyzable silyl group directly bonded to a carbon bond is obtained. On the other hand, a polysiloxane segment (a 1) was obtained in the same manner as in method 2. Further, a silane compound containing a silane compound having a polymerizable double bond is mixed with a general-purpose silane compound as needed, and a hydrolytic condensation reaction is performed.
Examples of the general silane compounds used in the above-mentioned methods (1) to (3) include: various organotrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane; various organodialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, methylcyclohexyldimethoxysilane and methylphenyldimethoxysilane; chlorosilanes such as methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane and diphenyldichlorosilane. Among them, organotrialkoxysilane and organodialkoxysilane are preferable, which are easy to carry out hydrolysis reaction and can easily remove by-products after reaction.
In addition, a 4-functional alkoxysilane compound such as tetramethoxysilane, tetraethoxysilane or tetra-n-propoxysilane, and a partial hydrolysis condensate of the 4-functional alkoxysilane compound may be used in combination within a range that does not impair the effects of the present invention. In the case of using the above-mentioned 4-functional alkoxysilane compound or a partial hydrolysis condensate thereof in combination, it is preferable to use the 4-functional alkoxysilane compound in combination so that the silicon atoms contained in the 4-functional alkoxysilane compound are not more than 20 mol% with respect to the total silicon atoms constituting the polysiloxane segment (a 1).
In addition, the above silane compound may be used in combination with a metal alkoxide compound other than a silicon atom of boron, titanium, zirconium, aluminum or the like within a range that does not impair the effect of the present invention. For example, the metal alkoxide compound is preferably used in combination so that the metal atoms contained in the metal alkoxide compound are not more than 25 mol% relative to the total silicon atoms constituting the polysiloxane segment (a 1).
The hydrolytic condensation reaction in the above-mentioned (methods 1) to (method 3) means a condensation reaction in which a part of the hydrolyzable groups is hydrolyzed under the influence of water or the like to form hydroxyl groups, and then the hydroxyl groups are condensed with each other or with the hydrolyzable groups. The hydrolysis condensation reaction can be carried out by a known method, but a method in which water and a catalyst are supplied to carry out the reaction in the above-described production step is simple and preferable.
Examples of the catalyst used include: 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 and potassium hydroxide; titanates such as tetraisopropyl titanate and tetrabutyl titanate; basic nitrogen atom-containing compounds such as 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, and 1-methylimidazole; various quaternary ammonium salts such as tetramethylammonium salt, tetrabutylammonium salt, dilauryldimethylammonium salt, etc., and the quaternary ammonium salts have chlorine, bromine, carboxylate or hydroxide as counter anions; tin carboxylates such as dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin dilaurate, dibutyltin diacetylacetone, tin octoate, and tin stearate. The catalyst may be used alone or in combination of 2 or more.
The amount of the catalyst to be added is not particularly limited, but is usually in the range of preferably 0.0001 to 10% by weight, more preferably 0.0005 to 3% by weight, and particularly preferably 0.001 to 1% by weight, based on the total amount of the silanol group-or hydrolyzable silyl group-containing compounds.
The amount of water to be supplied is preferably 0.05 mol or more, more preferably 0.1 mol or more, and particularly preferably 0.5 mol or more, based on 1 mol of the silanol group or hydrolyzable silyl group of each compound having the silanol group or hydrolyzable silyl group.
The catalyst and water may be supplied at one time, may be supplied sequentially, or may be supplied after being mixed in advance.
The reaction temperature at the time of carrying out the hydrolytic condensation reaction in the above-mentioned (methods 1) to (method 3) is suitably in the range of 0℃to 150℃and preferably in the range of 20℃to 100 ℃. The reaction pressure may be any one of normal pressure, increased pressure, and reduced pressure. Further, alcohol and water, which are by-products possibly produced in the hydrolysis condensation reaction, may be removed by distillation or the like as needed.
The ratio of the respective compounds (1) to (3) is appropriately selected according to the desired structure of the composite resin (a) used in the present invention. Among them, the composite resin (a) is preferably obtained such that the content of the polysiloxane segment (a 1) is 30 to 95% by weight, and more preferably 50 to 95% by weight, from the viewpoint of excellent durability of the obtained coating film.
In the above (methods 1) to (method 3), specific methods for block-compositing the polysiloxane segment and the vinyl polymer segment include the following methods: in the case of (method 1), for example, a silane compound having both a silanol group and/or a hydrolyzable silyl group and a polymerizable double bond, and if necessary, a general-purpose silane compound are mixed with a vinyl polymer segment having a structure such as the silanol group and/or the hydrolyzable silyl group at only one or both ends of the polymer chain as an intermediate, and a hydrolytic condensation reaction is carried out.
On the other hand, in the above (methods 1) to (method 3), specific methods for compounding the polysiloxane segment in a grafted state with the vinyl polymer segment include the following methods: the vinyl polymer segment having a structure in which the silanol groups and/or hydrolyzable silyl groups are randomly distributed with respect to the main chain of the vinyl polymer segment is used as an intermediate, and for example, in the case of (method 2), the silanol groups and/or hydrolyzable silyl groups of the vinyl polymer segment and the silanol groups and/or hydrolyzable silyl groups of the polysiloxane segment are subjected to a hydrolytic condensation reaction.
When the vinyl-based polymer segment (a 2) in the composite resin (a) has an alcoholic hydroxyl group, a polyisocyanate is preferably used in combination, and the polyisocyanate is preferably contained in an amount of 5 to 50% by weight based on the total solid content of the active energy ray-curable resin layer. By containing the polyisocyanate in this range, a coating film particularly excellent in long-term weather resistance (specifically, crack resistance) particularly outdoors can be obtained. This is presumably because the polyisocyanate reacts with hydroxyl groups in the system (which are hydroxyl groups in the vinyl polymer segment (a 2) and hydroxyl groups in an active energy ray-curable monomer having an alcoholic hydroxyl group described later) to form urethane bonds as soft segments, and serves to alleviate stress concentration caused by curing of the polymerizable double bonds.
The polyisocyanate to be used is not particularly limited, and a known polyisocyanate can be used, but it is preferable to minimize the amount of the polyisocyanate used because it causes yellowing of the cured coating film under long-term outdoor exposure, because it uses aromatic diisocyanates such as toluene diisocyanate and diphenylmethane-4, 4' -diisocyanate, and aralkyldiisocyanates such as isophthalene diisocyanate, α, α, α ', α ' -tetramethyl-isophthalene diisocyanate, and the like as main raw materials.
From the viewpoint of long-term use outdoors, aliphatic polyisocyanates containing aliphatic diisocyanates as the main raw materials are suitable as the polyisocyanate used in the present invention. Examples of the aliphatic diisocyanate include tetramethylene diisocyanate, 1, 5-pentamethylene diisocyanate, 1, 6-hexamethylene diisocyanate (hereinafter abbreviated as "HDI"), 2,4- (or 2, 4-) trimethyl-1, 6-hexamethylene diisocyanate, lysine isocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1, 4-diisocyanatocyclohexane, 1, 3-bis (diisocyanatomethyl) cyclohexane, and 4,4' -dicyclohexylmethane diisocyanate. Among them, HDI is particularly preferable from the viewpoints of crack resistance and cost.
Examples of aliphatic polyisocyanates obtained from aliphatic diisocyanates include allophanate type polyisocyanates, biuret type polyisocyanates, adduct type polyisocyanates and isocyanurate type polyisocyanates, and these can be suitably used.
As the polyisocyanate, a so-called blocked polyisocyanate compound blocked with various blocking agents may be used. Examples of the blocking agent include alcohols such as methanol, ethanol, and lactate; compounds containing phenolic hydroxyl groups such as phenol and salicylate; amides such as epsilon-caprolactam and 2-pyrrolidone; oximes such as acetone oxime and methyl ethyl ketoxime; active methylene compounds such as methyl acetoacetate, ethyl acetoacetate, and acetylacetone.
From the viewpoint of crack resistance and abrasion resistance of the obtained cured coating film, the isocyanate groups in the polyisocyanate are preferably 3 to 30% by weight. If the amount of isocyanate in the polyisocyanate is up to more than 30%, the molecular weight of the polyisocyanate may be reduced, and crack resistance due to stress relaxation may not be exhibited. The reaction of the polyisocyanate with the hydroxyl groups in the system (which are hydroxyl groups in the vinyl polymer segment (a 2) and hydroxyl groups in the active energy ray-curable monomer having an alcoholic hydroxyl group described later) does not require special heating or the like, and for example, in the case where the curing system is ultraviolet rays, the reaction is gradually performed by being left at room temperature after being coated or irradiated with ultraviolet rays. If necessary, the reaction between the alcoholic hydroxyl group and the isocyanate may be promoted by heating at 80℃for several minutes to several hours (20 minutes to 4 hours) after the irradiation with ultraviolet rays. In this case, a known urethane catalyst may be used as needed. The urethanization catalyst is appropriately selected according to the desired reaction temperature.
Examples of the acrylic (meth) acrylate resin (B) include: an acrylic (meth) acrylate resin obtained by introducing a (meth) acryloyl group by further reacting an acrylic resin intermediate obtained by polymerizing a (meth) acrylate monomer (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group as an essential component with a (meth) acrylate monomer (β) having a functional group capable of reacting with the reactive functional group.
In the present invention, "(meth) acrylate resin" means a resin having a (meth) acryloyl group in a molecule, and "(meth) acryloyl group" means one or both of an acryloyl group and a methacryloyl group. In addition, "(meth) acrylate" means one or both of acrylate and methacrylate.
Examples of the (meth) acrylate monomer (α) having a reactive functional group include: hydroxy group-containing (meth) acrylate monomers such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; carboxyl group-containing (meth) acrylate monomers such as (meth) acrylic acid; isocyanate group-containing (meth) acrylate monomers such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1, 1-bis (acryloyloxymethyl) ethyl isocyanate; glycidyl group-containing (meth) acrylate monomers such as glycidyl (meth) acrylate and 4-hydroxybutyl acrylate glycidyl ether. These (meth) acrylate monomers having a reactive functional group may be used alone or in combination of 2 or more.
The acrylic resin intermediate is preferably a copolymer of a (meth) acrylate monomer having a homopolymer glass transition temperature (Tg) of 50 ℃ or higher, from the viewpoint of forming a cured product having more excellent substrate adhesion and further excellent processability, scratch resistance and chemical resistance. Examples of such monomers include methyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and adamantyl (meth) acrylate. From the viewpoint of obtaining an acrylic (meth) acrylate resin capable of forming a cured product excellent in substrate adhesion and processability, scratch resistance and chemical resistance, at least 1 of these monomers is preferably used, more preferably 2 or more, and preferably at least 1 of these monomers is methyl (meth) acrylate. The values of the glass transition temperatures of the homopolymers of the respective components may be values described in "adhesion technical Handbook" of journal of industrial news, "Polymer Handbook" of Wiley-Interscience, resin entry for paint, HP of Ministry chemical Co., ltd., HP of Mitsubishi chemical Co., ltd., or the like.
In addition, other polymerizable unsaturated group-containing compounds may be copolymerized with the acrylic resin intermediate as needed. Examples of the other polymerizable unsaturated group-containing compound include: alkyl (meth) acrylates such as ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; ring-containing (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate; aromatic ring-containing (meth) acrylates such as phenyl (meth) acrylate and phenoxyethyl acrylate; silyl group-containing (meth) acrylates such as 3-methacryloxypropyl trimethoxysilane; styrene derivatives such as styrene, α -methylstyrene and chlorostyrene; (meth) acryloylmorpholine, diethylene glycol di (meth) acrylate, and the like. These other polymerizable unsaturated group-containing compounds may be used alone or in combination of 2 or more.
In the case where the acrylic resin intermediate is obtained by copolymerizing the (meth) acrylate monomer (α) and the other polymerizable unsaturated group-containing compound, the (meth) acrylate monomer (α) is preferably 5 to 95% by mass, more preferably 25 to 65% by mass, in the total of the two, from the viewpoint of obtaining an acrylic (meth) acrylate resin having excellent substrate adhesion, processability, scratch resistance and chemical resistance.
The method for producing the acrylic resin intermediate can be carried out by the same method as that for a usual acrylic resin. For example, it can be produced by polymerizing various monomers in the presence of a polymerization initiator at a temperature of 60 to 150 ℃. Examples of the polymerization method include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Examples of the polymerization form include random copolymers, block copolymers, and graft copolymers. In the case of performing the solution polymerization method, for example, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, a glycol ether solvent such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether may be preferably used.
The (meth) acrylate monomer (β) is not particularly limited as long as it can react with the reactive functional group of the (meth) acrylate monomer (α), and the following combination is preferable from the viewpoint of reactivity. That is, when the hydroxyl group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), it is preferable to use an isocyanate group-containing (meth) acrylate as the (meth) acrylate monomer (β). In the case of using the carboxyl group-containing (meth) acrylate as the (meth) acrylate monomer (α), it is preferable to use the glycidyl group-containing (meth) acrylate as the (meth) acrylate monomer (β). In the case of using the isocyanate group-containing (meth) acrylate as the (meth) acrylate monomer (α), it is preferable to use the hydroxyl group-containing (meth) acrylate as the (meth) acrylate monomer (β). In the case of using the glycidyl group-containing (meth) acrylate as the (meth) acrylate monomer (α), it is preferable to use the carboxyl group-containing (meth) acrylate as the (meth) acrylate monomer (β).
For example, when the reaction is an esterification reaction, the reaction between the acrylic resin intermediate and the (meth) acrylic acid ester monomer (. Beta.) may be carried out by using an esterification catalyst such as triphenylphosphine in a temperature range of 60 to 150 ℃. In the case where the reaction is a urethanization reaction, there may be mentioned a method in which the (meth) acrylate monomer (β) is added dropwise to the acrylic resin intermediate at a temperature in the range of 50 to 120 ℃. The (meth) acrylate monomer (. Beta.) is preferably used in a range of 0.95 to 1.1 mol based on 1 mol of the functional group in the acrylic resin intermediate.
Among these, from the viewpoint of having excellent substrate adhesion and further excellent processability, scratch resistance and chemical resistance, the acrylic (meth) acrylate resin (B) is preferably a polymer of a monomer mixture containing a (meth) acrylate monomer, and the polymer is a polymer of a monomer mixture containing 5 to 60 parts by mass of a glycidyl group-containing (meth) acrylate monomer (x 1) in 100 parts by mass of the monomer mixture, particularly more preferably a polymer obtained by reacting an acrylic polymer (B1) having the glycidyl group-containing (meth) acrylate monomer (x 1) as an essential raw material with a hydroxyl group-containing (meth) acrylate monomer (x 2) and/or a carboxyl group-containing (meth) acrylate monomer (x 3), and the polymer is more preferably a polymer obtained by using the glycidyl group-containing (meth) acrylate monomer (x 1) in 3 to 60 parts by mass, and more preferably a polymer obtained by using the glycidyl group-containing (meth) acrylate monomer (x 1) in 5 to 40 parts by mass.
The acrylic polymer (b 1) is preferably a copolymer of a glycidyl group-containing (meth) acrylate monomer (x 1) and an alkyl (meth) acrylate, and the alkyl (meth) acrylate is more preferably methyl (meth) acrylate.
The (meth) acryl equivalent of the acrylic (meth) acrylate resin (B) is preferably 300 to 3,000 g/equivalent, particularly preferably 400 to 2,000 g/equivalent, from the viewpoint of further improving the balance between durability such as weather resistance and processability. The (meth) acryl equivalent of the acrylic (meth) acrylate resin (B) in the present invention is a value calculated from the reaction raw materials in a theoretical value.
The weight average molecular weight (Mw) of the acrylic (meth) acrylate resin (B) is 10,000 ～ 70,000, and 20,000 ～ 40,000 is more preferable in view of excellent substrate adhesion and further improvement in balance of processability, scratch resistance and chemical resistance.
In the present invention, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mn/Mw) are values measured by Gel Permeation Chromatography (GPC).
The mass ratio (A/B) of the composite resin (A) to the (meth) acrylate resin (B) is preferably 2/98 to 90/10, more preferably 5/95 to 65/35, and even more preferably 10/90 to 50/50, from the viewpoint of obtaining a coating film excellent in durability such as weather resistance and processability.
The active energy ray-curable resin composition of the present invention contains the composite resin (a) and the acrylic (meth) acrylate resin (B), and may contain other active energy ray-curable components, but from the viewpoint of having excellent substrate adhesion, processability, scratch resistance and chemical resistance, the content of the active energy ray-curable component having a weight average molecular weight of 5,000 or less is preferably 30 mass% or less based on the total mass of the active energy ray-curable components.
Examples of the component having the above-mentioned other active energy ray curability include other (meth) acrylate compounds than the above-mentioned acrylic (meth) acrylate resin (B). Examples of the other (meth) acrylate compound include dendrimer-type (meth) acrylate resins, urethane (meth) acrylate resins, epoxy (meth) acrylate resins, mono (meth) acrylate compounds and modifications thereof, aliphatic hydrocarbon-type poly (meth) acrylate compounds and modifications thereof, alicyclic poly (meth) acrylate compounds and modifications thereof, aromatic poly (meth) acrylate compounds and modifications thereof, and the like. These may be used alone or in combination of 2 or more.
The content of the polysiloxane segment (a 1) in the total resin component including the composite resin (a) and the acrylic (meth) acrylate resin (B) is preferably 2 to 55 mass%, more preferably 4 to 40 mass%, from the viewpoint of further improving the balance between durability such as weather resistance and processability.
Examples of the photopolymerization initiator (C) include photo-radical polymerization initiators such as 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2' -dimethoxy-1, 2-diphenylethane-1-one, diphenyl (2, 4, 6-trimethoxybenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone.
Examples of the commercial products of the photopolymerization initiator (C) include those manufactured by ："Omnirad1173"、"Omnirad 184"、"Omnirad 127"、"Omnirad 2959"、"Omnirad 369"、"Omnirad 379"、"Omnirad 907"、"Omnirad4265"、"Omnirad 1000"、"Omnirad 651"、"Omnirad TPO"、"Omnirad 819"、"Omnirad 2022"、"Omnirad 2100"、"Omnirad754"、"Omnirad 784"、"Omnirad 500"、"Omnirad 81"(IGM Resins company; "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", "KAYACURE OA" (manufactured by Kagaku corporation); "Vicure 10", "Vicure 55" (Stoffa Chemical Co.); "Trigonal P1" (manufactured by Akzo Nobel Co., ltd.) "SANDORAY 1000" (manufactured by SANDOZ Co., ltd.); "DEAP" (manufactured by Upjohn Chemical Co., ltd.), "Quantacure PDO", "Quantacure ITX", "Quantacure EPD" (manufactured by Ward Blenkinsop Co.); "Runtecure 1104" (manufactured by Runtec corporation), and the like. These photopolymerization initiators may be used alone or in combination of 2 or more.
The amount of the photopolymerization initiator (C) to be added is, for example, preferably in the range of 0.05 to 15 mass%, more preferably in the range of 0.1 to 10 mass%, based on the total of the components of the active energy ray-curable resin composition excluding the solvent.
The photopolymerization initiator may be optionally used in combination with a photosensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, or a nitrile compound.
The active energy ray-curable resin composition of the present invention may contain other components than those described above. Examples of the other components include inorganic fine particles, silane coupling agents, phosphate compounds, solvents, ultraviolet absorbers, antioxidants, silicon-based additives, fluorine-based additives, antistatic agents, organic beads, quantum Dots (QDs), rheology control agents, deaerators, antifogging agents, colorants, and the like.
The inorganic fine particles are added for the purpose of adjusting the hardness, refractive index, etc. of the cured coating film of the active energy ray-curable resin composition, and various known and conventionally used inorganic fine particles can be used. Examples of the particles include fine particles of silica, alumina, zirconia, titania, barium titanate, antimony trioxide, and the like. These may be used alone or in combination of two or more.
Among these inorganic fine particles, silica particles are preferred in view of easy availability and ease of handling. Examples of the silica particles include various silica particles such as fumed silica, wet silica called precipitated silica, gel silica, sol-gel silica, and the like, and any of them can be used.
The inorganic fine particles may be obtained by introducing functional groups onto the surfaces of fine particles using various silane coupling agents. By introducing a functional group into the surface of the inorganic fine particles, the mixing property with the organic component such as the acrylic (meth) acrylate resin (B) is improved, and the storage stability is improved.
Examples of the silane coupling agent for modifying the inorganic fine particles include: (meth) acryloyloxy silane coupling agents such as [ (meth) acryloyloxy alkyl ] trialkylsilane, [ (meth) acryloyloxy alkyl ] dialkylalkoxysilane, [ (meth) acryloyloxy alkyl ] alkyldialkoxysilane, [ (meth) acryloyloxy alkyl ] trialkoxysilane; vinyl silane coupling agents such as trialkylvinyl silane, dialkylalkoxysilane, alkyldialkoxyvinyl silane, trialkoxyvinyl silane, trialkylallylsilane, dialkylalkoxyallylsilane, alkyldialkoxyallylsilane, trialkoxyallylsilane, and the like; styrene-based silane coupling agents such as styryltrialkylsilane, styryldialkylalkoxysilane, styrylalkyldialkoxysilane, and styryltrialkoxysilane; epoxy silane coupling agents such as (glycidoxyalkyl) trialkylsilane, (glycidoxyalkyl) dialkylalkoxysilane, (glycidoxyalkyl) alkyldialkoxysilane, (glycidoxyalkyl) trialkoxysilane, [ (3, 4-epoxycyclohexyl) alkyl ] trimethoxysilane, [ (3, 4-epoxycyclohexyl) alkyl ] trialkylsilane, [ (3, 4-epoxycyclohexyl) alkyl ] dialkylalkoxysilane, [ (3, 4-epoxycyclohexyl) alkyl ] alkyldialkoxysilane, [ (3, 4-epoxycyclohexyl) alkyl ] trialkoxysilane; isocyanate-based silane coupling agents such as (isocyanatoalkyl) trialkylsilane, (isocyanatoalkyl) dialkylalkoxysilane, (isocyanatoalkyl) alkyldialkoxysilane and (isocyanatoalkyl) trialkoxysilane. These may be used alone or in combination of 2 or more.
Among the silane coupling agents, a (meth) acryloyloxy silane coupling agent is preferable, and [ (meth) acryloyloxyalkyl ] trialkoxysilane such as 3- (meth) acryloyloxypropyl trimethoxysilane is particularly preferable, because it is an inorganic fine particle excellent in miscibility with the organic component such as the acrylic (meth) acrylate resin.
The average particle diameter of the inorganic fine particles is not particularly limited, and may be appropriately adjusted according to the desired cured product performance and the like. In particular, the average particle diameter of the inorganic fine particles is preferably in the range of 80 to 250nm, more preferably in the range of 90 to 180nm, and particularly preferably in the range of 100 to 150nm, from the viewpoint of obtaining a cured coating film excellent in not only scratch resistance and crack resistance but also blocking resistance, transparency, and the like.
The average particle diameter of the inorganic fine particles is a value obtained by measuring the particle diameter of the active energy ray-curable resin composition under the following conditions.
Particle diameter measuring device: "ELSZ-2" manufactured by tsukamurelus electronics Co., ltd "
Particle size measurement sample: an active energy ray-curable resin composition was prepared as a solution of methyl isobutyl ketone having a nonvolatile content of 1 mass%.
The content of the inorganic fine particles in the active energy ray-curable resin composition of the present invention is not particularly limited, and may be appropriately adjusted according to the desired cured product properties and the like. In particular, the content of the inorganic fine particles is preferably in the range of 10 to 100 parts by mass based on 100 parts by mass of the acrylic (meth) acrylate resin, from the viewpoint of obtaining a cured coating film excellent in scratch resistance.
Examples of the silane coupling agent added to the active energy ray-curable resin composition include: (meth) acryloyloxy silane coupling agents such as [ (meth) acryloyloxy alkyl ] trialkylsilane, [ (meth) acryloyloxy alkyl ] dialkylalkoxysilane, [ (meth) acryloyloxy alkyl ] alkyldialkoxysilane, [ (meth) acryloyloxy alkyl ] trialkoxysilane; vinyl silane coupling agents such as trialkylvinyl silane, dialkylalkoxysilane, alkyldialkoxyvinyl silane, trialkoxyvinyl silane, trialkylallylsilane, dialkylalkoxyallylsilane, alkyldialkoxyallylsilane, trialkoxyallylsilane, and the like; styrene-based silane coupling agents such as styryltrialkyl, styryldialkylalkoxysilane, styrylalkyldialkoxysilane, and styryltrialkoxysilane; epoxy silane coupling agents such as (glycidoxyalkyl) trialkylsilane, (glycidoxyalkyl) dialkylalkoxysilane, (glycidoxyalkyl) alkyldialkoxysilane, (glycidoxyalkyl) trialkoxysilane, [ (3, 4-epoxycyclohexyl) alkyl ] trimethoxysilane, [ (3, 4-epoxycyclohexyl) alkyl ] trialkylsilane, [ (3, 4-epoxycyclohexyl) alkyl ] dialkylalkoxysilane, [ (3, 4-epoxycyclohexyl) alkyl ] alkyldialkoxysilane, [ (3, 4-epoxycyclohexyl) alkyl ] trialkoxysilane; isocyanate-based silane coupling agents such as (isocyanatoalkyl) trialkylsilane, (isocyanatoalkyl) dialkylalkoxysilane, (isocyanatoalkyl) alkyldialkoxysilane and (isocyanatoalkyl) trialkoxysilane. These may be used alone or in combination of 2 or more.
Examples of commercial products of the phosphate compound include: "KAYAMER PM-2", "KAYAMER PM-21" manufactured by Kagaku corporation, co-mingled with the company, "LIGHT ESTER P-1M", "LIGHT ESTER P-2M", "LIGHT ACRYLATE P-1A (N)", manufactured by SOLVAY corporation, "SIPOMER PAM 100", "SIPOMER PAM 200", "SIPOMER PAM 300", "SIPOMER PAM 4000", manufactured by Osaka organic chemical industry Co., ltd. "VISCOAT #3PA", "VISCOAT #3PMA", and "NEW FRONTIER S-23A" manufactured by first Industrial pharmaceutical Co., ltd.; and "SIPOMER PAM 5000" manufactured by SOLVAY Co., ltd., which is a phosphate compound having an allyl ether group in its molecular structure.
The solvent is added for the purpose of adjusting the application viscosity of the active energy ray-curable resin composition, and the kind and the amount of the solvent to be added are appropriately adjusted according to the desired properties. Generally, the active energy ray-curable resin composition is used such that the nonvolatile content thereof is in the range of 10 to 90 mass%. Specific examples of the solvent include: ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; esters such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene and xylene; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether, and the like; glycol ether solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monopropyl ether. These solvents may be used alone or in combination of 2 or more.
Examples of the ultraviolet absorber include triazine derivatives such as 2- [4- { (2-hydroxy-3-dodecyloxypropyl) oxy } -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [4- { (2-hydroxy-3-tridecyloxypropyl) oxy } -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- (2 '-xanthenecarboxy-5' -methylphenyl) benzotriazole, 2- (2 '-o-nitrobenzyloxy-5' -methylphenyl) benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These ultraviolet absorbers may be used alone or in combination of 2 or more.
Examples of the antioxidant include hindered phenol antioxidants, hindered amine antioxidants, organic sulfur antioxidants, and phosphate antioxidants. These antioxidants may be used alone or in combination of 2 or more.
Examples of the silicon-based additive include a polydimethylsiloxane having an alkyl group or a phenyl group, a polydimethylsiloxane having a polyether-modified acryl group, and a polydimethylsiloxane having a polyester-modified acryl group, such as a dimethylpolysiloxane, a methylphenyl polysiloxane, a cyclic dimethylpolysiloxane, a methyl hydrogen polysiloxane, a polyether-modified dimethylpolysiloxane copolymer, a polyester-modified dimethylpolysiloxane copolymer, a fluorine-modified dimethylpolysiloxane copolymer, and an amino-modified dimethylpolysiloxane copolymer. These silicon-based additives may be used alone or in combination of 2 or more.
Examples of commercial products of the fluorine-based additive include "MEGAFACE" series manufactured by DIC corporation. These fluorine-based additives may be used alone or in combination of 2 or more.
Examples of the antistatic agent include pyridinium, imidazolium, phosphonium, ammonium, or lithium salts of bis (trifluoromethanesulfonyl) imide or bis (fluorosulfonyl) imide. These antistatic agents may be used alone or in combination of 2 or more.
Examples of the organic beads include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacrylic styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, polyester resin beads, polyamide resin beads, polyimide resin beads, polyvinyl fluoride resin beads, and polyethylene resin beads. These organic beads may be used alone or in combination of 2 or more. The average particle diameter of these organic beads is preferably in the range of 1 to 10. Mu.m.
Examples of the Quantum Dot (QD) include a group II-V semiconductor compound, a group II-VI semiconductor compound, a group III-IV semiconductor compound, a group III-V semiconductor compound, a group III-VI semiconductor compound, a group IV-VI semiconductor compound, a group I-III-VI semiconductor compound, a group II-IV-V semiconductor compound, a group I-II-IV-VI semiconductor compound, a group IV element, and a compound containing the same. Examples of the group II-VI semiconductor compounds include: a binary compound ;ZnSeS、ZnSeTe、ZnSTe、CdZnS、CdZnSe、CdZnTe、CdSeS、CdSeTe、CdSTe、CdHgS、CdHgSe、CdHgTe、HgSeS、HgSeTe、HgSTe、HgZnS、HgZnSe、HgZnTe such as ZnO, znS, znSe, znTe, cdS, cdSe, cdTe, hgS, hgSe, hgTe; CdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, cdHgZnTe, hgZnSeS, hgZnSeTe, hgZnSTe and the like. Examples of the group III-IV semiconductor compound include B 4C3、Al4C3、Ga4C3. Examples of the group III-V semiconductor compound include: BP, BN, alN, alP, alAs, alSb, gaN, gaP, gaAs, gaSb, inN, inP, inAs, inSb and other binary compounds; GaNP, gaNAs, gaNSb, gaPAs, gaPSb, alNP, alNAs, alNSb, alPAs, alPSb, inNP, inNAs, inNSb, inPAs, inPSb, gaAlNP and the like, ;GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs、InAlPSb and the like. Examples of the group III-VI semiconductor compound include Al2S3、Al2Se3、Al2Te3、Ga2S3、Ga2Se3、Ga2Te3、GaTe、In2S3、In2Se3、In2Te3、InTe. Examples of the group IV-VI semiconductor compound include: snS, snSe, snTe, pbS, pbSe, pbTe and other binary compounds; snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe and other ternary compounds; snPbSSe, snPbSeTe, snPbSTe and the like. Examples of the group I-III-VI semiconductor compound include CuInS2、CuInSe2、CuInTe2、CuGaS2、CuGaSe2、CuGaSe2、AgInS2、AgInSe2、AgInTe2、AgGaSe2、AgGaS2、AgGaTe2. Examples of the group IV element or the compound containing the same include C, si, ge, siC, siGe. The quantum dot may be formed of a single semiconductor compound or may have a core-shell structure formed of a plurality of semiconductor compounds. In addition, the surface of the substrate may be modified with an organic compound.
These various additives may be added in any amount depending on the desired properties and the like, and are usually used in a range of 0.01 to 40 mass% in the total 100 mass% of the components other than the solvent in the active energy ray-curable resin composition.
The active energy ray-curable resin composition used in the present invention is produced by mixing the above-mentioned blend components. The mixing method is not particularly limited, and a paint shaker, a dispersing machine, a roll mill, a bead mill, a ball mill, an attritor, a sand mill, a bead mill, or the like may be used.
The cured coating film of the present invention can be obtained by irradiating the active energy ray-curable resin composition with active energy rays. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. In the case of using ultraviolet rays as the active energy rays, the ultraviolet rays may be irradiated under an inert gas atmosphere such as nitrogen or under an air atmosphere in order to efficiently perform the curing reaction by the ultraviolet rays.
Ultraviolet lamps are generally used as ultraviolet light generating sources from the viewpoints of practicality and economy. Specifically, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, an LED, and the like can be cited.
The cumulative amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50kJ/m 2, more preferably 0.5 to 10kJ/m 2. If the accumulated light amount is in the above range, generation of uncured portions can be prevented or suppressed, so that it is preferable.
The irradiation with the active energy ray may be performed in one stage or may be performed in two or more stages.
In addition, the cured coating film preferably has a tan δ of 0.1 to 1 as measured by dynamic viscoelasticity spectrometry, from the viewpoint of excellent adhesion and excellent processability, scratch resistance and chemical resistance.
The article of the present invention has the cured coating film on the surface. Examples of the articles include interior and exterior materials in the field of architecture, mobile phones, home electric appliances, automobile interior and exterior materials, and plastic molded articles such as OA equipment.
Examples (example)
Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. The present invention is not limited to the examples listed below.
In this example, the weight average molecular weight (Mw) was measured by Gel Permeation Chromatography (GPC) under the following conditions.
Measurement device: HLC-8220 manufactured by Tosoh Co., ltd "
Column: "guard column H XL -H" manufactured by Tosoh Co., ltd "
"TSKgel G5000HXL" manufactured by Tosoh Co., ltd "
"TSKgel G4000HXL" manufactured by Tosoh Co., ltd "
"TSKgel G3000HXL" manufactured by Tosoh Co., ltd "
"TSKgel G2000HXL" manufactured by Tosoh Co., ltd "
A detector: RI (differential refractometer)
And (3) data processing: SC-8010 manufactured by Tosoh Co., ltd "
Measurement conditions: column temperature 40 DEG C
Solvent tetrahydrofuran
Flow rate 1.0 ml/min
Standard: polystyrene
Sample: a tetrahydrofuran solution having a resin solid content of 0.4% by mass was filtered through a microfilter (100. Mu.l)
Synthesis example 1 Synthesis of composite resin (A-1)
244 Parts by mass of butanol and 44 parts by mass of Phenyltrimethoxysilane (PTMS) were charged into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser, and a nitrogen inlet, and the temperature was raised to 100 ℃. Next, a mixture of 153 parts by mass of Methyl Methacrylate (MMA), 30 parts by mass of t-butyl methacrylate (t-BMA), 42 parts by mass of Butyl Acrylate (BA), 6 parts by mass of Acrylic Acid (AA), 60 parts by mass of cyclohexyl methacrylate (CHMA), 9 parts by mass of 3-methacryloxypropyl trimethoxysilane (MPTS), and 12 parts by mass of t-butyl peroxy-2-ethylhexanoate (TBPEH) was added dropwise to the reaction vessel at the same temperature under aeration of nitrogen gas with stirring for 5 hours. Then, the mixture was stirred at the same temperature for 5 hours to prepare 600 parts by mass of a vinyl polymer (a 2-1) having trimethoxysilyl groups.
Next, the temperature of the reaction vessel was adjusted to 80 ℃, and 64 parts by mass of methyltrimethoxysilane (MTMS), 269 parts by mass of 3-methacryloxypropyl trimethoxysilane (MPTS), and 53 parts by mass of dimethyldimethoxysilane (DMDMS) were added to the reaction vessel. Then, a mixture of 0.8 part by mass of "A-3" [ isopropyl acid phosphate made by Sakai chemical Co., ltd.) and 120 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 4 hours, whereby a hydrolytic condensation reaction was carried out to obtain a reaction product. The reaction product was analyzed by 1H-NMR, and as a result, the trimethoxysilyl group contained in the vinyl polymer (a 2-1) was hydrolyzed by almost 100%. Then, the reaction product was distilled under reduced pressure of 10 to 300kPa for 2 hours at 40 to 60 ℃ to remove methanol and water produced, and then 200 parts by mass of n-butyl acetate and 55 parts by mass of Methyl Ethyl Ketone (MEK) were added to obtain 1000 parts by mass of a solution of a composite resin (A1) comprising a polysiloxane segment (A1) and a vinyl polymer segment (a 2) having a nonvolatile content of 60.1%. The polysiloxane segment (a 1) in the composite resin (A-1) was 50% by mass.
Synthesis example 2 Synthesis of composite resin (A-2)
56 Parts by mass of n-butyl acetate and 13 parts by mass of PTMS were charged into the same reaction vessel as in Synthesis example 1, and the temperature was raised to 100 ℃. Next, a mixture of 128 parts by mass of MMA, 204 parts by mass of BA, 15 parts by mass of Methacrylic Acid (MA), 51 parts by mass of Ethyl Acrylate (EA), 77 parts by mass of styrene (St), 36 parts by mass of MPTS, and 20 parts by mass of TBPEH was added dropwise to the reaction vessel under nitrogen aeration for 5 hours while stirring. Then, the mixture was stirred at the same temperature for 7 hours to prepare 600 parts by mass of a vinyl polymer (a 2-2) having trimethoxysilyl groups.
Next, the temperature of the reaction vessel was adjusted to 90 ℃, and 18 parts by mass of MTMS, 83 parts by mass of MPTS, and 15 parts by mass DMDMS were added to the reaction vessel. Then, a mixture of 0.2 parts by mass of "A-3" [ isopropyl acid phosphate made by Sakai chemical Co., ltd.) and 40 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 2 hours, whereby a hydrolytic condensation reaction was carried out to obtain a reaction product. The reaction product was analyzed by 1H-NMR, and as a result, trimethoxysilyl groups contained in the vinyl polymer (a 2-2) were hydrolyzed by almost 100%. Then, the reaction product was distilled under reduced pressure of 10 to 300kPa for 2 hours at 40 to 60 ℃ to remove methanol and water formed, and then 250g of n-butyl acetate and 130g of Methyl Ethyl Ketone (MEK) were added to obtain 1000 parts by mass of a composite resin (A2) comprising a polysiloxane segment (a 1) and a vinyl polymer segment (A2) having a nonvolatile content of 60.2%. The polysiloxane segment (a 1) in the composite resin (A-2) was 15 mass%.
Synthesis example 3 Synthesis of composite resin (A-3)
128 Parts by mass of n-butyl acetate and 36 parts by mass of PTMS were charged into the same reaction vessel as in Synthesis example 1, and the temperature was raised to 120 ℃. Then, a mixture of 118 parts by mass of MMA, 126 parts by mass of t-BMA, 105 parts by mass of BA, 42 parts by mass of EA, 8.4 parts by mass of AA, 21 parts by mass of MPTS, and 16 parts by mass of TBPEH was added dropwise to the reaction vessel under aeration of nitrogen for 5 hours while stirring. Then, the mixture was stirred at the same temperature for 7 hours to prepare 600 parts by mass of a vinyl polymer (a 2-3) having trimethoxysilyl groups.
Next, the temperature of the reaction vessel was adjusted to 95 ℃, and 8.7 parts by mass of MTMS, 192 parts by mass of MPTS, and 11 parts by mass DMDMS were added to the reaction vessel. Then, a mixture of 0.8 parts by mass of "A-3" [ isopropyl acid phosphate made by Sakai chemical Co., ltd.) and 100 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 5 hours, whereby a hydrolytic condensation reaction was carried out to obtain a reaction product. The reaction product was analyzed by 1H-NMR, and as a result, trimethoxysilyl groups contained in the vinyl polymers (a 2-3) were hydrolyzed by almost 100%. Then, the reaction product was distilled under reduced pressure of 10 to 300kPa for 2 hours at 40 to 60℃to thereby remove methanol and water produced, and then 250g of n-butyl acetate and 120g of butanol (n-BuOH) were added to thereby obtain 1000 parts by mass of a composite resin (A3) comprising the polysiloxane segment (a 1) and the vinyl polymer segment (a 2) having a nonvolatile content of 60.0%. The polysiloxane segment (a 1) in the composite resin (A-3) was 30% by mass.
Synthesis example 4 Synthesis of composite resin (A-4)
313 Parts by mass of n-butyl acetate and 121 parts by mass of PTMS were charged into the same reaction vessel as in Synthesis example 1, and the temperature was raised to 120 ℃. Then, a mixture of 77 parts by mass of MMA, 15 parts by mass of t-BMA, 21 parts by mass of BA, 3 parts by mass of AA, 30 parts by mass of CHMA, 4.5 parts by mass of MPTS, and 16 parts by mass of TBPEH was added dropwise to the reaction vessel under aeration of nitrogen for 5 hours while stirring. Then, the mixture was stirred at the same temperature for 7 hours to prepare 600 parts by mass of a vinyl polymer (a 2-4) having trimethoxysilyl groups.
Next, the temperature of the reaction vessel was adjusted to 95 ℃, and 117 parts by mass of MTMS, 339 parts by mass of MPTS, and 73 parts by mass DMDMS were added to the reaction vessel. Then, a mixture of 2.3 parts by mass of "A-3" [ isopropyl acid phosphate made by Sakai chemical Co., ltd.) and 100 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 5 hours, whereby a hydrolytic condensation reaction was carried out to obtain a reaction product. The reaction product was analyzed by 1H-NMR, and as a result, trimethoxysilyl groups contained in the vinyl polymers (a 2-4) were hydrolyzed by almost 100%. Then, the reaction product was distilled under reduced pressure of 10 to 300kPa for 4 hours at 40 to 60℃to thereby remove methanol and water which were produced, and subsequently 70g of n-BuOH was added to thereby obtain 1000 parts by mass of a composite resin (A4) comprising the polysiloxane segment (a 1) and the vinyl polymer segment (a 2) having a nonvolatile content of 60.0%. The polysiloxane segment (a 1) in the composite resin (A-4) was 75% by mass.
Synthesis example 5 Synthesis of composite resin (A-5)
149 Parts by mass of n-butyl acetate and 113 parts by mass of PTMS were charged into the same reaction vessel as in Synthesis example 1, and the temperature was raised to 110 ℃. Then, a mixture of 15 parts by mass of MMA, 3 parts by mass of t-BMA, 4 parts by mass of BA, 0.6 part by mass of AA, 6 parts by mass of CHMA, 0.9 part by mass of MPTS, and 8 parts by mass of TBPEH was added dropwise to the reaction vessel under aeration of nitrogen for 5 hours while stirring. Then, the mixture was stirred at the same temperature for 7 hours to prepare 300 parts by mass of a vinyl polymer (a 2-5) having trimethoxysilyl groups.
Next, the temperature of the reaction vessel was adjusted to 95 ℃, and 103 parts by mass of MTMS, 478 parts by mass of MPTS, and 129 parts by mass DMDMS were added to the reaction vessel. Then, a mixture of 1.5 parts by mass of "A-3" [ isopropyl acid phosphate made by Sakai chemical Co., ltd.) and 185 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 5 hours, whereby a hydrolytic condensation reaction was carried out to obtain a reaction product. The reaction product was analyzed by 1H-NMR, and as a result, trimethoxysilyl groups contained in the vinyl polymers (a 2-5) were hydrolyzed by almost 100%. Then, the reaction product was distilled under reduced pressure of 10 to 300kPa for 5 hours at 40 to 60℃to remove methanol and water produced, and then 104 parts by mass of n-butyl acetate and 200g of n-BuOH were added to obtain 1000 parts by mass of a composite resin (A5) comprising a polysiloxane segment (a 1) and a vinyl polymer segment (a 2) having a nonvolatile content of 60.3%. The polysiloxane segment (a 1) in the composite resin (A-5) was 95% by mass.
( Synthesis example 6: preparation of acrylic (meth) acrylate resin (B-1) )
In the same reaction vessel as in Synthesis example 1, 387 parts by mass of methyl isobutyl ketone (MIBK) was charged, the temperature in the system was raised to 110℃with stirring, and then a mixed solution composed of 57 parts by mass of Glycidyl Methacrylate (GMA), 513 parts by mass of MMA and 10 parts by mass of TBPEH was added dropwise via a dropping funnel over 3 hours, followed by holding at 110℃for 15 hours. After cooling to 90℃and adding 0.3 part by mass of p-hydroxyanisole (MQ) and 29 parts by mass of AA, 3.1 parts by mass of Triphenylphosphine (TPP) was added thereto, and the mixture was further heated to 100℃and kept for 8 hours, to obtain 1000 parts by mass of a solution of an acrylic (meth) acrylate resin (B-1) having a nonvolatile content of 59.9%. The weight average molecular weight (Mw) of the acrylic (meth) acrylate resin (B-1) was 24300, and the theoretical value of the (meth) acryl equivalent calculated from the input ratio of the raw materials was 1530 g/equivalent.
( Synthesis examples 7 to 14: preparation of acrylic (meth) acrylate resins (B-2) to (B-9) )
Acrylic (meth) acrylates (B-2) to (B-9) were obtained in the same manner as in Synthesis example 6, except that the blending ratios shown in tables 2 and 3 were changed.
( Synthesis example 15: preparation of acrylic (meth) acrylate resin (RB-1) )
Acrylic (meth) acrylate (RB-1) was obtained in the same manner as in Synthesis example 6, except that the blending ratio was changed as shown in Table 3.
The compositions and properties of the acrylic (meth) acrylates (B-1) to (B-9) and (RB-1) obtained in Synthesis examples 6 to 15 are shown in tables 1 and 2.
TABLE 1
Abbreviations in table 1 are as follows.
MMA: methyl methacrylate (Tg of homopolymer: 105 ℃ C.)
GMA: glycidyl methacrylate (Tg of homopolymer: 4 ℃ C.)
AA: acrylic acid (Tg of homopolymer: -15 ℃ C.)
MIBK: methyl isobutyl ketone
P-O: tert-butyl peroxy-2-ethylhexanoate (PERBUTYL O from Japanese emulsifier Co., ltd.)
MQ: para-hydroxyanisole (para-methoxyphenol)
TPP: triphenylphosphine and process for preparing same
TABLE 2
Abbreviations in table 2 are as follows.
T-BMA: tert-butyl methacrylate (Tg of homopolymer: 107 ℃ C.)
CHMA: cyclohexyl methacrylate (Tg of homopolymer: 66 ℃ C.)
IBXMA: isobornyl methacrylate (Tg of homopolymer: 180 ℃ C.)
BZMA: benzyl methacrylate (Tg of homopolymer: 54 ℃ C.)
( Example 1: preparation and evaluation of active energy ray-curable resin composition (1) )
10 Parts by mass of the solution of the composite resin (A-1) obtained in Synthesis example 1 (6 parts by mass based on the composite resin (A-1)), 157 parts by mass of the solution of the acrylic (meth) acrylate resin (B-1) obtained in Synthesis example 6 (94 parts by mass based on the acrylic (meth) acrylate resin (B-1)) and 2.4 parts by mass of a photopolymerization initiator (Omnirad-184, manufactured by IGM RESINS Co.) were mixed to obtain an active energy ray-curable resin composition (1).
[ Method for producing cured coating film for evaluation ]
The active energy ray-curable resin composition obtained above was applied to a polycarbonate substrate so that the film thickness of the cured coating film became 20. Mu.m, dried at 80℃for 2 minutes, and then irradiated with a high-pressure mercury lamp of 80W/cm 2 for 1000mJ to obtain a cured coating film.
[ Evaluation of appearance of coating film ]
The cured coating film for evaluation obtained above was visually observed, and the appearance of the coating film was evaluated according to the following criteria.
O: the occurrence of cracks was not confirmed.
Delta: the occurrence of a small amount of cracks was confirmed.
X: the occurrence of cracks was confirmed.
[ Evaluation of adhesion ]
The cured coating film for evaluation obtained above was measured according to JIS K-5600 checkerboard test method. On the cured coating film, 1mm wide cuts were made by a cutter, the number of the checkerboard was set to 100, a transparent adhesive tape was attached so as to cover all the checkerboard, the transparent adhesive tape was peeled off rapidly, and the number of the remaining checkerboard attached was counted and evaluated according to the following criteria.
O: no peeling.
Delta: the peeled area is 1-64% of the total checkerboard area.
X: the peeled area is 65% or more of the total checkerboard area.
[ Evaluation of solvent resistance ]
The state of the cured coating film after 50 times of reciprocating friction on the cured coating film for evaluation obtained above was determined by finger touch and visual observation using a methyl ethyl ketone impregnated felt, and evaluation was performed according to the following criteria.
O: softening and gloss reduction were not confirmed.
Delta: a slight softening or a reduction in gloss was confirmed.
X: significant softening or reduction in gloss was confirmed.
[ Evaluation of scratch resistance ]
A disc-shaped indenter having a diameter of 2.4 cm was wrapped with 0.5g of steel wool (BONSTAR- #0000, manufactured by Japanese STEELWOOL Co., ltd.) and a load of 500g was applied to the indenter, and the abrasion test was performed by repeating 10 times on the cured coating film for evaluation obtained as described above. Haze values of the cured coating films before and after the abrasion test were measured using a "nephelometer NDH5000" manufactured by japan electric color industry co. The smaller the difference (dH), the higher the resistance to scratch.
And (2) the following steps: dH is 1.0% or less.
Delta: dH exceeds 1.0% and is 3.0% or less.
X: dH exceeds 3.0%.
[ Evaluation of weather resistance (appearance) ]
The cured coating film for evaluation obtained above was exposed to light by a duty photo-aging meter (Japanese (Utility: du Po) for 1,000 hours at 30W/m 2 at 70 ℃ under light irradiation, at 50 ℃ under light irradiation/wetting cycle=8 hours/4 hours, manufactured by Suga Test Instruments Co., ltd.), and the appearance of the coating film after the exposure was visually observed and evaluated according to the following criteria.
O: the occurrence of cracks was not confirmed.
Delta: the occurrence of a small amount of cracks was confirmed.
X: the occurrence of cracks was confirmed.
Evaluation of weather resistance (gloss retention)
The specular reflectance (gloss value) (%) of the cured coating film A for evaluation after the exposure for 1,000 hours was evaluated based on the specular reflectance (gloss value) (%) of the cured coating film A for evaluation after the exposure for 1,000 hours at a humidity of 90% or more at a humidity of 50 ℃ under a light irradiation of 0.71W/m 2 at 60 ℃ by a QUV ultraviolet fluorescent lamp type accelerated weathering tester (manufactured by Q-Lab Corporation, a control wavelength of 310 nm) with respect to the retention of the specular reflectance (gloss retention:%) [ the specular reflectance of the cured coating film after the exposure for 100X ]/(the specular reflectance of the cured coating film before the exposure ]. The larger the value of the retention, the better the weather resistance. Specular reflectance was measured using micro-TRI-gloss manufactured by BYK Co.
[ Evaluation of contamination resistance ]
The cured coating film for evaluation obtained above was exposed for 3 months in a factory made by DIC corporation of Dan Shi, osaka. The color difference (. DELTA.E) between the unwashed coating film after the exposure test and the coating film before the exposure test was evaluated by using "CM-3500d" manufactured by Konica Minolta Co. The smaller the above-mentioned color difference (Δe), the better the stain resistance.
[ Evaluation of processability ]
As an evaluation of processability, the elongation of the coating film was measured. The greater the elongation of the coating film, the more excellent the workability.
(Method for measuring elongation of coating film)
The active energy ray-curable resin composition obtained above was applied to a polyethylene terephthalate (PET) film having a thickness of 125 μm by a bar coater, and dried at 80℃for 1 minute. Next, ultraviolet rays (1000 mJ/cm 2) were irradiated with a high-pressure mercury lamp under an air atmosphere, whereby a laminate film in which a cured product having a film thickness of 5 μm was laminated on a PET film was obtained.
The laminate film was cut to obtain test pieces having a width of 10mm×a length of 100mm, and the obtained test pieces were subjected to a tensile test under the following conditions.
Autograph AGS-1kNG (stretching speed: 10 mm/min, distance between chucks: 40mm, measuring atmosphere: 25 ℃ C.) manufactured by Shimadzu corporation.
( Examples 2 to 15: preparation of active energy ray-curable resin compositions (2) to (15) )
The same procedure as in example 1 was repeated except that the blending ratios shown in tables 3 to 5 were changed, and the active energy ray-curable resin compositions (2) to (15) were obtained and then evaluated.
( Comparative examples 1 to 3: preparation of acrylic acrylate resins (R1) to (R3) )
The same procedure as in example 1 was repeated except that the blending ratios shown in table 6 were changed, and active energy ray-curable resin compositions (R1) to (R3) were obtained, and then each evaluation was performed.
The compositions and evaluation results of the active energy ray-curable resins (1) to (15) and (R1) to (R3) prepared in examples 1 to 15 and comparative examples 1 to 3 are shown in tables 3 to 6.
TABLE 3
TABLE 4
TABLE 5
Abbreviations in table 5 are as follows.
DPHA: mixtures of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate
PETA: mixtures of pentaerythritol tetraacrylate and pentaerythritol triacrylate
Photopolymerization initiator: omnirad184 (IGM RESINS company "Omnirad 184")
TABLE 6
The cured coatings obtained in examples 1 to 15, which were active energy ray-curable resin compositions of the present invention, were confirmed to be excellent in coating appearance, adhesion, solvent resistance, scratch resistance, weather resistance, stain resistance and processability.
On the other hand, comparative example 1 was an example in which the acrylic (meth) acrylate (B) as an essential component of the present invention was not contained, and it was confirmed that the elongation of the coating film was low and the processability was insufficient.
Comparative example 2 is an example in which the composite resin (a) which is an essential component of the present invention was not contained, and it was confirmed that the weather resistance was insufficient.
Comparative example 3 shows that the acrylic (meth) acrylate (B) has a weight average molecular weight lower than 10,000 as the lower limit, and the coating film elongation is low and the processability is insufficient.

Claims (7)

1. An active energy ray-curable resin composition comprising a composite resin (A) wherein a polysiloxane segment (a 1) and a vinyl polymer segment (a 2) are bonded to each other by a bond represented by the general formula (3), an acrylic (meth) acrylate resin (B) having a weight average molecular weight of 10000 to 70000, and a silanol group and/or hydrolyzable silyl group, wherein the polysiloxane segment (a 1) has a structural unit represented by the general formula (1) and/or the general formula (2), and the photopolymerization initiator (C),
In the general formulae (1) and (2), R 1、R2 and R 3 each independently represent a group having a polymerizable double bond selected from the group consisting of -R4-CH＝CH2、-R4-C(CH3)＝CH2、-R4-O-CO-C(CH3)＝CH2 and-R 4-O-CO-CH＝CH2, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, and an aralkyl group having 7 to 12 carbon atoms, wherein R 4 represents a single bond or an alkylene group having 1 to 6 carbon atoms,
In the general formula (3), a carbon atom forms part of the vinyl-based polymer segment (a 2), and only a silicon atom bonded to an oxygen atom forms part of the polysiloxane segment (a 1).
2. The active energy ray-curable resin composition according to claim 1, wherein the acrylic (meth) acrylate resin (B) is a reaction product of an acrylic polymer (B1) containing a glycidyl group-containing (meth) acrylate monomer (x 1) as an essential raw material and a hydroxyl group-containing (meth) acrylate monomer (x 2) and/or a carboxyl group-containing (meth) acrylate monomer (x 3).
3. The active energy ray-curable resin composition according to claim 1 or 2, wherein the (meth) acryl equivalent of the acrylic (meth) acrylate resin (B) is 300g/eq to 3000g/eq.
4. The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein a mass ratio of the composite resin (a) to the acrylic (meth) acrylate resin (B), i.e., a/B, is 2/98 to 90/10.
5. The active energy ray-curable resin composition according to any one of claims 1 to 4, wherein the content of the polysiloxane segment (a 1) in the total resin components is 2 to 55 mass%.
6. A cured coating film of the active energy ray-curable resin composition according to any one of claims 1 to 5.
7. An article having the cured coating film of claim 6.
CN202280070665.2A 2021-12-23 2022-12-01 Active energy ray-curable resin composition, cured coating film, and article Pending CN118234768A (en)

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