WO2023120089A1 - Composition de résine durcissable par rayonnement d'énergie active, revêtement durci et article - Google Patents

Composition de résine durcissable par rayonnement d'énergie active, revêtement durci et article Download PDF

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WO2023120089A1
WO2023120089A1 PCT/JP2022/044315 JP2022044315W WO2023120089A1 WO 2023120089 A1 WO2023120089 A1 WO 2023120089A1 JP 2022044315 W JP2022044315 W JP 2022044315W WO 2023120089 A1 WO2023120089 A1 WO 2023120089A1
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group
meth
acrylate
active energy
mass
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PCT/JP2022/044315
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English (en)
Japanese (ja)
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理恵 桐澤
直人 井上
隆 向井
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Dic株式会社
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Priority to JP2023562742A priority Critical patent/JP7495016B2/ja
Priority to CN202280070665.2A priority patent/CN118234768A/zh
Priority to KR1020247010310A priority patent/KR20240051227A/ko
Publication of WO2023120089A1 publication Critical patent/WO2023120089A1/fr

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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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to active energy ray-curable resin compositions, cured coating films, and articles.
  • thermoplastic resin materials typified by plastics have been widely used in the construction field, as well as in the automotive field, due to their lightness, impact resistance, workability, and recyclability.
  • plastics since it has problems such as poor weather resistance, stain resistance, heat resistance, solvent resistance, and yellowing resistance, it is often used to supplement performance by providing a coating layer.
  • This UV-curable resin composition contains a composite resin having a polysiloxane segment and a vinyl polymer segment. Due to its poor durability, there were problems such as cracks during processing with high designability and processing after painting.
  • the problem to be solved by the present invention is an active energy ray-curable resin capable of forming a coating film having excellent coating film appearance, adhesion, solvent resistance, scratch resistance, weather resistance, stain resistance, and workability. To provide compositions, cured coatings and articles.
  • an active energy ray-curable resin composition containing a specific composite resin, a specific acrylic (meth)acrylate resin, and a photopolymerization initiator can be used.
  • the inventors have found that the above problems can be solved, and have completed the present invention.
  • the present invention provides an active energy ray-curable resin composition containing a composite resin (A), an acrylic (meth)acrylate resin (B), and a photopolymerization initiator (C), wherein the composite resin (A ) has a structural unit represented by the general formula (1) and / or general formula (2), a polysiloxane segment (a1) having a silanol group and / or a hydrolyzable silyl group, and a vinyl polymer segment (a2) is bonded by a bond represented by general formula (3), and the acrylic (meth)acrylate resin (B) has a weight average molecular weight of 10,000 to 70,000. It relates to an active energy ray-curable resin composition, a cured coating film and an article characterized by
  • the active energy ray-curable resin composition of the present invention can form a cured coating film having excellent coating film appearance, adhesion, solvent resistance, scratch resistance, weather resistance, stain resistance, and workability, It can be used as a coating agent or an adhesive, and can be particularly preferably used as a coating agent.
  • the active energy ray-curable resin composition of the present invention is an active energy ray-curable resin composition containing a composite resin (A), an acrylic (meth)acrylate resin (B), and a photopolymerization initiator (C).
  • the composite resin (A) is a polysiloxane segment (a1) having a structural unit represented by general formula (1) and / or general formula (2) and a silanol group and / or a hydrolyzable silyl group and the vinyl polymer segment (a2) are bonded by the bond represented by the general formula (3), and the weight average molecular weight of the acrylic (meth)acrylate resin (B) is 10,000. ⁇ 70,000.
  • the composite resin (A) is a polysiloxane segment (a1) having a structural unit represented by the general formula (1) and / or the general formula (2) and a silanol group and / or a hydrolyzable silyl group. (hereinafter simply referred to as polysiloxane segment (a1)) and a vinyl polymer segment (a2) having an alcoholic hydroxyl group (hereinafter simply referred to as vinyl polymer segment (a2)) are represented by the general formula (3) It is a composite resin bonded by a bond represented by
  • the bond represented by the general formula (3) is generated. Therefore, in the general formula (3), the carbon atom constitutes a part of the vinyl polymer segment (a2), and the silicon atom bonded only to the oxygen atom constitutes a part of the polysiloxane segment (a1).
  • the form of the composite resin (A) is, for example, a composite resin having a graft structure in which the polysiloxane segment (a1) is chemically bonded as a side chain of the polymer segment (a2), or the polymer segment (a2) and a composite resin having a block structure in which the polysiloxane segment (a1) is chemically bonded.
  • the polysiloxane segment (a1) is a segment having a structural unit represented by general formula (1) and/or general formula (2) and a silanol group and/or a hydrolyzable silyl group.
  • a group having a polymerizable double bond is included in the structural unit represented by general formula (1) and/or general formula (2).
  • the structural unit represented by the general formula (1) and/or the general formula (2) has a group having a polymerizable double bond as an essential component.
  • alkylene group having 1 to 6 carbon atoms in R 4 examples include methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, Pentylene group, isopentylene group, neopentylene group, tert-pentylene group, 1-methylbutylene group, 2-methylbutylene group, 1,2-dimethylpropylene group, 1-ethylpropylene group, hexylene group, isohesylene group, 1-methylpentylene group Lene group, 2-methylpentylene group, 3-methylpentylene group, 1,1-dimethylbutylene group, 1,2-dimethylbutylene group, 2,2-dimethylbutylene group, 1-ethylbutylene group, 1,1 ,2-trimethylpropylene group, 1,2,2-trimethylpropylene group, 1-ethyl-2-methylpropylene group, 1-e
  • alkyl group having 1 to 6 carbon atoms examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group and isopentyl.
  • Examples of the cycloalkyl group having 3 to 8 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
  • Examples of the aryl group include phenyl group, naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-vinylphenyl group and 3-isopropylphenyl group.
  • Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group, diphenylmethyl group and naphthylmethyl group.
  • R 1 , R 2 and R 3 are a group having a polymerizable double bond
  • the polysiloxane segment (a1) is represented by the general formula (1)
  • R 1 is the group having a polymerizable double bond
  • R 2 and / or R 3 is a group having a polymerizable double bond
  • R At least one of 1 , R 2 and R 3 is a group having a polymerizable double bond.
  • polymerizable double bonds are present in the polysiloxane segment (a1), more preferably 3 to 200, even more preferably 3 to 50, to improve durability.
  • An excellent coating film can be obtained.
  • the content of polymerizable double bonds in the polysiloxane segment (a1) is 3 to 35% by weight, desired weather resistance and adhesion can be obtained.
  • the term "polymerizable double bond" as used herein is a general term for a group, among vinyl groups, vinylidene groups and vinylene groups, which can undergo a propagating reaction by free radicals.
  • the content of polymerizable double bonds indicates the weight percentage of the vinyl group, vinylidene group or vinylene group in the polysiloxane segment.
  • the structural unit represented by the general formula (1) and/or the general formula (2) is a three-dimensional network polysiloxane structural unit in which two or three silicon bonds are involved in cross-linking. Although it forms a three-dimensional network structure, it does not form a dense network structure, so that gelation or the like does not occur during production or primer formation, and storage stability is improved.
  • a silanol group in the present invention is a silicon-containing group having a hydroxyl group directly bonded to a silicon atom.
  • the silanol group is a silanol group formed by bonding an oxygen atom having a bond to a hydrogen atom in the structural unit represented by the general formula (1) and/or the general formula (2).
  • the structural unit represented by the general formula (1) and/or the general formula (2) Preferably.
  • the hydrolyzable silyl group is a silicon-containing group having a hydrolyzable group directly bonded to a silicon atom, and specific examples thereof include groups represented by general formula (4). .
  • R 5 is a monovalent organic group such as an alkyl group, an aryl group or an aralkyl group
  • R 6 is a halogen atom, an alkoxy group, an acyloxy group, a phenoxy group, an aryloxy group, a mercapto group
  • a hydrolyzable group selected from the group consisting of an amino group, an amido group, an aminooxy group, an iminooxy group and an alkenyloxy group, and b is an integer of 0 to 2.
  • alkyl group for R 5 examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert -pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, hexyl group, isohesyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group , 1-ethyl-2-methylpropyl group, 1-ethyl-1-methylpropyl group
  • aryl groups include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, and 3-isopropylphenyl groups.
  • Aralkyl groups include, for example, a benzyl group, a diphenylmethyl group, a naphthylmethyl group and the like.
  • the halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
  • alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, and tert-butoxy groups.
  • acyloxy groups include formyloxy, acetoxy, propanoyloxy, butanoyloxy, pivaloyloxy, pentanoyloxy, phenylacetoxy, acetoacetoxy, benzoyloxy, naphthoyloxy and the like.
  • aryloxy groups include phenyloxy and naphthyloxy.
  • alkenyloxy groups include vinyloxy, allyloxy, 1-propenyloxy, isopropenyloxy, 2-butenyloxy, 3-butenyloxy, 2-petenyloxy, 3-methyl-3-butenyloxy, 2 -hexenyloxy group and the like.
  • the hydrolyzable silyl group represented by general formula (4) becomes a silanol group.
  • a methoxy group and an ethoxy group are preferable because they are excellent in hydrolyzability.
  • the hydrolyzable silyl group is such that 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 the hydrolyzable group.
  • it is preferably a substituted hydrolyzable silyl group.
  • the silanol group and the hydrolyzable silyl group are added to the hydroxyl group in the silanol group and the hydrolyzable silyl group in parallel with the curing reaction during the coating film formation by the curing reaction of the group having the polymerizable double bond. Since the hydrolytic condensation reaction proceeds between the hydrolyzable groups in the groups, the cross-linking density of the polysiloxane structure of the resulting coating film increases, and a coating film having excellent solvent resistance and the like can be formed. Further, the polysiloxane segment (a1) containing the silanol group or the hydrolyzable silyl group and the vinyl-based polymer segment (a2) described later are bonded via the bond represented by the general formula (3). Use when
  • the polysiloxane segment (a1) is not particularly limited except that it has a structural unit represented by the general formula (1) and / or the general formula (2) and a silanol group and / or a hydrolyzable silyl group. , may contain other groups.
  • Polysiloxane in which a structural unit in which R 1 in the general formula (1) is a 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 methyl It may be the segment (a1), A structural unit in which R 1 in the general formula (1) is a group having a polymerizable double bond, a structural unit in which R 1 in the general formula (1) is an alkyl group such as a methyl group, and the general formula It may be a polysiloxane segment (a1) in which R 2 and R 3 in (2) coexist with a structural unit that is an alkyl group such as a methyl group, 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 2 and R 3 in the general formula (2) are an alkyl group such as a methyl group It may be a coexisting polysiloxane segment (a1), and is not particularly limited. Specifically
  • the vinyl polymer segment (a2) 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.
  • An acrylic polymer segment is preferable because the obtained coating film has excellent transparency and gloss.
  • 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 can also be copolymerized.
  • the vinyl-based polymer segment (a2) is more preferably a (meth)acrylic repeating unit having a cyclic hydrocarbon group from the viewpoint of improving adhesion to the plastic substrate.
  • the (meth)acrylic repeating unit having a cyclic hydrocarbon group is preferably cyclohexyl (meth)acrylate, cyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, tetracyclododecanyl ( (Meth)acrylates having a cyclic hydrocarbon group such as meth)acrylates, dicyclopentanyl (meth)acrylates, and isobornyl acrylates can be mentioned. These can be used alone or in combination of two or more.
  • the vinyl polymer segment (a2) can be obtained by a known method.
  • a vinyl polymer segment (a2) can be obtained using a polymerization initiator such as tert-butyl peroxide, cumene hydroperoxide, diisopropyl peroxycarbonate and the like.
  • the number average molecular weight of the vinyl polymer segment (a2) is preferably 500 to 200,000 in terms of number average molecular weight (hereinafter abbreviated as Mn). and gelation can be prevented, and the durability is excellent.
  • Mn is more preferably in the range of 700 to 100,000, and more preferably 1,000 to 50,000 for reasons of coating suitability and adhesion to substrates, which will be described later.
  • the vinyl polymer segment (a2) is a vinyl polymer segment ( It has a silanol group and/or a hydrolyzable silyl group directly bonded to the carbon bond in a2). 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, so the composite resin (A ) in the vinyl-based polymer segment (a2).
  • the vinyl polymer segment (a2) having a silanol group and/or a hydrolyzable silyl group directly bonded to a carbon bond specifically includes the general-purpose monomer, and a silanol group and/or a silanol group directly bonded to a carbon bond. It is obtained by copolymerizing a vinyl monomer containing a hydrolyzable silyl group.
  • Examples of vinyl-based monomers containing silanol groups and/or hydrolyzable silyl groups directly bonded to carbon bonds include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and vinyltri(2-methoxyethoxy)silane.
  • the vinyl polymer segment (a2) preferably has an alcoholic hydroxyl group.
  • the vinyl polymer segment (a2) having an alcoholic hydroxyl group can be obtained by copolymerizing a (meth)acrylic monomer having an alcoholic hydroxyl group.
  • (meth)acrylic monomers having an alcohol hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl mono Butyl fumarate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, "PLAXEL FM or PLAXEL FA” [caprolactone addition monomer manufactured by Daicel Chemical Industries, Ltd.] and other ⁇ , ⁇ -ethylenically unsaturated Hydroxyalkyl esters of saturated carboxylic acids, adducts of these with ⁇ -caprolactone, and the like
  • the amount of alcoholic hydroxyl groups is preferably calculated from the amount of polyisocyanate to be added, which will be described later, and determined appropriately. As will be described later, in the present invention, it is more preferable to use an active energy ray-curable monomer having an alcoholic hydroxyl group in combination. Therefore, the amount of alcoholic hydroxyl groups in the vinyl polymer segment (a2) having alcoholic hydroxyl groups can be determined by taking into consideration the amount of the active energy ray-curable monomer having alcoholic hydroxyl groups used in combination. It is preferable that the hydroxyl value of the vinyl polymer segment (a2) is substantially in the range of 30 to 300 in terms of hydroxyl value.
  • the composite resin (A) is specifically produced by the methods shown in (Method 1) to (Method 3) below.
  • Method 1 Copolymerizing the general-purpose (meth)acrylic monomer or the like and a vinyl monomer containing a silanol group and/or a hydrolyzable silyl group directly bonded to the carbon bond to directly bond to the carbon bond
  • a vinyl polymer segment (a2) containing a silanol group and/or a hydrolyzable silyl group is obtained.
  • This is mixed with 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, and is subjected to a hydrolytic condensation reaction.
  • 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 directly bonded to a carbon bond and/or hydrolyzed The silanol group and / or hydrolyzable silyl group of the vinyl polymer segment (a2) containing a silyl group undergoes a hydrolytic condensation reaction to form the polysiloxane segment (a1), and the polysiloxane
  • a composite resin (A) is obtained in which the segment (a1) and the vinyl polymer segment (a2) are combined by the bond represented by the general formula (3).
  • Method 2 In the same manner as in Method 1, a vinyl polymer segment (a2) containing silanol groups and/or hydrolyzable silyl groups directly bonded to carbon bonds is obtained.
  • 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 (a1).
  • Method 3 As in Method 1, a vinyl polymer segment (a2) containing silanol groups and/or hydrolyzable silyl groups directly bonded to carbon bonds is obtained. On the other hand, a polysiloxane segment (a1) is obtained in the same manner as in Method 2. Furthermore, a silane compound containing a silane compound having a polymerizable double bond and, if necessary, a general-purpose silane compound are mixed together for hydrolytic condensation reaction.
  • General-purpose silane compounds used in (Method 1) to (Method 3) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, n-propyl various organotrialkoxysilanes such as trimethoxysilane, iso-butyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane; , diethyldimethoxysilane, diphenyldimethoxysilane, methylcyclohexyldimethoxysilane or methylphenyldimethoxysilane; various diorganodialkoxysilanes; methylt
  • a tetrafunctional alkoxysilane compound such as tetramethoxysilane, tetraethoxysilane or tetra-n-propoxysilane, or a partial hydrolysis condensate of the tetrafunctional alkoxysilane compound may be used in combination as long as the effects of the present invention are not impaired. can.
  • the tetrafunctional alkoxysilane compound or a partial hydrolyzed condensate thereof is used in combination, the silicon atoms possessed by the tetrafunctional alkoxysilane compound are 20 relative to the total silicon atoms constituting the polysiloxane segment (a1). It is preferable to use them in combination so as not to exceed the molar percentage.
  • the silane compound can be used in combination with a metal alkoxide compound other than a silicon atom, such as boron, titanium, zirconium or aluminum, as long as the effects of the present invention are not impaired.
  • a metal alkoxide compound other than a silicon atom such as boron, titanium, zirconium or aluminum
  • catalysts to be 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 or potassium hydroxide; , Titanic acid esters such as tetrabutyl titanate; 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1 , 4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole, 1-methylimidazole, and various other compounds containing basic nitrogen atoms; Various quaternary ammonium salts such as tetramethylammonium salts, tetrabutylammonium salts and dilauryldimethyl
  • the amount of the catalyst added is not particularly limited, but it is generally preferable to use it in the range of 0.0001 to 10% by weight with respect to the total amount of each compound having a silanol group or a hydrolyzable silyl group. , more preferably in the range of 0.0005 to 3% by weight, and particularly preferably in the range of 0.001 to 1% by weight.
  • the amount of water to be supplied is preferably 0.05 mol or more, preferably 0.1 mol, per 1 mol of the silanol group or hydrolyzable silyl group possessed by each compound having a silanol group or hydrolyzable silyl group.
  • the above is more preferable, and 0.5 mol or more is particularly preferable.
  • These catalyst and water may be supplied all at once or sequentially, or may be supplied as a mixture of the catalyst and water in advance.
  • the reaction temperature for the hydrolytic condensation reaction in (Method 1) to (Method 3) is appropriately in the range of 0°C to 150°C, preferably in the range of 20°C to 100°C.
  • the reaction can be carried out under any conditions of normal pressure, increased pressure, or reduced pressure.
  • alcohol and water, which are by-products that may be produced in the hydrolytic condensation reaction may be removed by a method such as distillation, if necessary.
  • the charging ratio of each compound in (Method 1) to (Method 3) is appropriately selected according to the desired structure of the composite resin (A) used in the present invention. Among them, it is preferable to obtain the composite resin (A) so that the content of the polysiloxane segment (a1) is 30 to 95% by weight, and 50 to 95% by weight is preferable, because the durability of the resulting coating film is excellent. More preferred.
  • the vinyl polymer segment contains a silanol group and / or hydrolyzable A silane compound having both a silyl group and a polymerizable double bond and, if necessary, a general-purpose silane compound are mixed, and hydrolytic condensation reaction is carried out.
  • the main chain of the vinyl polymer segment is Using a vinyl polymer segment having a structure in which the silanol groups and/or hydrolyzable silyl groups are randomly distributed as an intermediate, for example, in (Method 2), the vinyl polymer segment is A method of hydrolyzing and condensing the silanol group and/or hydrolyzable silyl group possessed with the silanol group and/or hydrolyzable silyl group possessed by the polysiloxane segment described above can be mentioned.
  • the vinyl polymer segment (a2) in the composite resin (A) has an alcoholic hydroxyl group
  • a coating film having particularly excellent long-term weather resistance specifically, crack resistance
  • the polyisocyanate reacts with the hydroxyl group in the system (this is the hydroxyl group in the vinyl polymer segment (a2) or the hydroxyl group in the active energy ray-curable monomer having an alcoholic hydroxyl group described later).
  • urethane bonds which are soft segments, are formed, and it is presumed that the concentration of stress due to curing derived from polymerizable double bonds is alleviated.
  • the polyisocyanate to be used is not particularly limited, and known ones can be used.
  • ⁇ ', ⁇ '-tetramethyl-meta-xylylene diisocyanate and other aralkyl diisocyanates as main raw materials have the problem of yellowing of the cured coating film when exposed to the outdoors for a long period of time. Minimize is preferred.
  • aliphatic polyisocyanates containing aliphatic diisocyanates as main raw materials are suitable as the polyisocyanates used in the present invention.
  • Aliphatic diisocyanates include, for example, tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (hereinafter abbreviated as “HDI”), 2,2,4- (or 2,4,4 -trimethyl-1,6-hexamethylene diisocyanate, lysine isocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,4-diisocyanatocyclohexane, 1,3-bis(diisocyanatomethyl)cyclohexane, 4,4 '-dicyclohexylmethane diisocyanate, etc.
  • HDI is particularly prefer
  • Aliphatic polyisocyanates obtained from aliphatic diisocyanates include allophanate-type polyisocyanates, biuret-type polyisocyanates, adduct-type polyisocyanates and isocyanurate-type polyisocyanates, all of which can be suitably used.
  • blocked polyisocyanate compounds blocked with various blocking agents.
  • blocking agents include alcohols such as methanol, ethanol, and lactate; phenolic hydroxyl group-containing compounds such as phenol and salicylate; amides such as ⁇ -caprolactam and 2-pyrrolidone; oximes such as acetone oxime and methyl ethyl ketoxime. and active methylene compounds such as methyl acetoacetate, ethyl acetoacetate, and acetylacetone.
  • the content of isocyanate groups in the polyisocyanate is preferably 3 to 30% by weight from the viewpoint of crack resistance and abrasion resistance of the resulting cured coating film. If the isocyanate group content in the polyisocyanate is more than 30%, the molecular weight of the polyisocyanate becomes small, and crack resistance due to stress relaxation may not be exhibited.
  • the reaction between the polyisocyanate and the hydroxyl group in the system is particularly Heating or the like is not necessary.
  • the reaction gradually occurs by leaving it at room temperature after coating and irradiating with ultraviolet rays.
  • the reaction between the alcoholic hydroxyl group and the isocyanate may be accelerated by heating at 80° C. for several minutes to several hours (20 minutes to 4 hours) after the ultraviolet irradiation.
  • the urethanization catalyst is appropriately selected according to the desired reaction temperature.
  • acrylic (meth)acrylate resin (B) for example, a (meth)acrylate monomer ( ⁇ ) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group is polymerized as an essential component.
  • (meth)acryloyl group is introduced by further reacting the acrylic resin intermediate obtained above with a (meth)acrylate monomer ( ⁇ ) having a functional group capable of reacting with the reactive functional group.
  • (meth)acrylate resin refers to a resin having a (meth)acryloyl group in the molecule
  • (meth)acryloyl group refers to either an acryloyl group or a methacryloyl group, or I mean both.
  • (meth)acrylate refers to one or both of acrylate and methacrylate.
  • the (meth)acrylate monomer ( ⁇ ) having a reactive functional group includes, for example, hydroxyl group-containing (meth)acrylate monomers such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate; Group-containing (meth) acrylate monomer; isocyanate group-containing (meth) acrylate monomer such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate; glycidyl (meth) acrylate and glycidyl group-containing (meth)acrylate monomers such as 4-hydroxybutyl acrylate glycidyl ether.
  • These (meth)acrylate monomers having a reactive functional group can be used alone or in combination of two or more.
  • the acrylic resin intermediate has better adhesion to the substrate and forms a cured product with better workability, scratch resistance and chemical resistance, so the glass transition temperature (Tg) of the homopolymer is 50 C. or higher (meth)acrylate monomers are preferably copolymerized.
  • examples of such monomers include methyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, Acrylate, adamantyl (meth)acrylate and the like.
  • At least one of these monomers is used because it provides an acrylic (meth)acrylate resin that has excellent substrate adhesion and can form a cured product with excellent workability, scratch resistance, and chemical resistance. It is preferable to use them, more preferably two or more of them are used in combination, and at least one of them is preferably methyl (meth)acrylate.
  • the value of the glass transition temperature of the homopolymer of each component can be found in Nikkan Kogyo Shimbun's "Adhesive Technology Handbook", Wiley-Interscience's "Polymer Handbook", Introduction to Paint Resins, Kyoeisha Chemical Co., Ltd. HP, Values described in the website of Mitsubishi Chemical Corporation can be adopted.
  • polymerizable unsaturated group-containing compounds can be copolymerized with the acrylic resin intermediate, if necessary.
  • Other polymerizable unsaturated group-containing compounds for example, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate (meth) acrylic acid alkyl esters; isobornyl Cyclo ring-containing (meth) acrylates such as (meth) acrylate and dicyclopentanyl (meth) acrylate; Aromatic ring-containing (meth) acrylates such as phenyl (meth) acrylate and phenoxyethyl acrylate; 3-methacryloxypropyltrimethoxysilane silyl group-containing (meth)acrylates such as styrene; styrene derivatives such as styrene, ⁇ -methylstyrene and chlor
  • the reaction ratio of the two is excellent. Since it becomes an acrylic (meth)acrylate resin having adhesiveness, workability, scratch resistance and chemical resistance, the (meth)acrylate monomer ( ⁇ ) is 5 to 95% by mass in the total of both. is preferred, and 25 to 65% is more preferred.
  • the method for producing the acrylic resin intermediate can be produced in the same manner as for general acrylic resins.
  • it can be produced by polymerizing various monomers in a temperature range of 60 to 150° C. in the presence of a polymerization initiator.
  • Polymerization methods include, for example, bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.
  • the polymerization mode includes, for example, random copolymers, block copolymers, graft copolymers, and the like.
  • ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone
  • glycol ether solvents such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether are preferably used. can be done.
  • the (meth)acrylate monomer ( ⁇ ) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate monomer ( ⁇ ). From the viewpoint of reactivity, the following combinations are preferred: is preferred. That is, when the hydroxyl group-containing (meth)acrylate is used as the (meth)acrylate monomer ( ⁇ ), it is preferable to use an isocyanate group-containing (meth)acrylate as the (meth)acrylate monomer ( ⁇ ). When the carboxy group-containing (meth)acrylate is used as the (meth)acrylate monomer ( ⁇ ), it is preferable to use the glycidyl group-containing (meth)acrylate as the (meth)acrylate monomer ( ⁇ ).
  • the isocyanate group-containing (meth)acrylate is used as the (meth)acrylate monomer ( ⁇ )
  • the glycidyl group-containing (meth)acrylate is used as the (meth)acrylate monomer ( ⁇ )
  • the reaction between the acrylic resin intermediate and the (meth)acrylate monomer ( ⁇ ) is, for example, when the reaction is an esterification reaction, esterification of triphenylphosphine or the like at a temperature range of 60 to 150 ° C. Methods such as using a catalyst as appropriate can be mentioned. Further, when the reaction is a urethanization reaction, a method of reacting the acrylic resin intermediate while dropping the (meth)acrylate monomer ( ⁇ ) at a temperature range of 50 to 120° C. may be used. .
  • the reaction ratio between the two is preferably in the range of 0.95 to 1.1 mol of the (meth)acrylate monomer ( ⁇ ) per 1 mol of functional groups in the acrylic resin intermediate.
  • the acrylic (meth)acrylate resin (B) is composed of a (meth)acrylate monomer from the viewpoint of having excellent substrate adhesion and having better workability, scratch resistance, and chemical resistance.
  • an acrylic polymer (b1) containing a glycidyl group-containing (meth)acrylate monomer (x1) as an essential raw material is added to a hydroxyl group-containing (meth)acrylate monomer (x2) and / or a carboxy group-containing (meth) It is obtained by reacting an acrylate monomer (x3), and it is more preferable that the glycidyl group-containing (meth)acrylate monomer (x1) is used in an amount of 3 to 60 parts by mass, 5 to 40 parts by mass. It is more preferable to use the one used in the above.
  • the acrylic polymer (b1) is preferably a copolymer of a glycidyl group-containing (meth)acrylate monomer (x1) and a (meth)acrylic acid alkyl ester. More preferably, the alkyl ester is (meth)acrylic acid methyl ester.
  • the (meth)acryloyl group equivalent of the acrylic (meth)acrylate resin (B) is preferably 300 to 3,000 g/equivalent, particularly 400 to 2, because the balance of durability such as weather resistance and workability is further improved. ,000 g/equivalent is preferred.
  • the (meth)acryloyl group equivalent of the acrylic (meth)acrylate resin (B) in the present invention is a theoretical value calculated from reaction raw materials.
  • the weight average molecular weight (Mw) of the acrylic (meth)acrylate resin (B) is 10,000 to 70,000, and it has excellent substrate adhesion, workability, scratch resistance and resistance. 20,000 to 40,000 is more preferable because the chemical balance is further improved.
  • the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mn/Mw) are values measured by gel permeation chromatography (GPC).
  • the mass ratio (A/B) of the composite resin (A) and the (meth)acrylate resin (B) is 2/98 because a coating film having excellent durability such as weather resistance and workability can be obtained. ⁇ 90/10 is preferred, 5/95 to 65/35 is more preferred, and 10/90 to 50/50 is even more preferred.
  • the active energy ray-curable resin composition of the present invention contains the composite resin (A) and the acrylic (meth)acrylate resin (B), and contains other active energy ray-curable components.
  • the content of active energy ray-curable components with a weight average molecular weight of 5,000 or less is It is preferably 30% by mass or less in the total mass of the curable components.
  • Examples of the other active energy ray-curable components include (meth)acrylate compounds other than the acrylic (meth)acrylate resin (B).
  • Other (meth)acrylate compounds include, for example, dendrimer-type (meth)acrylate resins, urethane (meth)acrylate resins, epoxy (meth)acrylate resins, mono(meth)acrylate compounds and modified products thereof, aliphatic hydrocarbon-type poly (Meth)acrylate compounds and modified products thereof, alicyclic poly(meth)acrylate compounds and modified products thereof, aromatic poly(meth)acrylate compounds and modified products thereof, and the like. Each of these may be used alone, or two or more of them may be used in combination.
  • the content of the polysiloxane segment (a1) in all resin components including the composite resin (A) and the acrylic (meth)acrylate resin (B) further improves the balance between durability such as weather resistance and workability. Therefore, is preferably 2 to 55% by mass, more preferably 4 to 40% by mass.
  • Examples of the photopolymerization initiator (C) include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl] -2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethan-1-one, diphenyl (2,4,6-trimethoxy benzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone and other photoradical polymerization initiators.
  • the amount of the photopolymerization initiator (C) added is, for example, preferably in the range of 0.05 to 15% by mass in the total amount of components other than the solvent of the active energy ray-curable resin composition, and 0.1 It is more preferably in the range of ⁇ 10% by mass.
  • the photopolymerization initiator can also be 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, if necessary.
  • 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, if necessary.
  • the active energy ray-curable resin composition of the present invention may contain other components than those mentioned above.
  • other components include inorganic fine particles, silane coupling agents, phosphate ester compounds, solvents, ultraviolet absorbers, antioxidants, silicon-based additives, fluorine-based additives, antistatic agents, organic beads, quantum Dots (QD), rheology control agents, defoaming agents, anti-fogging 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 commonly used inorganic fine particles can be used. Examples include fine particles of silica, alumina, zirconia, titania, barium titanate, antimony trioxide, and the like. Each of these may be used alone, or two or more of them may be used in combination.
  • silica particles are preferable because they are easily available and easy to handle.
  • Silica particles include, for example, various silica particles such as fumed silica, wet silica called precipitated silica, gel silica, sol-gel silica, and the like, and any of them may be used.
  • the inorganic fine particles may be those in which a functional group is introduced on the fine particle surface using various silane coupling agents.
  • a functional group By introducing a functional group to the surface of the inorganic fine particles, miscibility with organic components such as the acrylic (meth)acrylate resin (B) is increased, and storage stability is improved.
  • Silane coupling agents that modify the inorganic fine particles include, for example, [(meth)acryloyloxyalkyl]trialkylsilane, [(meth)acryloyloxyalkyl]dialkylalkoxysilane, [(meth)acryloyloxyalkyl]alkyldialkoxysilane , [(meth)acryloyloxyalkyl]trialkoxysilane, corresponding (meth)acryloyloxy-based silane coupling agent; trialkylvinylsilane, dialkylalkoxyvinylsilane, alkyldialkoxyvinylsilane, trialkoxyvinylsilane, trialkylallylsilane, dialkylalkoxyallylsilane , alkyldialkoxyallylsilane, trialkoxyallylsilane and other vinyl-based silane coupling agents; styryltrialkyl, styryldialkylalkoxysilane,
  • the (meth) acryloyloxy-based silane coupling agent is preferable because it becomes inorganic fine particles having excellent miscibility with organic components such as the acrylic (meth) acrylate resin, and 3-(meth) [(Meth)acryloyloxyalkyl]trialkoxysilanes such as acryloyloxypropyltrimethoxysilane are particularly preferred.
  • the average particle size of the inorganic fine particles is not particularly limited, and may be adjusted as appropriate according to the desired performance of the cured product.
  • the average particle diameter of the inorganic fine particles is preferably in the range of 80 to 250 nm, since a cured coating film having excellent blocking resistance, transparency, etc., as well as scratch resistance and anti-cracking properties can be obtained.
  • a range of 90 to 180 nm is more preferred, and a range of 100 to 150 nm is particularly preferred.
  • the average particle size of the inorganic fine particles is a value obtained by measuring the particle size in the active energy ray-curable resin composition under the following conditions.
  • Particle size measuring device "ELSZ-2" manufactured by Otsuka Electronics Co., Ltd.
  • Particle size measurement sample A methyl isobutyl ketone solution having a non-volatile content of 1% by mass of an active energy ray-curable resin composition.
  • 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 performance of the cured product.
  • the content of the inorganic fine particles is preferably in the range of 10 to 100 parts by mass with respect to 100 parts by mass of the acrylic (meth)acrylate resin because a cured coating film having excellent scratch resistance can be obtained.
  • Silane coupling agents added to the active energy ray-curable resin composition include, for example, [(meth)acryloyloxyalkyl]trialkylsilane, [(meth)acryloyloxyalkyl]dialkylalkoxysilane, [(meth)acryloyloxy (meth)acryloyloxy-based silane coupling agents such as alkyl]alkyldialkoxysilanes and [(meth)acryloyloxyalkyl]trialkoxysilanes; trialkylvinylsilanes, dialkylalkoxyvinylsilanes, alkyldialkoxyvinylsilanes, trialkoxyvinylsilanes, trialkyl Vinyl silane coupling agents such as allylsilane, dialkylalkoxyallylsilane, alkyldialkoxyallylsilane, and trialkoxyallylsilane; styrene silane coupling agents such as styryl
  • phosphate ester compound Commercially available products of the phosphate ester compound include, for example, "Kayamer PM-2” and “Kayamer PM-21” manufactured by Nippon Kayaku Co., Ltd., which are phosphate ester compounds having a (meth)acryloyl group in the molecular structure, "Light Ester P-1M”, “Light Ester P-2M”, “Light Acrylate P-1A (N)” manufactured by Kyoeisha Chemical Co., Ltd.
  • the solvent is added for purposes such as adjusting the coating viscosity of the active energy ray-curable resin composition, and the type and amount added are appropriately adjusted according to the desired performance. Generally, it is used so that the non-volatile content of the active energy ray-curable resin composition is in the range of 10 to 90% by mass.
  • the solvent examples 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; Solvents; Alicyclic solvents such as cyclohexane and methylcyclohexane; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene Examples thereof include glycol ether solvents such as glycol monopropyl ether. These solvents can be used alone or in combination of two or more.
  • Examples of the ultraviolet absorber include 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, triazine derivatives such as 3,5-triazine, 2-(2′-xanthenecarboxy-5′-methylphenyl)benzotriazole, 2-(2′-o-nitrobenzyloxy-5′-methylphenyl)benzotriazole, 2 -xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, and the like. These ultraviolet absorbers can be used alone or in combination of two or more.
  • antioxidants examples include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, and phosphate-based antioxidants. These antioxidants can be used alone or in combination of two or more.
  • silicon-based additive examples include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, fluorine-modified polyorganosiloxane having an alkyl group or a phenyl group such as a dimethylpolysiloxane copolymer and an amino-modified dimethylpolysiloxane copolymer; polydimethylsiloxane having a polyether-modified acrylic group; polydimethylsiloxane having a polyester-modified acrylic group; mentioned.
  • silicon additives can be used alone or in combination of two or more.
  • fluorine-based additives examples include the "Megaface” series manufactured by DIC Corporation. These fluorine-based additives can be used alone or in combination of two or more.
  • antistatic agent examples include pyridinium, imidazolium, phosphonium, ammonium, or lithium salts of bis(trifluoromethanesulfonyl)imide or bis(fluorosulfonyl)imide. These antistatic agents can be used alone or in combination of two or more.
  • organic beads examples include polymethylmethacrylate beads, polycarbonate beads, polystyrene beads, polyacrylstyrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, and polyolefin resin beads. , polyester resin beads, polyamide resin beads, polyimide resin beads, polyethylene fluoride resin beads, polyethylene resin beads, and the like. These organic beads can be used alone or in combination of two or more. Moreover, the average particle size of these organic beads is preferably in the range of 1 to 10 ⁇ m.
  • the quantum dots include II-V group semiconductor compounds, II-VI group semiconductor compounds, III-IV group semiconductor compounds, III-V group semiconductor compounds, III-VI group semiconductor compounds, and IV-VI group semiconductor compounds. , I-III-VI group semiconductor compounds, II-IV-VI group semiconductor compounds, II-IV-V group semiconductor compounds, I-II-IV-VI group semiconductor compounds, IV group elements or compounds containing these, etc. be done.
  • the II-VI group semiconductor compound is, for example, binary compounds such as ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe; Ternary compounds such as CdSeTe, CdSTe, CdHgS, CdHgSe, CdHgTe, HgSeS, HgSeTe, HgSTe, HgZnS, HgZnSe, HgZnTe; CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgST Quaternary such as e, CdHgZnTe, HgZnSeS, HgZnSeTe, HgZnSTe compounds and the like.
  • binary compounds such as ZnO, ZnS, ZnSe, ZnTe,
  • III-IV group semiconductor compounds examples include B 4 C 3 , Al 4 C 3 , Ga 4 C 3 and the like.
  • the III-V group semiconductor compounds are, for example, binary compounds such as BP, BN, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb; Ternary compounds such as GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP; NP , InAlNAs, InAlNSb, InAlPAs, and InAlPSb.
  • III-VI group semiconductor compounds are, for example, Al 2 S 3 , Al 2 Se 3 , Al 2 Te 3 , Ga 2 S 3 , Ga 2 Se 3 , Ga 2 Te 3 , GaTe, In 2 S 3 , In 2 Se3 , In2Te3 , InTe , etc. are mentioned.
  • the IV-VI group semiconductor compounds include, for example, binary compounds such as SnS, SnSe, SnTe, PbS, PbSe, and PbTe; ternary compounds such as SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, and SnPbTe quaternary compounds such as SnPbSSe, SnPbSeTe and SnPbSTe;
  • Examples of the I-III-VI group semiconductor compounds include CuInS 2 , CuInSe 2 , CuInTe 2 , CuGaS 2 , CuGaSe 2 , CuGaSe 2 , AgInS 2 , AgInSe 2 , AgInTe 2 , AgGaSe 2 , AgGaS 2 , AgGaTe 2 and the like.
  • Examples of the Group IV element or a compound containing it include C, Si, Ge, SiC, SiGe and the like.
  • a quantum dot may consist of a single semiconductor compound, or may have a core-shell structure consisting of a plurality of semiconductor compounds. Also, the surface thereof may be modified with an organic compound.
  • additives can be added in arbitrary amounts depending on the desired performance and the like, but usually 0.00% of the total 100% by mass of the components excluding the solvent in the active energy ray-curable resin composition. It is preferably used in the range of 01 to 40% by mass.
  • the active energy ray-curable resin composition used in the present invention is produced by mixing the above ingredients.
  • the mixing method is not particularly limited, and a paint shaker, disper, roll mill, bead mill, ball mill, attritor, sand mill, 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 an active energy ray.
  • the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
  • the irradiation may be performed in an atmosphere of an inert gas such as nitrogen gas or in an air atmosphere in order to efficiently perform the curing reaction using the ultraviolet rays.
  • UV lamps are generally used as the source of UV light from the standpoint of practicality and economy. Specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.
  • the integrated amount of active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ/m 2 , more preferably 0.5 to 10 kJ/m 2 . It is preferable that the integrated amount of light is within the above range because the generation of uncured portions can be prevented or suppressed.
  • the irradiation with the active energy ray may be performed in one step, or may be performed in two or more steps.
  • the tan ⁇ measured by the dynamic viscoelasticity spectrum of the cured coating film has excellent adhesion and has excellent workability, scratch resistance and chemical resistance, so the range of 0.1 to 1 preferable.
  • the article of the present invention has the cured coating film on its surface.
  • the articles include interior and exterior materials in the construction field, mobile phones, home electric appliances, automobile interior and exterior materials, and plastic moldings such as OA equipment.
  • the weight average molecular weight (Mw) is a value measured under the following conditions using gel permeation chromatography (GPC).
  • HLC-8220 manufactured by Tosoh Corporation Column; "Guard Column H XL -H” manufactured by Tosoh Corporation + “TSKgel G5000HXL” manufactured by Tosoh Corporation + “TSKgel G4000HXL” manufactured by Tosoh Corporation + “TSKgel G3000HXL” manufactured by Tosoh Corporation + “TSKgel G2000HXL” manufactured by Tosoh Corporation Detector; RI (differential refractometer) Data processing: “SC-8010” manufactured by Tosoh Corporation Measurement conditions: Column temperature 40°C Solvent Tetrahydrofuran Flow rate 1.0 ml/min Standard; Polystyrene Sample; A tetrahydrofuran solution of 0.4% by mass in terms of resin solid content filtered through a microfilter (100 ⁇ 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 reactor equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, and heated to 100°C.
  • PTMS phenyltrimethoxysilane
  • a vinyl polymer (a2-1) having a trimethoxysilyl group 600 parts by mass of a vinyl polymer (a2-1) having a trimethoxysilyl group.
  • the temperature of the reaction vessel was adjusted to 80° C., and 64 parts by mass of methyltrimethoxysilane (MTMS), 269 parts by mass of 3-methacryloyloxypropyltrimethoxysilane (MPTS), and 53 parts by mass of dimethyldimethoxysilane (DMDMS) were added. , was added into the reaction vessel.
  • MTMS methyltrimethoxysilane
  • MPTS 3-methacryloyloxypropyltrimethoxysilane
  • DDMS dimethyldimethoxysilane
  • a composite resin (A1) composed of a polysiloxane segment (a1) having a nonvolatile content of 60.1% and a vinyl polymer segment (a2) was obtained. .
  • the polysiloxane segment (a1) in this 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°C.
  • a mixture consisting 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 heated at the same temperature. Then, the mixture was added dropwise to the reaction vessel over 5 hours while stirring under a nitrogen gas stream.
  • 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°C. Next, 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 stirred at the same temperature under nitrogen gas flow. was added dropwise into the reaction vessel over 5 hours.
  • 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°C. Next, a mixture consisting 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 stirred at the same temperature under nitrogen gas flow. , was added dropwise into the reaction vessel over 5 hours.
  • 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°C.
  • a mixture consisting of 15 parts by mass of MMA, 3 parts by mass of t-BMA, 4 parts by mass of BA, 0.6 parts by mass of AA, 6 parts by mass of CHMA, 0.9 parts by mass of MPTS, and 8 parts by mass of TBPEH is stirred at the same temperature under nitrogen gas flow. was added dropwise into the reaction vessel over 5 hours.
  • Tables 1 and 2 show the compositions and property values of the acrylic (meth)acrylates (B-1) to (B-9) and (RB-1) obtained in Synthesis Examples 6 to 15.
  • 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
  • PO t-butyl peroxy-2-ethylhexanoate ("Perbutyl O" manufactured by Nippon Nyukazai Co., Ltd.)
  • MQ Metoquinone (para-methoxyphenol)
  • TPP triphenylphosphine
  • t-BMA tert-butyl methacrylate (Tg of homopolymer: 107°C)
  • CHMA cyclohexyl methacrylate
  • 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)
  • 157 parts by weight of the solution (94 parts by weight as the acrylic (meth)acrylate resin (B-1)) and a photopolymerization initiator ("Omnirad-184" manufactured by IGM Resins) 2.4 parts by weight were mixed, and active energy ray A curable resin composition (1) was obtained.
  • the cured coating film for evaluation obtained above was measured based on the JIS K-5600 cross-cut test method. On the cured coating film, cuts with a width of 1 mm were made with a cutter so that the number of grids was 100, cellophane tape was attached so as to cover all the grids, and the grids that remained attached were quickly peeled off. was counted and evaluated according to the following criteria.
  • ⁇ No peeling.
  • ⁇ The peeling area is 1 to 64% of the total grid area.
  • x The peeling area is 65% or more of the total grid area.
  • test piece having a width of 10 mm and a length of 100 mm was cut out from the laminated film, and a tensile test was performed on the obtained test piece under the following conditions.
  • Shimadzu Corporation Autograph AGS-1kNG (tensile speed: 10 mm / min, distance between chucks: 40 mm, measurement atmosphere: 25 ° C.)"
  • Examples 2 to 15 Preparation of active energy ray-curable resin compositions (2) to (15)
  • 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.
  • DPHA mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate
  • PETA mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate
  • Photoinitiator Omnirad 184 ("Omnirad 184" manufactured by IGM Resins)
  • the cured coating films obtained from Examples 1 to 15, which are active energy ray-curable resin compositions of the present invention, have coating film appearance, adhesion, solvent resistance, scratch resistance, weather resistance, stain resistance and workability. was confirmed to be superior to
  • Comparative Example 1 is an example that does not contain acrylic (meth)acrylate (B), which is an essential component of the present invention, but it was confirmed that the coating film elongation was low and the workability was insufficient.
  • Comparative Example 2 is an example that does not contain the composite resin (A), which is an essential component of the present invention, but it was confirmed that the weather resistance was insufficient.
  • Comparative Example 3 is an example in which the weight average molecular weight of acrylic (meth)acrylate (B) is lower than the lower limit of 10,000. .

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne une composition de résine durcissable par rayonnement d'énergie active contenant une résine complexe (A), une résine de (méth)acrylate acrylique (B) et un initiateur de photopolymérisation (C). La composition de résine durcissable par rayonnement d'énergie active est caractérisée en ce que : la résine complexe (A) comprend un segment polysiloxane (a1) et un segment polymère à base de vinyle (a2), qui sont liés avec une liaison spécifique, le segment polysiloxane (a1) comprenant une unité structurale spécifique et un groupe silanol et/ou un groupe silyle hydrolysable ; et le poids moléculaire moyen en poids de la résine de (méth)acrylate acrylique (B) est de 10 000 à 70 000. Cette composition de résine durcissable par rayonnement d'énergie active est capable de former un revêtement qui présente un excellent aspect de revêtement, une excellente adhérence, une excellente résistance aux solvants, une excellente résistance aux rayures, une excellente résistance aux intempéries, une excellente résistance aux taches et une excellente aptitude au façonnage, et peut par conséquent être utilisée en tant qu'agent de revêtement et agent adhésif.
PCT/JP2022/044315 2021-12-23 2022-12-01 Composition de résine durcissable par rayonnement d'énergie active, revêtement durci et article WO2023120089A1 (fr)

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JP2023562742A JP7495016B2 (ja) 2021-12-23 2022-12-01 活性エネルギー線硬化性樹脂組成物、硬化塗膜及び物品
CN202280070665.2A CN118234768A (zh) 2021-12-23 2022-12-01 活性能量射线固化性树脂组合物、固化涂膜和物品
KR1020247010310A KR20240051227A (ko) 2021-12-23 2022-12-01 활성 에너지선 경화성 수지 조성물, 경화 도막 및 물품

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JP2021-209180 2021-12-23

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006328354A (ja) * 2005-03-08 2006-12-07 Dainippon Ink & Chem Inc 紫外線硬化性樹脂組成物、紫外線硬化性塗料及び塗装物。
JP2007224312A (ja) * 2007-04-06 2007-09-06 Nippon Shokubai Co Ltd 複合微粒子の製造方法
JP2013199522A (ja) * 2012-03-23 2013-10-03 Kansai Paint Co Ltd 活性エネルギー線硬化性組成物及び塗装フィルム
JP2016017151A (ja) * 2014-07-09 2016-02-01 Dic株式会社 硬化物及び硬化物の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006328354A (ja) * 2005-03-08 2006-12-07 Dainippon Ink & Chem Inc 紫外線硬化性樹脂組成物、紫外線硬化性塗料及び塗装物。
JP2007224312A (ja) * 2007-04-06 2007-09-06 Nippon Shokubai Co Ltd 複合微粒子の製造方法
JP2013199522A (ja) * 2012-03-23 2013-10-03 Kansai Paint Co Ltd 活性エネルギー線硬化性組成物及び塗装フィルム
JP2016017151A (ja) * 2014-07-09 2016-02-01 Dic株式会社 硬化物及び硬化物の製造方法

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