CN113248954A - Primer, cured product, and laminate - Google Patents

Primer, cured product, and laminate Download PDF

Info

Publication number
CN113248954A
CN113248954A CN202110104787.6A CN202110104787A CN113248954A CN 113248954 A CN113248954 A CN 113248954A CN 202110104787 A CN202110104787 A CN 202110104787A CN 113248954 A CN113248954 A CN 113248954A
Authority
CN
China
Prior art keywords
meth
mass
acrylate
examples
mol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110104787.6A
Other languages
Chinese (zh)
Other versions
CN113248954B (en
Inventor
石岛优树
佐藤仁宣
大江祐辅
小谷野浩寿
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arakawa Chemical Industries Ltd
Original Assignee
Arakawa Chemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arakawa Chemical Industries Ltd filed Critical Arakawa Chemical Industries Ltd
Publication of CN113248954A publication Critical patent/CN113248954A/en
Application granted granted Critical
Publication of CN113248954B publication Critical patent/CN113248954B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention provides a primer, a cured product and a laminated product. The present invention provides a primer containing a hydroxyl group-containing (meth) acrylic polymer (A) and a hydroxyl group-containing poly (meth) acrylate (B).

Description

Primer, cured product, and laminate
Technical Field
The present invention relates to a primer, a cured product and a laminate.
Background
As a method for producing a film, a method of applying a primer to a surface of a substrate and providing the primer is known. In addition, various primers have been developed according to the kind of the substrate.
Patent document 1 (jp 2011-195835 a) discloses an undercoat containing a polyethylenimine compound.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-195835
Disclosure of Invention
Problems to be solved by the invention
The primer described above is a primer for producing a primer layer provided between an inorganic film and a substrate. In recent years, an undercoating agent for producing an undercoating layer provided between an active energy ray-curable resin and a substrate has been demanded.
The problem to be solved by the present invention is to provide an undercoat agent which has good drying properties of a cured product of the undercoat agent, good adhesion between the cured product and an active energy ray-curable resin, and good adhesion between the cured product and a substrate, and which, when a laminate is produced, provides a good appearance of the laminate.
Means for solving the problems
As a result of intensive studies, the present inventors have found that the above problems can be solved by using specific components.
According to the present invention, the following items are provided.
(item 1)
A primer comprising a hydroxyl group-containing (meth) acrylic polymer (A) and a hydroxyl group-containing poly (meth) acrylate (B).
(item 2)
The primer according to the above item, wherein the hydroxyl group-containing poly (meth) acrylate (B) is a hydroxyl group-containing polymer poly (meth) acrylate.
(item 3)
A cured product of the primer according to any one of the above items.
(item 4)
A laminate comprising a cured primer layer comprising a cured primer according to the above item laminated on at least one surface of a film.
(item 5)
The laminate according to the above item, wherein an active energy ray-curable resin cured layer is laminated on the primer cured layer.
In the present invention, one or more of the above-described features may be provided in further combination in addition to the combinations explicitly described.
Effects of the invention
The primer is excellent in drying property, and the cured product thereof is excellent in adhesion to an active energy ray-curable resin, interlayer adhesion to a substrate, and appearance.
Detailed Description
Throughout the specification of the present invention, ranges of numerical values such as physical property values and contents may be appropriately set (for example, selected from upper and lower limits described in the following items). Specifically, as for the numerical value α, when the upper limit and the lower limit of the numerical value α are exemplified by A4, A3, a2, a1 (A4 > A3 > a2 > a1), etc., the range of the numerical value α may be exemplified by A4 or less, A3 or less, a2 or less, a1 or more, a2 or more, A3 or more, a1 to a2, a1 to A3, a1 to A4, a2 to A3, a2 to A4, A3 to A4, etc.
[ undercoating agent ]
The present invention provides a primer containing a hydroxyl group-containing (meth) acrylic polymer (A) and a hydroxyl group-containing poly (meth) acrylate (B).
< hydroxyl group-containing (meth) acrylic polymer (A): also called component (A) >
(A) The components may be used singly or in combination of two or more.
(A) Examples of the component (C) include a copolymer containing a constituent unit derived from a non-hydroxyl-containing alkyl (meth) acrylate and a constituent unit derived from a hydroxyl-containing alkyl (meth) acrylate.
In the present invention, "(meth) acrylic" means "at least one selected from the group consisting of acrylic and methacrylic". Likewise, "(meth) acrylate" means "at least one selected from the group consisting of acrylate and methacrylate". In addition, "(meth) acryloyl group" means "at least one selected from the group consisting of acryloyl groups and methacryloyl groups".
(alkyl (meth) acrylate having no hydroxyl group: also referred to as component (a 1))
The alkyl (meth) acrylate having no hydroxyl group is represented by the following formula. The alkyl (meth) acrylate having no hydroxyl group may be used alone or in combination of two or more.
Figure BDA0002916946050000031
(in the formula, Ra1Is a hydrogen atom or a methyl group, Ra2Is an alkyl group. )
Alkyl groups may be exemplified by straight-chain alkyl groups, branched-chain alkyl groups, cyclic alkyl groups, and the like.
Straight chain alkyl radical consisting ofnH2n+1(n is an integer of 1 or more). Examples of the straight-chain alkyl group include methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and the like.
Branched alkyl is a group in which at least one hydrogen atom of a linear alkyl group is substituted with an alkyl group. Examples of the branched alkyl group include diethylpentyl group, trimethylbutyl group, trimethylpentyl group, trimethylhexyl group and the like.
Examples of the cycloalkyl group include monocyclic cycloalkyl, bridged cycloalkyl, and fused cycloalkyl.
In the present invention, a monocyclic ring refers to a cyclic structure formed by covalent bonds of carbon and having no internal bridge structure. In addition, a fused ring refers to a cyclic structure in which 2 or more monocyclic rings share 2 atoms (i.e., only 1 side of each ring shares (is fused) with each other). A bridged ring is a cyclic structure in which 2 or more monocyclic rings share 3 or more atoms.
Examples of the monocyclic cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, 3,5, 5-trimethylcyclohexyl, and the like.
Examples of the bridged cycloalkyl group include tricyclodecyl, adamantyl, norbornyl and the like.
Examples of the fused cyclic alkyl group include bicyclodecyl and the like.
Examples of the alkyl (meth) acrylate having no hydroxyl group include a linear alkyl (meth) acrylate having no hydroxyl group, a branched alkyl (meth) acrylate having no hydroxyl group, a cyclic alkyl (meth) acrylate having no hydroxyl group, and the like.
Examples of the linear alkyl (meth) acrylate having no hydroxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, n-hexadecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-octadecyl (meth) acrylate, n-eicosyl (meth) acrylate, and n-docosyl (meth) acrylate.
Examples of the branched alkyl (meth) acrylate having no hydroxyl group include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
Examples of the cycloalkyl (meth) acrylate having no hydroxyl group include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, isobornyl (meth) acrylate, and the like.
Among these, from the viewpoint of contributing to leveling property and adhesion in the primer, a hydroxyl group-free alkyl (meth) acrylate having an alkyl group with a carbon number of about 1 to about 20 is preferable. Further, by using a combination of alkyl (meth) acrylates having different alkyl groups in carbon number and having no hydroxyl group, physical properties such as glass transition temperature of the component (a) can be adjusted.
Examples of the upper limit and the lower limit of the content of the constituent unit derived from the hydroxyl group-free alkyl (meth) acrylate in 100 mol% of the total constituent units of the component (a) include 98 mol%, 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 62 mol%, and the like. In one embodiment, the content is preferably 62 to 98 mol%.
Examples of the upper limit and the lower limit of the content of the constituent unit derived from the hydroxyl group-free alkyl (meth) acrylate in 100% by mass of the total constituent units of the component (a) include 98% by mass, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, and 65% by mass. In one embodiment, the content is preferably 65 to 98% by mass.
(hydroxyl group-containing alkyl (meth) acrylate: also referred to as component (a 2))
The hydroxyl group-containing alkyl (meth) acrylate is represented by the following structural formula. The hydroxyl group-containing alkyl (meth) acrylate may be used alone or in combination of two or more.
Figure BDA0002916946050000061
(in the formula, Ra3Is a hydrogen atom or a methyl group, Ra4Is a linear alkylene, branched alkylene or cycloalkylene group. )
The linear alkylene group is represented by the general formula: - (CH)2)n- (n is an integer of 1 or more). Examples of the linear alkylene group include a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, and an n-decylene group.
The branched alkylene group is a group in which at least one hydrogen atom of a linear alkylene group is substituted with an alkyl group. Examples of the branched alkylene group include diethylpentylene, trimethylbutylene, trimethylpentylene, trimethylhexylene (trimethylhexamethylene), and the like.
Examples of the cycloalkylene group include monocyclic cycloalkylene group, bridged cycloalkylene group, fused cycloalkylene group and the like. In addition, in the cycloalkylene group, 1 or more hydrogen atoms may be substituted with a straight-chain or branched-chain alkyl group.
Examples of the monocyclic cycloalkylene group include cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclodecylene group, 3,5, 5-trimethylcyclohexylene group and the like.
Examples of the bridged cycloalkylene group include tricyclodecylene, adamantylene, norbornylene and the like.
Examples of the fused ring cycloalkylene group include bicyclodecenylene and the like.
Examples of the hydroxyl group-containing alkyl (meth) acrylate include hydroxyl group-containing linear alkyl (meth) acrylate, hydroxyl group-containing branched alkyl (meth) acrylate, and hydroxyl group-containing cycloalkyl (meth) acrylate.
Examples of the hydroxyl group-containing linear alkyl (meth) acrylate include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the branched alkyl (meth) acrylate containing a hydroxyl group include 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl (meth) acrylate.
Examples of the cycloalkyl (meth) acrylate containing a hydroxyl group include hydroxycyclohexyl (meth) acrylate, 4- (hydroxymethyl) cyclohexylmethyl (meth) acrylate and the like.
Examples of the upper limit and the lower limit of the content of the constituent unit derived from the hydroxyl group-containing alkyl (meth) acrylate in 100 mol% of the total constituent units of the component (a) include 38 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 2.5 mol%, 2 mol%, 1.5 mol%. In one embodiment, the content is preferably 1.5 to 38 mol%.
Examples of the upper limit and the lower limit of the content of the constituent unit derived from the hydroxyl group-containing alkyl (meth) acrylate in 100% by mass of the total constituent units of the component (a) include 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, 2.5% by mass, and 2% by mass. In one embodiment, the content is preferably 2 to 35% by mass.
(A) The molar ratio of the constituent unit derived from the hydroxyl group-free alkyl (meth) acrylate to the constituent unit derived from the hydroxyl group-containing alkyl (meth) acrylate in the component (the hydroxyl group-free alkyl (meth) acrylate)molHydroxyl group-containing alkyl (meth) acrylatemol) Examples of the upper limit and the lower limit of (b) include 57, 50, 40, 30, 20, 10, 5, 2, 1.6 and the like. In one embodiment, the molar ratio is preferably 1.6 to 57.
(A) The mass ratio of the constituent unit derived from the hydroxyl group-free alkyl (meth) acrylate to the constituent unit derived from the hydroxyl group-containing alkyl (meth) acrylate in the component (excluding the hydroxyl group-free alkyl (meth) acrylate)Alkyl (meth) acrylates of hydroxyl groupsmassHydroxyl group-containing alkyl (meth) acrylatemass) Examples of the upper limit and the lower limit of (b) include 49, 40, 30, 20, 10, 5, 2, 1.8 and the like. In one embodiment, the mass ratio is preferably 1.8 to 49.
(a monomer (a3) other than the component (a1) and the component (a 2): also referred to as a component (a 3))
In the production of the component (a), the monomer (a3) which does not belong to any of the components (a1) and (a2) may be used. (a3) The components may be used singly or in combination of two or more. When the component (a3) is used in the production of the component (a), the component (a) is incorporated into the polymer in the form of a constitutional unit derived from the component (a 3).
(a3) Examples of the component (a) include an α, β -unsaturated carboxylic acid, an epoxy group-containing (meth) acrylate, a styrene, an α -olefin, an unsaturated alcohol, an aryl (meth) acrylate, a dialkylaminoalkyl (meth) acrylate, (meth) acrylonitrile, a (meth) acrylamide group-containing compound, a di (meth) acrylate, a divinyl ester, a trifunctional monomer, and a tetrafunctional monomer.
Examples of the α, β -unsaturated carboxylic acid include (meth) acrylic acid, maleic acid, crotonic acid, fumaric acid, and itaconic acid.
Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate and β -methylglycidyl (meth) acrylate.
The styrene may, for example, be styrene, α -methylstyrene or tert-butylstyrene.
Examples of the α -olefin include 2,4, 4-trimethyl-1-pentene, 3-methyl-1-butene, 3-methyl-1-pentene, and 1-hexene.
Examples of the unsaturated alcohol include (meth) allyl alcohol, 4-penten-1-ol, 1-methyl-3-buten-1-ol, and 5-hexen-1-ol.
Examples of aryl (meth) acrylates include phenyl (meth) acrylate, benzyl (meth) acrylate, and 4-methylbenzyl (meth) acrylate.
Examples of the dialkylaminoalkyl (meth) acrylate include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (meth) acrylate.
Examples of the (meth) acrylamide group-containing compound include (meth) acrylamides such as (meth) acrylamide and N-methylol (meth) acrylamide, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, isopropyl (meth) acrylamide, 2- (meth) acrylamide-2-methylpropanesulfonic acid, 2- (meth) acrylamide-2-methylpropionic acid, methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, hexamethylenebis (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl (meth) acrylamide.
Examples of di (meth) acrylate include ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate.
Examples of the divinyl ester include divinyl adipate and divinyl sebacate.
Examples of the trifunctional monomer include 1,3, 5-triacryloylhexahydro-S-triazine, triallylisocyanurate, triallylamine, triallyl trimellitate, and N, N-diallylacrylamide.
Examples of the tetrafunctional monomer include tetramethylolmethane tetraacrylate, tetraallyl pyromellitate, and N, N, N ', N' -tetraallyl-1, 4-diaminobutane.
Examples of the upper limit and the lower limit of the content of the constituent unit derived from the component (a3) in 100 mol% of the total constituent units of the component (a) include 13 mol%, 10 mol%, 9 mol%, 5 mol%, 4 mol%, 1 mol%, 0 mol% and the like. In one embodiment, the content is preferably 0 to 13 mol%.
Examples of the upper limit and the lower limit of the content of the constituent unit derived from the component (a3) in 100% by mass of the total constituent units of the component (a) include 10% by mass, 9% by mass, 5% by mass, 4% by mass, 1% by mass, and 0% by mass. In one embodiment, the content is preferably 0 to 10% by mass.
(A) The molar ratio of the constituent unit derived from the component (a1) to the constituent unit derived from the component (a3) in the component ((a3)mol/(a1)mol) Examples of the upper limit and the lower limit of (b) include 0.22, 0.20, 0.15, 0.10, 0.05, 0 and the like. In one embodiment, the molar ratio is preferably 0 to 0.22.
(A) The mass ratio of the constituent unit derived from the component (a1) to the constituent unit derived from the component (a3) in the component ((a3)mass/(a1)mass) Examples of the upper limit and the lower limit of (b) include 0.19, 0.15, 0.10, 0.05 and 0. In one embodiment, the mass ratio is preferably about 0 to about 0.19.
(A) The molar ratio of the constituent unit derived from the component (a2) to the constituent unit derived from the component (a3) in the component ((a3)mol/(a2)mol) Examples of the upper limit and the lower limit of (b) include 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0 and the like. In one embodiment, the molar ratio is preferably 0 to 8.
(A) The mass ratio of the constituent unit derived from the component (a2) to the constituent unit derived from the component (a3) in the component ((a3)mass/(a2)mass) Examples of the upper limit and the lower limit of (b) include 5, 4, 3, 2, 1, 0.5, 0 and the like. In one embodiment, the mass ratio is preferably 0 to 5.
< Properties of component (A), etc. >
(A) Examples of the upper and lower limits of the glass transition temperature of the component (A) include 100 ℃, 90 ℃, 88 ℃, 85 ℃, 80 ℃, 70 ℃, 60 ℃, 50 ℃, 40 ℃, 35 ℃, 20 ℃ and the like. In one embodiment, the glass transition temperature of the component (A) is preferably 20 to 100 ℃, more preferably 40 to 90 ℃.
The glass transition temperature was measured under appropriate conditions (temperature rising rate: 10 ℃ C./min) using a commercially available differential scanning calorimeter (for example, product name "DSC 8230B", manufactured by KOKAI Co., Ltd.).
(A) Examples of the upper limit and the lower limit of the hydroxyl value of the component (in terms of solid content) include 150mgKOH/g, 140mgKOH/g, 130mgKOH/g, 120mgKOH/g, 110mgKOH/g, 100mgKOH/g, 90mgKOH/g, 80mgKOH/g, 70mgKOH/g, 60mgKOH/g, 50mgKOH/g, 48mgKOH/g, 45mgKOH/g, 40mgKOH/g, 30mgKOH/g, 20mgKOH/g, 15mgKOH/g, and 10 mgKOH/g. In one embodiment, the hydroxyl value (in terms of solid content) of the component (A) is preferably 10 to 150mgKOH/g, more preferably 30 to 100 mgKOH/g.
In the present invention, the hydroxyl value is measured, for example, by a method in accordance with JIS K1557-1.
(A) Examples of the upper limit and the lower limit of the hydroxyl group equivalent of the component (B) may include 5611g/eq, 5500g/eq, 5000g/eq, 4500g/eq, 4000g/eq, 3500g/eq, 3000g/eq, 2500g/eq, 2000g/eq, 1500g/eq, 1000g/eq, 500g/eq, 400g/eq, 370g/eq and the like. In one embodiment, the hydroxyl group equivalent of the component (A) is preferably 370 to 5611 g/eq.
In the present invention, the hydroxyl group equivalent means a calculated value (g/eq) of mass per 1 mole of hydroxyl group.
(A) Examples of the upper limit and the lower limit of the acid value of the component include 0.4mgKOH/g, 0.3mgKOH/g, 0.2mgKOH/g, 0.18mgKOH/g, 0.1mgKOH/g, 0.09mgKOH/g, 0.05mgKOH/g, and 0.04 mgKOH/g. In one embodiment, the acid value of the component (A) is preferably from about 0.04mgKOH/g to about 0.4mgKOH/g, more preferably from 0.09mgKOH/g to 0.18mgKOH/g, particularly in view of curability.
In the present invention, the acid value is measured, for example, by a method in accordance with JIS K0070.
(A) Examples of the upper limit and the lower limit of the weight average molecular weight (Mw) of the component (a) may include 100000, 90000, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 5000, 4000, 3000, and the like. In one embodiment, the weight average molecular weight (Mw) of the component (a) is preferably 3000 to 100000, more preferably 10000 to 80000.
(A) Examples of the upper limit and the lower limit of the number average molecular weight (Mn) of the component (B) include 100000, 90000, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 5000, 4000, and 3000. In one embodiment, the number average molecular weight (Mn) of the component (a) is preferably 3000 to 100000, more preferably 10000 to 80000.
The weight average molecular weight and the number average molecular weight were measured by using a commercially available gel permeation chromatograph (for example, product name "HLC-8220 GPC", manufactured by Tosoh corporation).
(A) Examples of the upper limit and the lower limit of the molecular weight distribution (Mw/Mn) of the component (B) include 10, 7.5, 5, 2.5, 2, 1.5 and the like. In one embodiment, the molecular weight distribution (Mw/Mn) of the component (A) is preferably 1.5 to 10.
(A) The component (b) can be produced by various known methods. (A) The method for producing the component (a) includes a method of copolymerizing the component (a1), the component (a2) and, if necessary, the component (a3) in the absence of a solvent or in an organic solvent in the presence of a polymerization initiator at about 80 to about 180 ℃ for about 1 to about 10 hours. Examples of the organic solvent and the polymerization initiator used in the production of the component (A) include an organic solvent and a polymerization initiator, which will be described later.
Examples of the upper limit and the lower limit of the content of the component (a) in the primer include 88 mass%, 85 mass%, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 10 mass%, 5 mass%, 3 mass%, and the like. In one embodiment, the content is preferably 3 to 88% by mass.
< hydroxyl group-containing poly (meth) acrylate (B): also referred to as component (B) >
(B) The components may be used singly or in combination of two or more.
In the present invention, "poly (meth) acrylate containing a hydroxyl group" means a compound having 1 or more hydroxyl groups and 2 or more (meth) acryloyl groups.
Examples of the hydroxyl group-containing poly (meth) acrylate include a hydroxyl group-containing polymer poly (meth) acrylate, a hydroxyl group-containing oligomer poly (meth) acrylate, and the like.
(Polymer containing hydroxyl group Poly (meth) acrylate)
In the present invention, the "hydroxyl group-containing polymer poly (meth) acrylate" means a polymer having 1 or more hydroxyl groups and 2 or more (meth) acryloyl groups.
The hydroxyl group-containing polymer poly (meth) acrylate can be produced by a known method. Examples of the method for producing the polymer poly (meth) acrylate include a method of reacting an epoxy group-containing (meth) acrylic polymer with an α, β -unsaturated carboxylic acid.
Examples of the upper limit and the lower limit of the content of the constituent unit derived from the epoxy group-containing (meth) acrylate in 100 mol% of the total constituent units of the epoxy group-containing (meth) acrylic polymer include 100 mol%, 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 7 mol%. In one embodiment, the content is preferably 7 to 100 mol%.
Examples of the upper limit and the lower limit of the content of the constituent unit derived from the epoxy group-containing (meth) acrylate in 100% by mass of the total constituent units of the epoxy group-containing (meth) acrylic polymer include 100% by mass, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 62% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, and 10% by mass. In one embodiment, the content is preferably 10 to 100% by mass.
Examples of the upper limit and the lower limit of the content of the constituent unit derived from the hydroxyl group-free alkyl (meth) acrylate in 100 mol% of the total constituent unit of the epoxy group-containing (meth) acrylic polymer include 93 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 0 mol% and the like. In one embodiment, the content is preferably 0 to 93 mol%.
Examples of the upper limit and the lower limit of the content of the constituent unit derived from the hydroxyl group-free alkyl (meth) acrylate in 100% by mass of the total constituent unit of the epoxy group-containing (meth) acrylic polymer include 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 38% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, and 0% by mass. In one embodiment, the content is preferably 0 to 90% by mass.
Examples of the upper limit and the lower limit of the amount of the α, β -unsaturated carboxylic acid to be reacted with 100 mol% of the constituent unit derived from the epoxy group-containing (meth) acrylate include 100 mol%, 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%. In one embodiment, the amount is preferably 10 to 100 mol%.
Examples of the upper limit and the lower limit of the amount of the α, β -unsaturated carboxylic acid to be reacted with 100 mass% of the constituent unit derived from the epoxy group-containing (meth) acrylate include 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, and the like. In one embodiment, the amount is preferably 5 to 50% by mass.
The epoxy group-containing (meth) acrylic polymer can be produced by a known radical polymerization method.
(oligomer Poly (meth) acrylate containing hydroxyl group)
Examples of the hydroxyl group-containing oligomer poly (meth) acrylate include hydroxyl group-containing (poly) pentaerythritol poly (meth) acrylate, hydroxyl group-containing (poly) trimethylolpropane poly (meth) acrylate, hydroxyl group-containing glycerol di (meth) acrylate, and the like.
(hydroxyl group-containing (poly) pentaerythritol poly (meth) acrylate)
The hydroxyl group-containing (poly) pentaerythritol poly (meth) acrylate is a compound represented by the following structural formula.
Figure BDA0002916946050000151
(wherein m is an integer of 0 or more, Rb1～Rb6Each independently is a hydrogen atom or a (meth) acryloyl group, and Rb1～Rb6At least two of (meth) acryloyl groups, Rb1～Rb6At least one of which is a hydrogen atom. In addition, R isb3And Rb5The groups may be different in each constituent unit. )
In the present invention, "(poly) pentaerythritol poly (meth) acrylate" means "at least one selected from the group consisting of pentaerythritol poly (meth) acrylate and polypentaerythritol poly (meth) acrylate".
Further, "the groups may be different in each constituent unit" means that, for example, in the above structural formula, when m is 2,
Figure BDA0002916946050000161
Rb3Aand Rb3BMay be different radicals Rb5AAnd Rb5BMay be different groups (the same applies hereinafter).
Examples of the hydroxyl group-containing pentaerythritol poly (meth) acrylate include pentaerythritol di (meth) acrylate and pentaerythritol tri (meth) acrylate.
Examples of the hydroxyl group-containing polypentaerythritol poly (meth) acrylate include dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol di (meth) acrylate, tripentaerythritol tri (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, and the like.
(hydroxyl group-containing (poly) trimethylolpropane poly (meth) acrylate)
The (poly) trimethylolpropane poly (meth) acrylate is a compound represented by the following structural formula.
Figure BDA0002916946050000171
(wherein p is an integer of 0 or more, Rb7～Rb10Is a hydrogen atom or a (meth) acryloyl group, and Rb7～Rb10At least two of (meth) acryloyl groups, Rb7～Rb10At least one of which is a hydrogen atom. In addition, R isb9The groups may be different in each constituent unit. )
In the present invention, "(poly) trimethylolpropane poly (meth) acrylate" means "at least one selected from the group consisting of trimethylolpropane poly (meth) acrylate and polytrimethylolpropane poly (meth) acrylate".
Examples of the hydroxyl group-containing trimethylolpropane poly (meth) acrylate include trimethylolpropane di (meth) acrylate and the like.
Examples of the hydroxyl group-containing poly (trimethylolpropane poly (meth) acrylate) include ditrimethylolpropane di (meth) acrylate and ditrimethylolpropane tri (meth) acrylate.
(hydroxyl-containing Glycerol di (meth) acrylate)
The hydroxyl group-containing glycerol (meth) acrylate is a compound represented by the following structural formula.
Figure BDA0002916946050000172
(in the formula, Rb11～Rb13Two of (meth) acryloyl groups, Rb11～Rb13One of them is a hydrogen atom. )
Examples of the hydroxyl group-containing glycerol (meth) acrylate include 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate and 1-hydroxy-2- (meth) acryloyloxypropyl (meth) acrylate.
(physical Properties of the hydroxyl group-containing Poly (meth) acrylate (B))
Examples of the upper limit and the lower limit of the acrylic equivalent of the hydroxyl group-containing poly (meth) acrylate include 400g/eq, 375g/eq, 360g/eq, 350g/eq, 325g/eq, 310g/eq, 305g/eq, 300g/eq, 275g/eq, 250g/eq, 225g/eq, 220g/eq, 216g/eq, 214g/eq, and the like. In one embodiment, the (meth) acrylic acid equivalent is preferably 214 to 400g/eq, and more preferably 214 to 375g/eq from the viewpoint of improving the heating elongation.
In the present invention, the (meth) acrylic acid equivalent means a calculated value (g/eq) of mass per 1 mole of (meth) acryloyl group.
Examples of the upper limit and the lower limit of the hydroxyl value of the hydroxyl group-containing poly (meth) acrylate include 300mgKOH/g, 290mgKOH/g, 270mgKOH/g, 250mgKOH/g, 225mgKOH/g, 200mgKOH/g, 175mgKOH/g, 150mgKOH/g, 130mgKOH/g, 110mgKOH/g, and 100 mgKOH/g. In one embodiment, the hydroxyl value of the hydroxyl group-containing poly (meth) acrylate is preferably 100 to 300mgKOH/g, more preferably 130 to 270 mgKOH/g.
Examples of the upper limit and the lower limit of the hydroxyl group equivalent of the hydroxyl group-containing poly (meth) acrylate include 562g/eq, 550g/eq, 500g/eq, 450g/eq, 400g/eq, 350g/eq, 300g/eq, 250g/eq, 200g/eq, and 185 g/eq. In one embodiment, the hydroxyl equivalent is preferably 185 to 562 g/eq.
Examples of the upper limit and the lower limit of the content of the component (B) in the primer include 85 mass%, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 10 mass%, 5 mass%, 2 mass%, and the like. In one embodiment, the content is preferably 2 to 85% by mass.
Examples of the upper limit and the lower limit of the solid content mass ratio ((a)/(B)) of the hydroxyl group-containing poly (meth) acrylic polymer (a) to the hydroxyl group-containing poly (meth) acrylate (B) include 44, 40, 35, 30, 25, 20, 15, 10, 9, 7, 5, 4, 3, 2, 1, 0.9, 0.5, 0.3, 0.2, 0.1, 0.09, 0.05 and 0.04. In one embodiment, the solid content mass ratio is preferably 0.04 to 44.
< photopolymerization initiator (C): also referred to as component (C) >
In one embodiment, the primer may contain a photopolymerization initiator. (C) The components may be used singly or in combination of two or more.
Examples of the photopolymerization initiator include a photo radical polymerization initiator, a photo cation polymerization initiator, and a photo anion polymerization initiator.
Examples of the photo radical polymerization initiator include α -hydroxyalkylphenone, unsubstituted or substituted alkylphenone, unsubstituted or substituted benzil, unsubstituted or substituted benzophenone, acylphosphine oxide, substituted thioxanthone and the like.
Examples of the α -hydroxyalkylphenone include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone (1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-methylpropanone), and 2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropanoyl) benzyl) phenyl) -2-methylpropan-1-one).
Examples of the unsubstituted or substituted alkylphenones include benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin ethyl ether, acetophenone, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, 2-phenyl-2- (p-toluenesulfonyloxy) acetophenone, benzoin, 2-benzyl-2- (dimethylamino) -4 '-morpholinylbutanone, 2-methyl-4' - (methylthio) -2-morpholinylpropenone, 2-isonitro-propiophenone, and 2, 2-dimethoxy-1, 2-diphenylethan-1-one.
Examples of the unsubstituted or substituted benzil include unsubstituted or substituted benzil such as benzil and p-anisyl.
Examples of the unsubstituted or substituted benzophenone include benzophenone, 4 ' -bis (diethylamino) benzophenone, 4 ' -bis (dimethylamino) benzophenone, 4 ' -dichlorobenzophenone, 1, 4-dibenzoylbenzene, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and methyl 2-benzoylbenzoate.
Examples of acylphosphine oxides include 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, and the like.
Examples of the substituted thioxanthone include 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2, 4-diethylthioxanthone.
Examples of the photo radical polymerization initiator other than the above include lithium phenyl (2,4, 6-trimethylbenzoyl) phosphonate and 2-ethylanthraceneQuinone, 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -biimidazole, 2- (1, 3-benzodiazepine)
Figure BDA0002916946050000201
Cyclopentadienyl-5-yl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, methyl phenylglyoxylate, and the like.
Examples of the photo cation polymerization initiator include iodine
Figure BDA0002916946050000202
A salt polymerization initiator, a sulfonium salt polymerization initiator, a diazonium salt polymerization initiator, and the like.
Iodine
Figure BDA0002916946050000203
The salt polymerization initiator may be exemplified by bis (4-t-butylphenyl) iodide
Figure BDA0002916946050000204
Hexafluorophosphate, bis (4-fluorophenyl) iodide
Figure BDA0002916946050000205
Triflate, diphenyl iodide
Figure BDA0002916946050000206
Hexafluorophosphate and diphenyl iodide
Figure BDA0002916946050000207
Hexafluoroarsenate, diphenyl iodide
Figure BDA0002916946050000208
Trifluoromethanesulfonic acid, 4-isopropyl-4' -methyldiphenyliodide
Figure BDA0002916946050000209
Tetrakis (pentafluorophenyl) borate, and (2-methylphenyl) (2,4, 6-trimethylphenyl) iodine
Figure BDA00029169460500002010
Triflate, (3-methylphenyl) (2,4, 6-trimethylphenyl) iodine
Figure BDA00029169460500002011
Triflate, (4-methylphenyl) (2,4, 6-trimethylphenyl) iodine
Figure BDA00029169460500002012
Triflate, (4-nitrophenyl) (phenyl) iodide
Figure BDA00029169460500002013
Triflate, phenyl [4- (trimethylsilyl) thiophen-3-yl]Iodine
Figure BDA00029169460500002014
Triflate, [3- (trifluoromethyl) phenyl](2,4, 6-trimethylphenyl) iodine
Figure BDA00029169460500002015
Triflate, [4- (trifluoromethyl) phenyl](2,4, 6-trimethylphenyl) iodine
Figure BDA0002916946050000211
Triflate salts and the like.
Examples of the sulfonium salt polymerization initiator include cyclopropyldiphenylsulfonium tetrafluoroborate, dimethylbenzoylmethylthioninium tetrafluoroborate, triphenylsulfonium bromide, tri-p-tolylsulfonium hexafluorophosphate, and tri-p-tolylsulfonium trifluoromethanesulfonate.
Examples of the diazonium salt polymerization initiator include 4-nitrophenyldiazonium tetrafluoroborate and the like.
Examples of the photo cation polymerization initiator other than the above-mentioned photo cation polymerization initiators include 2- (3, 4-dimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- [2- (furan-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- [2- (5-methylfuran-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxystyryl) -4, 6-bis (trichloromethyl) -1, substituted 4, 6-bis (trichloromethyl) -1,3, 5-triazine, such as 3, 5-triazine.
Examples of the photo-anionic polymerization initiator include cyclohexylcarbamate and 2- (9-oxoxanthen-2-yl) propionate.
Examples of the cyclohexylcarbamate include 1, 2-bis (4-methoxyphenyl) -2-oxoethyl cyclohexylcarbamate and 2-nitrobenzyl cyclohexylcarbamate.
Examples of the 2- (9-oxoxanthen-2-yl) propionate include 1,5, 7-triazabicyclo [4.4.0] dec-5-ene 2- (9-oxoxanthen-2-yl) propionate, 1, 5-diazabicyclo [4.3.0] non-5-ene 2- (9-oxoxanthen-2-yl) propionate, and 1, 8-diazabicyclo [5.4.0] undec-7-ene 2- (9-oxoxanthen-2-yl) propionate.
Examples of the photo-anionic polymerization initiator other than those described above include acetophenone O-benzoyl oxime and nifedipine.
Examples of the upper limit and the lower limit of the content of the photopolymerization initiator in the primer include 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, and 0 mass%. In one embodiment, the content is preferably 0 to 10% by mass.
< polyisocyanate (D): also referred to as component (D) >
In one embodiment, the primer may contain a polyisocyanate. (D) The components may be used singly or in combination of two or more.
In the present invention, the "polyisocyanate" refers to a compound having 2 or more isocyanate groups (-N ═ C ═ O).
Examples of the polyisocyanate include linear aliphatic polyisocyanates, branched aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and biuret, isocyanurate (uretate), allophanate, and adduct thereof.
Examples of the linear aliphatic polyisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanate.
Examples of the branched aliphatic polyisocyanate include diethylpentamethylenediisocyanate, trimethylbutylenediisocyanate, trimethylpentamethylenediisocyanate, trimethylhexamethylenediisocyanate, and the like.
Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanate, bridged alicyclic polyisocyanate, and condensed alicyclic polyisocyanate.
Examples of the monocyclic alicyclic polyisocyanate include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5, 5-trimethylcyclohexylene diisocyanate, dicyclohexylmethane diisocyanate and the like.
Examples of the bridged alicyclic polyisocyanate include tricyclodecanediisocyanate, adamantane diisocyanate, norbornane diisocyanate and the like.
Examples of the fused ring alicyclic polyisocyanate include dicyclodedecylidene diisocyanate and the like.
Examples of the aromatic group include monocyclic aromatic group and fused ring aromatic group. In addition, in the aromatic group, 1 or more hydrogen atoms may be substituted with a linear or branched alkyl group.
Examples of the monocyclic aromatic group include a phenyl group (phenylene group), a tolyl group (tolylene group), and a mesityl group (mesitylene group). Examples of the fused aromatic group include naphthyl (naphthylene) and the like.
Examples of the aromatic polyisocyanate include monocyclic aromatic polyisocyanate and fused aromatic polyisocyanate.
Examples of the monocyclic aromatic polyisocyanate include dialkyldiphenylmethane diisocyanate such as 4,4 '-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate such as 4, 4' -diphenyltetramethylmethane diisocyanate, 4 '-diphenylmethane diisocyanate, 4' -dibenzyl isocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, toluene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate.
Examples of the fused aromatic polyisocyanate include 1, 5-naphthalene diisocyanate and the like.
The biuret product of the polyisocyanate may be exemplified by a compound represented by the following structural formula.
Figure BDA0002916946050000231
[ in the formula,
nbis an integer of 0 or more, and,
RbA～RbEeach independently being an alkylene or arylene group,
Rbα～Rbβeach independently is an isocyanate group or
Figure BDA0002916946050000241
(nb1Is an integer of 0 or more, and,
Rb1～Rb5each independently being an alkylene or arylene group,
Rb’～Rb"are each independently an isocyanate group or Rbα～RbβA group per se.
Rb4～Rb5、Rb"the groups may be different in each constituent unit. ).
RbD～RbE、RbβThe groups may be different in each constituent unit.]
Examples of the biuret products of the polyisocyanate include デュラネート 24A-100, デュラネート 22A-75P, デュラネート 21S-75E (manufactured by Asahi Kasei Co., Ltd.), デスモジュール N3200A (the biuret product of hexamethylene diisocyanate) (manufactured by Sui Kasei コベストロウレタン).
The isocyanurate compound of the polyisocyanate may be exemplified by a compound represented by the following structural formula.
Figure BDA0002916946050000242
[ in the formula, niIs an integer of 0 or more, and,
RiA～RiEeach independently being an alkylene or arylene group,
Riα～Riβeach independently is an isocyanate group or
Figure BDA0002916946050000251
(ni1Is an integer of 0 or more, and,
Ri1～Ri5each independently being an alkylene or arylene group,
Ri’～Ri"are each independently an isocyanate group or Riα～RiβA group per se.
Ri5、Ri"the groups may be different in each constituent unit. ).
RiD～RiE、RiβThe groups may be different in each constituent unit.]
Commercially available products of isocyanurate bodies of polyisocyanates include デュラネート TPA-100, デュラネート TKA-100, デュラネート MFA-75B, デュラネート MHG-80B (manufactured by Asahi Kasei Co., Ltd.), コロネート HXR, コロネート HX, コロネート HK (isocyanurate body of hexamethylene diisocyanate), コロネート 2037 (manufactured by Tosoh Corp.), タケネート D-127N (isocyanurate body of hydrogenated xylylene diisocyanate), タケネート D-131N (isocyanurate body of xylylene diisocyanate), タケネート D-204EA-1 (isocyanurate body of tolylene diisocyanate) (manufactured by Mitsui chemical Co., Ltd.), VESTANATT1890/100 (isocyanurate body of isophorone diisocyanate) (manufactured by Chuangyao Kaisha Co., Ltd.), and the like.
Examples of the allophanate of the polyisocyanate include compounds represented by the following structural formulae.
Figure BDA0002916946050000261
[ wherein n is an integer of 0 or more, RAIs alkyl or aryl, RB～RGEach independently being alkylene or arylene, Rα～RγEach independently is an isocyanate group or
Figure BDA0002916946050000262
(n1 is an integer of 0 or more, R1～R6Each independently alkylene or arylene, each R 'to R' "independently is an isocyanate group or Rα～RγA group per se. R1～R4R 'to R' may be different in each constituent unit. ).
RB～RE、Rα～RβThe groups may be different in each constituent unit.]
Examples of commercially available allophanate products of polyisocyanates include コロネート 2793 (manufactured by Tosoh corporation) and タケネート D-178N (manufactured by Mitsui chemical Co., Ltd.).
The adduct of polyisocyanate may be exemplified by:
an adduct of trimethylolpropane and polyisocyanate represented by the following structural formula,
Figure BDA0002916946050000263
[ in the formula, nadIs an integer of 0 or more, RadA～RadEEach independently being alkylene or arylene, Rad1～Rad2Each independently is
Figure BDA0002916946050000271
(in the formula, nad’Is an integer of 0 or more, and,
Rad’～Rad”each independently being an alkylene or arylene group,
Rad”’is Rad1～Rad2The radical as such or a combination thereof,
Rad’～Rad”’the groups may be different in each constituent unit. ),
RadD～RadE、Rad2the groups may be different in each constituent unit.]；
An adduct of glycerin and polyisocyanate represented by the following structural formula,
Figure BDA0002916946050000272
[ in the formula, nad1Is an integer of 0 or more, and,
Radα～Radεeach independently being an alkylene or arylene group,
RadA～RadBeach independently is
Figure BDA0002916946050000281
(in the formula, nad1’Is an integer of 0 or more, and,
Radδ’～Radε’each independently being an alkylene or arylene group,
RadB’is RadA～RadBThe radical as such or a combination thereof,
Radδ’～Radε’、RadB’the groups may be different in each constituent unit. ),
Radδ～Radεthe groups may be different in each constituent unit.](ii) a And the like.
Examples of the adduct of the polyisocyanate include デュラネート P301-75E (manufactured by Asahi Kasei Co., Ltd.), タケネート D110N, タケネート D160N (manufactured by Mitsui chemical Co., Ltd.), コロネート L and コロネート HL (manufactured by Tosoh Co., Ltd.).
Examples of the upper limit and the lower limit of the NCO content (NCO%) of the polyisocyanate include 30%, 25%, 20%, 15%, 10%, and the like. In one embodiment, the NCO content (NCO%) is preferably 10 to 30%.
Examples of the upper limit and the lower limit of the isocyanate group equivalent of the polyisocyanate include 420g/eq, 400g/eq, 350g/eq, 300g/eq, 250g/eq, 200g/eq, 150g/eq, 140g/eq, and the like. In one embodiment, the isocyanate group equivalent is preferably 140 to 420 g/eq.
In the present invention, the isocyanate group equivalent means a calculated value (g/eq) of mass per 1 mole of isocyanate group.
Examples of the upper limit and the lower limit of the ratio (NCO/OH) of the isocyanate group equivalent of the polyisocyanate to the total of the hydroxyl group equivalents of the component (a) and the component (B) include 1, 0.9, 0.75, 0.5, 0.25, 0.1, 0.05, and 0. In one embodiment, the ratio (NCO/OH) is preferably 0 to 1.
Examples of the upper limit and the lower limit of the amount of OH groups consumed include 150mgKOH/g, 125mgKOH/g, 100mgKOH/g, 75mgKOH/g, 50mgKOH/g, 25mgKOH/g, and 10 mgKOH/g. In one embodiment, the amount of the OH groups consumed is preferably 10 to 150 mgKOH/g.
In the present invention, the amount of OH groups consumed is an index indicating how much NCO is added to consume OH groups in the components (A) and (B). The amount of OH groups consumed was calculated from the following equation.
OH groups consumed-amount of polyisocyanate added/isocyanate group equivalent X56.1
Examples of the upper limit and the lower limit of the content of the polyisocyanate in the primer include 40 mass%, 30 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 0 mass%, and the like. In one embodiment, the content is preferably 0 to 40% by mass.
< organic solvent (E): also known as component (E) >
In one embodiment, the primer may contain an organic solvent. The organic solvent may be used alone or in combination of two or more.
Examples of the organic solvent include: ketone solvents such as methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, and cyclohexanone; aromatic solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, and butanol; glycol ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and propylene glycol monomethyl ether acetate; ester solvents such as ethyl acetate, butyl acetate, methyl cellosolve acetate and cellosolve acetate; ソルベッソ #100 and ソルベッソ #150 (both trade names. エクソン) and other petroleum solvents; halogenated alkane solvents such as chloroform; amide solvents such as dimethylformamide, and the like. Among them, ketone solvents are preferable, and among the ketone solvents, acetylacetone is preferable, from the viewpoint of the pot life of the primer of the present invention.
Examples of the upper limit and the lower limit of the content of the organic solvent in the primer include 95 mass%, 90 mass%, 80 mass%, 70 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 0 mass%, and the like. In one embodiment, the content is preferably about 50% by mass to about 95% by mass. The organic solvent contained in the primer may contain an organic solvent used in the production of the components (a) to (D).
< curing catalyst (F): also known as component (F) >
In one embodiment, the primer may contain a curing catalyst. The curing catalyst may be used alone or in combination of two or more.
(F) Examples of the component (B) include inorganic catalysts and organic catalysts.
The inorganic catalyst may be exemplified by typical metal catalysts, transition metal catalysts, and the like.
Typical examples of the metal catalyst include tin catalysts, bismuth catalysts, and the like.
Examples of the tin catalyst include dibutyltin dilaurate and dioctyltin dilaurate.
Examples of the bismuth catalyst include bismuth octoate.
Examples of the transition metal catalyst include a titanium catalyst, a zirconium catalyst, and an iron catalyst.
Examples of the titanium catalyst include titanium ethyl acetoacetate.
Examples of the zirconium catalyst include zirconium tetraacetylacetonate.
Examples of the iron catalyst include iron acetylacetonate.
Examples of the organic catalyst include amine catalysts.
Examples of the amine catalyst include diazabicyclooctane, dimethylcyclohexylamine, tetramethylpropylenediamine, ethylmorpholine, dimethylethanolamine, triethylamine, and triethylenediamine.
Examples of the upper limit and the lower limit of the content of the curing catalyst in the primer include 1 mass%, 0.9 mass%, 0.75 mass%, 0.5 mass%, 0.25 mass%, 0.1 mass%, 0.09 mass%, 0.05 mass%, 0.02 mass%, 0.01 mass%, 0 mass%, and the like. In one embodiment, the content of the curing catalyst in the primer is preferably about 0% by mass to about 1% by mass.
< additive >
The primer may contain, as an additive, an agent other than the components (a) to (F). Examples of the additives include polymerization inhibitors, antioxidants, light stabilizers, antifoaming agents, surface conditioners, pigments, antistatic agents, metal oxide fine particle dispersions, organic fine particle dispersions, and the like. In one embodiment, the content of the additive may be, for example, 0.1 to 10 mass%, less than 5 mass%, less than 1 mass%, less than 0.1 mass%, less than 0.01 mass%, 0 mass%, or the like of the primer. Examples of the component (a) to (F) include 0.1 to 10 mass%, less than 5 mass%, less than 1 mass%, less than 0.1 mass%, less than 0.01 mass%, 0 mass%, and the like.
The primer can be obtained by mixing the components (a) to (B) and, if necessary, the components (C) to (F) and/or additives by various known means. The order of addition of the components is not particularly limited. As the dispersing and mixing means, various known apparatuses (an emulsion dispersing machine, an ultrasonic dispersing apparatus, and the like) can be used.
In one embodiment, the primer is used as a primer for an active energy ray-curable resin or the like.
[ cured product ]
The present invention provides a cured product of the above primer.
In one embodiment, the cured product is a cured product obtained by irradiating the primer with an active energy ray, or a cured product obtained by thermally curing the primer and then irradiating the primer with an active energy ray. The curing conditions include the conditions described below.
[ laminate ]
The present invention provides a laminate in which an undercoat cured product layer containing a cured product of the aforementioned undercoat agent is laminated on at least one surface of a substrate. In one embodiment, an active energy ray-curable resin cured layer is laminated on the primer cured layer.
The substrate used is a variety of known substrates. Examples of the substrate include a polycarbonate substrate, an acrylic substrate (e.g., a polymethyl methacrylate substrate), a polystyrene substrate, a polyester substrate, a polyolefin substrate, an epoxy resin substrate, a melamine resin substrate, a triacetylcellulose substrate, an ABS substrate, an AS substrate, a norbornene resin substrate, a cyclic olefin substrate, and a polyvinyl alcohol substrate. Further, a vapor deposition layer of metal oxide or the like, an easy adhesion layer, a hard coat layer, or the like may be provided on the surface thereof. The thickness of the substrate is not particularly limited, but is preferably about 50 μm to about 2000. mu.m. The thickness of the primer layer is not particularly limited, but is preferably about 0.1 μm to about 5 μm.
The laminate can be produced by various known methods. In one embodiment, the method for producing a laminate includes a step of applying the primer to at least one surface of the substrate (coating step) and a step of forming a cured primer layer by heat curing if necessary (heat curing step). In one embodiment, in the above film, an active energy ray-curable resin cured layer is stacked on the primer cured layer. In this case, the primer composition further includes a step of applying an active energy ray-curable resin to the primer cured layer (coating step), a step of drying the primer cured layer as needed (drying step), and a step of forming an active energy ray-curable resin cured layer by irradiation with an active energy ray (active energy ray-curing step).
(coating Process)
Examples of the coating method include bar coater coating, wire bar coating, meyer bar coating, air knife coating, gravure coating, reverse gravure coating, flow coating, offset printing, flexographic printing, and screen printing.
The amount of coating is not particularly limited. As for the coating amount, the mass after drying is preferably about 0.1g/m2About 30g/m2More preferably about 1g/m2About 20g/m2。
(Heat curing step)
Examples of the drying method include drying with a hot air circulation dryer. The drying conditions may be, for example, 30 seconds to 10 minutes at 80 to 120 ℃.
In the production of the film, the film is dried and then aged as necessary. As an example, an aging treatment at 40 ℃ for 72 hours or the like can be exemplified.
(active energy ray curing step)
Examples of the active energy ray used for the active energy ray curing reaction include ultraviolet rays and electron rays. Examples of the light source of ultraviolet rays include an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, or a metal halide lamp. The light amount, the light source arrangement, the conveyance speed, and the like can be adjusted as necessary. In the case of using a high-pressure mercury lamp, it is preferable to carry out curing at a carrying speed of about 2 m/min to about 50 m/min with respect to 1 lamp having a light amount of about 80W/cm to about 160W/cm. On the other hand, when an electron beam is used, it is preferable to perform curing at a transport speed of about 5 m/min to about 50 m/min by using an electron beam accelerator having an acceleration voltage of about 10kV to about 300 kV.
Examples of the active energy ray-curable resin include resins curable with a radical (for example, "ビームセットシリーズ" manufactured by seikagawa chemical corporation) such as (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and polyacrylic (meth) acrylate, resins curable with a cation or anion such as epoxy, oxetane, and vinyl ether, and resins curable by an ene-thiol reaction between an olefin and a thiol. These resins may be used in combination.
[ examples ]
The present invention will be specifically described below with reference to examples and comparative examples. However, the description of the preferred embodiments and the examples below are provided for illustrative purposes only and are not provided for the purpose of limiting the present invention. Therefore, the scope of the present invention is not limited to the embodiments and examples specifically described in the present specification, but is defined only by the claims. In the examples and comparative examples, the numerical values of parts,% and the like are based on mass unless otherwise specified.
< component (A) >
Production example 1-1: production of hydroxyl group-containing (meth) acrylic Polymer
275.6 parts of methyl methacrylate (79.9 mass% in monomer component), 10.3 parts of n-butyl acrylate (3 mass% in monomer component), 58.6 parts of 2-hydroxyethyl acrylate (17 mass% in monomer component), 0.4 part of styrene (0.1 mass% in monomer component), 125 parts of methyl ethyl ketone and 525 parts of ethyl acetate were put into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube, and the reaction system was set to 80 ℃. Subsequently, 2.1 parts of 2, 2' -azobis (2, 4-methylpentanenitrile) was charged and the mixture was incubated at about 80 ℃ for 5 hours. Then, 5.2 parts of 2, 2' -azobis (2, 4-dimethylbutyronitrile) was charged, and the reaction system was further incubated at about the temperature for 4 hours. Then, the reaction system was cooled to room temperature, thereby obtaining a solution (nonvolatile content: 35%) of the hydroxyl group-containing (meth) acrylic polymer 1.
A hydroxyl group-containing (meth) acrylic polymer other than that of production example 1-1 was produced in the same manner as in production example 1-1, except that the amount of the monomer used was changed as shown in the following table.
[ Table 1]
Figure BDA0002916946050000351
MMA: methacrylic acid methyl ester
BA: acrylic acid n-butyl ester
HEA: 2-Hydroxyethyl acrylate
St: styrene (meth) acrylic acid ester
EA: acrylic acid ethyl ester
< ingredient (B) >
Production example 2-1
125 parts of butyl acetate, 50 parts of glycidyl methacrylate (hereinafter referred to as GMA), 50 parts of MMA, and 1 part of azobisisobutyronitrile (hereinafter referred to as AIBN) were put into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet, stirred, heated to 100 ℃ under a nitrogen stream, and reacted for 10 hours. After the reaction, the reaction mixture was cooled to 60 ℃, 25 parts of acrylic acid, 0.1 part of triphenylphosphine, and 0.05 part of p-methoxyphenol were added, the nitrogen inlet was replaced with an air bubbling device, air was stirred while bubbling in the reaction solution, the temperature was raised to 110 ℃, and the reaction was carried out while maintaining the temperature for 9 hours, whereby resin 1 having a resin solid content of 50% was obtained. The weight average molecular weight (polystyrene equivalent based on GPC) was 9000. The weight average molecular weight is a value measured by using a gel permeation chromatograph (trade name "HLC-8220" manufactured by Tosoh corporation, column: 3 series of trade names "TSKgel SuperHM-L" manufactured by Tosoh corporation).
A hydroxyl group-containing poly (meth) acrylate other than that produced in production example 2-1 was produced in the same manner as in production example 2-1, except that the amount of the monomer used was changed as shown in the following table. In the table, the values of GMA and MMA show the contents of the polymer before addition of Acrylic Acid (AA), and the value of acrylic acid shows a value of 100 mass% with respect to GMA.
[ Table 2]
Figure BDA0002916946050000361
GMA: glycidyl methacrylate
MMA: methacrylic acid methyl ester
AA: acrylic acid
The unit of acrylic acid equivalent is g/eq.
(example 1)
70 parts of the hydroxyl group-containing (meth) acrylic polymer 1 of production example 1-1 as component (A), 30 parts of the hydroxyl group-containing poly (meth) acrylate A of production example 2-1 as component (B), and 5 parts of Omnirad184 (manufactured by IGM) as component (C) were charged and stirred for 15 minutes to produce a primer.
Primers other than those of example 1 were produced in the same manner as in example 1, except that the component composition was changed as shown in the following table.
[ Table 3]
Figure BDA0002916946050000362
[ Table 4]
Figure BDA0002916946050000371
コロネート HX: an isocyanurate of hexamethylene diisocyanate, manufactured by Tosoh corporation, having a solid content of 100% by mass and an NCO% of 20.5 to 22.0%
(production of laminate)
(1) Formation of a layer of primer cure
The primers of examples 1 to 13 and comparative examples 1 to 5 were applied to a PC/PMMA bilayer sheet (テクノロイ C001: manufactured by Sumitomo chemical Co., Ltd.) so that the film thickness after drying was 2 μm, and the ratios of examples 1 to 12 were adjustedComparative examples 1 to 5, after drying at 100 ℃ for 60 seconds, the dried product was dried at 300mJ/cm2UV curing is performed. Examples 13 and 14 were dried at 100 ℃ for 5 minutes, and then UV-cured.
(2) Formation of active energy ray-curable resin cured layer
An active energy ray-curable resin is applied to the primer cured layer so that the film thickness after drying is 5 to 6 μm, dried at 80 ℃ for 60 seconds, and then dried at 300mJ/cm2UV curing is performed. As the active energy ray-curable resin, ビームセット 700 (manufactured by seikagawa chemical corporation) of a polyfunctional acrylate (dipentaerythritol polyacrylate) was used for evaluation. As a photopolymerization initiator, Omnirad184 was added in an amount of 5% based on the solid content of the active energy ray-curable resin.
(drying Property)
The state of the cured primer layer was evaluated according to the following criteria.
No stickiness of O …
X … tacky
(adhesion to substrate)
After the formation of the primer cured layer, the adhesion was evaluated by a cellophane tape checkerboard peel test defined in JIS K5400. The evaluation criteria are as follows.
O … was 100/100 in a100 grid checkerboard test
The delta … is 50-70/100 in a 100-grid checkerboard test
X … is 20 or less/100 in a100 grid test
(appearance)
The appearance of the laminate (the primer cured layer and the active energy ray-curable resin cured layer) was evaluated according to the following criteria.
O … colorless and transparent
X … whitening
(adhesion to active energy ray-curable resin cured layer)
After the formation of the active energy ray-curable resin cured layer, the adhesion was evaluated by the same method and evaluation criteria as those for the adhesion to the substrate.
Evaluation examples
The primers of the evaluation examples were produced in the same manner as in example 1, except that the component compositions were changed as shown in the following table.
[ Table 5]
Figure BDA0002916946050000391
(elongation by heating)
A primer cured product was produced on a PET film (コスモシャイン A4100: manufactured by Toyo Boseki Co., Ltd.) in the same manner as described above, and the film cut into 1.5cm X13 cm was stretched in a hot air circulating dryer at 150 ℃ until cracks were formed in the coating film by using a TENSILON universal material tester (manufactured by A & D Co., Ltd.), and the thermal elongation was calculated by the following formula.
The heating elongation (%) (film length after stretching) - (film length before stretching) ]/(film length before stretching) × 100.

Claims (5)

1. A primer comprising a hydroxyl group-containing (meth) acrylic polymer (A) and a hydroxyl group-containing poly (meth) acrylate (B).
2. The primer according to claim 1, wherein the hydroxyl group-containing poly (meth) acrylate (B) is a hydroxyl group-containing polymer poly (meth) acrylate.
3. A cured product of the primer according to claim 1 or 2.
4. A laminate comprising a cured primer layer comprising a cured product of the primer according to claim 3 laminated on at least one surface of a substrate.
5. The laminate according to claim 4, wherein an active energy ray-curable resin cured layer is laminated on the primer cured layer.
CN202110104787.6A 2020-01-28 2021-01-26 Primer, cured product, and laminate Active CN113248954B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-011466 2020-01-28
JP2020011466A JP2021116374A (en) 2020-01-28 2020-01-28 Undercoat agent, cured product, and laminate

Publications (2)

Publication Number Publication Date
CN113248954A true CN113248954A (en) 2021-08-13
CN113248954B CN113248954B (en) 2023-06-06

Family

ID=77174189

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110104787.6A Active CN113248954B (en) 2020-01-28 2021-01-26 Primer, cured product, and laminate

Country Status (4)

Country Link
JP (1) JP2021116374A (en)
KR (1) KR102290594B1 (en)
CN (1) CN113248954B (en)
TW (1) TW202134063A (en)

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101203537A (en) * 2005-04-25 2008-06-18 大日本油墨化学工业株式会社 Active energy ray-curable resin composition and article and molded product using the same
CN102803313A (en) * 2010-03-18 2012-11-28 新日铁化学株式会社 Epoxy acrylate, acrylic composition, cured substance, and manufacturing method therefor
CN105418820A (en) * 2015-12-23 2016-03-23 华南理工大学 Hydroxyl-containing styrene-acrylate copolymer/SiO2 hybrid emulsion, preparation method and application thereof
CN105612227A (en) * 2013-09-10 2016-05-25 关西涂料株式会社 Coating material composition and coated article
WO2016104423A1 (en) * 2014-12-25 2016-06-30 株式会社Ｄｎｐファインケミカル Laminate, laminate with colored layer, production method for laminate, production method for laminate with colored layer, and ink recording method
WO2016179787A1 (en) * 2015-05-12 2016-11-17 浙江纳美新材料股份有限公司 Pigment-type ultraviolet light curable coating for window film and preparation method therefor
JP2017105953A (en) * 2015-12-11 2017-06-15 Dic株式会社 Active energy ray-curable resin composition and laminated film
CN107428894A (en) * 2015-03-31 2017-12-01 日本合成化学工业株式会社 Actinic energy ray curable resion composition, coating agent composition and layered product
JP2018062649A (en) * 2016-10-07 2018-04-19 日本合成化学工業株式会社 Active energy ray-curable resin composition, coating agent, base film with undercoat layer and laminate film with metal thin film layer
WO2018152498A1 (en) * 2017-02-20 2018-08-23 Swimc, Llc Process for the preparation of resin-inorganic fibers composite and the obtained resin-inorganic fibers composite for coating
CN108624095A (en) * 2017-03-23 2018-10-09 荒川化学工业株式会社 The hard paint of active energy ray curable, cured coating film, stacked film
CN108779277A (en) * 2016-04-01 2018-11-09 阿克佐诺贝尔国际涂料股份有限公司 The method for repairing film, the purposes of adhesion primer in this method and the base material with reparation film
CN110643270A (en) * 2018-06-27 2020-01-03 荒川化学工业株式会社 Heat-curable coating agent, cured product, and film
CN113493574A (en) * 2020-03-19 2021-10-12 荒川化学工业株式会社 Primer for substrate with metal thin film, cured product, substrate with metal thin film and method for producing same, and film

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110098665A (en) 2010-02-26 2011-09-01 아라까와 가가꾸 고교 가부시끼가이샤 An undercoating agent for a plastic product with inorganic thin layer, a plastic product with inorganic thin layer, and a decoration film for in-mold molding or insert molding
TWI526506B (en) * 2010-09-21 2016-03-21 Arakawa Chem Ind Non-aqueous primer with plastic film with reactive energy ray hardening film, plastic film with hardening film with active energy line
JP2015217333A (en) * 2014-05-15 2015-12-07 関西ペイント株式会社 Substrate film forming method
JP2015226891A (en) * 2014-06-02 2015-12-17 関西ペイント株式会社 Film formation method of substrate
JP6537364B2 (en) * 2014-06-19 2019-07-03 関西ペイント株式会社 Method of forming a film on a substrate
JP6708946B2 (en) * 2014-10-31 2020-06-10 荒川化学工業株式会社 Undercoat agent for plastic with aluminum thin film, plastic with aluminum thin film, plastic film with aluminum thin film, decorative film for in-mold molding and decorative film for insert molding
JP6583889B2 (en) * 2015-12-23 2019-10-02 関西ペイント株式会社 Film formation method
JP2017113689A (en) * 2015-12-23 2017-06-29 関西ペイント株式会社 Hydrophilic film formation method on base material

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101203537A (en) * 2005-04-25 2008-06-18 大日本油墨化学工业株式会社 Active energy ray-curable resin composition and article and molded product using the same
CN102803313A (en) * 2010-03-18 2012-11-28 新日铁化学株式会社 Epoxy acrylate, acrylic composition, cured substance, and manufacturing method therefor
CN105612227A (en) * 2013-09-10 2016-05-25 关西涂料株式会社 Coating material composition and coated article
WO2016104423A1 (en) * 2014-12-25 2016-06-30 株式会社Ｄｎｐファインケミカル Laminate, laminate with colored layer, production method for laminate, production method for laminate with colored layer, and ink recording method
CN107428894A (en) * 2015-03-31 2017-12-01 日本合成化学工业株式会社 Actinic energy ray curable resion composition, coating agent composition and layered product
WO2016179787A1 (en) * 2015-05-12 2016-11-17 浙江纳美新材料股份有限公司 Pigment-type ultraviolet light curable coating for window film and preparation method therefor
JP2017105953A (en) * 2015-12-11 2017-06-15 Dic株式会社 Active energy ray-curable resin composition and laminated film
CN105418820A (en) * 2015-12-23 2016-03-23 华南理工大学 Hydroxyl-containing styrene-acrylate copolymer/SiO2 hybrid emulsion, preparation method and application thereof
CN108779277A (en) * 2016-04-01 2018-11-09 阿克佐诺贝尔国际涂料股份有限公司 The method for repairing film, the purposes of adhesion primer in this method and the base material with reparation film
JP2018062649A (en) * 2016-10-07 2018-04-19 日本合成化学工業株式会社 Active energy ray-curable resin composition, coating agent, base film with undercoat layer and laminate film with metal thin film layer
WO2018152498A1 (en) * 2017-02-20 2018-08-23 Swimc, Llc Process for the preparation of resin-inorganic fibers composite and the obtained resin-inorganic fibers composite for coating
CN108624095A (en) * 2017-03-23 2018-10-09 荒川化学工业株式会社 The hard paint of active energy ray curable, cured coating film, stacked film
CN110643270A (en) * 2018-06-27 2020-01-03 荒川化学工业株式会社 Heat-curable coating agent, cured product, and film
CN113493574A (en) * 2020-03-19 2021-10-12 荒川化学工业株式会社 Primer for substrate with metal thin film, cured product, substrate with metal thin film and method for producing same, and film

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘玉;陈小琴;王杰;: "新型耐候性丙烯酸阳极电泳涂料的研制", 现代涂料与涂装, no. 10, pages 6 - 8 *

Also Published As

Publication number Publication date
KR102290594B1 (en) 2021-08-17
CN113248954B (en) 2023-06-06
TW202134063A (en) 2021-09-16
JP2021116374A (en) 2021-08-10
KR20210096546A (en) 2021-08-05

Similar Documents

Publication Publication Date Title
WO2011111430A1 (en) Vehicle member and manufacturing method therefor
JP6543489B2 (en) Aqueous curable resin composition
JP5504988B2 (en) Active energy ray curable compound
JP2008069303A (en) Curl inhibitor, active energy ray-curable resin composition and film substrate
TWI830005B (en) Primer for base material with metal thin film, hardened material, base material with metal thin film, manufacturing method thereof, and film
CN113248954A (en) Primer, cured product, and laminate
TWI659075B (en) Curable composition, cured product, molded article, and display member
JP6258662B2 (en) Water-based ink composition
JP2021046483A (en) Active energy ray-curable antifogging composition and cured product
JP5643534B2 (en) MULTILAYER COATING FORMATION METHOD AND COATED ARTICLE
JP7205100B2 (en) Undercoating agents and films
JP5374997B2 (en) Active energy ray-curable resin composition for coating and film substrate
JP2004143344A (en) Crosslinkable resin composition having ultraviolet light-absorbing ability
JP7013822B2 (en) Adhesive resin composition and adhesive sheet
WO2017183634A1 (en) Composition for decorative sheets, decorative sheet and molded product
JP7322396B2 (en) Active energy ray-curable resin composition and coating agent for pre-coated metal production
WO2013141163A1 (en) Compound, process for producing said compound, polymer, curable composition, and cured object
WO2019182155A1 (en) Curable composition, cured product, method for producing cured product, and method for repairing damage of cured product
JP5585206B2 (en) Active energy ray-curable compound and active energy ray-curable composition containing the compound
JP5585205B2 (en) Active energy ray-curable compound and active energy ray-curable composition containing the compound
JP2021105170A (en) Active energy ray-curable composition and method for producing the same
JP2008163064A (en) Photosensitive material, method for producing the same and laminated material by using the same
TWI773674B (en) Active energy ray-curable resin composition and coating agent composed of the same
TW201807107A (en) Composition for decorative sheets, decorative sheet and molded product
US9982161B2 (en) Graft copolymers with grafted polymeric arms, their preparation and use

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant