Classifications

• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/067—Polyurethanes; Polyureas
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
• • 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
  • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
• • 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
  • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• • 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
  • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/24—Catalysts containing metal compounds of tin
  • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
  • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
  • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
  • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/81—Unsaturated isocyanates or isothiocyanates
  • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
  • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
  • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
  • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
• • 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
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • 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
  • 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
  • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
• • 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
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
• • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2150/00—Compositions for coatings
  • C08G2150/20—Compositions for powder coatings
• • 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
  • C08G2150/00—Compositions for coatings
  • C08G2150/90—Compositions for anticorrosive coatings

Definitions

• the present invention relates to an active energy ray-curable composition, a laminate, and a method for producing the laminate.
• Resin materials especially transparent resin materials such as polycarbonate, are used widely in many fields, taking advantage of their characteristics of low specific gravity, light weight, ease of processing, and high impact resistance compared to inorganic glass.
• resin primers are applied to glass and metal steel sheets for the purpose of coloring, preventing rust, and bonding with other materials.
• resin materials and resin primers have drawbacks such as their surfaces being easily scratched and losing gloss and transparency, being easily corroded by organic solvents, poor weather resistance (e.g., light stability against ultraviolet rays, etc.), and poor heat resistance. Therefore, resin materials are often used after being covered with various protective films in order to improve their surface properties. Examples of such protective films include hard coat layers formed by curing active energy ray-curable compositions.
• Patent Document 1 discloses an active energy ray-curable composition having adhesion, abrasion resistance, and weather resistance, which contains inorganic oxide fine particles, a poly[(meth)acryloyloxyalkyl]isocyanurate having at least two (meth)acryloyl groups in the molecule, a urethane poly(meth)acrylate having at least two (meth)acryloyl groups in one molecule and an alicyclic skeleton, an alkyl di(meth)acrylate having 4 to 12 carbon atoms, and a photopolymerization initiator in specific ratios.
• the invention described in the above Patent Document 1 does not consider chemical resistance.
• the composition described in Patent Document 1 contains an organic monomer that is highly corrosive to substrates, such as an alkyl di(meth)acrylate having 4 to 12 carbon atoms, and therefore when a resin substrate such as a polycarbonate that is susceptible to erosion or various resin primers is used, the composition may excessively corrode these, resulting in poor appearance of the coating film and deterioration of weather resistance. Therefore, the invention described in Patent Document 1 does not solve both the problems of chemical resistance and weather resistance, and does not enable the formation of a coating film or cured coating with a good appearance.
• the present invention has been made in consideration of the above problems, and aims to provide an active energy ray-curable composition capable of forming a cured coating film or cured layer that has weather resistance and chemical resistance and has an excellent appearance, as well as a laminate having the cured layer and a method for producing the laminate.
• An active energy ray-curable composition comprising a compound (A) having a chain hydrocarbon group having 2 to 12 carbon atoms and two (meth)acryloyloxy groups, and a compound having an isocyanurate bond or an allophanate bond.
• the active energy ray-curable composition according to (1) wherein the compound having an isocyanurate bond or an allophanate bond is a urethane (meth)acrylate compound (B) having an isocyanurate bond or an allophanate bond.
• a method for producing a laminate comprising: step 1 of applying an active energy ray-curable composition according to any one of (1) to (6) onto a substrate to obtain a coating film; and step 2 of irradiating the coating film with active energy rays to cure a part or the whole of the coating film. (9) The method for producing a laminate according to (8), wherein after the step 2, the step 1 and the step 2 are repeated in this order at least once or more.
• the active energy ray-curable composition of the present invention can form a cured coating with excellent appearance, excellent chemical resistance, and high weather resistance while satisfying the properties required of a cured coating, such as adhesion and abrasion resistance.
• This cured coating has excellent adhesion to resin substrates such as polycarbonate and resin primers, and has excellent durability even in high temperature and high humidity environments and environments where it may come into contact with chemicals. Therefore, the active energy ray-curable composition of the present invention can be suitably used as a hard coat for resin materials in automotive and building material applications, and is particularly suitable for automotive exterior and automotive glazing applications.
• the active energy ray-curable composition of the present invention (hereinafter may be simply referred to as the "composition” or “composition”) contains a compound (A) (hereinafter may be referred to as the “component (A)”) consisting of a chain hydrocarbon group having 2 to 12 carbon atoms and two (meth)acryloyloxy groups, and a compound having an isocyanurate bond or an allophanate bond.
• the compound represented by formula (1) is referred to as “compound (1)”, and the same applies to compounds represented by other formulas.
• “acrylate” and “methacrylate” are collectively referred to as "(meth)acrylate”.
• Component (A) is a compound consisting of a chain hydrocarbon group having 2 to 12 carbon atoms and two (meth)acryloyloxy groups, and by including component (A) in the composition, the adhesion to substrates and weather resistance of the cured coating are improved.
• the chain hydrocarbon group having 2 to 12 carbon atoms may be linear or branched, but is preferably linear.
• the number of carbon atoms is preferably 4 to 10, and more preferably 6 to 10. In particular, from the viewpoint of reducing skin irritation to workers during production work, 8 to 10 is preferable.
• component (A) include (meth)acrylates having a linear hydrocarbon group, such as 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate; and (meth)acrylates having a branched hydrocarbon group, such as neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, and 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate.
• linear hydrocarbon group such as 1,
• the component (A) may be used as a single compound, or as a combination of two or more compounds.
• the content of the (A) component is preferably 10 to 60% by mass, more preferably 15 to 55% by mass, and even more preferably 20 to 50% by mass, based on the total 100% by mass of the (A) component, the compound having an isocyanurate bond or an allophanate bond (specifically, one or more selected from the group consisting of a urethane (meth)acrylate compound (B) having an isocyanurate bond or an allophanate bond, and a (meth)acrylate compound (C) having an isocyanurate bond), and the optionally contained (D) component (hereinafter referred to as "100% by mass of the total of the (A) to (D) components").
• composition of the present invention contains a compound having an isocyanurate bond or an allophanate bond.
• the isocyanurate bond and the allophanate bond are represented by the following formulas (i) and (ii), respectively.
• this compound has an isocyanurate bond or an allophanate bond
• the compound having an isocyanurate bond or an allophanate bond is preferably one or more selected from the group consisting of a urethane (meth)acrylate compound (B) having an isocyanurate bond or an allophanate bond, and a (meth)acrylate compound (C) having an isocyanurate bond.
• Component (B) The urethane (meth)acrylate compound (B) having an isocyanurate bond or an allophanate bond (hereinafter sometimes referred to as “component (B)”) is a component that contributes to the weather resistance and adhesion of the cured coating.
• R 21 to R 25 each independently represent a group having a polymerizable group.
• the polymerizable group possessed by R 21 to R 25 is preferably a (meth)acryloyl group (CH 2 ⁇ CR 4 —CO— (R 4 is the same as above), and R 21 to R 25 are preferably a combination of a (meth)acryloyl group and a divalent linking group.
• the hydrogen atom of the groups listed as the divalent linking group may be substituted with an alkyl group, an alkoxy group, an acyl group, or the like.
• L 21 and L 22 each independently represent a divalent linking group.
• the divalent linking groups of L and L preferably have a structure in which hydroxyl groups have been removed from both ends of an alkylene diol, a caprolactone-modified diol, or polytetramethylene glycol.
• the alkylene diol is preferably an alkylene diol having 2 to 10 carbon atoms, and the number of repeating tetramethylene groups in polytetramethylene glycol is preferably 8 to 30.
• caprolactone-modified diol examples include "PLACCEL 205", a polycaprolactone diol having a mass average molecular weight of 530, “PLACCEL 205BA”, a polycaprolactone diol having a mass average molecular weight of 530 and having a carboxyl group in the side chain, “PLACCEL L205AL”, a polycaprolactone diol having a mass average molecular weight of 500 in a liquid at room temperature, "PLACCEL 205H”, a polycaprolactone diol having a mass average molecular weight of 530 and having improved water resistance compared to PLACCEL 205, “PLACCEL 205U”, a polycaprolactone diol having a mass average molecular weight of 530 and lower viscosity and acid value compared to PLACCEL 205, “PLACCEL 208”, a polycaprolactone diol having a mass average molecular weight of 830 in a liquid at room temperature, and "PL
• PLAACCEL L208AL "PLACCEL 210”, a polycaprolactone diol with a mass average molecular weight of 1000
• PLAACCEL 210BA a polycaprolactone diol with a mass average molecular weight of 1000 having a carboxyl group on the side chain
• PLACCEL 210CP a polycaprolactone diol with a mass average molecular weight of 1000 having a lower acid value and improved water resistance compared to PLACCEL 210
• PLAACCEL 210N a polycaprolactone diol with a mass average molecular weight of 1000 and a narrower molecular weight distribution compared to PLACCEL 210
• PLAACCEL 212 a polycaprolactone diol with a mass average molecular weight of 1250
• PLAACCEL L212AL a polycaprolactone diol with a mass average molecular weight of 1250 as a liquid at room temperature
• PLACCEL “PLACCEL 220BA is
• L 21 to L 22 preferably have another linking group in addition to any one of the structures obtained by removing a hydroxyl group from the terminal of an alkylene diol, a caprolactone-modified diol, or polytetramethylene glycol.
• the other linking group those exemplified as "divalent linking groups possessed by R 21 to R 25 " are preferable.
• Z 21 to Z 23 each independently represent a structure represented by the following formula (2z).
• X 21 is an alkylene group having 2 to 17 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms, and even more preferably an alkylene group having 2 to 6 carbon atoms.
• the * in formula (2z) represents a bond
• formula (2z) is Z21 in formula (2)
• the bond * represented by B1 is directly bonded to R21
• the bond represented by B2 is directly bonded to L21 or R22
• the bond represented by B3 is directly bonded to L22 or R23
• formula (2z) is Z22 in formula (2)
• the bond * represented by B1 is directly bonded to L22
• the bond represented by B2 is directly bonded to R24
• the bond represented by B3 is directly bonded to R23
• formula (2z) is Z23 in formula (2)
• the bond * represented by B1 is directly bonded to L21
• the bond represented by B2 is directly bonded to R22
• the bond represented by B3 is directly bonded to R25 .
• Z 1 is an oxygen atom or a nitrogen atom
• Z 1 is an oxygen atom (-O-)
• Z 2 is a hydrogen atom (-H).
• Z 1 is a nitrogen atom
• the nitrogen atom of Z 1 and -C( O)- of Z 2 bond to form a ring. That is, when Z 1 is an oxygen atom, formula (2z) has an allophanate bond, and when Z 1 is a nitrogen atom, formula (2z) has an isocyanurate bond.
• As the component (B) those having an isocyanurate bond as formula (2z) are preferred.
• R 26 is each independently a hydrogen atom or a methyl group.
• R 27 is each independently an alkylene group having 2 to 10 carbon atoms (preferably, 2 to 4 carbon atoms), R A -(O-CO-(CH 2 ) 5 ) n - or R A -(O-(CH 2 ) 4 ) n -.
• R A represents an alkylene group, preferably an alkylene group having 2 to 4 carbon atoms.
• Each n independently represents an integer of 1 to 10, and preferably an integer of 1 to 5.
• X 22 each independently represents an alkylene group having 2 to 17 carbon atoms, preferably an alkylene group having 2 to 10 carbon atoms, and more preferably an alkylene group having 2 to 6 carbon atoms.
• a 1 represents a structure in which a hydroxyl group has been removed from the terminal of any one of an alkylene diol, a caprolactone-modified diol, or polytetramethylene glycol, and is the same as those explained in L 21 to L 22 .
• a plurality of R 26 , R 27 and X 22 may be the same or different.
• the (B) component may be a single compound or a combination of two or more compounds.
• nA represents an integer of 1 to 6
• nA represents an integer of 1 to 6
• the component (B) contains a component (B11) and a component (B22).
• the component (B11) include a compound in which at least one of R 27 in the formula (2-1) or the formula (2-3) is R A -(O-CO-(CH 2 ) 5 ) n -, or R A -(O-(CH 2 ) 4 ) n -, or a compound in which A 1 in the formula (2-2) or the formula (2-4) is a polytetramethylene glycol or a polycaprolactone diol with a hydroxyl group removed from the terminal.
• Examples of the component (B22) include a compound in which R 27 in the formula (2-1) or the formula ( 2-3 ) is an alkylene group, or a compound in which A 1 in the formula (2-2) or the formula (2-4) is an alkylene diol with a hydroxyl group removed from the terminal.
• a combination of the component (B11) represented by formula (2-1) and a component (B22) represented by formula (2-1), or a combination of the component (B11) represented by formula (2-2) in which A1 has a polycaprolactone structure and a component (B22) represented by formula (2-1) is preferred.
• the content of the (B1) component or the (B11) component is preferably 9 to 90 mass% of the total solid content of the (A) to (C) components, more preferably 20 to 70 mass%, even more preferably 30 to 60 mass%, and particularly preferably 45 to 60 mass%.
• the content of the (B2) component or the (B22) component is preferably 5 to 60 mass% of the total solid content of the (A) to (C) components, more preferably 10 to 50 mass%, even more preferably 15 to 40 mass%, and particularly preferably 20 to 30 mass%.
• the total content of component (B) is preferably 10 to 80 mass%, more preferably 15 to 70 mass%, and even more preferably 25 to 60 mass%, of the total 100 mass% of components (A) to (D).
• the content is preferably 10 to 80 mass%, more preferably 15 to 70 mass%, and even more preferably 25 to 60 mass%, of the total 100 mass% of components (A) to (D).
• the (meth)acrylate compound (C) having an isocyanurate bond (hereinafter sometimes referred to as "component (C)") is a component that contributes to the abrasion resistance and adhesion of the cured coating.
• the component (C) is a compound that does not fall under the category of the above-mentioned component (B), and is a compound that does not have a urethane bond but has an isocyanurate bond and a (meth)acrylate structure ((meth)acryloyl group).
• the component (C) is preferably a compound represented by the following formula (1):
• R 1 , R 2 and R 3 each independently represent an oxyalkylene group or a polyoxyalkylene group.
• the oxyalkylene group preferably has 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
• the number of carbon atoms per repeating unit is preferably 1 to 8, more preferably 1 to 5, and particularly preferably 1 to 3.
• the number of repeating oxyalkylene groups in the polyoxyalkylene group is preferably in the range of 1 to 10.
• the oxygen atom of the oxyalkylene group and the terminal oxygen atom of the polyoxyalkylene group are bonded to X 1 , X 2 or X 3 in the formula.
• X 1 , X 2 and X 3 each independently represent CH 2 ⁇ CR 4 -CO-, CH 2 ⁇ CR 4 -CO(O(CH 2 ) 5 -CO) a1 -, a hydrogen atom or an alkyl group, provided that at least two of X 1 to X 3 are CH 2 ⁇ CR 4 -CO- or CH 2 ⁇ CR 4 -CO(O(CH 2 ) 5 -CO) a1 -.
• compound (1) is a difunctional or trifunctional (meth)acrylate.
• R 4 represents a hydrogen atom or a methyl group, and a plurality of R 4s may be the same or different, but is preferably a hydrogen atom.
• a1 is an integer of 1 or more, preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1.
• X 1 , X 2 and X 3 are preferably CH 2 ⁇ CR 4 —CO—, CH 2 ⁇ CR 4 —CO(O(CH 2 ) 5 —CO) a1 — or a hydrogen atom, more preferably at least two of X 1 to X 3 are CH 2 ⁇ CR 4 —CO—, and particularly preferably all three are CH 2 ⁇ CR 4 —CO—.
• Particularly preferred examples of the compound (1) include compounds represented by the following formula (1-1).
• R 4 is the same as defined above, and R 1' to R 3' are alkylene groups having 1 to 5 carbon atoms (preferably 1 to 3).
• component (C) include bis(2-acryloyloxyethyl)hydroxyethyl isocyanurate, tris(2-acryloyloxyethyl)isocyanurate (manufactured by Toagosei Co., Ltd. under the trade names Aronix M-313 and Aronix M-315, manufactured by Shin-Nakamura Chemical Co., Ltd. under the trade names NK Ester A9300 and A9300S, manufactured by Arkema SR368 and SR368NS), and bis(2-acryloyloxypropyl)hydroxyethyl.
• isocyanurate examples include tris(2-acryloyloxypropyl)isocyanurate, tris(2-acryloyloxyethyl)isocyanurate modified with one caprolactone per molecule (manufactured by Toagosei Co., Ltd., product name ARONIX M-325), and tris(2-acryloyloxyethyl)isocyanurate modified with three caprolactones per molecule (manufactured by Toagosei Co., Ltd., product name ARONIX M-327).
• the component (C) may be used as a single compound, or as a combination of two or more compounds.
• the content of component (C) is preferably 1 to 79 mass%, more preferably 3 to 67.5 mass%, and even more preferably 5 to 50 mass%, based on 100 mass% of the total of components (A) to (D).
• the compound having an isocyanurate bond or an allophanate bond may be component (B), may be component (C), or may be components (B) and (C).
• component (B) and (C) it is preferable to use components (B) and (C) in combination, since the use of these in combination makes it easier to achieve improvements in weather resistance, chemical resistance, and adhesion, and to reduce appearance defects.
• Component (D) is a compound that does not fall under the category of components (A) to (C) and contains four or more (meth)acryloyl groups in one molecule. By including component (D) in the composition, the abrasion resistance and chemical resistance of the cured coating are improved.
• the component (D) is not particularly limited as long as it has four or more (meth)acryloyl groups in one molecule, and examples thereof include polyfunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, polypentaerythritol poly(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate; and urethane (meth)acrylates obtained by reacting an isocyanate compound with a (meth)acrylate compound.
• the polyfunctional (meth)acrylate used as component (D) is preferably a compound represented by the following formula (3-0):
• R 30 At least four of the multiple R 30 represent CH 2 ⁇ CR B -COO- or a (meth)acryloyloxy group modified with caprolactone, CH 2 ⁇ CR B -CO(O(CH 2 ) 5 C ⁇ O) y -O-, and the remaining R 30 represent a hydroxyl group, CH 2 ⁇ CR B -COO-, or CH2 ⁇ CR 8 -CO(O(CH 2 ) 5 C ⁇ O) y -O-.
• R 3 B represents a hydrogen atom or a methyl group.
• R 3 B is a hydrogen atom
• the group is an acryloyl group
• R 3 B is a methyl group
• the group is a methacryloyl group
• y is an integer of 1 or more. That is, compound (3-0) is a polymerizable compound having a pentaerythritol skeleton and having four or more (meth)acryloyloxy groups in the structure. By having four or more (meth)acryloyloxy groups, the crosslink density increases when cured, and as a result, abrasion resistance and chemical resistance can be improved.
• the compound (3-0) may be used alone or in combination of two or more kinds.
• the urethane (meth)acrylate as component (D) can be obtained by reacting a (meth)acrylate compound having a hydroxyl group with an isocyanate compound.
• R 31 and R 32 each independently represent a hydrogen atom or a methyl group, and a plurality of R 31 s and R 32 s in the formula may be the same or different.
• the isocyanate compound used in the production of the urethane (meth)acrylate is preferably an aliphatic polyisocyanate or alicyclic polyisocyanate having two or more isocyanate groups.
• the polyisocyanate include aliphatic polyisocyanates such as 1,4-butane diisocyanate, 1,5-pentane diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate, or dimers or trimers thereof; and alicyclic polyisocyanates such as norbornane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, hydrogenated xylylene diisocyanate
• isocyanate compound a triisocyanate compound represented by the following formula (3-3) or a diisocyanate compound represented by the following formula (3-4) is also preferred.
• X 31 and X 32 each independently represent an alkylene group having 2 to 17 carbon atoms, and preferably an alkylene group having 2 to 6 carbon atoms.
• a plurality of X 31 and X 32 in the formula may be the same or different.
• the total content of component (D) is preferably 1.0 to 40 mass%, more preferably 2.5 to 20 mass%, and even more preferably 5.0 to 10 mass%, based on 100 mass% of the total of components (A) to (D).
• the content is preferably 1.0 to 40 mass%, more preferably 2.5 to 20 mass%, and even more preferably 5.0 to 10 mass%, based on 100 mass% of the total of components (A) to (D).
• composition of the present invention may contain any other components in addition to the above components (A) to (D) as long as the effects of the present invention can be obtained.
• other components include organic solvents, reactive compounds, various resins, fillers, polymerization initiators, stabilizers, UV absorbers, and leveling agents.
• inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, catalysts, surfactants, flow control agents, coupling agents, dyes, rheology control agents, antioxidants, plasticizers, etc. may also be contained.
• the composition of the present invention may contain an organic solvent or may not contain an organic solvent.
• the composition is a solvent-free composition that does not contain an organic solvent, or a high solids composition that has a relatively low content of organic solvent.
• VOCs volatile organic compounds
• the content thereof is preferably 30 mass % or less, more preferably 25 mass % or less, even more preferably 20 mass % or less, particularly preferably 15 mass % or less, and most preferably 10 mass % or less, based on the total amount of the composition.
• Examples of the organic solvent include ester-based solvents, ketone-based solvents, ether-based solvents, aliphatic solvents, aromatic solvents, and alcohol-based solvents.
• examples of ester solvents include ethyl acetate, propyl acetate, and butyl acetate
• examples of ketone solvents include acetone, 2-butanone, methyl ethyl ketone, and methyl isobutyl ketone
• examples of ether solvents include tetrahydrofuran and dioxolane
• examples of aliphatic solvents include hexane and cyclohexane
• examples of aromatic solvents include toluene and xylene
• examples of alcohol solvents include ethanol, methanol, propanol, butanol, and propylene glycol monomethyl ether.
• (meth)acrylate compounds other than components (A) to (D) and compounds with double bonds such as vinyl groups may be blended.
• (Meth)acryloyl-based compounds include monofunctional (meth)acrylates and di- and trifunctional (meth)acrylates that do not fall under components (A) to (D).
• Examples of monofunctional (meth)acrylates include alkyl (meth)acrylates having an alkyl group having 1 to 22 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate; cycloalkyl (meth)acrylates, such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; and ⁇ -alkoxyalkyl (meth)acrylates, such as 2-methoxyethyl (meth)acrylate and 4-methoxybutyl (meth)acrylate.
• alkyl (meth)acrylates having an alkyl group having 1 to 22 carbon atoms such as
• Examples of such an acid include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, caprolactone-modified hydroxy(meth)acrylate (for example, trade name "Placcel” manufactured by Daicel Chemical Industries, Ltd.), polycarbonate-modified hydroxy(meth)acrylate, mono(meth)acrylate of polyester diol obtained from phthalic acid and propylene glycol, mono(meth)acrylate of polyester diol obtained from succinic acid and propylene glycol, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, and (meth)acrylic acid adducts of various epoxy esters.
• difunctional or trifunctional (meth)acrylates include dihydric alcohol di(meth)acrylates such as tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate; Polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, di(meth)acrylate of tris(2-hydroxyethyl)isocyanurate, di(meth)acrylate of diol obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol
• the reactive compounds may be used alone or in combination of two or more.
• the amount of the reactive compound used is preferably 0 to 300% by mass relative to 100% by mass of the total solid content of components (A) to (D).
• thermosetting resin is a resin that has the property of being substantially insoluble and infusible when cured by heating, radiation, a catalyst, or the like.
• thermosetting resin include phenolic resin, urea resin, melamine resin, benzoguanamine resin, alkyd resin, unsaturated polyester resin, vinyl ester resin, diallyl terephthalate resin, epoxy resin, silicone resin, urethane resin, furan resin, ketone resin, xylene resin, thermosetting polyimide resin, benzoxazine resin, active ester resin, aniline resin, cyanate ester resin, styrene-maleic anhydride (SMA) resin, etc.
• SMA styrene-maleic anhydride
• Thermoplastic resins are resins that can be melt-molded by heating. Specific examples include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethyl methacrylate resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyethersulfone resin, polyarylate resin, thermoplastic polyimide resin, polyamideimide resin, polyether
• liquid organic polymers may be used to adjust the viscosity.
• Liquid organic polymers are those that do not directly contribute to the curing reaction, and examples include modified carboxyl group-containing polymers (Floren G-900, NC-500: Kyoeisha), acrylic polymers (Floren WK-20: Kyoeisha), amine salts of special modified phosphate esters (HIPLAAD ED-251: Kusumoto Chemicals), and modified acrylic block copolymers (DISPERBYK2000; BYK-Chemie).
• silica can be blended for the purpose of improving abrasion resistance.
• the silica is not limited, and known silica fine particles such as powdered silica, colloidal silica, nanosilica, etc. can be used.
• commercially available powdered silica fine particles include Aerosil 50 and 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, and H122 manufactured by Asahi Glass Co., Ltd., E220A and E220 manufactured by Nippon Silica Industries Co., Ltd., SYLYSIA 470 manufactured by Fuji Silysia Ltd., and SG Flake manufactured by Nippon Sheet Glass Co., Ltd.
• colloidal silica examples include methanol silica sol, IPA-ST, MEK-ST, PGM-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, and ST-OL, all of which are manufactured by Nissan Chemical Industries, Ltd.
• Silica may be reactive silica.
• reactive silica include reactive compound modified silica.
• reactive compounds include reactive silane coupling agents having hydrophobic groups, compounds having (meth)acryloyl groups, compounds having maleimide groups, and compounds having glycidyl groups.
• Examples of commercially available powdered silica modified with a compound having a (meth)acryloyl group include Aerosil RM50 and R711 manufactured by Nippon Aerosil Co., Ltd., and examples of commercially available colloidal silica modified with a compound having a (meth)acryloyl group include MIBK-SD, MIBK-SD-L, MIBK-AC-2140Z, MEK-AC-2140Z, and the like manufactured by Nissan Chemical Industries, Ltd.
• reactive silica examples include silica modified with a glycidyl group such as 3-glycidoxypropyltrimethoxysilane and then subjected to an addition reaction with acrylic acid, and silica modified with a compound having a urethane reaction of 3-isocyanatepropyltriethoxysilane, a hydroxyl group, and a (meth)acryloyl group.
• the shape of the silica fine particles is not particularly limited, and spherical, hollow, porous, rod-like, plate-like, fibrous, or amorphous silica fine particles can be used.
• hollow silica fine particles such as Silinax manufactured by Nittetsu Mining Co., Ltd. can be used.
• the primary particle size is preferably in the range of 5 to 200 nm. If it is 5 nm or more, the inorganic fine particles are sufficiently dispersed in the composition, and if it is 200 nm or less, the cured product can maintain sufficient strength.
• the amount of silica blended is preferably 3 to 60% by mass based on 100% by mass of the composition.
• Fillers other than silica include inorganic fillers and organic fillers.
• the filler include particulate, plate-like, and fibrous fillers.
• Examples of fillers with excellent heat resistance include alumina, magnesia, titania, zirconia, etc.
• examples of fillers with excellent thermal conductivity include boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, etc.
• examples of fillers with excellent electrical conductivity include metal fillers and/or metal-coated fillers using a metal element or an alloy (e.g., iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.)
• examples of fillers with excellent barrier properties include minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, smectite, etc., potassium titanate, magnesium sulfate, sepiolite, zono
• those having a high refractive index include barium titanate, zirconia oxide, titanium oxide, etc.; those exhibiting photocatalytic properties include photocatalytic metals such as titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, cerium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, lead, etc., composites of the above metals, and oxides thereof; those having excellent abrasion resistance include metals such as alumina, zirconia, magnesium oxide, etc., and composites and oxides thereof; those having excellent electrical conductivity include metals such as silver and copper, tin oxide, indium oxide, etc.; and those having excellent ultraviolet ray shielding properties include titanium oxide, zinc oxide, etc.
• These inorganic fine particles may be selected according to the intended use, and may be used alone or in combination of two or more kinds. In addition, the inorganic fine particles have various properties other than those exemplified, so
• Inorganic fibers include inorganic fibers such as carbon fiber, glass fiber, boron fiber, alumina fiber, and silicon carbide fiber, as well as carbon fiber, activated carbon fiber, graphite fiber, glass fiber, tungsten carbide fiber, silicon carbide fiber (silicon carbide fiber), ceramic fiber, alumina fiber, natural fiber, mineral fibers such as basalt, boron fiber, boron nitride fiber, boron carbide fiber, and metal fibers.
• the metal fibers include aluminum fiber, copper fiber, brass fiber, stainless steel fiber, and steel fiber.
• organic fibers examples include synthetic fibers made from resin materials such as polybenzazole, aramid, PBO (polyparaphenylene benzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, and polyarylate; natural fibers such as cellulose, pulp, cotton, wool, and silk; and regenerated fibers such as proteins, polypeptides, and alginic acid.
• resin materials such as polybenzazole, aramid, PBO (polyparaphenylene benzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, and polyarylate
• natural fibers such as cellulose, pulp, cotton, wool, and silk
• regenerated fibers such as proteins, polypeptides, and alginic acid.
• the amount of filler is preferably 3 to 60% by mass out of 100% by mass of the composition.
• composition of the present invention is cured by active energy rays, it is preferable to use a polymerization initiator, particularly a photopolymerization initiator.
• a polymerization initiator particularly a photopolymerization initiator.
• Any known photopolymerization initiator may be used, and for example, one or more selected from the group consisting of acetophenones, benzil ketals, and benzophenones can be preferably used.
• photoinitiated polymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, di Acetophenone compounds such as ethoxyacetophenone, oligo ⁇ 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone ⁇ and 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl ⁇ -2-methyl-propan-1-one; benzophenone compounds such as benzophenone, 4-phenone
• the photopolymerization initiator may be used alone or in combination of two or more kinds.
• the amount of the photopolymerization initiator used is preferably 1 to 15% by mass, more preferably 2 to 10% by mass, based on 100% by mass of the composition.
• the composition of the present invention may contain an ultraviolet absorbing agent for the purpose of improving weather resistance.
• an ultraviolet absorbing agent various compounds or substances can be used.
• Specific examples of ultraviolet absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2-ethylhexyloxy)propyl]oxy]-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, Benzotriazine-based ultraviolet absorbers such as 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(
• UV absorbers can also be used.
• Commercially available UV absorbers include TINUVIN PS, TINUVIN 99-2, TINUVIN 234, TINUVIN 326, TINUVIN 329, TINUVIN 900, TINUVIN 928, TINUVIN 360, TINUVIN 384-2, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, and TINUVIN 479 (all manufactured by BASF); Adeka STAB LA-46, Adeka STAB LA-F70, Adeka STAB LA-29, Adeka STAB LA-31G, Adeka STAB LA-32, and Adeka STAB LA-36 (all manufactured by ADEKA); and RUVA-93 (manufactured by Otsuka Chemical).
• benzotriazine-type ultraviolet absorbers or ultraviolet absorbers having a (meth)acryloyl group are preferred.
• TINUVIN 400, TINUVIN 405, TINUVIN 479 are preferred.
• Adeka STAB LA-46, manufactured by ADEKA), and RUVA-93 are preferred.
• the amount of the UV absorber used is preferably 0.5 to 20% by mass, and more preferably 1 to 10% by mass, relative to 100% by mass of the composition.
• the composition of the present invention may contain a hindered amine light stabilizer (HALS) for the purpose of improving weather resistance.
• HALS hindered amine light stabilizer
• known hindered amine-based light stabilizers can be used. Specifically, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-methoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-ethoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1 -butoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-pentyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate,
• hindered amine light stabilizers can also be used.
• Commercially available products include TINUVIN 123, TINUVIN 292, TINUVIN 152, TINUVIN 144, TINUVIN 622SF), TINUVIN 111FDL, TINUVIN 249, Adeka STAB LA-52 (all manufactured by BASF); Adeka STAB LA-57, Adeka STAB LA-63P, Adeka STAB LA-68, Adeka STAB LA-72, Adeka STAB LA-81, Adeka STAB LA-82, and Adeka STAB LA-87 (all manufactured by ADEKA).
• TINUVIN123, TINUVIN152, TINUVIN144 (all manufactured by BASF Corporation); Adeka STAB LA-52, Adeka STAB LA-57, Adeka STAB LA-63P, Adeka STAB LA-68, Adeka STAB LA-72, Adeka STAB LA-81 (manufactured by ADEKA Corporation), Adeka STAB LA-82 (manufactured by ADEKA Corporation), and Adeka STAB LA-87 (manufactured by ADEKA Corporation) are preferred.
• TINUVIN123 More preferred are TINUVIN123, TINUVIN152 (all manufactured by BASF Corporation); Adeka STAB LA-63P, Adeka STAB LA-82 (manufactured by ADEKA Corporation), and Adeka STAB LA-87 (manufactured by ADEKA Corporation).
• the amount of the hindered amine light stabilizer used is preferably 0.01 to 10% by mass, and more preferably 0.1 to 5% by mass, relative to 100% by mass of the composition.
• Various surface modifiers may be added to the composition of the present invention for the purpose of improving the leveling property during application, or for the purpose of improving the slipperiness of the cured film to improve the scratch resistance.
• various additives that modify the surface properties and are commercially available under the names of surface conditioners, leveling agents, slipperiness imparting agents, antifouling agents, etc. can be used. Among them, silicone-based surface modifiers and fluorine-based surface modifiers are preferred.
• silicone-based polymers and oligomers having a silicone chain and a polyalkylene oxide chain silicone-based polymers and oligomers having a silicone chain and a polyester chain, fluorine-based polymers and oligomers having a perfluoroalkyl group and a polyalkylene oxide chain, fluorine-based polymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain, etc.
• a material containing a (meth)acryloyl group in the molecule may be used.
• Specific surface modifiers include EBECRYL350 (Daicel Allnex Corporation), BYK-333 (BYK Japan Co., Ltd.), BYK-377 (BYK Japan Co., Ltd.), BYK-378 (BYK Japan Co., Ltd.), BYK-UV3500 (BYK Japan Co., Ltd.), BYK-UV3505 (BYK Japan Co., Ltd.), BYK-UV3576 (BYK Japan Co., Ltd.), Megafac RS-75 (DIC Corporation), Megafac RS-76-E (DIC Corporation), Megafac RS-72-K (DIC Corporation), Megafac RS-76-NS (DIC Corporation), Megafac RS-90 (DIC Corporation), Megafac RS-91 (DIC Corporation), Megafac RS-55 (DIC Corporation), Optool DAC-HP (Daikin Industries, Ltd.), ZX-058-A (T&K Corporation), TOKA), ZX-201 (T & K
• the active energy ray curable composition of the present invention can be suitably used as a cured coating film for protecting a substrate by applying it to at least one surface of various materials and then irradiating it with active energy rays.
• the cured coating film made of the composition of the present invention has weather resistance and abrasion resistance, high chemical resistance, and excellent adhesion to various materials even under harsh environments such as high temperature and high humidity, so that it exerts excellent effects when used as a protective coating film for materials used for a long period of time under harsh environments such as outdoors and around automobiles.
• the active energy ray curable composition of the present invention has a moderate substrate erosion property and therefore has particularly excellent adhesion to the substrate, a coating with high adhesion can be formed on a coating film obtained by partially or completely curing the active energy ray curable composition. Therefore, when the thickness of the cured coating film is not sufficient by one application and curing, a thick cured coating film with excellent durability can be formed by repeating the application and curing.
• the laminate of the present invention has a cured layer of the above-mentioned active energy ray curable composition.
• the laminate may have one or more other layers in addition to the cured layer, and the other layers may include, for example, a substrate layer. The manufacturing methods of the substrate and the laminate will be described later.
• the method for producing a laminate of the present invention includes step 1 of applying the above-mentioned active energy ray-curable composition onto a substrate to obtain a coating film, and step 2 of irradiating the coating film with active energy rays to cure a part or all of the coating film.
• Step 1 the above-mentioned active energy ray-curable composition is applied onto a substrate to obtain a coating film.
• the substrate is not particularly limited and may be appropriately selected depending on the application.Specific examples include plastic, wood, metal (steel, stainless steel, aluminum, etc.), metal oxide, paper, silicon, modified silicon, etc., and may be a substrate obtained by bonding different materials, or a substrate on which the active energy ray curable composition of the present invention or another composition is laminated as a primer.
• the active energy ray curable composition of the present invention has excellent adhesion to plastic substrates (resin substrates) and resin primers.
• plastic substrates and resin primers are preferred as substrates for laminates.
• the plastic substrate is not particularly limited as long as it is made of resin, and can be selected according to the purpose. Specifically, the above-mentioned thermosetting resin and thermoplastic resin can be used. In the case of obtaining a transparent laminate, polycarbonate resin (e.g., aliphatic polycarbonate, aromatic polycarbonate, alicyclic polycarbonate, etc.), polymethyl methacrylate resin, polystyrene resin, etc. are preferably used.
• the plastic substrate may be made of a single resin or a mixture of multiple resins, and may be a single layer or may already have a laminated structure of two or more layers.
• the plastic substrate may contain known additives such as known antistatic agents, antifogging agents, antiblocking agents, ultraviolet absorbers, antioxidants, pigments, organic fillers, inorganic fillers, light stabilizers, crystal nucleating agents, and lubricants, and may be fiber-reinforced plastic (FRP).
• known additives such as known antistatic agents, antifogging agents, antiblocking agents, ultraviolet absorbers, antioxidants, pigments, organic fillers, inorganic fillers, light stabilizers, crystal nucleating agents, and lubricants, and may be fiber-reinforced plastic (FRP).
• the resin primer may be a known water-soluble or water-dispersed paint, an organic solvent-based or organic solvent-dispersed paint, or a powder paint.
• various types of paints such as acrylic resin paint, polyester resin paint, alkyd resin paint, epoxy resin paint, fatty acid-modified epoxy resin paint, silicon resin paint, polyurethane resin paint, fluoroolefin paint, or amine-modified epoxy resin paint may be used.
• the undercoat paint may be a clear paint that does not contain a pigment, an enamel paint that contains the pigment, or a metallic paint that contains aluminum flakes, or it may be a paint used in electrodeposition paint, undercoat paint, topcoat paint, or precoat metal used on automobile bodies.
• the shape of the substrate is not particularly limited, and may be any shape according to the purpose, such as a flat plate, a sheet, or a three-dimensional shape having a curvature (bend) entirely or partially. Furthermore, the hardness, thickness, etc. of the substrate are not particularly limited and can be determined arbitrarily.
• the method for applying the composition is not particularly limited, and methods that can be used include inkjet, spray, spin coating, dip, roll coating, blade coating, doctor roll, doctor blade, curtain coating, slit coating, and screen printing.
• a coating film can be obtained by applying the composition to a substrate using these methods.
• the inkjet and spray methods are preferred from the viewpoint of coating technique.
• Step 2 the coating film obtained in step 1 is irradiated with active energy rays to cure a part or the whole of the coating film.
• the composition of the present invention contains a compound having a polymerizable unsaturated group, so it can be cured by irradiating with active energy rays to form a cured coating (cured layer).
• the entire coating film may be cured by one irradiation to form a cured coating, or only a part of the coating film may be cured by irradiation, and then the degree of curing may be gradually increased by multiple irradiations to finally form a cured coating.
• an active energy ray curable composition may be further applied from above.
• Examples of active energy rays include ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, ⁇ rays, and other ionizing radiation.
• ultraviolet rays ultraviolet rays (UV) are preferred from the standpoints of curability and convenience.
• examples of the device for irradiating the ultraviolet light include a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an electrodeless lamp (fusion lamp), a chemical lamp, a black light lamp, a mercury-xenon lamp, a short arc lamp, a helium-cadmium laser, an argon laser, sunlight, an LED lamp, etc.
• a cured coating or a cured product by irradiating the coated or molded composition with ultraviolet light having a wavelength of about 180 to 400 nm.
• the amount of ultraviolet light irradiation is appropriately selected depending on the type and amount of the photopolymerization initiator used.
• steps 1 and 2 may be repeated in this order at least once.
• step 1 application
• step 2 curing
• the cured coating can be made thicker. This method is useful when the thickness of the cured coating is insufficient after one application and curing due to a balance between the application method and the required coating thickness.
• the composition of the present invention has an appropriate degree of substrate erosion, and therefore adhesion is not impaired even when a cured coating is formed on the coating made of the cured composition.
• the coating film may be left partially cured (semi-cured) rather than completely cured in step 2. By leaving a portion uncured, adhesion to the lower layer is improved.
• the degree of curing can be adjusted by the amount of irradiation with active energy rays.
• the laminate of the present invention may further have a second substrate on the substrate and the cured layer.
• a second substrate on the substrate and the cured layer.
• the material of the second substrate include wood, metal, metal oxide, plastic, paper, silicon, or modified silicon
• the second substrate may be a substrate obtained by bonding different materials.
• the shape of the substrate and the substrate may have any shape according to the purpose, such as a flat plate, a sheet, or a three-dimensional shape having curvature over the entire surface or part of it.
• the hardness, thickness, etc. of the substrate There are also no limitations on the hardness, thickness, etc. of the substrate.
• the laminate of the present invention can be preferably used as an interlayer material between different materials because the cured layer has high adhesion to both plastics and inorganic materials.
• the substrate is plastic and the second substrate is an inorganic layer.
• inorganic layers include quartz, sapphire, glass, optical films, ceramic materials, inorganic oxides, vapor deposition films (CVD, PVD, sputtering), magnetic films, reflective films, metals such as Ni, Cu, Cr, Fe, and stainless steel, paper, SOG (spin on glass), SOC (spin on carbon), plastic layers such as polyester, polycarbonate, and polyimide, TFT array substrates, electrode plates for PDPs, conductive substrates such as ITO and metals, insulating substrates, silicon-based substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon.
• the cured layer of the present invention has excellent processability even after the active energy ray curable composition is cured to become a cured layer, so it can be bent together with the substrate.
• the coating is irradiated with active energy rays to form a substrate with a cured coating (i.e., a laminate), and then the substrate can be bent. Therefore, there is no need to take care when applying the composition to a curved substrate, and the productivity of the bending material can be significantly improved.
• the molded product of the present invention not only has excellent bending properties under heating, but also has excellent hard coat properties after hot bending.
• the thickness of the coating film obtained by applying the composition of the present invention is preferably 0.5 to 40 ⁇ m, more preferably 3 to 35 ⁇ m, even more preferably 5 to 30 ⁇ m, and particularly preferably 10 to 25 ⁇ m.
• the bending method is not particularly limited, and in addition to bending in which the laminate is directly bent, processing methods such as press molding, free blow molding, vacuum molding, pressure molding, and twin composite molding can be mentioned.
• the hot bending temperature is preferably 80° C. or higher, and more preferably 150° C. or higher.
• the upper limit temperature can be appropriately set below the melting temperature of the base material.
• the laminate of the present application has excellent weather resistance, abrasion resistance, chemical resistance, adhesion and appearance, and is therefore particularly suitable for use as a variety of protective materials.
• it can be used for building materials, housing equipment, transportation equipment such as automobiles, ships, aircraft and railways, electronic materials, recording materials, optical materials, lighting, packaging materials, protection of outdoor installations, optical fiber coating, and resin glass protection, and is particularly suitable for use in automobile headlamp lenses, automobile glazing, automobile body exteriors, plastic building materials, and steel plate building materials.
• Examples 2 to 44, Comparative Examples 1 to 5 The active energy ray-curable compositions of each example were obtained in the same manner as in Example 1, except that the compositions and solid content ratios were changed as shown in Tables 1 to 6. Note that, although the description of the photopolymerization initiator and the type of organic solvent is omitted in the tables, they were used in all examples in the same manner as in Example 1.
• Tables 1 to 6 respectively represent the following compounds or the compounds obtained in the above-mentioned synthesis examples.
• 1,4-BDA 1,4-butanediol diacrylate
• 1,6-HDA 1,6-hexanediol diacrylate
• 1,9-NDA 1,9-nonanediol diacrylate
• 1,10-DDA 1,10-decanediol diacrylate
• DPGDA dipropylene glycol diacrylate (manufactured by Daicel Allnex Corporation)
• A-200 Polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
• A-DCP Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
• A9300 Tris(2-acryloxyethyl)isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
• A9300-CL
• EP Epoxy resin-coated steel plate (a substrate prepared by applying a white acid-epoxy curing paint with a PWC of 60% to the surface of a zinc-treated steel plate with a thickness of 2 mm so that the dry film thickness is 30 to 40 ⁇ m, and then heat-curing the paint at 80° C. for 30 minutes, substrate thickness 2 mm)
• Examples 1 to 44 confirmed that the cured coating of the active energy ray-curable composition of the present invention is excellent in appearance, chemical resistance, weather resistance, and adhesion. On the other hand, it was confirmed that Comparative Examples 1 to 5, which do not contain any of the components, are inferior in at least one of the characteristics.
• Example 45 The active energy ray-curable composition of Example 2 was applied to a polyester resin-coated steel plate substrate similar to that described above using a bar coater, dried at 80°C for 4 minutes, and then irradiated in the atmosphere using an ultraviolet ray irradiation device (GS-YUASA, high-pressure mercury lamp) at an illuminance of 200 mW/ cm2 and an irradiation amount of 1 (unit: mJ/ cm2 ) shown in Table 7, to obtain a laminate having a coating film with a thickness of 10 ⁇ m.
• GS-YUASA ultraviolet ray irradiation device
• the same active energy ray-curable composition was applied onto the obtained coating film using a bar coater, dried at 80°C for 4 minutes, and then irradiated under atmospheric conditions using a similar ultraviolet irradiation device with an illuminance of 200 mW/ cm2 and an irradiation light amount 2 (unit: mJ/ cm2 ) shown in Table 7, to obtain a laminate having a cured coating film with a total thickness of 20 ⁇ m.
• Example 46 to 50 Comparative Examples 6 to 9
• the active energy ray-curable compositions of the examples or comparative examples shown in Tables 7 to 8 were used, and laminates of each example were obtained in the same manner as in Example 45, except that the irradiation amount was changed to 1 or 2 in Tables 7 to 8.
• Example 8 The laminates obtained in each example were used as evaluation samples, and similarly to Example 1, an appearance evaluation, a chemical resistance evaluation, and weather resistance evaluations A and B were performed. The results are shown in Tables 7 and 8. Note that in the weather resistance evaluation B of Comparative Example 8, peeling was observed before the start of the test, so the result was set to "0".
• Examples 45 to 50 confirmed that the cured coating of the active energy ray-curable composition of the present invention is excellent in appearance, chemical resistance, weather resistance, and adhesion. On the other hand, it was confirmed that Comparative Examples 6 to 9 are inferior in at least one of the properties.

Landscapes

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

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=92674458

Family Applications (1)

Country Status (7)

Citations (5)

• 2024
  • 2024-02-15 JP JP2024540766A patent/JP7658516B2/ja active Active
  • 2024-02-15 EP EP24766805.6A patent/EP4640724A4/en active Pending
  • 2024-02-15 KR KR1020257025045A patent/KR20250157347A/ko active Pending
  • 2024-02-15 MX MX2025010015A patent/MX2025010015A/es unknown
  • 2024-02-15 CN CN202480014567.6A patent/CN120752271A/zh active Pending
  • 2024-02-15 WO PCT/JP2024/005139 patent/WO2024185433A1/ja not_active Ceased
  • 2024-02-17 TW TW113105664A patent/TW202500606A/zh unknown

Patent Citations (5)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events