WO2023038001A1 - 紫外線硬化性樹脂組成物、接着剤、封止剤、絶縁保護剤及び電子回路基板 - Google Patents

紫外線硬化性樹脂組成物、接着剤、封止剤、絶縁保護剤及び電子回路基板 Download PDF

Info

Publication number
WO2023038001A1
WO2023038001A1 PCT/JP2022/033250 JP2022033250W WO2023038001A1 WO 2023038001 A1 WO2023038001 A1 WO 2023038001A1 JP 2022033250 W JP2022033250 W JP 2022033250W WO 2023038001 A1 WO2023038001 A1 WO 2023038001A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
acrylate
resin composition
mass
curable resin
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.)
Ceased
Application number
PCT/JP2022/033250
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
和毅 木村
登史宏 安永
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
Pelnox Ltd
Original Assignee
Arakawa Chemical Industries Ltd
Pelnox 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, Pelnox Ltd filed Critical Arakawa Chemical Industries Ltd
Priority to JP2023546930A priority Critical patent/JPWO2023038001A1/ja
Priority to CN202280060867.9A priority patent/CN117916289A/zh
Priority to KR1020247005035A priority patent/KR20240052935A/ko
Priority to US18/689,648 priority patent/US20250026917A1/en
Priority to TW111133843A priority patent/TW202319404A/zh
Publication of WO2023038001A1 publication Critical patent/WO2023038001A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5397—Phosphine oxides
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/353—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J135/00—Adhesives 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 a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J135/02—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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0254—High voltage adaptations; Electrical insulation details; Overvoltage or electrostatic discharge protection ; Arrangements for regulating voltages or for using plural voltages
    • H05K1/0256—Electrical insulation details, e.g. around high voltage areas
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/071—Connecting or disconnecting
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2003/1034—Materials or components characterised by specific properties
    • C09K2003/1062—UV-curable materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0112—Absorbing light, e.g. dielectric layer with carbon filler for laser processing
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0179—Thin film deposited insulating layer, e.g. inorganic layer for printed capacitor

Definitions

  • the present invention relates to ultraviolet curable resin compositions, adhesives, sealants, insulation protection agents, and electronic circuit boards.
  • UV-curable resin compositions generally generate active radicals or acids from photopolymerization initiators by irradiating UV rays, and polymerizable compounds such as (meth)acrylates and epoxy compounds are polymerized. hardened by However, in the environment where the UV-curable resin composition is used, if there is a portion (light-shielding portion) where light does not reach, such as a shaded portion or a narrow gap, ultraviolet light cannot sufficiently reach the portion shaded by the light-shielding portion. Therefore, there is a problem that curing of the ultraviolet curable resin composition is insufficient.
  • UV-curable resins As a method for curing such light-shielding parts and deep parts, some commercially available UV-curable resins use not only UV curing but also curing by heat and moisture. However, these curable resins are not necessarily satisfactory due to problems such as deformation due to heat, reduced adhesion, and the fact that moisture curing takes time.
  • Patent Documents 1 and 2 As another method for curing the light-shielding portion, addition of a material that emits light having a wavelength that promotes the curing reaction to the ultraviolet-curable resin composition has been investigated (Patent Documents 1 and 2). However, in the methods of Patent Documents 1 and 2, the distance at which the curing of the light shielding portion is confirmed is about 1 mm or less, and it is difficult to cure the light shielding portion to a practical level only by ultraviolet irradiation. rice field.
  • An object of the present invention is to provide a novel UV-curable resin composition that can sufficiently cure even in light-shielded areas and deep areas when cured by irradiation with UV rays.
  • the present inventors have found that at least one selected from the group consisting of poly (meth) acrylates and polyvinyl ethers, a compound having a predetermined thiol group, a predetermined photopolymerization initiator and It has been found that a composition containing an organic compound that absorbs predetermined ultraviolet rays and emits light can contribute to solving the above-described problems. As a result of further research and analysis by the present inventors, it was found that the above-described problems can be solved with high accuracy by the composition containing a specific amount of the compound having a thiol group, and the present invention was completed.
  • One ultraviolet curable resin composition of the present invention includes at least one (A) selected from the group consisting of poly(meth)acrylate (a1) and polyvinyl ether (a2), a compound (B) having at least two secondary thiol groups in the molecule; A photopolymerization initiator (C) having an absorbance at 385 nm of 0.50 or more at an optical path length of 10 mm in an acetonitrile solution with a concentration of 500 ppm; an organic compound (D) that absorbs ultraviolet light and emits light, having a maximum absorption wavelength in the range of 300 nm or more and 450 nm or less and an emission spectrum maximum wavelength in the range of 350 nm or more and 500 nm or less;
  • the content of the aforementioned compound (B) is 10% by mass or more and 70% by mass or less in terms of solid content with respect to 100% by mass of the resin composition.
  • the component (B) is a compound having at least three secondary thiol groups in the molecule.
  • the content of the above-described component (D) is 0.00001% by mass or more with respect to 100% by mass of the resin composition in terms of solid content. It is 0.05% by mass or less.
  • the above component (D) is selected from the group consisting of benzoxazole compounds, naphthalene compounds, anthracene compounds, pyrene compounds, stilbene compounds, and coumarin compounds. is at least one
  • the above component (C) is an acylphosphine oxide compound.
  • one of the more preferred inventions further contains a polymerization inhibitor (E).
  • the above component (E) is at least one selected from the group consisting of N-nitrosophenylhydroxylamine aluminum salt and phenothiazine.
  • one more preferred application example is an adhesive containing the ultraviolet curable resin composition of each of the above inventions.
  • one more preferred application example of the invention is a sealant containing the ultraviolet curable resin composition of each of the above inventions.
  • one more preferred application example of the invention is an insulating protective agent containing the ultraviolet curable resin composition of each of the above inventions.
  • one more preferred application example of the invention is an electronic circuit board containing the insulation protection agent of each of the above inventions.
  • One UV-curable resin composition of the present invention can be sufficiently cured even when a light-shielding portion is present during curing by UV irradiation.
  • one ultraviolet curable resin composition of the present invention can be sufficiently cured even in the deep part of a cured product such as a thick coating film or a deep molded article.
  • one UV-curable resin composition of the present invention is excellent in curability in light-shielding portions and deep portions even when cured using ultraviolet light from a UV-LED light source.
  • One ultraviolet curable resin composition of the present invention is excellent in curability in the light shielding part and deep part, so it is used as an adhesive for shadow parts and narrow gaps, for example, protective panels and touch panels such as image display devices. and as an adhesive used for bonding various electronic components on an electronic circuit board.
  • One ultraviolet curable resin composition of the present invention is excellent in curability in the light shielding part and deep part, so it is a sealant used for parts that are complicated in shape and difficult to be exposed to ultraviolet rays, and the shielding part in the usage environment. It is suitable as an existing sealant, for example a sealant used in optical lens units, a leaded electronic component sealant and an underfill agent.
  • One of the UV-curable resin compositions of the present invention is excellent in curability in light-shielding parts and deep parts, so it is suitable as an insulating protective agent used for electronic circuit boards on which electronic components are mounted.
  • FIG. 2 is a schematic diagram of a case where spacers are arranged on an FRP substrate in the evaluation of shadow curability in Examples.
  • FIG. 4 is a schematic diagram of a case where an ultraviolet curable resin composition is applied to a portion not covered with a spacer in the evaluation of shadow curability in Examples.
  • FIG. 2 is a schematic diagram of a case where PET films are bonded together in the evaluation of shadow curability in Examples.
  • FIG. 2 is a schematic diagram of a case where a light-shielding plate is placed in the evaluation of shadow curability in Examples.
  • FIG. 4 is a schematic diagram of peeling off the light-shielding plate and the PET film after ultraviolet irradiation in the evaluation of the shadow curability in Examples.
  • FIG. 2 is a schematic cross-sectional view during ultraviolet irradiation in evaluation of shadow curability in Examples.
  • One ultraviolet curable resin composition of the present embodiment is from the group consisting of poly(meth)acrylate (a1) (hereinafter referred to as (a1) component) and polyvinyl ether (a2) (hereinafter referred to as (a2) component) At least one selected (hereinafter referred to as (A) component), a compound (B) having at least two secondary thiol groups in the molecule (hereinafter referred to as (B) component), and an acetonitrile solution with a concentration of 500 ppm.
  • a photopolymerization initiator (C) (hereinafter referred to as component (C)) having an absorbance at a length of 10 mm of 0.50 or more at 385 nm; contains an organic compound (D) (hereinafter referred to as component (D)) that absorbs and emits ultraviolet light and has a maximum wavelength in the range of 350 nm or more and 500 nm or less.
  • (meth)acrylic means “at least one selected from the group consisting of acrylic and methacrylic”.
  • (meth)acrylate means “at least one selected from the group consisting of acrylate and methacrylate”
  • (meth)acryloyl group is selected from the group consisting of "acryloyl group and methacryloyl group means "at least one
  • any compound having at least two (meth)acryloyl groups in the molecule can be used without particular limitation.
  • the component (a1) may be used singly or in combination of two or more.
  • the use of the poly(meth)acrylate of the present embodiment together with polyvinyl ether, which will be described later, is also an aspect that can be adopted. Even when the poly(meth)acrylate and the polyvinyl ether are used together, the same effects as those of the present invention can be obtained.
  • component (a1) examples include alkylene glycol poly(meth)acrylate, polyalkylene glycol poly(meth)acrylate, glycerin poly(meth)acrylate, polyglycerin poly(meth)acrylate, and pentaerythritol poly(meth)acrylate.
  • polypentaerythritol poly (meth) acrylate trimethylolpropane poly (meth) acrylate, polymethylol propane poly (meth) acrylate, ethylene oxide isocyanurate modified di (meth) acrylate, ethylene oxide isocyanurate modified tri (meth) acrylate, Propylene oxide isocyanurate-modified di(meth)acrylate, propylene oxide isocyanurate-modified tri(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate , polyether (meth)acrylate, polyacrylic (meth)acrylate, etc., but are not limited thereto.
  • alkylene glycol poly(meth)acrylates include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1, 6-hexanediol di(meth)acrylate and the like, but are not limited to these.
  • Typical examples of the above polyalkylene glycol poly(meth)acrylates include diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene Glycol di(meth)acrylate and the like, but are not limited to these.
  • glycerin poly(meth)acrylates include glycerin di(meth)acrylate, glycerin tri(meth)acrylate, ethylene oxide-modified glycerin di(meth)acrylate, propylene oxide-modified glycerin di(meth)acrylate, ethylene oxide.
  • polyglycerin poly(meth)acrylates include diglycerin di(meth)acrylate, diglycerin tri(meth)acrylate, diglycerin tetra(meth)acrylate, triglycerin di(meth)acrylate, triglycerin tri(meth)acrylate. ) acrylate, triglycerin tetra(meth)acrylate, triglycerin penta(meth)acrylate and the like, but are not limited thereto.
  • pentaerythritol poly(meth)acrylate examples include pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethylene oxide-modified pentaerythritol di(meth)acrylate, Propylene oxide-modified pentaerythritol di(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, propylene oxide-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, propylene oxide-modified pentaerythritol tetra(meth)acrylate (Meth)acrylate and at least two selected from the group consisting of pentaerythritol mono(meth)acrylate,
  • polypentaerythritol poly(meth)acrylates include dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth) Acrylates, dipentaerythritol hexa(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, tripentaerythritol octa(meth)acrylate, and a mixture of at
  • trimethylolpropane poly(meth)acrylates include trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane di(meth)acrylate, propylene oxide-modified trimethylolpropane di(meth)acrylate, Methylolpropane di(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, etc., but not limited thereto.
  • polytrimethylolpropane poly(meth)acrylates include, but are not limited to, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate. not.
  • urethane (meth)acrylate Typical examples of the above urethane (meth)acrylates include reaction products of hydroxyl group-containing (meth)acrylates and polyisocyanates, and reaction products of hydroxyl group-containing (meth)acrylates, polyols and polyisocyanates. is not limited to
  • hydroxyl group-containing (meth)acrylate various known compounds can be used without particular limitation as long as they are compounds having at least one hydroxyl group in the molecule.
  • the hydroxyl group-containing (meth)acrylates may be used singly or in combination of two or more.
  • hydroxyl group-containing (meth)acrylate examples include, but are not limited to, the hydroxyl group-containing mono(meth)acrylate and the hydroxyl group-containing poly(meth)acrylate.
  • hydroxyl group-containing mono (meth) acrylates include hydroxyl group-containing linear alkyl (meth) acrylates, hydroxyl group-containing branched alkyl (meth) acrylates, hydroxyl group-containing cycloalkyl (meth) acrylates, and hydroxyl group-containing aryl (meth) acrylates.
  • polyalkylene glycol mono (meth) acrylate polyalkylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, ethylene oxide-modified glycerin mono (meth) acrylate, propylene oxide-modified glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, and these mono ( Examples include, but are not limited to, caprolactone adducts of meth)acrylates.
  • hydroxyl group-containing linear alkyl (meth)acrylates are 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and the like. Not limited.
  • hydroxyl group-containing branched alkyl (meth)acrylates include 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate and the like, but are limited to these. not.
  • a typical example of the hydroxyl group-containing cycloalkyl (meth)acrylate is 1,4-cyclohexanedimethanol mono(meth)acrylate, but is not limited to these.
  • a representative example of the hydroxyl group-containing aryl (meth)acrylate is 1,4-benzenedimethanol mono(meth)acrylate, but is not limited thereto.
  • polyalkylene glycol mono(meth)acrylates include oxy-polyethylene glycols such as dipropylene glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and polyethylene glycol mono(meth)acrylate).
  • (meth) acrylates having an alkylene chain (meth) acrylates having a block structure oxyalkylene chain such as polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) acrylate; poly (ethylene Glycol-tetramethylene glycol) mono(meth)acrylate, poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate and the like (meth)acrylate having a random structure of oxyalkylene chain, etc., but not limited thereto.
  • hydroxyl group-containing poly(meth)acrylate examples include the alkylene glycol poly(meth)acrylate, the polyalkylene glycol poly(meth)acrylate, the glycerin poly(meth)acrylate, and the polyglycerin poly(meth)acrylate. , the pentaerythritol poly(meth)acrylate, the polypentaerythritol poly(meth)acrylate, the trimethylolpropane poly(meth)acrylate, and the polymethylolpropane poly(meth)acrylate having at least one hydroxyl group in the molecule. However, it is not limited to these.
  • hydroxyl group-containing (meth)acrylates include hydroxyl group-containing (meth)acrylates having at least three (meth)acryloyl groups in the molecule from the viewpoint of excellent curability and scratch resistance of the cured film. More preferred are hydroxyl group-containing (meth)acrylates having one hydroxyl group and at least three (meth)acryloyl groups in the molecule.
  • the hydroxyl group-containing (meth)acrylate is preferably hydroxyl group-containing pentaerythritol poly(meth)acrylate or hydroxyl group-containing polypentaerythritol poly(meth)acrylate from the viewpoint of excellent curability and scratch resistance of the cured film.
  • any known compound having at least two isocyanate groups in the molecule can be used without particular limitation.
  • One of the polyisocyanates may be used alone, or two or more may be used in combination.
  • Typical examples of the above polyisocyanates include linear aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, biuret, isocyanurate, allophanate, adduct and biuret forms of these diisocyanates. , an isocyanurate, an allophanate, and an adduct.
  • linear aliphatic diisocyanates include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, and the like. but not limited to these.
  • Typical examples of the branched aliphatic diisocyanate include, but are not limited to, diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, trimethylhexamethylene diisocyanate, and the like.
  • alicyclic diisocyanate examples include hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, and tricyclodecylene diisocyanate.
  • adamantane diisocyanate, norbornene diisocyanate, bicyclodecylene diisocyanate, and the like but are not limited thereto.
  • aromatic diisocyanates include dialkyldiphenylmethane diisocyanates such as 4,4′-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanates such as 4,4′-diphenyltetramethylmethane diisocyanate, and 4,4′-diphenylmethane diisocyanate.
  • 4,4′-dibenzyl isocyanate 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 1,5-naphthylene diisocyanate and the like. but not limited to these.
  • n b is an integer of 1 or more
  • R bA to R bE are each independently a linear aliphatic diisocyanate residue, a branched aliphatic diisocyanate residue, an alicyclic diisocyanate residue and an aromatic diisocyanate any one or more selected from the group consisting of residues
  • each of R b ⁇ to R b ⁇ independently represents an isocyanate group or
  • n b1 is an integer of 0 or more
  • R b1 to R b5 are the same as R bA to R bE
  • R b ' to R b '' are each independently an isocyanate group or R b ⁇ to R b ⁇ themselves
  • the groups of R b4 to R b5 and R b ′′ may be different for each structural unit.).
  • R bD to R bE and R b ⁇ may have different groups for each structural unit.
  • biuret form of the above diisocyanate examples include Duranate 24A-100, Duranate 22A-75P, Duranate 21S-75E (manufactured by Asahi Kasei Corporation), Desmodul N3200A (biuret form of hexamethylene diisocyanate) ( The above are manufactured by Sumika Covestro Urethane Co., Ltd.) and the like, but are not limited to these.
  • isocyanurate form of the diisocyanate include: Structural formula below: [Wherein, n i is an integer of 0 or more, R iA to R iE are each independently a linear aliphatic diisocyanate residue, a branched aliphatic diisocyanate residue, an alicyclic diisocyanate residue and an aromatic diisocyanate any one or more selected from the group consisting of residues, and R i ⁇ to R i ⁇ are each independently an isocyanate group or (n i1 is an integer of 0 or more, R i1 to R i5 are the same as R iA to R iE , R i ′ to R i '' are each independently an isocyanate group or R i ⁇ to R i ⁇ themselves The groups of R i5 and R i ′′ may be different for each structural unit.). R iD to R iE and R i ⁇ may have different groups for each structural unit. ],
  • isocyanurate forms of the diisocyanates include Duranate TPA-100, Duranate TKA-100, Duranate MFA-75B, Duranate MHG-80B (manufactured by Asahi Kasei Corporation), Coronate HXR, and Coronate HX (manufactured by Asahi Kasei Corporation).
  • isocyanurate of hexamethylene diisocyanate (manufactured by Tosoh Corporation), Takenate D-127N (isocyanurate of hydrogenated xylylene diisocyanate) (manufactured by Mitsui Chemicals, Inc.), VESTANAT T1890/100 (manufactured by Mitsui Chemicals, Inc.) isocyanurate form of isophorone diisocyanate) (manufactured by Evonik Japan Ltd.), etc., but not limited thereto.
  • n a is an integer of 0 or more
  • R aA is an alkyl group, an aryl group, a polyether group, a polyester group or a polycarbonate group
  • R aB to R aG are , each independently any one or two or more selected from the group consisting of linear aliphatic diisocyanate residues, branched aliphatic diisocyanate residues, alicyclic diisocyanate residues and aromatic diisocyanate residues
  • R a ⁇ to R a ⁇ are each independently an isocyanate group or
  • n a1 is an integer of 0 or more
  • R a1 to R a6 are the same as R aB to R aG
  • R a ' to R a ''' are each independently an isocyanate group or R a ⁇ to R a ⁇
  • allophanate form of the diisocyanate include Coronate 2793 (manufactured by Tosoh Corporation) and Takenate D-178N (manufactured by Mitsui Chemicals, Inc.), but are not limited thereto.
  • Typical examples of the adduct of the diisocyanate are Structural formula below: [Wherein, n ad is an integer of 0 or more, R adA to R adE are each independently a linear aliphatic diisocyanate residue, a branched aliphatic diisocyanate residue, an alicyclic diisocyanate residue and an aromatic diisocyanate Any one or two or more selected from the group consisting of residues, and R ad1 to R ad2 are each independently (Wherein, n ad′ is an integer of 0 or more, R ad′ to R ad′′ are the same as R adA to R adE , and R ad′′′ is a group of R ad1 to R ad2 itself.
  • R ad′ to R ad′′′ may have different groups for each structural unit.
  • R adD 1 to R adE and R ad2 may have different groups for each structural unit.
  • An adduct of trimethylolpropane and diisocyanate represented by Structural formula below [Wherein, n ad1 is an integer of 0 or more, R ad ⁇ to R ad ⁇ are each independently a linear aliphatic diisocyanate residue, a branched aliphatic diisocyanate residue, an alicyclic diisocyanate residue and an aromatic diisocyanate Any one or more selected from the group consisting of residues, and R adA to R adB are each independently (Wherein, n ad1′ is an integer of 0 or more, R ad ⁇ ′ to R ad ⁇ ′ are the same as R ad ⁇ to R ad ⁇ , R adB′ is a group of R a
  • adduct of the diisocyanate examples include Duranate P301-75E (manufactured by Asahi Kasei Corporation), Takenate D-110N, Takenate D-160N (manufactured by Mitsui Chemicals, Inc.), Coronate L, Coronate HL (manufactured by Tosoh Corporation) and the like, but not limited thereto.
  • linear aliphatic diisocyanate residue, branched aliphatic diisocyanate residue, alicyclic diisocyanate residue and aromatic diisocyanate residue refers to the linear aliphatic diisocyanate, the branched aliphatic group diisocyanate, the above alicyclic diisocyanate and the above aromatic diisocyanate, excluding the isocyanate group.
  • the above polyisocyanate is preferably a polyisocyanate having at least three isocyanate groups in the molecule from the viewpoint of excellent scratch resistance of the cured film.
  • the polyisocyanate having at least three isocyanate groups in the molecule the biuret, isocyanurate, allophanate, and adduct are preferred.
  • polystyrene resin Various known polyols can be used without particular limitation as long as they are compounds having at least two hydroxyl groups in the molecule.
  • the above polyols may be used alone or in combination of two or more.
  • Typical examples of the above polyols include aliphatic polyols, alicyclic polyols, polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, (meth)acrylic polyols, etc. It is not limited to these.
  • aliphatic polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, dimethylolpropane, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2- Butyl-2-ethyl-1,3-propanediol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 1,5-pentamethylenediol, 1 ,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, pentaerythritol diacrylate, 1,9-nonanediol, 2-methyl-1 , 8-octanediol and the like containing two hydroxyl groups, sugar alcohols such as
  • alicyclic polyols include cyclohexanediols such as 1,4-cyclohexanediol and cyclohexyldimethanol, hydrogenated bisphenols such as hydrogenated bisphenol A, and tricyclodecanedimethanol. is not limited to
  • polyether-based polyols include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polypentamethylene glycol and polyhexamethylene glycol, and random or polyalkylene glycols of these polyalkylene glycols. Block copolymers and the like, but are not limited to these.
  • polyester-based polyols include condensation polymers of polyhydric alcohols and polycarboxylic acids or anhydrides thereof; ring-opening polymers of cyclic esters (lactones); polyhydric alcohols, polycarboxylic acids or their Examples include, but are not limited to, triatomic reactants such as anhydrides and cyclic esters.
  • polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3 -trimethylenediol, 1,5-pentamethylenediol, neopentyl glycol, 1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol , glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (1,4-cyclohexanediol, etc.), bisphenols (bisphenol A, etc.), sugar alcohols (xylitol, sorbitol, etc.), etc., but are not limited to these. .
  • polyvalent carboxylic acids or their anhydrides include aliphatic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.
  • dicarboxylic acids alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; or its anhydride, etc., but not limited thereto.
  • cyclic esters include, but are not limited to, propiolactone, butyrolactone, valerolactone, ⁇ -methyl- ⁇ -valerolactone, ⁇ -caprolactone, and the like.
  • polycarbonate-based polyols include, but are not limited to, reaction products of polyhydric alcohols and phosgene; ring-opening polymers of cyclic carbonates (such as alkylene carbonates);
  • polyhydric alcohol examples include the polyhydric alcohols exemplified in the polyester-based polyol, such as the alkylene carbonate, ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, etc. It is not limited to these.
  • polycarbonate polyol may be a compound having a carbonate bond in the molecule and a terminal hydroxyl group, and may have an ester bond as well as a carbonate bond.
  • Typical examples of the above polyolefin-based polyols include, but are not limited to, those having a homopolymer or copolymer of ethylene, propylene, butene, etc. as a saturated hydrocarbon skeleton and hydroxyl groups at the molecular ends.
  • Typical examples of the above polybutadiene-based polyols include those having a butadiene copolymer as a hydrocarbon skeleton and hydroxyl groups at the molecular ends, but are not limited to these.
  • the polybutadiene-based polyol may be a hydrogenated polybutadiene polyol in which all or part of the ethylenically unsaturated groups contained in its structure are hydrogenated.
  • Typical examples of the (meth)acrylic polyols include those having at least two hydroxyl groups in the molecule of a (meth)acrylic acid ester polymer or copolymer, but are limited to these. not.
  • Representative examples of the above (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, ( (meth)acrylic acid alkyl esters such as octyl methacrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, and octadecyl (meth)acrylate; is not limited to
  • the molar ratio (NCO:OH) between the isocyanate group contained in the polyisocyanate and the hydroxyl group contained in the hydroxyl group-containing (meth)acrylate and the hydroxyl group contained in the polyol is not particularly limited. .
  • the ratio is preferably 1:1 to 10, more preferably about 1:1 to 8, from the viewpoint of excellent balance of flexibility and scratch resistance of the cured film.
  • the method for producing the urethane (meth)acrylate is not particularly limited as long as it is a method of reacting the hydroxyl group-containing (meth)acrylate, the polyisocyanate and, if necessary, the polyol, and various known production methods are exemplified. be.
  • a method of reacting a hydroxyl group-containing (meth)acrylate, a polyisocyanate, and optionally a polyol in the presence of a catalyst at an appropriate reaction temperature (eg, 60°C to 90°C) is employed. obtain.
  • the order in which the hydroxyl group-containing (meth)acrylate, polyisocyanate and polyol are reacted is not particularly limited, and methods such as a method of reacting by mixing them arbitrarily, a method of reacting by mixing all the components at once, and the like are adopted. obtain, but are not limited to:
  • Typical examples of the above catalysts include organic tin catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, organic acid tin catalysts such as tin octylate, organic titanium catalysts such as titanium ethylacetoacetate, and organic zirconium catalysts such as zirconium tetraacetylacetonate. catalysts, organic iron catalysts such as iron acetylacetonate, and the like, but are not limited thereto. The above catalysts may be used singly or in combination of two or more.
  • polyester (meth)acrylate A representative example of the polyester (meth)acrylate is, but not limited to, a dehydration condensate of the polyester polyol and (meth)acrylic acid.
  • epoxy (meth)acrylate A representative example of the epoxy (meth)acrylate is, but not limited to, a compound obtained by an addition reaction between a terminal epoxy group of an epoxy resin and (meth)acrylic acid.
  • epoxy resins include, but are not limited to, aromatic epoxy resins and aliphatic epoxy resins.
  • aromatic epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type novolak type epoxy resin, naphthalene.
  • aliphatic epoxy resins include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; diglycidyl ethers of polyethylene glycol and polypropylene glycol; diglycidyl ethers of polyalkylene glycols of neopentyl glycol, dibromoneopentyl glycol and diglycidyl ethers of alkylene oxide adducts thereof; trimethylolethane, trimethylolpropane, glycerin and di- or triglycidyl ethers of their alkylene oxide adducts and polyglycidyl ethers of polyhydric alcohols such as di-, tri- or tetra-glycidyl ethers of pentaerythritol and its alkylene oxide adducts; di- or polyglycidyl ethers
  • Polyether (meth)acrylate Typical examples of the above polyether (meth)acrylates include, but are not limited to, dehydration condensates of the above polyether-based polyols and (meth)acrylic acid.
  • Polyacrylic (meth)acrylate Typical examples of the polyacrylic (meth) acrylate include an epoxy group-containing mono (meth) acrylate, and optionally an acrylic copolymer obtained by polymerizing the mono (meth) acrylate, and (meth) acrylic acid and the like, but are not limited to these.
  • epoxy group-containing mono(meth)acrylates include glycidyl (meth)acrylate, ⁇ -methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, vinylcyclohexene monoxide (that is, 1,2-epoxy-4-vinylcyclohexane) and the like, but are not limited to these.
  • component (a1) is preferably trimethylolpropane poly(meth)acrylate, ditrimethylolpropane poly(meth)acrylate, pentaerythritol (poly)acrylate, or dipentaerythritol poly(meth)acrylate.
  • any known vinyl ether compound having at least two vinyl groups in the molecule can be used without particular limitation.
  • component (a2) include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether bisphenol A alkylene oxide divinyl ether, and bisphenol F.
  • Alkylene oxide divinyl ether trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, and the like, but are not limited thereto.
  • the physical properties of component (a1) are not particularly limited.
  • the number of (meth)acryloyl groups in the molecule in the component (a1) is preferably at least 3 from the viewpoint of excellent hardness of the cured film, and more preferably from 3 to 15 from the same viewpoint. preferable.
  • the content of the component (a1) in the ultraviolet curable resin composition is not particularly limited, but from the viewpoint of excellent moist heat resistance and appearance, it is 25% by mass based on 100% by mass of the ultraviolet curable resin composition in terms of solid content. % or more and 85 mass % or less is preferable.
  • the physical properties of component (a2) are not particularly limited.
  • the number of vinyl groups in the molecule of component (a2) is preferably at least 3 from the viewpoint of excellent hardness of the cured film, and more preferably from 3 to 15 from the same viewpoint.
  • the content of the component (a2) in the ultraviolet curable resin composition is not particularly limited, but from the viewpoint of excellent wet heat resistance and appearance, it is 25% by mass in terms of solid content with respect to 100% by mass of the ultraviolet curable resin composition. % or more and 85 mass % or less is preferable.
  • Compound (B) having at least two secondary thiol groups in the molecule any known compound having at least two secondary thiol groups in the molecule can be used without particular limitation.
  • component (B) component may be used individually by 1 type, and may use 2 or more types together.
  • the component (B) has a secondary thiol group
  • the curability of the shielding part and the deep part is excellent in the UV-curable resin composition.
  • a compound having a primary thiol group in the molecule is used instead of the component (B)
  • curing of the shielding portion and the deep portion of the UV-curable resin composition is insufficient.
  • the component (B) has at least two secondary thiol groups in the molecule, the UV-curable resin composition has excellent curability in the shielding part and the deep part, but the secondary thiol group in the molecule
  • a compound having one is used, curing of the shielding part and the deep part in the ultraviolet curable resin composition is insufficient.
  • a representative example of the component (B) is a compound represented by the following general formula (1), but is not limited to these.
  • X represents an n-valent organic group, and n represents an integer of 2 to 6.
  • component (B) are 1,4-bis(3-mercaptobutyryloxy)butane and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine -2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), and the like, but are not limited thereto.
  • Component (B) is 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H ,3H,5H)-trione, trimethylolpropane tris(3-mercaptobutyrate) and pentaerythritol tetrakis(3-mercaptobutyrate).
  • the physical properties of component (B) are not particularly limited.
  • the number of intramolecular secondary thiol groups in the component (B) is preferably at least 3 from the viewpoint of excellent curability in the shielded part and the deep part, and from the same point, it is 3 to 4. is more preferred.
  • a representative example of the content of component (B) in the ultraviolet curable resin composition is 10% by mass or more (more narrowly, 10% by mass) with respect to 100% by mass of the ultraviolet curable resin composition in terms of solid content. %) is 70% by mass or less (more narrowly, less than 70% by mass).
  • the content of component (B) is 10% by mass or more (in a narrower sense, more than 10% by mass)
  • the UV-curable resin composition exhibits excellent curability in shielded portions and deep portions.
  • the lower limit in the above numerical range is preferably 30% by mass or more (more narrowly, more than 30% by mass), and 50% by mass. % or more (more narrowly, more than 50% by mass).
  • the cured product has excellent chemical resistance.
  • the upper limit in the above numerical range is preferably 40% by mass or less (more narrowly, less than 40% by mass), and 20% by mass. or less (more narrowly, less than 20% by mass). Therefore, the upper limit and the lower limit can be obtained with more suitable numerical values based on mutually independent viewpoints.
  • one preferable numerical range for the content of the component (B) is 20% by mass or more (more narrowly, 20 mass %) is 50 mass % or less (more narrowly, less than 50 mass %).
  • one preferable numerical range for the content of component (B) is 40% by mass or more (more narrowly, 40% by mass more than) 50% by mass or less (more narrowly, less than 50% by mass).
  • the content of the component (B) in the UV-curable resin composition is 25% by mass with respect to 100% by mass of the UV-curable resin composition in terms of solid content from the viewpoint of excellent curability in the shielding part and deep part. It is preferably at least 70% by mass, and from the same point of view, more preferably at least 35% by mass and not more than 70% by mass.
  • the molar ratio ((meth)acryloyl group: thiol group) between the (meth)acryloyl group contained in the component (a1) and the secondary thiol group contained in the component (B) is Although not limited, 1:0.5 to 1.5 is preferable, and 1:0.8 to 1.2 is more preferable from the viewpoint of excellent curability in the shielding part and deep part.
  • the molar ratio (vinyl group: thiol group) between the vinyl group contained in the component (a2) and the thiol group contained in the component (B) is not particularly limited. 1:0.5 to 1.5 is preferred, and 1:0.8 to 1.2 is more preferred, from the viewpoint of excellent curability in .
  • various known components can be used without particular limitation as long as the absorbance of an acetonitrile solution with a concentration of 500 ppm at an optical path length of 10 mm at 385 nm is 0.50 or more.
  • Component may be used individually by 1 type, and may use 2 or more types together.
  • a typical example of the component (C) is an acylphosphine oxide compound, etc., but is not limited to these.
  • acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenyl Phosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and the like, but are not limited thereto.
  • the component (C) is preferably an acylphosphine oxide compound from the viewpoint of excellent curability in the shielding part and the deep part.
  • the component (C) is 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, bis(2,4,6-trimethylbenzoyl )-phenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide.
  • Component (C) has an absorbance of 0.50 or more at 385 nm in an acetonitrile solution with a concentration of 500 ppm at an optical path length of 10 mm.
  • the absorbance of component (C) at 385 nm is determined by preparing an acetonitrile solution (concentration of 500 ppm) of component (C), using a two-sided transmission quartz cell with an optical path length of 10 mm, and measuring the absorbance at 385 nm with a spectrophotometer. obtained by A commercially available spectrophotometer can be used.
  • the above UV-curable resin composition has sufficient curing in the shielding part and the deep part.
  • the component (C) has an absorbance of 0.50 or more at 385 nm, so that the component (C) can absorb the light emitted by the component (D) described later. It is presumed that the polymerization initiation action (radical generation reaction) of the component (C) present in is sufficiently expressed, and the curing in the shielding part and the deep part is sufficient in the ultraviolet curable resin composition.
  • UV-LEDs ultraviolet light sources in ultraviolet curing from the viewpoint of energy saving and space saving. It was sometimes insufficient.
  • Component (C) has an absorbance of 0.5 or more at 385 nm, so that it has sufficient absorption of ultraviolet light from a UV-LED light source (350 nm to 420 nm), so even when using a UV-LED , the UV-curable resin composition can be sufficiently cured.
  • component (C) other than the absorbance at 385 nm are not particularly limited.
  • the content of component (C) in the ultraviolet curable resin composition is not particularly limited.
  • 0.1% by mass or more (more narrowly, more than 0.1% by mass) with respect to 100% by mass of the ultraviolet curable resin composition ) is preferably 15% by mass or less (more narrowly, less than 15% by mass), and 0.1% by mass or more (more narrowly, more than 0.1% by mass) 5% by mass or less (more narrowly , less than 5% by mass).
  • Component (D) that absorbs ultraviolet light and emits light
  • Component (D) is an organic compound that has an absorption spectrum with a maximum wavelength of 300 nm or more and 450 nm or less, an emission spectrum with a maximum wavelength of 350 nm or more and 500 nm or less, and absorbs ultraviolet light and emits light.
  • various known ones can be used without particular limitation.
  • Component may be used individually by 1 type, and may use 2 or more types together.
  • component (D) include, but are not limited to, anthracene compounds, coumarin compounds, carbazole compounds, benzoxazole compounds, naphthalene compounds, stilbene compounds, oxadiazole compounds, pyrene compounds, and perylene compounds.
  • a representative example of the anthracene compound is a compound having a skeleton represented by the following general formula (2), but is not limited to these.
  • each R 1 independently represents a hydrogen atom, a phenyl group, a phenylmethylene group, a phenylethylene group, a phenylpropylene group or a phenylethynyl group; each Y independently represents a hydrogen atom or a halogen atom; n each independently represents an integer of 1 to 4.
  • the phenyl group for R 1 in general formula (2) above specifically has a structure represented by general formula (3) below.
  • each R 11 independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; m represents an integer of 1 to 5; indicate the part.
  • phenylmethylene group, phenylethylene group, phenylpropylene group and phenylethynyl group for R 1 in the general formula (2) include a phenylmethylene group, a phenylethylene group and a phenylpropylene group in which the benzene ring has no substituents. and a phenylethynyl group, or a phenylmethylene group, a phenylethylene group, a phenylpropylene group and a phenylethynyl group having an alkyl group having 1 to 3 carbon atoms as a substituent, but are not limited thereto.
  • R 1 in general formula (2) above is particularly preferably a phenyl group represented by general formula (3) above, and Y in general formula (2) above is preferably a hydrogen atom. Moreover, all R 11 in the general formula (3) are preferably hydrogen atoms.
  • anthracene compound examples include halogenated anthracene, 9,10-diphenylanthracene, 9,10-bis(phenylethynyl)anthracene and 2-chloro-9,10-bis(phenylethynyl)anthracene. , but not limited to.
  • coumarin compounds are coumarin, 7-hydroxy-4-methylcoumarin, 4-hydroxy-7-methylcoumarin, 3-(2-benzimidazolyl)-7-(diethylamino)coumarin, 3-(2 -benzothiazolyl)-7-(diethylamino)coumarin, 7-diethylamino-4-methylcoumarin, 3-phenyl-7-aminocoumarin, 3-phenyl-7-(imino-1′,3′,5′-triazine-2 '-diethylamino-4'-chloro)-coumarin, 3-phenyl-7-naphthotriazolecoumarin, 7-(4'-chloro-6''-diethylamino-1',3',5'-triazine-4'- yl)-amino-3-phenyl-coumarin and the like, but are not limited thereto.
  • carbazole compounds include 1,3,5-tri(9H-carbazol-9-yl)benzene, 4,4'-bis(9H-carbazol-9-yl)biphenyl, 9,9'- (2,2′-dimethylbiphenyl-4,4′-diyl)bis(9H-carbazole) and 9-phenylcarbazole and the like, but are not limited thereto.
  • a representative example of the benzoxazole compound is a compound having a skeleton represented by the following general formula (4), but is not limited to these.
  • each R 2 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R 3 represents an alkylene group having 1 to 3 carbon atoms or a group represented by the following general formula (5): (Wherein, the * mark indicates a linking site to the skeleton represented by the general formula (4)), and p represents an integer of 1-4. )
  • R 2 in the general formula (4) is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a branched alkyl group having 4 to 6 carbon atoms, and is a tert-butyl group. is more preferred.
  • R 3 in the above general formula (4) is preferably a group represented by the above general formula (5).
  • benzoxazole compounds include 2,5-thiophenediyl (5-tert-butyl-1,3-benzoxazole), 2,2′-(thiophenediyl)-bis(tert-butyl-benzoxazole ), 2,5-bis(6,6′-bis(tert-butyl)-benzoxazol-2-yl)thiophene 4-(benzoxazol-2-yl)-4′-(5-methylbenzoxazol-2 -yl)stilbene, 4,4′-bis(benzoxazol-2-yl)stilbene, 2,4,4′-bis(benzoxazol-2-yl)furan, 1,2-bis(5-methyl-2 -benzoxazolyl)ethylene, 1,4-bis(2-benzoxazolyl)naphthalene, and the like, but are not limited thereto.
  • naphthalene compound is naphthalene, but is not limited to these.
  • a representative example of the stilbene compound is a compound having a skeleton represented by the following general formula (6), but is not limited to these.
  • each R 4 independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each q independently represents an integer of 1 to 5.
  • Each of R 4 in the above general formula (6) is preferably a hydrogen atom.
  • stilbene compounds include stilbene, trans-1,2-diphenylethylene, 4,4′-bis(diphenyltriazinyl)stilbene, stilbenyl-naphthotriazole, 4,4′-bis(diphenyltriazinyl). nyl)stilbene, stilbenyl-naphthotriazole, 2-(stilbyl-4)-(naphtho-1′,2′,4,5)-1,2,3-triazole-2′′-sulfonic acid phenyl ester, and the like. but not limited to these.
  • pyrene compound examples include pyrene, benzopyrene, etc., but are not limited to these.
  • Component (D) is preferably at least one selected from the group consisting of benzoxazole compounds, naphthalene compounds, anthracene compounds, pyrene compounds and stilbene compounds, from the viewpoint of excellent curability in the shielding part and deep part. from the point of view, it is more preferably at least one selected from the group consisting of benzoxazole compounds, pyrene compounds and stilbene compounds. , 3-benzoxazole) and pyrene are particularly preferred.
  • Component (D) has an absorption spectrum with a maximum wavelength of 300 nm or more and 450 nm or less, and an emission spectrum with a maximum wavelength of 350 nm or more and 500 nm or less.
  • the absorption spectrum and emission spectrum of component (D) can be confirmed by preparing a DMF (dimethylformaldehyde) solution of component (D) and measuring the absorption spectrum and emission spectrum of the obtained solution.
  • the absorption spectrum can be measured using a commercially available spectrophotometer, and the emission spectrum can be measured using a commercially available fluorophotometer.
  • Component (D) has a maximum wavelength in the absorption spectrum of 300 nm or more and 450 nm or less, so that it has sufficient absorption of light (ultraviolet rays) from a UV-LED light source (350 nm or more and 420 nm or less). - Even when LEDs are used, the UV-curable resin composition can be sufficiently cured.
  • the above UV-curable resin composition has sufficient curing in the shielding part and the deep part.
  • the maximum wavelength of the emission spectrum of the component (D) is in the range of 350 nm or more and 500 nm or less, so that the component (C) can absorb the light emitted by the component (D). It is presumed that the polymerization initiation action (radical generation reaction) of the component (C) present in the part and the deep part is sufficiently expressed, and the curing in the shielding part and the deep part is sufficient in the above UV-curable resin composition.
  • Physical properties other than the maximum wavelength of the absorption spectrum and the maximum wavelength of the emission spectrum of the component (D) are not particularly limited.
  • the content of component (D) in the UV-curable resin composition is not particularly limited.
  • 0.00001% by mass or more (more narrowly, more than 0.00001% by mass) with respect to 100% by mass of the ultraviolet curable resin composition ) is preferably 0.05% by mass or less (more narrowly, less than 0.05% by mass).
  • the upper limit in the above numerical range is 0.03% by mass or less (more narrowly, less than 0.03% by mass) from the viewpoint of not impairing the reactivity of the photopolymerization initiator. preferable.
  • the lower limit value in the above numerical range is preferably 0.0001% by mass or more (more narrowly, more than 0.0001% by mass) from the viewpoint of improving curability with higher accuracy. It is more preferably 0.001% by mass or more (more narrowly, more than 0.001% by mass). Therefore, the upper limit and the lower limit can be obtained with more suitable numerical values based on mutually independent viewpoints. In addition, for example, if a more preferable numerical value is applied to both the upper limit and the lower limit, one preferable numerical range for the content of the component (D) is 0.0001% by mass or more (more narrowly , more than 0.0001% by mass) is 0.03% by mass or less (more narrowly, less than 0.03% by mass).
  • one preferable numerical range is 0.001% by mass or more (more narrowly, more than 0.001% by mass) 0.03 mass % or less (more narrowly, less than 0.03% by mass).
  • one preferable numerical range is 0.01% by mass or more (more narrowly, more than 0.01% by mass ) is 0.03% by mass or less (more narrowly, less than 0.03% by mass).
  • the ultraviolet curable resin composition of the present embodiment may contain a polymerization inhibitor (E) (hereinafter referred to as component (E)).
  • component (E) is not particularly limited, and various known components can be used.
  • Component (E) may be used alone or in combination of two or more.
  • component (E) is hydroquinone, trimethylhydroquinone, p-methoxyphenol, phenothiazine, N-nitrosophenylhydroxylamine aluminum salt, 2,6-di-tert-butyl-4-methylphenol and the like. , but not limited to.
  • a representative example of component (E) is preferably at least one selected from the group consisting of N-nitrosophenylhydroxylamine aluminum salts and phenothiazines.
  • the content of component (E) in the ultraviolet curable resin composition is not particularly limited. From the viewpoint of not impairing the reactivity of the photopolymerization initiator, in terms of solid content, 0.0001% by mass or more (more narrowly, more than 0.0001% by mass) relative to 100% by mass of the composition It is preferably 0.05% by mass or less (more narrowly, less than 0.05%).
  • the ultraviolet curable resin composition of this embodiment may contain a reactive diluent.
  • the reactive diluent is a compound other than the component (A) having a UV-reactive functional group such as a carbon-carbon unsaturated bond. Reactive diluents may be used singly or in combination of two or more.
  • reactive diluents include (meth)acrylic acid, mono(meth)acrylate, styrene, ⁇ -methylstyrene, ethyl carbitol acrylate, etc., but are not limited to these.
  • mono(meth)acrylates include, but are not limited to, the above hydroxyl group-containing mono(meth)acrylates, alkyl(meth)acrylates, and the like.
  • alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate ) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, isopropyl (meth) acrylate, tert-butyl (meth) acrylate,
  • the total content of the component (A) and the reactive diluent in the composition is calculated as a solid content and is based on 100% by mass of the composition. It is preferably 25% by mass or more (in a narrower sense, more than 25% by mass) and 85% by mass or less (in a more narrow sense, less than 85% by mass).
  • the content ratio of the component (A) and the reactive diluent in the above ultraviolet curable resin composition is not particularly limited. From the viewpoint of adjusting the crosslink density, when the sum of the component (A) and the reactive diluent is 100% by mass, the component (A) is 20% by mass or more (more narrowly, more than 20% by mass). It is preferably 100 mass % or less, and the reactive diluent is 0 mass % or more and 80 mass % or less (more narrowly, less than 80 mass %). In addition, considering the hardness and scratch resistance of the cured product, the component (A) is 50% by mass or more (more narrowly, more than 50% by mass) and 95% by mass or less (more narrowly, less than 95% by mass). and the reactive diluent is preferably 5% by mass or more (more narrowly, more than 5% by mass) and 50% by mass or less (more narrowly, less than 50% by mass).
  • the UV-curable resin composition may optionally contain a photopolymerization initiator other than component (C) as long as the effects of the present invention are not impaired. Two or more of these photopolymerization initiators may be used in combination.
  • photoinitiator examples include 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]- 2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy -2-methyl-propionyl)-benzyl]-phenyl ⁇ -2-methyl-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2- benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl) -butan-1-one, 1-[4-(phenylthio)]-1,2-octanedione, 2-
  • the content of photopolymerization initiators other than component (C) in the ultraviolet-curable resin composition is not particularly limited. From the viewpoint of progress of the reaction of the (meth)acryloyl group, the content of the photopolymerization initiator is preferably 0.5 parts by mass or more and 15 parts by mass or less per 100 parts by mass of the composition in terms of solid content.
  • the ultraviolet curable resin composition may contain a solvent in consideration of coating workability and the like.
  • solvents are methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, diacetone alcohol, acetylacetone.
  • the solvent is preferably at least one selected from the group consisting of glycol ethers, alcohols and ketones.
  • the content of the solvent in the ultraviolet curable resin composition is not particularly limited.
  • the content of the solvent is preferably in the range of 1 mass % or more and 60 mass % or less of the solid content concentration of the composition from the viewpoint of coatability.
  • the UV-curable resin composition may optionally contain an agent other than the solvent, the reactive diluent, or the photopolymerization initiator as an additive.
  • Additives may be used singly or in combination of two or more. Typical examples of additives include antistatic agents, antioxidants, ultraviolet absorbers, light stabilizers, antifoaming agents, surface conditioners, antifog agents, hydrophilic agents, antifouling agents, pigments, metal oxides Fine particle dispersions, organic fine particle dispersions, etc., but are not limited to these.
  • the content of the additive in the ultraviolet curable resin composition is not particularly limited.
  • the content of the additive is preferably 0.05 parts by mass or more and 1 part by mass or less in terms of solid content with respect to 100 parts by mass of the composition.
  • the adhesive of the present embodiment contains the ultraviolet curable resin composition.
  • the adhesive of the present embodiment may contain solvents and additives as necessary as long as the effects of the present invention are not impaired. Solvents and additives may be used singly or in combination of two or more.
  • the solvent is not particularly limited.
  • Representative examples of the above solvents include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-propylbenzene, t-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, and aromatic naphtha.
  • the above additives are not particularly limited. Typical examples of the above additives include tackifiers, plasticizers, antioxidants, surface conditioners, surfactants, UV absorbers, antioxidants, light stabilizers, inorganic fillers, silane coupling agents, colloidal Silica, antifoaming agents, wetting agents, rust inhibitors, crystal nucleating agents, crystallization accelerators, etc., but not limited to these.
  • the content of the additive in the adhesive is not particularly limited. From the viewpoint of adjusting curability or curing inhibition, the content of the additive is preferably 0.05 parts by mass or more and 1 part by mass or less based on 100 parts by mass of the adhesive in terms of solid content. .
  • the adhesive of the present embodiment has excellent curability in light-shielding areas and deep areas, it is used in areas such as shadow areas and narrow gaps, such as between a protective panel and a touch panel such as an image display device. It is suitable as an adhesive used for bonding various electronic parts on an electronic circuit board.
  • the encapsulant of the present embodiment contains the ultraviolet curable resin composition.
  • the sealant of the present embodiment may contain additives as necessary as long as the effects of the present invention are not impaired. Additives may be used singly or in combination of two or more.
  • the sealant is not particularly limited. Typical examples of the sealant include ion scavengers, silane coupling agents, fluorine coupling agents, leveling agents, antifoaming agents, antioxidants, surface lubricants, wetting and dispersing agents, stress relaxation agents, and flame retardants. , colorants (such as carbon black) and diluents, but are not limited to these.
  • the content of the additive in the sealant is not particularly limited. From the viewpoint of adjusting the curability or curing inhibition, the content of the additive may be 0.1 parts by mass or more and 5 parts by mass or less in terms of solid content with respect to 100 parts by mass of the sealant. preferable.
  • the encapsulant of the present embodiment Since the encapsulant of the present embodiment has excellent curability in the light-shielding part and deep part, it is used for parts that are complicated in shape and difficult to be exposed to ultraviolet rays, or for encapsulation where the light-shielding part exists in the usage environment. agent.
  • the sealant of the present embodiment is suitable as a sealant used for optical lens units, a sealant for electronic components with leads, and an underfill agent.
  • the insulating protective agent of the present embodiment contains the above ultraviolet-curable resin composition.
  • the insulating protective agent of this embodiment can also be used as an insulating protective agent for electronic circuit boards.
  • the insulating protective agent of the present embodiment can form a cured film (cured product) having insulation and moisture resistance by coating and curing on an electronic circuit board, and can protect the electronic circuit board from the external environment. .
  • the insulation protection agent of this embodiment may contain diluents and additives as necessary as long as the effects of the present invention are not impaired. Diluents and additives may be used singly or in combination of two or more.
  • diluents are dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, ethyl acetate, ⁇ -butyl lactone ( ⁇ -butyrolactone), acetone, methyl isobutyl ketone, ethyl methyl ketone, cyclohexanone, diisopropyl ether, Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dioxane, tetrahydrofuran, methanol, ethanol, n-propanol, benzene, toluene, xylene, dimethylsulfoxide, phenylglycidyl ether, and the like, but are not limited thereto.
  • additives are not particularly limited. Typical examples of the additive include surfactants, adhesion improvers, antifoaming agents, sensitizers, and fluorescent agents other than component (D), but are not limited to these.
  • the content of the additive in the insulation protection agent is not particularly limited.
  • the content of the additive is preferably 0.05 parts by mass or more and 100 parts by mass or less in terms of solid content with respect to 100 parts by mass of the insulating protective agent.
  • the insulation protection agent of the present embodiment has excellent curability in the light shielding part and deep part, it can be a suitable insulation protection agent for electronic circuit boards on which electronic components are mounted and shadowed parts and narrow gaps exist. .
  • the electronic circuit board of the present embodiment contains a cured product of the insulating protective agent.
  • a representative example of the cured product is obtained by coating an electronic circuit board with the insulating protective agent and irradiating it with ultraviolet rays.
  • Typical examples of the electronic circuit board include rigid printed circuit boards and flexible printed circuit boards, but are not limited to these.
  • Typical examples of ultraviolet light sources used for the curing reaction include, but are not limited to, xenon lamps, high-pressure mercury lamps, metal halide lamps, and LED lamps.
  • An LED lamp is preferable for the ultraviolet light source from the viewpoint of energy saving and space saving.
  • the amount of light, the arrangement of the light source, the transport speed, etc. can be adjusted as necessary.
  • Typical examples of coating methods include bar coater coating, Meyer bar coating, air knife coating, dispenser coating, spray coating, gravure printing, reverse gravure printing, offset printing, flexographic printing, screen printing, and jet printing. , dip coating and curtain coating, but are not limited to these.
  • Example 1 100 parts of trimethylolpropane triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “Viscoat #295”) (hereinafter referred to as component (A1)) as component (A), and pentaerythritol tetrakis as component (B) 137 parts of (3-mercaptobutyrate) (manufactured by Showa Denko K.K., trade name “Karenzu MT (registered trademark) PE1”) (hereinafter referred to as component (B1)), and bis(2, 0.2 parts of 4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by IGM Resins B.V., trade name "Omnirad 819”) (hereinafter referred to as component (C1)), and 2 parts as component (D).
  • component (A1) trimethylolpropane triacrylate
  • component (B) pentaerythritol tetraki
  • component (D1) 0.002 parts of 5-thiophenediyl (5-tert-butyl-1,3-benzoxazole) (manufactured by BASF Japan Ltd., trade name “Tinopal OB”) (hereinafter referred to as component (D1)), and 0.005 part of N-nitrosophenylhydroxylamine aluminum salt (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., trade name "Q-1301”) as a polymerization inhibitor was blended at a solid content ratio, diluted with methyl ethyl ketone, An ultraviolet curable resin composition having a solid content of 50% was prepared.
  • Example 2 to 21 and Comparative Examples 1 to 8 In Example 1, except that the compositions and blending amounts of components (A) to (D) were changed to those shown in Tables 1 to 3, an ultraviolet curable resin composition was produced in the same manner as in Example 1.
  • Tables 1 to 3 are values in parts by mass converted to solid content. Abbreviations in Tables 1-3 are as follows.
  • the maximum wavelength of the absorption spectrum and the maximum wavelength of the emission spectrum of the components (D1) to (D2) are the values described in the catalogs of each manufacturer.
  • a blank in each table means that the component corresponding to the blank is not included.
  • A1 Trimethylolpropane triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “Viscoat #295”)
  • A2 Bisphenol F EO-modified (n ⁇ 2) diacrylate (manufactured by Toagosei Co., Ltd., trade name “Aronix M-208”)
  • A3 Tricyclodecanedimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “A-DCP”)
  • A4 isocyanuric acid EO-modified di- and triacrylate (manufactured by Toagosei Co., Ltd., trade name “Aronix M-313”)
  • A5 A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK Ester A-9550W”)
  • A6
  • a PET film having a width of 70 mm, a length of 100 mm, and a thickness of 75 ⁇ m having a release layer was attached to the composition with the release layer facing the UV-curable resin composition so that no air entered (FIG. 3).
  • a light shielding plate of 150 mm in width ⁇ 50 mm in length ⁇ 2 mm in thickness was placed on the PET film (Fig. 4).
  • An irradiation device UV-LED irradiation wavelength: 385 nm
  • UV-LED irradiation wavelength: 385 nm was used to irradiate ultraviolet rays with an integrated light amount of 10,000 mJ/cm 2 .
  • the shadow curability of the UV-curable resin composition of Example 12 was evaluated by the above evaluation method using an UV irradiation device (manufactured by Multiply Co., Ltd., belt conveyor type UV irradiation device, 120 W/cm high-pressure mercury lamp).
  • the shadow curability was evaluated in the same manner as the evaluation method described above, except that the ultraviolet rays were irradiated at 10,000 mJ/cm 2 . Table 1 shows the results.
  • the ultraviolet curable resin compositions of Examples 1 to 21 have a long shadow curing distance, so they have sufficient curability even in shielded and deep areas where ultraviolet rays do not reach.
  • the ultraviolet curable resin compositions of Comparative Examples 1 to 8 have a short shadow curing distance, so that the curability in the shielded part and deep part where ultraviolet rays do not reach is insufficient, or the curability cannot be confirmed. state.
  • the ultraviolet curable resin composition of Example 12 uses a high-pressure mercury lamp with higher energy than an LED lamp as an ultraviolet light source, so that the distance of shadow curing is very long, and the curing of the shielding part and the deep part is very long. is better.
  • a non-transparent FRP base material is used as the base material in the evaluation of shadow curability.
  • the reason for this is that when a transparent substrate such as a glass plate is used, the ultraviolet rays travel through the substrate and reach the resin composition in the shadow area, so the curability of the shadow area cannot be evaluated correctly. This is because In non-transparent FRP substrates, it is difficult for ultraviolet rays to travel through the interior of the substrate, and as a result, the shadow curability can be evaluated correctly.
  • the ultraviolet curable resin composition of the present invention can be used, for example, as an adhesive, as a sealant, as an insulating protective agent, or as an electronic circuit board or the like containing a cured product of the insulating protective agent. Or it can be widely used in the electronic equipment field or the optical field.

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)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Paints Or Removers (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Adhesives Or Adhesive Processes (AREA)
PCT/JP2022/033250 2021-09-10 2022-09-05 紫外線硬化性樹脂組成物、接着剤、封止剤、絶縁保護剤及び電子回路基板 Ceased WO2023038001A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2023546930A JPWO2023038001A1 (https=) 2021-09-10 2022-09-05
CN202280060867.9A CN117916289A (zh) 2021-09-10 2022-09-05 紫外线固化性树脂组合物、粘接剂、密封剂、绝缘保护剂和电子电路基板
KR1020247005035A KR20240052935A (ko) 2021-09-10 2022-09-05 자외선 경화성 수지 조성물, 접착제, 밀봉제, 절연 보호제 및 전자 회로 기판
US18/689,648 US20250026917A1 (en) 2021-09-10 2022-09-05 Ultraviolet-curable resin composition, adhesive, sealant, insulating protective agent, and electronic circuit board
TW111133843A TW202319404A (zh) 2021-09-10 2022-09-07 紫外線固化性樹脂組合物、黏著劑、密封劑、絕緣保護劑和電子電路板

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021147511 2021-09-10
JP2021-147511 2021-09-10

Publications (1)

Publication Number Publication Date
WO2023038001A1 true WO2023038001A1 (ja) 2023-03-16

Family

ID=85507614

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/033250 Ceased WO2023038001A1 (ja) 2021-09-10 2022-09-05 紫外線硬化性樹脂組成物、接着剤、封止剤、絶縁保護剤及び電子回路基板

Country Status (6)

Country Link
US (1) US20250026917A1 (https=)
JP (1) JPWO2023038001A1 (https=)
KR (1) KR20240052935A (https=)
CN (1) CN117916289A (https=)
TW (1) TW202319404A (https=)
WO (1) WO2023038001A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20250036675A (ko) 2023-09-07 2025-03-14 린텍 가부시키가이샤 에너지선 경화성 수지 조성물, 도포액, 수지막 형성 필름 및 적층체의 제조 방법

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016117832A (ja) * 2014-12-22 2016-06-30 昭和電工株式会社 光硬化性組成物およびその用途
JP2016204585A (ja) * 2015-04-28 2016-12-08 富士フイルム株式会社 硬化性組成物、硬化膜、有機ｅｌ表示装置、液晶表示装置、タッチパネル及びタッチパネル表示装置
JP2020023620A (ja) * 2018-08-07 2020-02-13 ゼネラル株式会社 インクジェットインク、インクセット、および印刷方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140320770A1 (en) 2012-01-13 2014-10-30 Nippon Kayaku Kabushikikaisha Optical member and ultraviolet-curable adhesive to be used for producing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016117832A (ja) * 2014-12-22 2016-06-30 昭和電工株式会社 光硬化性組成物およびその用途
JP2016204585A (ja) * 2015-04-28 2016-12-08 富士フイルム株式会社 硬化性組成物、硬化膜、有機ｅｌ表示装置、液晶表示装置、タッチパネル及びタッチパネル表示装置
JP2020023620A (ja) * 2018-08-07 2020-02-13 ゼネラル株式会社 インクジェットインク、インクセット、および印刷方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20250036675A (ko) 2023-09-07 2025-03-14 린텍 가부시키가이샤 에너지선 경화성 수지 조성물, 도포액, 수지막 형성 필름 및 적층체의 제조 방법

Also Published As

Publication number Publication date
JPWO2023038001A1 (https=) 2023-03-16
TW202319404A (zh) 2023-05-16
KR20240052935A (ko) 2024-04-23
CN117916289A (zh) 2024-04-19
US20250026917A1 (en) 2025-01-23

Similar Documents

Publication Publication Date Title
US11535766B2 (en) Curable composition for inkjet printing, cured product of same, and electronic component having the cured product
JP6643846B2 (ja) ポリウレタン化合物及びそれを含有する樹脂組成物
JP6320255B2 (ja) 樹脂組成物
KR101588537B1 (ko) 프린트 배선판용 경화형 조성물, 이것을 사용한 경화 도막 및 프린트 배선판
CN105705525A (zh) 印刷电路板用固化型组合物、使用其的固化涂膜和印刷电路板
CN111918939A (zh) 喷墨用固化性组合物、其固化物和具有该固化物的电子部件
WO2016031952A1 (ja) ポリウレタン化合物及びそれを含有する樹脂組成物
WO2015083795A1 (ja) ポリウレタン化合物、感光性樹脂組成物、感光性樹脂組成物の製造方法、及び、硬化物
WO2016121706A1 (ja) 感光性樹脂組成物及びその硬化物
WO2023038001A1 (ja) 紫外線硬化性樹脂組成物、接着剤、封止剤、絶縁保護剤及び電子回路基板
JP6265424B2 (ja) （メタ）アクリレート化合物及び樹脂組成物
KR101473614B1 (ko) 프린트 배선판 제조용 광경화성 조성물, 그의 경화물 및 프린트 배선판
JP7725835B2 (ja) 光硬化性組成物
WO2023038003A1 (ja) 紫外線硬化性樹脂組成物、接着剤、封止剤、絶縁保護剤及び電子回路基板
JP2022137835A (ja) 重合性化合物
US20220315704A1 (en) Curable resin composition, dry film and cured product thereof, and electronic component including cured product
KR20200140295A (ko) 경화성 수지 조성물
JP2005343816A (ja) （メタ）アクリレート化合物の混合物の製造方法、及びそれによって得られた混合物を含有する感光性樹脂組成物
JP6465487B2 (ja) （メタ）アクリレート化合物及びそれを含有する活性エネルギー線硬化型樹脂組成物並びにその硬化物
JP6475571B2 (ja) （メタ）アクリレート化合物及び感光性樹脂組成物
JP7729032B2 (ja) 酸基含有（メタ）アクリレート樹脂、硬化性樹脂組成物、硬化物、絶縁材料、ソルダーレジスト用樹脂材料及びレジスト部材
JP2018070778A (ja) 活性エネルギー線硬化性樹脂組成物
JP2023155902A (ja) 活性エネルギー線硬化性組成物
KR20240175578A (ko) 적층 필름 및 이를 포함하는 화상표시장치
KR20220086071A (ko) 경화성 조성물, 이로부터 제조된 경화막 및 표시장치

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22867323

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023546930

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 202280060867.9

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22867323

Country of ref document: EP

Kind code of ref document: A1