WO2023038003A1 - 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

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WO2023038003A1
WO2023038003A1 PCT/JP2022/033258 JP2022033258W WO2023038003A1 WO 2023038003 A1 WO2023038003 A1 WO 2023038003A1 JP 2022033258 W JP2022033258 W JP 2022033258W WO 2023038003 A1 WO2023038003 A1 WO 2023038003A1
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meth
acrylate
resin composition
curable resin
mass
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English (en)
French (fr)
Japanese (ja)
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和毅 木村
登史宏 安永
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Arakawa Chemical Industries Ltd
Pelnox Ltd
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Arakawa Chemical Industries Ltd
Pelnox Ltd
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Priority to JP2023546931A priority Critical patent/JPWO2023038003A1/ja
Priority to CN202280060869.8A priority patent/CN117916290A/zh
Priority to KR1020247005036A priority patent/KR20240055730A/ko
Priority to TW111133862A priority patent/TW202319405A/zh
Publication of WO2023038003A1 publication Critical patent/WO2023038003A1/ja
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    • 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
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
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    • C08K5/10—Esters; Ether-esters
    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/357—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
    • C08K5/36—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
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    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C08K5/5397—Phosphine oxides
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    • 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
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    • 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
    • H05K1/03—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
    • 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
    • C08G2170/00—Compositions for adhesives
    • 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
    • C08G2190/00—Compositions for sealing or packing joints

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 part was confirmed is about 1 mm or less, and it has been difficult to cure the light shielding part to a practical level only by ultraviolet irradiation. Met.
  • 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 a given photosensitizer can contribute to solving the above 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 thiol groups in the molecule; A photopolymerization initiator (C) having an absorbance of 0.10 or more at 385 nm in an acetonitrile solution with a concentration of 500 ppm at an optical path length of 10 mm; and a photosensitizer (D),
  • the content of the aforementioned compound (B) is 15% 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 thiol groups in the molecule.
  • the content of the above-described component (D) is 0.0001% by mass or more with respect to 100% by mass of the resin composition in terms of solid content. It is 0.02% by mass or less.
  • the above component (D) is at least one selected from the group consisting of benzophenone compounds, thioxanthone compounds, naphthalene compounds and anthracene compounds.
  • the above component (C) is at least one compound selected from the group consisting of alkylphenone compounds and acylphosphine oxide compounds.
  • 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 thiol groups in the molecule (hereinafter referred to as (B) component), an acetonitrile solution with a concentration of 500 ppm, an optical path length of 10 mm absorbance at 385 nm is 0.10 or more at 385 nm photoinitiator (C) (hereinafter referred to as component (C)) and photosensitizer (D) (hereinafter referred to as component (D)).
  • (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 embodiment 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)acrylate examples include trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane di(meth)acrylate, propylene oxide-modified trimethylol.
  • Typical examples of the above polytrimethylolpropane poly(meth)acrylate include ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, etc., but are limited to these. 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, etc., 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, Examples include, but are not limited to, complexes obtained by reacting two or more selected from the group consisting of isocyanurate, allophanate and 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.
  • the biuret form of the diisocyanate is 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.
  • 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 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 ad
  • 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);
  • Typical examples of the above polyhydric alcohols include the polyhydric alcohols exemplified in the above polyester polyols, and typical examples of the above alkylene carbonates are ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate. etc., but 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)acrylate, ) octyl acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate and the like (meth) acrylic acid alkyl esters, etc., but these Not limited.
  • 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 to 90° C.) can be employed. .
  • 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 Typical examples of the epoxy (meth)acrylates include, but are not limited to, compounds 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 80% by mass 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 component (a2) in the UV-curable resin composition is not particularly limited, but from the viewpoint of excellent moist heat resistance and appearance, it is 25% by mass in terms of solid content with respect to 100% by mass of the UV-curable resin composition. % or more and 85 mass % or less is preferable.
  • Compound (B) having at least two thiol groups in the molecule any compound having at least two 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 UV-curable resin composition has excellent curability in the shielding part and the deep part.
  • a compound having one thiol group in the molecule is used instead of the component (B)
  • curing of the blocking portion and the deep portion of the UV-curable resin composition is insufficient.
  • component (B) is compounds represented by the following general formulas (1) and (2), but are not limited to these.
  • X represents an n-valent organic group, and n represents an integer of 2 to 6.
  • Y represents an m-valent organic group, and m 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), trimethylolpropane tris(3-mercaptopropionate) ), tris-[3-mercaptopropionyloxy]-ethyl]-isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3 - Mercaptopropionate) and the like, but are not limited to these.
  • component (B) may be, in addition to general formulas (1) and (2), for example, 1,3-dimercapto-2-propanol, 2,2-bis(mercaptomethyl)-1,3-propanediol, 3-mercapto-2,2-bis(mercaptomethyl)-1-propanol, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, 2-ethyl-2-(mercaptomethyl)-1,3- Examples include, but are not limited to, polysilsesquioxane-based polythiol obtained by condensing propanedithiol and 3-mercaptopropyltrimethoxysilane.
  • Component (B) is 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 pentaerythritol tetrakis(3-mercaptopropionate).
  • a single compound is more preferred.
  • the physical properties of component (B) are not particularly limited.
  • the number of intramolecular thiol groups in the component (B) is preferably at least 3 from the viewpoint of excellent curability in the shielding part and the deep part, and more preferably 3 to 4 from the same viewpoint. .
  • the thiol group in component (B) is not particularly limited, and may be one or more of a primary thiol group, a secondary thiol group and a tertiary thiol group.
  • a representative example of the content of the component (B) in the ultraviolet curable resin composition is 15% by mass or more (more narrowly, 15% by mass) relative 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 the component (B) is 15% by mass or more (in a narrower sense, more than 15% by mass)
  • the UV-curable resin composition exhibits excellent curability in the shielding portion and the deep portion.
  • 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.
  • 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 (in a narrower sense, 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 % by mass) is 50% by mass or less (more narrowly, less than 50% by mass). Further, when more preferable numerical values are applied to both the upper limit value and the lower limit value, 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 50% 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 thiol group contained in the component (B) is not particularly limited. However, 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 0.10 or more.
  • Component may be used individually by 1 type, and may use 2 or more types together.
  • component (C) include, but are not limited to, alkylphenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, and the like.
  • alkylphenone compounds are 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, and the like, but are not limited thereto.
  • 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.
  • oxime ester compounds are 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime), 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazol-3-yl]ethanone-1-(0-acetyloxime), oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester and oxy -Phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester mixtures and the like, but not limited thereto.
  • Component (C) is preferably at least one compound selected from the group consisting of alkylphenone compounds and acylphosphine oxide compounds from the viewpoint of excellent curability in the shielded portion and the deep portion.
  • -benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl )-butan-1-one
  • Component (C) has an absorbance of 0.10 or more at 385 nm for 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.
  • UV-LEDs ultraviolet light emitting diodes
  • UV-LEDs have relatively low energy, so curing is insufficient.
  • Component (C) has an absorbance of 0.1 or more at 385 nm, so that it has sufficient absorption of ultraviolet rays from a UV-LED light source (350 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, but from the viewpoint of excellent curability in the shielding part and the deep part, in terms of solid content, relative to 100% by mass of the ultraviolet curable resin composition , preferably 0.1% by mass or more (more narrowly, more than 0.1% by mass) or less than 15% by mass (more narrowly, less than 15% by mass), and 0.1% by mass or more (more In a narrow sense, more than 0.1% by mass) is 5% by mass or less (more narrowly, less than 5% by mass).
  • Component (D) is not particularly limited, and 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.
  • the (D) component has the property of absorbing light (ultraviolet rays) and transitioning to an electron-excited singlet state, and then transitioning to a triplet state due to intersystem crossing.
  • the above UV-curable resin composition has sufficient curing in the shielding part and the deep part. Although the details are unknown, the following reasons are presumed. Energy transfer occurs when the component (D) in the triplet state collides with the component (C) in the ground state, thereby promoting the polymerization initiation action (radical generation reaction) in the component (C). Even if the component (C) is present in the deep part, the component (D) sufficiently exhibits the polymerization initiation action (radical generation reaction). As a result, it is presumed that the UV-curable resin composition is sufficiently cured in the shielding portion and deep portion.
  • component (D) include, but are not limited to, benzophenone compounds, thioxanthone compounds, naphthalene compounds, anthracene compounds, anthraquinone compounds, benzoin compounds, and coumarin compounds.
  • benzophenone compounds include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4-(methylphenylthio)phenylphenyl methane, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, hydroxybenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone, 4,4′-aminobenzophenone, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino) Benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, p-dimethylaminobenzophen
  • a representative example of the thioxanthone compound is a compound represented by the following general formula (3), but is not limited thereto.
  • R 1 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a halogen atom.
  • thioxanthone compounds include thioxanthone, 2-methylthioxanthone, 4-methylthioxanthone, 2-ethylthioxanthone, 4-ethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2 ,4-dimethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthone ammonium salt, 3-[3,4-dimethyl-9-oxo9H-thioxanthone-2-yl] oxy]-2-hydroxypropyl-N,N,N-trimethylammonium chloride, fluorothioxanthone, and the like, but are not limited thereto.
  • naphthalene compounds are naphthalene, 1-benzyloxynaphthalene, 2-benzyloxynaphthalene, 2-p-chlorobenzyloxynaphthalene, 2-p-isopropylbenzyloxynaphthalene, 1,4-dimethoxynaphthalene, 1 -ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, 1,4-dibutoxynaphthalene, 2-dodecyloxynaphthalene, 2-decanoyloxynaphthalene, 2-myristoyloxynaphthalene , 2-pt-butylbenzoyloxynaphthalene, 2-benzoyloxynaphthalene, 2-benzyloxy-3-N-(3-dodecyloxypropyl)carbamoylnaphthalene, 2-benzoyloxy
  • a representative example of the anthracene compound is a compound represented by the following general formula (4), but is not limited thereto.
  • R 2 represents a hydrogen atom or an alkyl group.
  • the alkyl group is a linear or branched alkyl group having 1 to 20 carbon atoms.
  • R 3 and R 4 are the same or Differently, it represents a hydrogen atom, an alkyl group, an alkoxy group or an alkylyloxy (alkylyloxy) group, wherein the alkyl group is a linear or branched alkyl group having 1 to 20 carbon atoms.
  • the alkoxy group is - Represented by O—R 5 , where R 5 is a linear or branched alkyl group having 1 to 20 carbon atoms, the alkylyloxy (alkylyloxy) group is represented by —O—CO—R 6 , R 6 is a linear or branched alkyl group having 1 to 20 carbon atoms.
  • anthracene compounds include anthracene, dimethylanthracene, 9-ethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9-hydroxymethylanthracene, 9,10-diphenylanthracene, 9,10-bis(octanoyloxy)-anthracene, halogenated anthracene, 9,10-bis(phenylethynyl)anthracene, 2-chloro-9,10-bis(phenylethynyl)anthracene, etc. but not limited to these.
  • anthraquinone compounds include anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1,2-dihydroxyanthraquinone, 2-diethylanthraquinone, 1,2-benzanthraquinone, etc., but are limited to these. not.
  • benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl )-benzyl]-phenyl]-2-methylpropan-1-one and the like, but are not limited thereto.
  • 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, 3,3′-carbonyl-bis(5,7-dimethoxycarbonylcoumarin), and the like, but are not limited thereto.
  • the component (D) is preferably at least one selected from the group consisting of benzophenone compounds, thioxanthone compounds, naphthalene compounds, and anthracene compounds, from the viewpoint of excellent curability in shielded areas and deep areas.
  • component (D) is at least one selected from the group consisting of benzophenone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 9,10-bis(octanoyloxy)-anthracene from the same point as described above. Seeds are more preferred.
  • the physical properties of component (D) are not particularly limited.
  • the content of component (D) in the UV-curable resin composition is not particularly limited.
  • 0.0001% by mass or more (more narrowly, more than 0.0001% by mass) with respect to 100% by mass of the ultraviolet curable resin composition ) is preferably 0.02% by mass or less (more narrowly, less than 0.02% by mass), and 0.0004% by mass or more (more narrowly, more than 0.0004% by mass) 0.009% by mass or less (more narrowly, less than 0.009% 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.
  • the (E) component 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, but in terms of solid content, 0.0001% by mass or more and 0.05% by mass or less with respect to 100% by mass of the composition (more than In a narrow sense, less than 0.05% by mass).
  • 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 80% by mass or less (in a more narrow sense, less than 80% 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, benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, and the like, but are not limited thereto.
  • 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.
  • the above additives are not particularly limited. Typical examples of the above additives include, but are not limited to, surfactants, adhesion improvers, antifoaming agents, sensitizers other than component (D), and fluorescent agents.
  • 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)); 0.2 parts of 6-trimethylbenzoyldiphenylphosphine oxide (manufactured by IGM Resins B.V., trade name "Omnirad TPO H”) (hereinafter referred to as component (C1)), and benzophenone (IGM Resins B) as component (D).
  • component (A1) trimethylolpropane triacrylate
  • component (B) pentaerythritol
  • Examples 2 to 16 and Comparative Examples 1 to 6 A UV-curable resin composition was produced in the same manner as in Example 1, except that the composition and amount of components (A) to (D) in Example 1 were changed to those shown in Tables 1 and 2.
  • Tables 1 and 2 are values in parts by mass converted to solid content. Abbreviations in Tables 1-2 are as follows. 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 1,4-cyclohexanedimethanol divinyl ether (manufactured by Nippon Carbide Industry Co., Ltd., trade name “CHDVE”)
  • B1 Pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko K.K., trade name “Karens MT (registered trademark) PE1”)
  • B2 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Showa Denko K.K.) , trade name “Karenzu MT (registered trademark) NR1”)
  • B3 1,4-bis(3-mercaptobutan
  • 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 15 was evaluated by the above evaluation method using a high-pressure mercury lamp (manufactured by Multiply Co., Ltd., belt conveyor type UV irradiation device, 120 W/cm high-pressure mercury lamp) as an ultraviolet irradiation device.
  • the shadow curability was evaluated in the same manner as the evaluation method described above, except that the ultraviolet rays were irradiated at an integrated light amount of 10,000 mJ/cm 2 . Table 2 shows the results.
  • the ultraviolet curable resin compositions of Examples 1 to 16 have a long shadow curability distance, so they have sufficient curability even in shielded areas and deep areas where ultraviolet rays do not reach.
  • the ultraviolet curable resin compositions of Comparative Examples 1 to 6 have a short shadow curability distance, so the curability in the shielded portion and deep portion where ultraviolet rays do not reach is insufficient, or the curability is confirmed. I am in a state where I cannot.
  • 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.

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PCT/JP2022/033258 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 WO2023038003A1 (ja)

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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
JP2017101112A (ja) * 2015-11-30 2017-06-08 味の素株式会社 光および熱硬化性樹脂組成物
JP2018177924A (ja) * 2017-04-11 2018-11-15 三洋化成工業株式会社 活性エネルギー線硬化性樹脂組成物
JP2020100795A (ja) * 2018-12-25 2020-07-02 パナソニックＩｐマネジメント株式会社 発光素子封止用組成物、及び発光装置

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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
JP2017101112A (ja) * 2015-11-30 2017-06-08 味の素株式会社 光および熱硬化性樹脂組成物
JP2018177924A (ja) * 2017-04-11 2018-11-15 三洋化成工業株式会社 活性エネルギー線硬化性樹脂組成物
JP2020100795A (ja) * 2018-12-25 2020-07-02 パナソニックＩｐマネジメント株式会社 発光素子封止用組成物、及び発光装置

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