WO2016121706A1 - Composition de résine photosensible et produit durci associé - Google Patents

Composition de résine photosensible et produit durci associé Download PDF

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Publication number
WO2016121706A1
WO2016121706A1 PCT/JP2016/052048 JP2016052048W WO2016121706A1 WO 2016121706 A1 WO2016121706 A1 WO 2016121706A1 JP 2016052048 W JP2016052048 W JP 2016052048W WO 2016121706 A1 WO2016121706 A1 WO 2016121706A1
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Prior art keywords
meth
acrylate
resin composition
compound
photosensitive resin
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PCT/JP2016/052048
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English (en)
Japanese (ja)
Inventor
英照 亀谷
真之 飯塚
隼 本橋
貴文 水口
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日本化薬株式会社
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Priority to CN201680007340.4A priority Critical patent/CN107207680A/zh
Priority to KR1020177021050A priority patent/KR20170107462A/ko
Publication of WO2016121706A1 publication Critical patent/WO2016121706A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a photosensitive resin composition containing a self-polymerizing photopolymerizable compound and a cured product thereof. Furthermore, the present invention relates to a resin composition containing a urethane (meth) acrylate having a hydrogenated polybutadiene polyol as a main skeleton and a specific polymerizable compound, and a cured product thereof.
  • the volatile component can be reduced in the curing process, and the cured film is flexible. In particular, it is excellent in adhesion, transparency, moisture resistance, adhesion to a substrate, and has little curing shrinkage.
  • a photopolymerization initiator that transfers absorbed light energy to a polymerization component is an essential component in a resin composition that is cured with an active energy ray such as ultraviolet rays.
  • an active energy ray such as ultraviolet rays.
  • Specific examples thereof include benzophenones, benzoin ethers, benzyl ketals, dibenzosuberones, anthraquinones, xanthones, thioxanthones, halogenoacetophenones, dialkoxyacetophenones, hydroxyacetophenones, halogenobisimidazoles, Halogenotriazines, acylphosphine oxides, oxime esters and the like can be mentioned.
  • Patent Document 1 proposes a material having a skeleton having a photopolymerization initiating function and a polymerizable double bond portion in the same molecule. By using such materials, it is possible to maintain high hardness and reduce outgas generation.
  • the photopolymerization initiator used in Patent Document 2 for example, the same idea is used for countermeasures against contamination of liquid crystal by decomposition products that bleed out after photocuring, and the density has been further increased. It is expected that it will continue to be used in the future to improve the reliability of peripheral materials of electronic information materials.
  • hydrogenated polybutadiene may be selected as a polyol compound to improve yellowing or weather resistance.
  • urethane (meth) acrylate is produced using hydrogenated polybutadiene polyol.
  • the decomposition products of the initiator used are volatile and are not mentioned regarding the above-mentioned problems.
  • the present invention improves the above requirements, reduces outgassing during the bonding process or after curing, provides excellent weather resistance and light resistance, gives a cured film with excellent flexibility, and has a shrinkage ratio upon curing. It aims at providing a low resin composition.
  • a self-polymerizing photopolymerizable compound (A) represented by the following general formula (1), a urethane (meth) acrylate compound (B), and a polymerizable compound (C) other than (B) are used as essential components.
  • Photosensitive resin composition (D) A self-polymerizing photopolymerizable compound represented by the following general formula (1), a urethane (meth) acrylate compound (B), and a polymerizable compound (C) other than (B) are used as essential components.
  • R represents a hydrogen atom or a methyl group.
  • the cured film of the photosensitive resin composition containing the self-polymerizing photopolymerizable compound of the present invention has no outgas and unpleasant odor, excellent flexibility, high weather resistance and light resistance, and needs to maintain transparency.
  • various coating fields such as ink, plastic paint, paper printing, metal coating, furniture coating, linings, adhesives, and insulating varnishes, insulating sheets and laminates in the electronics field It can be applied to many fields such as boards, printed boards, resist inks, and semiconductor encapsulants.
  • the self-polymerizing photopolymerizable compound (A) represented by the following general formula (1) used in the present invention is a commercially available photopolymerization initiator Irgacure 2959 (manufactured by BASF), a primary hydroxyl group, Karenz MOI, and Karenz AOI. It can be obtained by reacting an isocyanate group (manufactured by Showa Denko Co., Ltd.). In the reaction, the ratio of the number of moles of primary hydroxyl group to the number of moles of isocyanate is 0.8: 1.2 to 1.2 : 0.8, preferably 0.9: 1.1 to 1.1: 0.9.
  • R represents a hydrogen atom or a methyl group.
  • the reaction can be carried out without a solvent, but it is preferably carried out in a solvent having a high crystallinity of the product and having no alcoholic hydroxyl group or a polymerizable compound (C) described later for improving workability.
  • the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbons such as benzene, toluene, xylene, and tetramethylbenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dipropylene glycol.
  • Glycol ethers such as dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate, esters such as dialkyl glutarate, dialkyl succinate, dialkyl adipate, cyclic esters such as ⁇ -butyrolactone, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. Or a mixed organic solvent.
  • petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naph
  • the reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C.
  • the end point of the reaction is confirmed by a decrease in the amount of isocyanate.
  • a catalyst may be added for the purpose of shortening the reaction time.
  • this catalyst either a basic catalyst or an acidic catalyst is used.
  • the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine and ammonia, and phosphines such as tributylphosphine and triphenylphosphine.
  • acidic catalysts examples include copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, titanium tetraisopropoxide, zirconium tetrabutoxide, aluminum chloride, tin octylate, octyltin trilaurate, dibutyltin dilaurate, Mention may be made of Lewis acid catalysts such as octyltin diacetate. The amount of the catalyst added is usually 0.1 to 1 part by weight with respect to 100 parts by weight of the total reaction raw material mixture.
  • a polymerization inhibitor such as 4-methoxyphenol has already been added to the (meth) acrylate compound used as a raw material, but a polymerization inhibitor may be added again during the reaction.
  • examples of such polymerization inhibitors include hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-4-cresol, 3-hydroxythiophenol, Examples include p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, and phenothiazine.
  • the amount used is 0.01 to 1 part by weight based on 100 parts by weight of the total reaction raw material mixture.
  • a self-polymerization type photopolymerizable compound (A) used in the present invention by performing known operations such as a purification step by washing with water or crystallization, a solvent used under reduced pressure, or a crystal drying step as necessary. ) Can be obtained.
  • a self-polymerization type photopolymerizable compound (A) used in the present invention by performing known operations such as a purification step by washing with water or crystallization, a solvent used under reduced pressure, or a crystal drying step as necessary.
  • Irgacure 2959 or a compound of the following formula (3) may exist before the purification step.
  • R represents a hydrogen atom or a methyl group.
  • the compound represented by the above formula (1) is 70 area% to 90 area%, the Irgacure 2959 or the compound of the above formula (3) is 5 area%. There are ⁇ 20 area%. Therefore, the purity of the compound represented by the above formula (1) can be improved through the recrystallization step.
  • the purity of the compound represented by the formula (1) is preferably 95% or more, more preferably 97% or more, and particularly preferably 98% or more.
  • a solvent used in order to obtain recrystallization From the surface of the environmental load in a drying process, it is preferable that it is an alcohol solvent, and it is more preferable to carry out with primary alcohols, such as methanol and ethanol.
  • the urethane (meth) acrylate compound (B) used in the present invention first reacts with a hydrogenated polybutadiene polyol and / or other diol compound and a polyisocyanate compound (hereinafter referred to as a first reaction), and then remains.
  • a yellow-free urethane (meth) acrylate capable of reacting hereinafter referred to as a second reaction
  • a (meth) acrylate compound having at least one hydroxyl group with respect to an isocyanate group is preferred.
  • the non-yellowing urethane (meth) acrylate refers to urethane (meth) acrylate that is visually uncolored, and as a specific example, urethane obtained by using an aliphatic polyisocyanate as the polyisocyanate. (Meth) acrylate is mentioned.
  • the hydrogenated polybutadiene polyol used in the first reaction can be used as long as it is a hydrogenated reduction product of a general polybutadiene polyol. Is more preferably 20 or less, and particularly preferably 15 or less.
  • the molecular weight of the hydrogenated polybutadiene polyol any generally available molecular weight distribution can be used, but those having a number average molecular weight of 500 to 5000 are particularly preferred when a balance between flexibility and curability is achieved. 500 to 3000 are particularly preferred.
  • diol compounds other than hydrogenated polybutadiene polyol in the first reaction include, for example, polyether polyols such as polyethylene glycol, polybutylene glycol, polytetramethylene glycol, polypropylene glycol, and polyethylene glycol, polyethylene glycol adipate, poly Polyester polyols such as 1,4-butanediol adipate and polycaprolactone, glycols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol and neopentylglycol, cyclohexanedimethylol, hydrogenated bisphenol A, hydrogenated bisphenol F, spiro skeleton-containing alcohol, tricyclodecane dimethylol, pentacyclopentadecane dimethylol, etc.
  • polyether polyols such as polyethylene glycol, polybutylene glycol, polytetramethylene glycol,
  • the molecular weight of such a compound any generally available molecular weight distribution can be used. Particularly, when the balance between flexibility and curability is achieved, the number average molecular weight is preferably 500 to 6000, Particularly preferred are those of ⁇ 4000.
  • the polyisocyanate compound used in the first reaction is a compound containing two or more isocyanate groups in one molecule.
  • aliphatic diisocyanate compounds, aromatic diisocyanate compounds, these 3 Examples include a polymer.
  • the aliphatic diisocyanate compound as used herein means a diisocyanate compound in which an isocyanate group is bonded to a chain carbon atom, and a diisocyanate compound in which an isocyanate group is bonded to a carbon atom of a cyclic saturated hydrocarbon, and an aromatic diisocyanate compound.
  • Examples of the aliphatic diisocyanate compound include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-diisocyanate cyclohexane, 1,4-diisocyanate.
  • aromatic diisocyanate compound examples include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, 1,6-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,6-phenylene.
  • diisocyanate monomers such as diisocyanate.
  • an aliphatic diisocyanate compound and a trimer of the aliphatic diisocyanate compound are preferable because the weather resistance of the coating film is improved.
  • the trimer of the aliphatic diisocyanate compound include the above-mentioned aliphatic isocyanate-based isocyanurate-type polyisocyanates, and specific examples include hexamethylene diisocyanate and isophorone diisocyanate. These may be used alone or in a mixture.
  • the first reaction is charged in an equivalent relationship ([NCO] / [OH] molar ratio:> 1) such that isocyanate groups remain after the reaction.
  • [NCO] / [OH] molar ratio:> 1) such that isocyanate groups remain after the reaction.
  • the charging ratio is increased, a large amount of unreacted polyisocyanate compound is present, which may affect the flexibility of the photosensitive resin composition.
  • the preparation ratio is reduced, the molecular weight is increased and the curability of the photosensitive resin composition may be affected.
  • the OH group of the alcohol compound is preferably 0.01 to 0.99 mol, more preferably 0.10 to 0.95 mol, relative to 1.0 mol of the NCO group of the polyisocyanate compound.
  • the first reaction can be carried out in the absence of a solvent, but it is preferably carried out in a solvent having a high viscosity of the product and not having an alcoholic hydroxyl group or a polymerizable compound (C) described later in order to improve workability.
  • the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbons such as benzene, toluene, xylene, and tetramethylbenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dipropylene glycol.
  • Glycol ethers such as dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate, esters such as dialkyl glutarate, dialkyl succinate, dialkyl adipate, cyclic esters such as ⁇ -butyrolactone, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. Can be carried out alone or in a mixed organic solvent.
  • the reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C.
  • the end point of the reaction is confirmed by a decrease in the amount of isocyanate.
  • a catalyst may be added for the purpose of shortening the reaction time.
  • this catalyst either a basic catalyst or an acidic catalyst is used.
  • the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine and ammonia, and phosphines such as tributylphosphine and triphenylphosphine.
  • acidic catalysts examples include copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, titanium tetraisopropoxide, zirconium tetrabutoxide, aluminum chloride, tin octylate, octyltin trilaurate, dibutyltin dilaurate, Mention may be made of Lewis acid catalysts such as octyltin diacetate. The amount of these catalysts added is usually 0.1 to 1 part by weight based on 100 parts by weight of the total weight of the diol compound and the polyisocyanate compound.
  • the urethane (meth) acrylate compound (B) used in the present invention can be obtained by reacting the hydroxyl group-containing (meth) acrylate with the remaining isocyanate group (second reaction) after the first reaction.
  • the hydroxyl group-containing (meth) acrylate used in the second reaction is a compound having at least one hydroxyl group and one (meth) acrylate in one molecule, specifically, 2-hydroxyethyl (meth).
  • one hydroxyl group is preferred, and 2-hydroxyethyl (meth) acrylate is particularly preferred from the viewpoint of excellent curability and flexibility.
  • a polymerizable compound (C) described later in this specification may be added during the reaction.
  • the second reaction is charged in an equivalent relationship such that the isocyanate group of the intermediate obtained after the first reaction is eliminated.
  • the OH group of at least one hydroxyl group-containing (meth) acrylate is preferably 1.0 to 3.0 mol, more preferably 1.0 mol of the NCO group of the intermediate obtained after the first reaction. Is 1.0 to 2.0 mol.
  • the second reaction can also be carried out in the absence of a solvent, but is carried out in the above-mentioned solvent and / or in the polymerizable compound (C) described later in this specification in order to improve the workability because the product has a high viscosity. Is preferred.
  • the reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C.
  • the end point of the reaction is confirmed by a decrease in the amount of isocyanate.
  • the aforementioned catalyst may be added for the purpose of shortening the reaction time.
  • a polymerization inhibitor such as 4-methoxyphenol has already been added to the (meth) acrylate compound used as a raw material, but a polymerization inhibitor may be added again during the reaction.
  • examples of such polymerization inhibitors include hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-4-cresol, 3-hydroxythiophenol, Examples include p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, and phenothiazine. The amount used is 0.01 to 1% by weight based on the reaction raw material mixture.
  • urethane (meth) acrylate compound (B) used in the present invention commercially available products may be used.
  • the photosensitive resin composition (D) of the present invention comprises a self-polymerizing photopolymerizable compound (A), a urethane (meth) acrylate compound (B) and a polymerizable compound (C) other than the component (B) as essential components. Obtained by configuring.
  • Specific examples of the polymerizable compound (C) that can be used include a compound having a (meth) acryloyloxy group, a maleimide compound, a (meth) acrylamide compound, and an unsaturated polyester.
  • Specific examples of the compound having a (meth) acryloyloxy group that can be used in combination with the photosensitive resin composition of the present invention include (poly) ester (meth) acrylate (C-1); urethane (meth) acrylate (C-2).
  • the (poly) ester (meth) acrylate (C-1) that can be used in combination with the photosensitive resin composition of the present invention is a generic term for (meth) acrylate having one or more ester bonds in the main chain, and urethane (meth) Acrylate (C-2) is a general term for (meth) acrylate having one or more urethane bonds in the main chain.
  • Epoxy (meth) acrylate (C-3) is a monofunctional or higher functional epoxy compound and (meth).
  • (meth) acrylate obtained by reacting acrylic acid is a generic term for (meth) acrylate having one or more ether bonds in the main chain
  • Alkyl (meth) acrylate or alkylene (meth) acrylate (C-5) is a linear alkyl, branched alkyl, or halogenated at the end or main chain.
  • (meth) acrylate (C-6) having an aromatic ring is (meth) acrylate having an aromatic ring in the main chain or side chain.
  • (meth) acrylate (C-7) having an alicyclic structure has (meth) an alicyclic structure in which the main unit or side chain may contain an oxygen atom or a nitrogen atom in the structural unit. These are used as a general term for acrylates.
  • Examples of the (poly) ester (meth) acrylate (C-1) that can be used in combination with the photosensitive resin composition of the present invention include caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide-modified phthalate.
  • Monofunctional (poly) ester (meth) acrylates such as acid (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate; hydroxypivalate ester neopentyl glycol di (meth) Acrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol di (meth) acrylate, epichlorohydrin-modified phthalic acid di (meth) acrylate; trimethylolpropane or glycerin 1 1 mole or more ⁇ - caprolactone Le, .gamma.-butyrolactone, a triol obtained by adding a cyclic lactone compound such as ⁇ - valerolactone mono-, di- or tri (meth) acrylate;
  • a cyclic lactone compound such as ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone
  • ⁇ -valerolactone Mono- or poly (meth) acrylate of hexaol obtained by adding 1 mol or more of cyclic lactone compound such as ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone to 1 mol of dipentaerythritol;
  • Diol components such as (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, 3-methyl-1,5-pentanediol, hexanediol, and maleic acid, fumaric acid, succinic acid Acids, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, polybasic acids such as 5-sodiumsulfoisophthalic acid, and their reactants (Meth) acrylates of polyester polyols such as: (meth) acrylates of cyclic lactone-modified polyester diols composed of the diol components and polybasic acids and their anhydrides and ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone, etc. Multifunctional (pol
  • the urethane (meth) acrylate (C-2) that can be used in combination with the photosensitive resin composition of the present invention includes at least one hydroxy compound (C-2-i) having an (meth) acryloyloxy group and an isocyanate compound (C—).
  • C-2-i hydroxy compound having an (meth) acryloyloxy group
  • C— isocyanate compound
  • hydroxy compound (C-2-i) having at least one (meth) acryloyloxy group include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, 4-hydroxyethyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-hydroxy Ring-opening reaction of (meth) acrylate compounds having various hydroxyl groups such as -3-phenoxypropyl (meth) acrylate, and the above-mentioned (meth) acrylate compounds having a hydroxyl group and ⁇ -caprolactone And the like.
  • isocyanate compound (C-2-ro) examples include, for example, P-phenylene diisocyanate, m-phenylene diisocyanate, P-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate.
  • Aromatic diisocyanates such as diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate; aliphatics such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate Or diisocyanates having an alicyclic structure; one or more burettes of isocyanate monomers, or the above diisocyanate Compound trimer polyisocyanates of the isocyanate and the like; the and the isocyanate compound include polyisocyanates obtained by urethane reaction of the polyol compound.
  • a polyol is optionally reacted. It doesn't matter.
  • examples of polyols that can be used include those having 1 to 10 carbon atoms such as neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol.
  • Triols such as alkylene glycol, trimethylolpropane, pentaerythritol, alcohols having a cyclic skeleton such as tricyclodecane dimethylol, bis- [hydroxymethyl] -cyclohexane, and the like; and these polyhydric alcohols and polybasic acids (for example, succinic acid) , Phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, tetrahydrophthalic anhydride, etc.) polyester polyol obtained by reaction with polyhydric alcohol and ⁇ -caprolactone Lactone alcohol, polycarbonate polyol (for example, polycarbonate diol obtained by reaction of 1,6-hexanediol and diphenyl carbonate) or polyether polyol (for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide modified bisphenol A, etc.) Etc
  • the epoxy (meth) acrylate (C-3) that can be used in combination with the photosensitive resin composition of the present invention is obtained by reacting an epoxy resin containing one or more functional epoxy groups with (meth) acrylic acid ( A generic term for (meth) acrylate.
  • epoxy resins used as raw materials for epoxy (meth) acrylates include phenyl diglycidyl ethers such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether; bisphenol-A type epoxy resin, bisphenol-F type epoxy Bisphenol-type epoxy compounds such as resins, bisphenol-S type epoxy resins, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxy compounds; A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexa Fluoropropane Epoxy Hydrogenated bisphenol-type epoxy compounds such as compounds; Halogenated bisphenol-type epoxy compounds such as brominated bisphenol-A type epoxy resins and brominated bisphenol-F type epoxy resins; Alicyclic diglycidyl such as cyclohex
  • Examples of the (poly) ether (meth) acrylate (C-4) that can be used in combination with the photosensitive resin composition of the present invention include butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, epichlorohydrin-modified butyl ( (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, etc.
  • Functional (poly) ether (meth) acrylates include butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, epichlorohydrin-modified butyl ( (Meth) acrylate, dicyclopentenyloxyethyl (meth)
  • Alkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate; ethylene oxide and propylene oxide Copolymer, copolymer of propylene glycol and tetrahydrofuran, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, polyhydric hydroxyl compounds such as hydrogenated polybutadiene glycol and other polyhydric hydroxyl compounds and (meth) acrylic Polyfunctional (meth) acrylates derived from acids; 1 mole or more of ethylene oxide, propylene oxide, butylene oxide, etc. per mole of neopentyl glycol Di diol obtained by adding a cyclic ether (meth) acrylate;
  • Mono-, di-, tri-, or tetra (meth) acrylates of triols obtained by adding 1 mol or more of a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide to 1 mol of pentaerythritol or ditrimethylolpropane; 1 mol of dipentaerythritol
  • a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide
  • pentaerythritol or ditrimethylolpropane 1 mol of dipentaerythritol
  • examples thereof include polyfunctional (poly) ether (meth) acrylates such as hexaol tri- to hexafunctional (meth) acrylates to which cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide and the like are added in a molar amount or more.
  • alkyl (meth) acrylate or alkylene (meth) acrylate (C-5) examples include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate.
  • Mono (meth) acrylate, di (meth) acrylate or tri (meth) acrylate of trimethylolpropane (hereinafter, “poly” is used as a general term for polyfunctionality such as di, tri, tetra, etc.), mono (meth) of glycerin Triols such as acrylate or poly (meth) acrylate, mono- or poly (meth) acrylate of pentaerythritol, mono- or poly (meth) acrylate of ditrimethylolpropane, mono- or poly (meth) acrylate of dipentaerythritol, tetraol, hexa Mono- or poly (meth) acrylates of polyhydric alcohols such as oar;
  • Hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate; it can.
  • Examples of the (meth) acrylate (C-6) having an aromatic ring that can be used in combination with the photosensitive resin composition of the present invention include monofunctional (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate. And di (meth) acrylates such as bisphenol A di (meth) acrylate and bisphenol F di (meth) acrylate, but are not limited thereto.
  • Examples of the (meth) acrylate (C-7) having an alicyclic structure that can be used in combination with the photosensitive resin composition of the present invention include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, isobornyl (meth) acrylate, Monofunctional (meth) acrylates having an alicyclic structure such as cyclopentenyl (meth) acrylate; di (meth) acrylates of hydrogenated bisphenols such as hydrogenated bisphenol A and hydrogenated bisphenol F; tricyclodecane dimethylol di ( Examples thereof include polyfunctional (meth) acrylates having a cyclic structure such as (meth) acrylate; alicyclic (meth) acrylates having an oxygen atom or the like in the structure such as tetrafurfuryl (meth) acrylate. However, it is not limited to these.
  • Examples of the compound (C-8) having a (meth) acryloyl group that can be used in combination with the photosensitive resin composition of the present invention include, for example, (meth) acrylic acid polymer and glycidyl (meth) in addition to the above-described compounds.
  • Poly (meth) acrylic polymer (meth) acrylate such as a reaction product of acrylate or a reaction product of glycidyl (meth) acrylate polymer and (meth) acrylic acid; amino group such as dimethylaminoethyl (meth) acrylate (meta ) Acrylates; isocyanuric (meth) acrylates such as tris (meth) acryloxyethyl isocyanurate; (meth) acrylates having a polysiloxane skeleton; polybutadiene (meth) acrylates, melamine (meth) acrylates, and the like.
  • maleimide group-containing compound (C-9) examples include Nn-butylmaleimide, N-hexylmaleimide, 2-maleimidoethyl-ethyl carbonate, 2- Monofunctional aliphatic maleimides such as maleimidoethyl-propyl carbonate and N-ethyl- (2-maleimidoethyl) carbamate; Alicyclic monofunctional maleimides such as N-cyclohexylmaleimide; N, N-hexamethylene bismaleimide, polypropylene Aliphatic bismaleimides such as glycol-bis (3-maleimidopropyl) ether and bis (2-maleimidoethyl) carbonate; cycloaliphatic such as 1,4-dimaleimidocyclohexane and isophorone bisurethane bis (N-ethylmaleimide) Bismaleimide; with maleimidoacetic acid Ester
  • Examples of the (meth) acrylamide compound (C-10) that can be used in combination with the photosensitive resin composition of the present invention include monofunctional (meth) acrylamides such as acryloylmorpholine and N-isopropyl (meth) acrylamide; Examples thereof include polyfunctional (meth) acrylamides such as (meth) acrylamide.
  • Examples of the unsaturated polyester (C-11) that can be used in the photosensitive resin composition of the present invention include fumaric acid esters such as dimethyl malate and diethyl malate; polyunsaturated such as maleic acid and fumaric acid.
  • the esterification reaction product of carboxylic acid and a polyhydric alcohol can be mentioned.
  • the polymerizable compound (C) that can be used in combination with the photosensitive resin composition of the present invention is a combination of alkyl (meth) acrylate or alkylene (meth) acrylate (C-5) that has low viscosity, excellent light resistance and workability.
  • the compound is not limited to the above-described compounds, and one or a plurality of compounds are used in combination without any particular limitation as long as the compounds are copolymerizable with the components (A) and (B). be able to.
  • compounds having a (meth) acryloyloxy group having a long chain of C5 to C35, more preferably C15 to C35, such as alkyl (meth) acrylate or alkylene (meth) acrylate are suitable. This is because a photosensitive resin composition having excellent compatibility and transparency can be obtained by having such a structure.
  • the ratio of the components (A), (B), and (C) is not particularly limited, but the component (B) is added to 1% by weight of the component (A). It is preferable to contain 10 to 3000% by weight, (C) component 10 to 3000% by weight, particularly preferably (B) component 20 to 2000% by weight, and (C) component 20 to 2000% by weight.
  • a softening component (E) can be used as necessary.
  • Specific examples of the softening component that can be used include polymers, oligomers, phthalates, phosphate esters, glycol esters, citrate esters, aliphatic dibasic esters, fatty acids that are compatible in the composition. Examples include esters, epoxy plasticizers, castor oils, terpene resins, hydrogenated terpene resins, and liquid terpenes.
  • Examples of the oligomer and polymer include a polyisoprene skeleton, a hydrogenated polyisoprene skeleton, a polybutadiene skeleton, a hydrogenated polybutadiene skeleton or an xylene skeleton, an esterified product thereof, polybutene, and the like. From the viewpoint of transparency, hydrogenated terpene resins, hydrogenated polyisoprene, hydrogenated polybutadiene, polybutene, and liquid terpenes are preferable.
  • hydroxyl group-containing polymers such as hydrogenated polybutadiene contained in the side chain, and liquid terpene resins are particularly preferable.
  • two or more kinds of the softening components (E) may be used in combination.
  • the weight ratio of the softening component in the photosensitive resin composition is usually 5 to 40% by weight, preferably 10 to 35% by weight when a solid softening component is used.
  • a liquid softening component is used, it is usually 10 to 70% by weight, preferably 20 to 60% by weight.
  • the photosensitive resin composition of the present invention may be used in combination with an existing photopolymerization initiator as necessary.
  • Specific examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl.
  • Benzoins such as ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl Acetophenones such as ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-chloroanthraquinone, 2-amylan Anthraquinones such as laquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benz
  • tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester
  • an accelerator such as a benzoic acid derivative.
  • an amount of 100% by weight or less is added to the photopolymerization initiator as necessary.
  • the photosensitive resin composition of the present invention includes an antioxidant, an organic solvent, a silane coupling agent, a polymerization inhibitor, a leveling agent, an antistatic agent, a surface lubricant, a fluorescent whitening agent, and a light stabilizer as necessary. You may add additives, such as a hindered amine compound (for example) and a filler.
  • antioxidants include, for example, BHT, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine Pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3-t -Butyl-5-methyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, , N-hexamethylenebis (3,5-di-di
  • organic solvent examples include alcohols such as methanol, ethanol and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, dioxane, toluene, xylene and the like.
  • silane coupling agent examples include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy) (Cyclohexyl) ethyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, ⁇ -mercapropropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltri
  • polymerization inhibitor examples include paramethoxyphenol and methylhydroquinone.
  • the light stabilizer include, for example, 1,2,2,6,6-pentamethyl-4-piperidyl alcohol, 2,2,6,6-tetramethyl-4-piperidyl alcohol, 1,2,2, 6,6-pentamethyl-4-piperidyl (meth) acrylate (LA-82, manufactured by ADEKA Corporation), tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3 4-butanetetracarboxylate, tetrakis (2,2,6,6-totramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] Unde Mixed ester with decanoic acid bis (2,2,6,6-tetramethyl-4-
  • the filler include, for example, crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc and the like.
  • examples thereof include powder or beads obtained by spheroidizing these.
  • the weight ratio of the various additives in the photosensitive resin composition is 0.01 to 3% by weight, preferably 0.01 to 1% by weight, more preferably 0.8%. 02 to 0.5% by weight.
  • the photosensitive resin composition of the present invention can be obtained by mixing and dissolving the above-described components at room temperature to 80 ° C. If necessary, impurities may be removed by an operation such as filtration. In the photosensitive resin composition of the present invention, it is preferable to appropriately adjust the blending ratio of the components so that the viscosity at 25 ° C. is in the range of 300 to 40,000 mPa ⁇ s in view of applicability.
  • the photosensitive resin composition of the present invention does not substantially require a solvent.
  • a solvent for example, ketones such as methyl ethyl ketone and methyl isobutyl ketone, acetates such as ethyl acetate and butyl acetate, benzene, toluene, xylene and the like It is also possible to dilute and use the photosensitive resin composition of the present invention with other generally used organic solvents such as aromatic hydrocarbons.
  • the photosensitive resin composition of the present invention can be polymerized by irradiation with ultraviolet rays or visible rays having a wavelength of 180 to 500 nm. Further, it can be cured by irradiation with energy rays other than ultraviolet rays or by heat.
  • Examples of the light generation source of ultraviolet light or visible light having a wavelength of 180 to 500 nm include, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp, an excimer lamp, and a short.
  • Examples include arc lamps, helium / cadmium lasers, argon lasers, excimer lasers, and sunlight.
  • the photosensitive resin composition of the present invention is excellent in flexibility, weather resistance, light resistance, and optical applications that need to maintain transparency, as well as ink, plastic paint, paper printing, metal coating, furniture It is useful in many fields such as various coating fields such as painting, linings, adhesives, and insulating varnishes, insulating sheets, laminates, printed boards, resist inks, and semiconductor encapsulants in the electronics field.
  • More specific applications include planographic relief inks, flexographic inks, gravure inks, screen inks and other ink fields, glossy fields, paper coating materials fields, wood coating materials fields, beverage can coating materials or printing ink fields, Soft packaging film coating agent, printing ink or adhesive, thermal paper, thermal film coating agent, printing ink, adhesive, adhesive or optical fiber coating agent, liquid crystal display device, organic EL display device, touch panel type image display device It is useful for applications such as air gap fillers for display devices (fillers for gaps between display devices and face plates).
  • the present invention is a particularly useful field of application because the generation of bubbles after vacuum bonding is reduced when it is used in a field where vacuum bonding such as an air gap filler is assumed.
  • Synthesis example 1 In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature controller, 224.3 g of Irgacure 2959 (BASF), 130 g of methyl isobutyl ketone (MIBK) as a reaction solvent, and 4-methoxyphenol as a polymerization inhibitor 0.8 g was added and mixed and dissolved at 80 ° C. After dissolution, 155.2 g of Karenz MOI (manufactured by Showa Denko KK) was added and reacted at 80 ° C. for 12 hours, and it was confirmed that the peak derived from the isocyanate group disappeared by infrared absorption spectrum (IR) measurement.
  • IR infrared absorption spectrum
  • reaction solution is washed with water three times and concentrated to obtain a crystalline crude product, which is recrystallized with a methanol solvent, and the resulting crystal is filtered and vacuum dried.
  • 182 g of a self-polymerizing photopolymerizable compound (A-1) represented by the following general formula (2) was obtained. The purity was 98% or more.
  • the photosensitive resin composition (D) containing the self-polymerizing photopolymerizable compound (A) of the present invention has a photoreactivity equivalent to that of a commercially available photopolymerization initiator. It is possible to form a cured film equivalent to the conventional one. Furthermore, the film coated with the photosensitive resin composition (D) of the present invention is excellent in pencil hardness and scratch resistance while maintaining adhesion, and is a residue derived from an initiator as compared with a conventional initiator. The unpleasant odor due to the above is also reduced, and it can be seen that it is also useful in terms of environmental friendliness and safety due to impure residual compounds.
  • Synthesis example 2 To a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, GI-2000 manufactured by Nippon Soda Co., Ltd. (iodine value: 12.2, hydroxyl value: 46.8 mg ⁇ KOH) as a hydrogenated polybutadiene polyol compound / G) is 569.73 g (0.24 mol), 7.50 g (0.0024 mol) of Exenol 3020 (polypropylene glycol, hydroxyl value: 35.9 mg ⁇ KOH / g) manufactured by Asahi Glass Co., Ltd. as a diol compound is polymerizable.
  • GI-2000 manufactured by Nippon Soda Co., Ltd.
  • Examples 6-8, Comparative Example 2 A photosensitive resin composition was prepared with the composition shown in Table 2 below, and the following evaluation was performed. In addition, sclerosis
  • the refractive index (25 ° C.) of the resin was measured with an Abbe refractometer (DR-M2: manufactured by Atago Co., Ltd.).
  • Two slide glasses having a thickness of 1 mm coated with a fluorine-based release agent were prepared, and the obtained photosensitive resin composition was applied to one of the release agent application surfaces so as to have a film thickness of 200 ⁇ m. Thereafter, the two slide glasses were bonded so that the respective release agent application surfaces face each other.
  • the resin composition was cured by irradiating the resin composition with ultraviolet rays having an integrated light quantity of 3000 mJ / cm 2 through a glass with a high-pressure mercury lamp (80 W / cm, ozone-less). Thereafter, the two slide glasses were peeled off to produce a cured product for measuring the film specific gravity.
  • the photosensitive resin composition containing the self-polymerizing photopolymerizable compound of the present invention is excellent in curability and can reduce adverse effects such as outgassing due to impurities derived from a conventional photopolymerization initiator. Furthermore, since the photosensitive resin composition of the present invention has low shrinkage, high weather resistance and light resistance, and is excellent in transparency, it is useful as an optical member application such as an adhesive for bonding a transparent display substrate.

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Abstract

La présente invention concerne une composition de résine présentant un faible rapport de retrait une fois durcie et fournissant un film durci présentant un dégagement gazeux réduit pendant un processus de liaison ou après le durcissement et présentant une excellente flexibilité en plus de présenter une excellente résistance aux intempéries et une excellente résistance à la lumière. La composition de résine photosensible (D) contient un composé photopolymérisable (A) de type auto-polymérisable représenté par la formule générale (1), un composé (B) de (méth)acrylate d'uréthane et un composé polymérisable (C) autre que (B). (Dans la formule, R représente un atome d'hydrogène ou un groupe méthyle.)
PCT/JP2016/052048 2015-01-26 2016-01-25 Composition de résine photosensible et produit durci associé WO2016121706A1 (fr)

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WO2017110845A1 (fr) * 2015-12-22 2017-06-29 日本合成化学工業株式会社 Composition de résine durcissable par un rayonnement d'énergie active et son procédé de production
CN111690367A (zh) * 2019-03-15 2020-09-22 日本化药株式会社 显示器用密封剂及液晶显示器
US11759298B2 (en) 2017-11-22 2023-09-19 3M Innovative Properties Company Photopolymerizable compositions including a urethane component and a monofunctional reactive diluent, articles, and methods

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WO2018180735A1 (fr) * 2017-03-31 2018-10-04 富士フイルム株式会社 Procédé de raffinage de solution chimique, procédé de production de solution chimique et solution chimique
WO2019198490A1 (fr) * 2018-04-10 2019-10-17 Dic株式会社 Composition de résine photosensible, objet durci, matériau isolant, matériau de résine pour réserve de soudure, et élément de soudure
JP7131504B2 (ja) * 2019-08-02 2022-09-06 三菱ケミカル株式会社 硬化性重合体組成物、硬化物、積層体
JP7391364B2 (ja) * 2019-12-13 2023-12-05 Ｋｊケミカルズ株式会社 光重合開始性ｎ－置換（メタ）アクリルアミド

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CN111690367B (zh) * 2019-03-15 2023-01-17 日本化药株式会社 显示器用密封剂及液晶显示器

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