Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
• • 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
  • C08F290/08—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 side groups
  • C08F290/12—Polymers provided for in subclasses C08C or C08F
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/14—Esterification
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • 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
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/22—Secondary treatment of printed circuits
  • H05K3/28—Applying non-metallic protective coatings
  • H05K3/285—Permanent coating compositions

Definitions

• the present invention is an acid group-containing (meth) acrylate resin having high light sensitivity and excellent alkali developability, and capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity, and curability containing the acid group-containing (meth) acrylate resin.
• the present invention relates to a resin composition, a cured product of the curable resin composition, an insulating material, a resin material for solder resist, and a resist member.
• curable compositions such as active energy ray-curable compositions that can be cured by active energy rays such as ultraviolet rays and thermosetting compositions that can be cured by heat have been introduced into inks, paints, coating agents, adhesives, and optics. It is widely used in the field of materials and the like.
• the coating agent application generally, it is possible to impart designability to the surface of various base materials, have excellent curability, and form a coating film capable of preventing deterioration of the base material surface. Is required.
• a curable composition for a solder resist for a printed wiring board it is required to be cured with a small exposure amount, and to be excellent in heat resistance, heat-resistant yellowing, etc. in the cured product.
• an acid group-containing epoxy obtained by further reacting tetrahydrophthalic anhydride with an intermediate obtained by reacting a cresol novolac type epoxy resin with acrylic acid and phthalic anhydride.
• a photosensitive resin composition containing an acrylate resin is known (see, for example, Patent Document 1), but the heat resistance of the cured product is not sufficient, and the heat-resistant yellowing is insufficient due to the high aromatic concentration. There was a problem such as.
• the problem to be solved by the present invention is an acid group-containing (meth) acrylate resin having high light sensitivity and excellent alkali developability, and capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity. It is an object of the present invention to provide a curable resin composition containing this, a cured product of the curable resin composition, an insulating material, a resin material for solder resist, and a resist member.
• the present inventors have made a methacrylate compound having an aromatic ring, and a compound having a reactive functional group and a polymerizable unsaturated group other than the compound (a1) (a2). ) As an essential raw material, and the compound having a functional group capable of reacting with the reactive functional group derived from the compound (a2) contained in the copolymer (A).
• the present invention has been completed by finding that the above problems can be solved by using a compound (B) having a polymerizable unsaturated group other than (a1) and the compound (a2) and a polybasic acid anhydride (C). I let you.
• the present invention uses a methacrylate compound (a1) having an aromatic ring and a compound (a2) having a reactive functional group and polymerizable unsaturated group other than the compound (a1) as essential raw materials.
• a methacrylate compound (a1) having an aromatic ring and a compound (a2) having a reactive functional group and polymerizable unsaturated group other than the compound (a1) as essential raw materials.
• the acid group-containing (meth) acrylate resin of the present invention has high photosensitivity and excellent alkali developability, and can form a cured product having excellent heat resistance, heat-resistant yellowing, and reflectivity.
• a curable resin composition containing a meta) acrylate resin and a photopolymerization initiator can be used as a coating agent or an adhesive, and the coating agent can be particularly preferably used for solder resist applications.
• the acid group-containing (meth) acrylate resin of the present invention has a methacrylate compound (a1) having an aromatic ring (hereinafter, may be referred to as “compound (a1)”), and a reactive functional other than the compound (a1).
• (meth) acrylate means acrylate and / or methacrylate.
• (meta) acryloyl means acryloyl and / or methacryloyl.
• (meth) acrylic means acrylic and / or methacryl.
• the methacrylate compound (a1) and the compound (a2) having a polymerizable unsaturated group are essential raw materials.
• Examples of the compound (a1) include benzyl methacrylate, phenyl methacrylate, phenylbenzyl methacrylate, phenoxybenzyl methacrylate, biphenylmethyl methacrylate, phenol EO modified methacrylate, phenol PO modified methacrylate, nonylphenol EO modified methacrylate, nonylphenol PO modified methacrylate, and phenyl.
• Phenol EO modified methacrylate Phenol EO modified methacrylate, phenylphenol PO modified methacrylate, monohydroxyethyl methacrylate phthalate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, N-phenylmethacrylate, bisphenol A type EO modification Examples thereof include dimethacrylate, bisphenol A-type PO-modified dimethacrylate, bisphenol F-type EO-modified dimethacrylate, bisphenol F-type PO-modified dimethacrylate, and biphenol dimethacrylate. These compounds (a1) can be used alone or in combination of two or more.
• an acid group-containing (meth) acrylate resin having high photosensitivity and excellent alkali developability and capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity can be obtained.
• Monofunctional methacrylate is preferable, and benzyl methacrylate is more preferable.
• the content of the compound (a1) is an acid group-containing (meth) acrylate resin having high photosensitivity and excellent alkali developability, and capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity. From the above, it is preferably more than 3% by mass and 18% by mass or less in the copolymer (A), and more preferably 5 to 15% by mass.
• the compound (a2) a compound having a reactive functional group and a polymerizable unsaturated group is used.
• Examples of the reactive functional group include a hydroxyl group, an epoxy group, an isocyanate group, a carboxyl group, an alkoxy group and the like. These reactive functional groups may have alone or may have two or more kinds.
• Examples of the polymerizable unsaturated group include a (meth) acryloyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, a vinyl ether group, a (meth) acrylamide group and the like. Can be mentioned.
• Examples of the compound having a hydroxyl group as the reactive functional group and the (meth) acryloyl group as the polymerizable unsaturated group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and trimethylolpropane (meth).
• a (poly) oxyalkylene modified product obtained by introducing a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain into the molecular structure of the various compounds.
• a lactone modified product in which a (poly) lactone structure is introduced into the molecular structure of the various compounds can also be used. These compounds may be used alone or in combination of two or more.
• Examples of the compound having an epoxy group as the reactive functional group and a (meth) acryloyl group as the polymerizable unsaturated group include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and epoxy.
• Glycidyl group-containing (meth) acrylate monomer such as cyclohexylmethyl (meth) acrylate; mono (meth) of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalenediglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. Examples thereof include acrylate compounds. These compounds may be used alone or in combination of two or more.
• Examples of the compound having an isocyanate group as the reactive functional group and a (meth) acryloyl group as the polymerizable unsaturated group include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-. Examples thereof include bis (acryloyloxymethyl) ethyl isocyanate. These compounds may be used alone or in combination of two or more.
• Examples of the compound having a carboxyl group as the reactive functional group and a (meth) acryloyl group as the polymerizable unsaturated group include (meth) acrylic acid, ⁇ -carboxy-polycaprolactone monoacrylate and the like. .. These compounds may be used alone or in combination of two or more.
• Examples of the compound having an alkoxy group as the reactive functional group and a (meth) acrylamide group as the polymerizable unsaturated group include N-methoxymethyl (meth) acrylamide and N-ethoxymethyl (meth) acrylamide. Examples thereof include N-butoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide and the like. These compounds may be used alone or in combination of two or more.
• the compound (a2) a compound having a reactive functional group and a polymerizable unsaturated group in one molecule can also be used.
• the "polymerizable unsaturated group” means an unsaturated group capable of radical polymerization.
• Examples of the compound having a reactive functional group and a polymerizable unsaturated group in one molecule include an unsaturated acid such as cinnamic acid, a tetrahydrophthalic anhydride, and a maleic anhydride, which have an unsaturated bond in the molecule.
• Allyl compounds having reactive functional groups such as anhydrides and allyl alcohols, vinyl ether compounds having reactive functional groups such as 2-hydroxyethyl vinyl ether, maleimides having reactive functional groups such as N- (4-aminophenyl) maleimide, etc.
• Examples thereof include compounds and styryl compounds having a reactive functional group such as 4-vinylbenzoic acid.
• the content of the compound (a2) is an acid group-containing (meth) acrylate resin having high photosensitivity and excellent alkali developability, and capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity.
• the copolymer (A) is preferably in the range of 40 to 90% by mass, more preferably in the range of 50 to 90% by mass.
• the copolymer (A) may contain other polymerization components other than the compound (a1) and the compound (a2), if necessary.
• Examples of the other polymerization component include a (meth) acrylate compound (a3), a compound having a polymerizable unsaturated group other than the (meth) acrylate compound (a4), and the like.
• Examples of the (meth) acrylate compound (a3) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) acrylate.
• An aliphatic mono (meth) acrylate compound such as 2-ethylhexyl (meth) acrylate and octyl (meth) acrylate; an alicyclic mono (meth) such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate.
• Acrylate compound Acrylate compound; heterocyclic mono (meth) acrylate compound such as tetrahydrofurfuryl acrylate; benzyl acrylate, phenyl acrylate, phenyl benzyl acrylate, phenoxy acrylate, phenoxy ethyl acrylate, phenoxy ethoxyethyl acrylate, phenoxy benzyl acrylate, phenyl phenoxy ethyl acrylate.
• Monoacrylate compounds such as aromatic monoacrylate compounds such as: (poly) oxyethylene chains, (poly) oxypropylene chains, (poly) oxytetramethylene chains, etc.
• An aliphatic di (meth) acrylate such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate.
• Alicyclic di (meth) acrylate compounds such as acrylates; aromatic diacrylate compounds such as biphenol diacrylates and bisphenol diacrylates; (poly) oxyethylene chains, (poly) oxyethylene chains in the molecular structure of the various di (meth) acrylate compounds.
• (Poly) oxyalkylene such as (poly) oxypropylene chain and (poly) oxytetramethylene chain
• a chain-introduced polyoxyalkylene-modified di (meth) acrylate compound a lactone-modified di (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the various di (meth) acrylate compounds; trimethylolpropane tri
• An aliphatic tri (meth) acrylate compound such as (meth) acrylate and glycerin tri (meth) acrylate; a (poly) oxyethylene chain, a (poly) oxypropylene chain, etc.
• a (poly) oxyalkylene-modified tri (meth) acrylate compound introduced with a (poly) oxyalkylene chain such as a (poly) oxytetramethylene chain; a (poly) lactone structure in the molecular structure of the aliphatic tri (meth) acrylate compound.
• a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain is introduced into the molecular structure of the aliphatic poly (meth) acrylate compound.
• These compounds (a3) can be used alone or in combination of two or more. Further, among these, an acid group-containing (meth) acrylate resin having high photosensitivity and excellent alkali developability and capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity can be obtained. , Methacrylate compounds are preferred.
• the compound (a4) having a polymerizable unsaturated group is not particularly limited as long as it is a compound having one or more polymerizable unsaturated groups in the molecule.
• Examples of the polymerizable unsaturated group include an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, a vinyl ether group and the like.
• These compounds (a4) can be used alone or in combination of two or more.
• the method for producing the copolymer (A) is not particularly limited, and any method may be used for producing the copolymer (A). For example, a method obtained by polymerizing all of the polymerization components containing the compound (a1) and the compound (a2) at 50 to 200 ° C. can be mentioned.
• a polymerization initiator can be used if necessary.
• the polymerization initiator examples include radical polymerization initiators such as persulfate, organic peroxide, and hydrogen peroxide, and 4,4'-azobis (4-cyanovaleric acid) and 2,2'-azobis ( 2-Amidinopropane) An azo initiator such as dihydrochloride can be mentioned. Further, the radical polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent such as ascorbic acid, for example. These polymerization initiators can be used alone or in combination of two or more.
• persulfate examples include potassium persulfate, sodium persulfate, ammonium persulfate and the like. These persulfates can be used alone or in combination of two or more.
• organic peroxide examples include diacyl peroxides such as benzoyl peroxide, lauroyl peroxide and decanoyl peroxide, dialkyl peroxides such as t-butylcumyl peroxide and dicumyl peroxide, and t-butyl peroxide.
• Peroxyesters such as -2-ethylhexanoate, t-butylperoxylaurate, and t-butylperoxybenzoate, hydroperoxides such as cumenehydroperoxide, paramentanhydroperoxide, and t-butylperoxybenzoate. And so on.
• These organic peroxides can be used alone or in combination of two or more.
• an acid group-containing (meth) acrylate resin having high photosensitivity and excellent alkali developability and capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity can be obtained. Oxyesters are preferred.
• the amount of the polymerization initiator used may be an amount that allows the polymerization to proceed smoothly, but with respect to a total of 100 parts by mass of the polymerization component containing the compound (a1) and the compound (a2).
• the range of 0.1 to 20 parts by mass is preferable, and the range of 0.5 to 10 parts by mass is more preferable.
• the compound (B) has a functional group capable of reacting with the reactive functional group derived from the compound (a2) of the copolymer (A).
• Examples of the compound (B) include the same compounds as those exemplified as the above-mentioned compound (a2), but when a compound having a hydroxyl group and a (meth) acryloyl group is used as the compound (a2).
• a compound having an isocyanate group and (meth) acryloyl group and / or a compound having an alkoxy group and (meth) acrylamide group is preferably used, and as compound (a2), an epoxy group and (meth) acryloyl are used.
• a compound having a group it is preferable to use a compound having a carboxyl group and a (meth) acryloyl group as the compound (B), and a compound having an isocyanate group and a (meth) acryloyl group as the compound (a2).
• a compound having a hydroxyl group and a (meth) acryloyl group it is preferable to use a compound having a hydroxyl group and a (meth) acryloyl group as the compound (B), and when using a compound having a carboxyl group and a (meth) acryloyl group as the compound (a2), it is preferable to use a compound having a hydroxyl group and a (meth) acryloyl group.
• a compound having an epoxy group and a (meth) acryloyl group as the compound (B), and when a compound having an alkoxy group and a (meth) acrylamide group is used as the compound (a2), the compound (B) is used. It is preferable to use a compound having a hydroxyl group and a (meth) acryloyl group.
• These compounds (B) can be used alone or in combination of two or more. Further, among these, an acid group-containing (meth) acrylate resin having high light sensitivity and excellent alkali developability and capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity can be obtained. It is preferable to use a compound having an epoxy group and a (meth) acryloyl group as the compound (a2), and a compound having a carboxyl group and a (meth) acryloyl group as the compound (B).
• polybasic acid anhydride (C) examples include saturated polybasic acid anhydride and unsaturated polybasic acid anhydride.
• the saturated polybasic acid anhydride means a polybasic acid anhydride having no carbon-carbon double bond
• unsaturated polybasic acid anhydride means a carbon-carbon double bond. It means a polybasic acid anhydride having.
• saturated polybasic acid anhydride examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, 1,2,3,4-butanetetracarboxylic acid.
• Examples of the unsaturated polybasic acid anhydride include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, tetrahydrophthalic acid, phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid and naphthalenetricarboxylic acid.
• Naphthalene tetracarboxylic acid biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, 4- (2,5-dioxotetracarboxylic acid) -1,2,3,4-tetrahydronaphthalene
• acids such as -1,2-dicarboxylic acid.
• polybasic acid anhydrides can be used alone or in combination of two or more. Further, among these, an acid group-containing (meth) acrylate resin having high light sensitivity and excellent alkali developability and capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity can be obtained. , Saturated polybasic acid anhydride is preferable, and saturated polybasic acid anhydride having an alicyclic structure is more preferable.
• the acid group-containing (meth) acrylate resin of the present invention has high photosensitivity and excellent alkali developability, and can form a cured product having excellent heat resistance, heat yellowing, and reflectivity.
• the total content of the polymer (A), the compound (B) and the polybasic acid anhydride (C) is preferably 90% by mass or more, preferably 95% by mass or more in the acid group-containing (meth) acrylate resin. Is more preferable.
• the acid group-containing (meth) acrylate resin of the present invention may further contain a compound (D) having a phenolic hydroxyl group and a tert-butyl group as a raw material thereof, if necessary.
• Examples of the compound (D) include tert-butylcatechol, tert-butylhydroquinone, tert-butylresorcin, 2,5-di-tert-amylhydroquinone, tert-butyl-p-benzoquinone, and 2,6-di-.
• the content of the compound (D) is preferably in the range of 0.01 to 10% by mass, more preferably in the range of 0.01 to 5% by mass in the acid group-containing (meth) acrylate resin.
• the double bond equivalent of the acid group-containing (meth) acrylate resin of the present invention has high photosensitivity and excellent alkali developability, and can form a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity. Therefore, 500 or less is preferable, and 450 or less is more preferable.
• the method for producing the acid group-containing (meth) acrylate resin of the present invention is not particularly limited, and any method may be used for producing the acid group-containing (meth) acrylate resin.
• it may be produced by the method ⁇ Method 1> in which all the raw materials containing the copolymer (A), the compound (B), and the polybasic acid anhydride (C) are reacted at once. Then, it may be produced by the method ⁇ method 2> in which the raw materials are sequentially reacted.
• a reaction raw material containing the copolymer (A), the compound (B), and the polybasic acid anhydride (C) is used in the presence of a basic catalyst or an acidic catalyst.
• a basic catalyst or an acidic catalyst examples thereof include a method obtained by reacting at 50 to 150 ° C.
• Examples of the basic catalyst include N-methylmorpholin, pyridine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), and 1,5-diazabicyclo [4.3.0] nonen-. 5 (DBN), 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1 -Methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, 3-( Amine compounds such as 2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl
• phosphine compounds such as trimethylphosphine, tributylphosphine, triphenylphosphine; tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl (2-hydroxylpropyl) phosphonium chloride , Triphenylphosphonium chloride, phosphonium salts such as benzylphosphonium chloride; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, 1 , 1,3,3-Tetrabutyl-1,3-Dodecan
• the acidic catalyst examples include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. And so on. These acidic catalysts can be used alone or in combination of two or more.
• the amount of the basic catalyst or the acidic catalyst used in the method 1 is 100 parts by mass of the total mass of the copolymer (A), the compound (B), and the polybasic acid anhydride (C).
• the range of 0.01 to 5 parts by mass is preferable.
• the copolymer (A) and the compound (B) are reacted in advance at 70 to 140 ° C. in the presence of a basic catalyst or an acidic catalyst to obtain a reaction product (I).
• a method obtained by reacting the reaction product (I) with the polybasic acid anhydride (C) at 70 to 140 ° C. in the presence of a basic catalyst or an acidic catalyst can be mentioned.
• the same catalyst as those exemplified as the above-mentioned basic catalyst can be used.
• These basic catalysts can be used alone or in combination of two or more.
• the same ones as those exemplified as the above-mentioned acidic catalyst can be used. These acidic catalysts can be used alone or in combination of two or more.
• the amount of the basic catalyst or the acidic catalyst used in the reaction of the copolymer (A) and the compound (B) of the method 2 is the total mass of the copolymer (A) and the compound (B) of 100 mass.
• the range of 0.01 to 5 parts by mass is preferable with respect to the part.
• the amount of the basic catalyst or the acidic catalyst used in the reaction of the reaction product (I) and the polybasic acid anhydride (C) is the amount of the reaction product (I) and the polybasic acid anhydride (C). ) Is preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass.
• the catalyst used in the reaction is a phosphorus-based catalyst such as a phosphine compound or a phosphonium salt. Is preferable, and a phosphine compound is more preferable.
• phosphine compound the same compound as those exemplified as the above-mentioned phosphine compound can be used.
• these phosphine compounds can be used alone or in combination of two or more.
• phosphonium salt the same ones as those exemplified as the above-mentioned phosphonium salt can be used.
• these phosphonium salts can be used alone or in combination of two or more.
• the ratio of the copolymer (A) to the compound (B) used is 1 mol of the reactive functional group of the copolymer (A).
• the compound (B) is preferably in the range of 0.9 to 1.1 mol, more preferably in the range of 0.95 to 1.05.
• the ratio of the copolymer (A) to the heavy polybasic anhydride (C) is determined by the copolymer (A).
• the polybasic acid anhydride (C) is preferably in the range of 0.25 to 0.95 mol, more preferably in the range of 0.3 to 0.9 with respect to 1 mol of the reactive functional group having.
• the acid group-containing (meth) acrylate resin of the present invention a polymerization inhibitor, an antioxidant or the like can be used in addition to the compound (D), if necessary.
• polymerization inhibitor examples include p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3- (N).
• -Salicyloyl amino-1,2,4-triazole, N'1, N'12-bis (2-hydroxybenzoyl) dodecandihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine , 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinone and other phenolic compounds, hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy- Quinone compounds such as 1,4-naphthoquinone, anthraquinone, diphenoquinone, melamine, p-phenylenediamine, 4-aminodiphenylamine, N.
• N'-diphenyl-p-phenylenediamine Ni-propyl-N'-phenyl-p-phenylenediamine, N- (1.3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, diphenylamine, 4 , 4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly (2,2,4-trimethyl-1,2-dihydroquinoline), styrene diphenylamine, styrene diphenylamine and 2,4,4-trimethyl Penten reaction products, amine compounds such as diphenylamine and 2,4,4-trimethylpenten reaction products, phenothiazine, distearylthiodipropionate, 2,2-bis ( ⁇ [3- (dodecylthio) propionyl] oxy ⁇ Methyl) -1,3-propanediyl-bis [3- (
• the same compounds as those exemplified in the polymerization inhibitor can be used, and the antioxidant may be used alone or in combination of two or more.
• Examples of commercially available products of the polymerization inhibitor and the antioxidant include “Q-1300” and “Q-1301” manufactured by Wako Pure Chemical Industries, Ltd. and “Sumilyzer BBM-S” manufactured by Sumitomo Chemical Industries, Ltd. , “Smilizer GA-80” and the like.
• the acid group-containing (meth) acrylate resin of the present invention can be used as a curable resin composition by adding a photopolymerization initiator.
• photopolymerization initiator examples include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2-. Hydroxy-2-methyl-1-propane-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, diphenyl (2,4,6-trimethoxybenzoyl) phosphenyl Oxide, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphenyl oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone and the like can be mentioned.
• Examples of commercially available products of the other photopolymerization initiator include “Omnirad-1173”, “Omnirad-184", “Omnirad-127”, “Omnirad-2959”, “Omnirad-369”, and “Omnirad-379".
• the amount of the photopolymerization initiator added is preferably in the range of 0.5 to 20% by mass in the curable resin composition, for example.
• the curable resin composition of the present invention may contain a resin component (hereinafter, may be referred to as "other resin component") other than the acid group-containing (meth) acrylate resin described above.
• other resin component include resins having an acid group and a polymerizable unsaturated group, various (meth) acrylate monomers, and the like.
• the resin having an acid group and a polymerizable unsaturated group may be any resin having an acid group and a polymerizable unsaturated group in the resin, for example, an epoxy resin having an acid group and a polymerizable unsaturated group.
• Urethane resin having an acid group and a polymerizable unsaturated group acrylic resin having an acid group and a polymerizable unsaturated group, an amidoimide resin having an acid group and a polymerizable unsaturated group, having an acid group and a polymerizable unsaturated group.
• examples thereof include an acrylamide resin, an ester resin having an acid group and a polymerizable unsaturated group.
• Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.
• Examples of the epoxy resin having an acid group and a polymerizable unsaturated group include an acid group-containing epoxy (meth) acrylate resin containing an epoxy resin, an unsaturated monobasic acid, and a polybasic acid anhydride as essential raw materials.
• Examples thereof include epoxy resins, unsaturated monobasic acids, polybasic acid anhydrides, polyisocyanate compounds, and acid group- and urethane group-containing epoxy (meth) acrylate resins using a hydroxyl group-containing (meth) acrylate compound as a reaction raw material.
• epoxy resin examples include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin.
• Bisphenol novolac type epoxy resin Bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-shrink novolak type epoxy resin, naphthol-cresol co-shrink novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Examples thereof include reactive epoxy resin, biphenylaralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, and oxazolidone type epoxy resin. These epoxy resins can be used alone or in combination of two or more.
• bisphenol type epoxy resin examples include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy. Examples include resin.
• Examples of the hydrogenated bisphenol type epoxy resin include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy resin. Examples include resin.
• biphenol type epoxy resin examples include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, and tetramethyl-2,2'.
• -Biphenol type epoxy resin and the like can be mentioned.
• hydrogenated biphenol type epoxy resin examples include hydrogenated 4,4'-biphenol type epoxy resin, hydrogenated 2,2'-biphenol type epoxy resin, and hydrogenated tetramethyl-4,4'-biphenol type epoxy resin. , Hydrophobic tetramethyl-2,2'-biphenol type epoxy resin and the like.
• Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, ⁇ -cyanocinnamic acid, ⁇ -styrylacrylic acid, ⁇ -flufurylacrylic acid and the like. Further, an esterified product of the unsaturated monobasic acid, an acid halide, an acid anhydride and the like can also be used. Further, a compound represented by the following structural formula (1) can also be used.
• X represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly) ester chain, an aromatic hydrocarbon chain, or a (poly) carbonate chain, and a halogen atom in the structure. Or an alkoxy group or the like.
• Y is a hydrogen atom or a methyl group.
• polyoxyalkylene chain examples include a polyoxyethylene chain and a polyoxypropylene chain.
• Examples of the (poly) ester chain include a (poly) ester chain represented by the following structural formula (X-1).
• R 1 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.
• aromatic hydrocarbon chain examples include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, and a binaphthylene chain.
• a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring can also be used.
• polybasic acid anhydride the same ones as those exemplified as the above-mentioned polybasic acid anhydride (C) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. It can also be used together.
• polyisocyanate compound examples include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornan diisocyanate and isophorone diisocyanate.
• Alicyclic diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalenedisocyanate, 4,4'-diisocyanato-3 , 3'-Aromatic diisocyanate compounds such as dimethylbiphenyl and o-trizine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (2); these isocyanurate modified products, biuret modified products, Examples thereof include a modified allophanate. Further, these polyisocyanate compounds may be used alone or in combination of two or more.
• R 1 is independently either a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
• R 2 is either an alkyl group having 1 to 4 carbon atoms independently, or a bond point connected to a structural site represented by the structural formula (2) via a methylene group marked with *.
• l is an integer of 0 or 1 to 3
• m is an integer of 1 to 15.
• hydroxyl group-containing (meth) acrylate compound the same compounds as those exemplified as the above-mentioned compounds having a hydroxyl group and a (meth) acryloyl group can be used, and the hydroxyl group-containing (meth) acrylate compound is used alone. It is also possible to use two or more kinds together.
• the method for producing the epoxy resin having the acid group and the polymerizable unsaturated group is not particularly limited, and any method may be used for producing the epoxy resin.
• it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.
• organic solvent examples include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; toluene, xylene and solvent.
• ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide and methyl isobutyl ketone
• cyclic ether solvents such as tetrahydrofuran and dioxolane
• ester solvents such as methyl acetate, ethyl acetate and butyl acetate
• toluene, xylene and solvent examples of the organic solvent.
• Aromatic solvents such as naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol and propylene glycol monomethyl ether; alkylene glycol monoalkyl ethers and dialkylene glycol monoalkyl ethers.
• Glycol ether solvent such as dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and the like.
• These organic solvents can be used alone or in combination of two or more. Further, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials because the reaction efficiency is good.
• the same catalyst as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst can be used alone or in combination of two or more.
• Examples of the urethane resin having an acid group and a polymerizable unsaturated group include a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound, a carboxyl group-containing polyol compound, and if necessary, a polybasic acid anhydride and the carboxyl group. It is obtained by reacting with a polyol compound other than the contained polyol compound, or by reacting with a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound, a polybasic acid anhydride, and a polyol compound other than the carboxyl group-containing polyol compound. The ones obtained from the above can be mentioned.
• polyisocyanate compound the same compound as those exemplified as the above-mentioned polyisocyanate compound can be used, and the polyisocyanate compound may be used alone or in combination of two or more.
• hydroxyl group-containing (meth) acrylate compound the same compounds as those exemplified as the above-mentioned compounds having a hydroxyl group and a (meth) acryloyl group can be used, and the hydroxyl group-containing (meth) acrylate compound is used alone. It is also possible to use two or more kinds together.
• carboxyl group-containing polyol compound examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolpropane valeric acid.
• the carboxyl group-containing polyol compound may be used alone or in combination of two or more.
• polybasic acid anhydride the same ones as those exemplified as the above-mentioned polybasic acid anhydride (C) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. It can also be used together.
• polyol compound other than the carboxyl group-containing polyol compound examples include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; Aromatic polyol compounds such as biphenols and bisphenols; (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains are included in the molecular structures of the various polyol compounds.
• aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and
• polystyrene resin a lactone modified product in which a (poly) lactone structure is introduced into the molecular structure of the various polyol compounds
• the polyol compounds other than the carboxyl group-containing polyol compound may be used alone or in combination of two or more.
• the method for producing the urethane resin having the acid group and the polymerizable unsaturated group is not particularly limited, and any method may be used for producing the urethane resin.
• it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.
• organic solvent the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.
• the same catalyst as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst can be used alone or in combination of two or more.
• the acrylic resin having an acid group and a polymerizable unsaturated group for example, a (meth) acrylate compound ( ⁇ ) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group or a glycidyl group is polymerized as an essential component.
• examples thereof include a product and a product obtained by reacting a hydroxyl group in the reaction product with a polybasic acid anhydride.
• the acrylic resin intermediate may be a copolymer of the (meth) acrylate compound ( ⁇ ) and other polymerizable unsaturated group-containing compounds, if necessary.
• the other polymerizable unsaturated group-containing compound is, for example, (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
• Acrylic acid alkyl ester alicyclic structure-containing (meth) acrylate such as cyclohexyl (meth) acrylate, isobolonyl (meth) acrylate, dicyclopentanyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxy
• Aromatic ring-containing (meth) acrylates such as ethyl acrylate; silyl group-containing (meth) acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, ⁇ -methylstyrene and chlorostyrene can be mentioned. These can be used alone or in combination of two or more.
• the (meth) acrylate compound ( ⁇ ) is not particularly limited as long as it can react with the reactive functional group of the (meth) acrylate compound ( ⁇ ), but the combination is as follows from the viewpoint of reactivity. Is preferable. That is, when a hydroxyl group-containing (meth) acrylate is used as the (meth) acrylate compound ( ⁇ ), it is preferable to use an isocyanate group-containing (meth) acrylate as the (meth) acrylate compound ( ⁇ ).
• the (meth) acrylate compound ( ⁇ ) When a glycidyl group-containing (meth) acrylate is used as the (meth) acrylate compound ( ⁇ ), it is preferable to use a carboxyl group-containing (meth) acrylate as the (meth) acrylate compound ( ⁇ ).
• the (meth) acrylate compound ( ⁇ ) can be used alone or in combination of two or more.
• polybasic acid anhydride the same ones as those exemplified as the above-mentioned polybasic acid anhydride (C) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. You can also do it.
• the method for producing the acrylic resin having the acid group and the polymerizable unsaturated group is not particularly limited, and any method may be used for producing the acrylic resin.
• it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.
• organic solvent the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.
• the same catalyst as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst can be used alone or in combination of two or more.
• Examples of the amideimide resin having an acid group and a polymerizable unsaturated group include an amideimide resin having an acid group and / or an acid anhydride group, a hydroxyl group-containing (meth) acrylate compound and / or an epoxy group-containing (meth) acrylate.
• Examples thereof are those obtained by reacting a compound with a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group, if necessary. Be done.
• the compound having a reactive functional group may or may not have a (meth) acryloyl group.
• the amideimide resin may have either an acid group or an acid anhydride group, or may have both. From the viewpoint of reactivity with a hydroxyl group-containing (meth) acrylate compound and a (meth) acryloyl group-containing epoxy compound and reaction control, it is preferable that the compound has an acid anhydride group, and both the acid group and the acid anhydride group are used. It is more preferable that the compound has.
• the solid acid value of the amideimide resin is preferably in the range of 60 to 350 mgKOH / g under neutral conditions, that is, under conditions where the acid anhydride group is not opened.
• the measured value under the condition that the acid anhydride group is opened is preferably in the range of 61 to 360 mgKOH / g.
• amidoimide resin examples include those obtained by using a polyisocyanate compound and a polybasic acid anhydride as reaction raw materials.
• polyisocyanate compound the same compound as those exemplified as the above-mentioned polyisocyanate compound can be used, and the polyisocyanate compound may be used alone or in combination of two or more.
• polybasic acid anhydride the same ones as those exemplified as the above-mentioned polybasic acid anhydride (C) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. It can also be used together.
• a polybasic acid can be used as a reaction raw material in addition to the polyisocyanate compound and the polybasic acid anhydride, if necessary.
• any compound having two or more carboxyl groups in one molecule can be used.
• Phthalic acid methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo [2.2.1] heptane- 2,3-Dicarboxylic acid, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, 4- (2,5-dioxo tetrahydrofuran-3-yl) -1,2,3,4-tetrahydro Naphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenylt
• polybasic acid for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used.
• polybasic acids can be used alone or in combination of two or more.
• hydroxyl group-containing (meth) acrylate compound the same compounds as those exemplified as the above-mentioned compounds having a hydroxyl group and a (meth) acryloyl group can be used, and the hydroxyl group-containing (meth) acrylate compound is used alone. It is also possible to use two or more kinds together.
• epoxy group-containing (meth) acrylate compound the same compounds as those exemplified as the above-mentioned compounds having an epoxy group and a (meth) acryloyl group can be used, and the epoxy group-containing (meth) acrylate compound can be used. It can be used alone or in combination of two or more.
• the method for producing the amidoimide resin having the acid group and the polymerizable unsaturated group is not particularly limited, and any method may be used for producing the amidimide resin.
• the amidoimide resin having an acid group and a polymerizable unsaturated group it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.
• organic solvent the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.
• the same catalyst as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst can be used alone or in combination of two or more.
• Examples of the acrylamide resin having an acid group and a polymerizable unsaturated group include a phenolic hydroxyl group-containing compound, an alkylene oxide or an alkylene carbonate, an N-alkoxyalkyl (meth) acrylamide compound, and a polybasic acid anhydride. Examples thereof include those obtained by reacting with an unsaturated monobasic acid as needed.
• the compound having a phenolic hydroxyl group means a compound having at least one phenolic hydroxyl group in the molecule.
• Examples of the compound having at least one phenolic hydroxyl group in the molecule include compounds represented by the following general formulas (3-1) to (3-4).
• R 1 is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom.
• R 2 are independently hydrogen atoms or methyl groups.
• p is an integer of 0 or 1 or more, preferably an integer of 0 or 1 to 3, and more preferably 0 or 1 of 1.
• q is an integer of 1 or more, preferably 2 or 3.
• the position of the substituent on the aromatic ring in the above general formula is arbitrary. For example, in the naphthalene ring of the general formula (3-2), it may be substituted on any ring, and the general formula (3-2) may be substituted.
• Examples of the compound having a phenolic hydroxyl group include a compound having at least one phenolic hydroxyl group in the molecule and a compound represented by any of the following general formulas (x-1) to (x-5).
• a reaction product or the like using the above as an essential reaction raw material can also be used.
• a novolak type phenol resin or the like using one or more compounds having at least one phenolic hydroxyl group in the molecule as a reaction raw material can also be used.
• h is 0 or 1.
• R 3 is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom, and i. Is 0 or an integer from 1 to 4.
• Z is any one of a vinyl group, a halomethyl group, a hydroxymethyl group and an alkyloxymethyl group.
• Y is any of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group, and j is an integer of 1 to 4.
• phenolic hydroxyl group-containing compounds can be used alone or in combination of two or more.
• alkylene oxide examples include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide.
• ethylene oxide or propylene can be obtained because a curable resin composition having high photosensitivity and excellent alkali developability and capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity can be obtained.
• Oxide is preferred.
• the alkylene oxide may be used alone or in combination of two or more.
• alkylene carbonate examples include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate.
• ethylene carbonate or propylene can be obtained because a curable resin composition having high photosensitivity and excellent alkali developability and capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity can be obtained.
• Carbonate is preferred.
• the alkylene carbonate can be used alone or in combination of two or more.
• N-alkoxyalkyl (meth) acrylamide compound examples include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and N-methoxyethyl (meth) acrylamide. , N-ethoxyethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide and the like.
• the N-alkoxyalkyl (meth) acrylamide compound may be used alone or in combination of two or more.
• polybasic acid anhydride the same ones as those exemplified as the above-mentioned polybasic acid anhydride (C) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. It can also be used together.
• unsaturated monobasic acid the same as those exemplified as the above-mentioned unsaturated monobasic acid can be used, and the unsaturated monobasic acid can be used alone or in combination of two or more. ..
• the method for producing the acrylamide resin having the acid group and the polymerizable unsaturated group is not particularly limited, and any method may be used for producing the acrylamide resin.
• the acrylamide resin having an acid group and a polymerizable unsaturated group it may be carried out in an organic solvent if necessary, or a basic catalyst and an acidic catalyst may be used if necessary.
• organic solvent the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.
• the same catalyst as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst can be used alone or in combination of two or more.
• the same ones as those exemplified as the above-mentioned acidic catalyst can be used, and the acidic catalyst can be used alone or in combination of two or more.
• the ester resin having an acid group and a polymerizable unsaturated group is obtained by reacting, for example, a phenolic hydroxyl group-containing compound, an alkylene oxide or an alkylene carbonate, an unsaturated monobasic acid, and a polybasic acid anhydride.
• a phenolic hydroxyl group-containing compound for example, an alkylene oxide or an alkylene carbonate, an unsaturated monobasic acid, and a polybasic acid anhydride.
• the same compounds as those exemplified as the above-mentioned phenolic hydroxyl group-containing compound can be used, and the phenolic hydroxyl group-containing compound may be used alone or in combination of two or more. You can also.
• alkylene oxide the same ones as those exemplified as the above-mentioned alkylene oxide can be used.
• ethylene oxide or propylene can be obtained because a curable resin composition having high photosensitivity and excellent alkali developability and capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity can be obtained.
• Oxide is preferred.
• the alkylene oxide may be used alone or in combination of two or more.
• alkylene carbonate the same ones as those exemplified as the above-mentioned alkylene carbonate can be used.
• ethylene carbonate or propylene can be obtained because a curable resin composition having high photosensitivity and excellent alkali developability and capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity can be obtained.
• Carbonate is preferred.
• the alkylene carbonate can be used alone or in combination of two or more.
• unsaturated monobasic acid the same as those exemplified as the above-mentioned unsaturated monobasic acid can be used, and the unsaturated monobasic acid can be used alone or in combination of two or more. ..
• polybasic acid anhydride the same ones as those exemplified as the above-mentioned polybasic acid anhydride (C) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. It can also be used together.
• the method for producing the ester resin having the acid group and the polymerizable unsaturated group is not particularly limited, and any method may be used for producing the ester resin.
• the ester resin having an acid group and a polymerizable unsaturated group it may be carried out in an organic solvent if necessary, or a basic catalyst and an acidic catalyst may be used if necessary.
• organic solvent the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.
• the same catalyst as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst can be used alone or in combination of two or more.
• the same ones as those exemplified as the above-mentioned acidic catalyst can be used, and the acidic catalyst can be used alone or in combination of two or more.
• the amount of the resin having an acid group and a polymerizable unsaturated group is preferably in the range of 10 to 900 parts by mass with respect to 100 parts by mass of the acid group-containing (meth) acrylate resin of the present invention.
• Examples of the various (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) acrylate, 2 -Alipid mono (meth) acrylate compounds such as ethylhexyl (meth) acrylate and octyl (meth) acrylate; alicyclic mono (meth) such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate.
• Acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, phenylbenzyl (meth) acrylate, phenoxy (meth) acrylate, Aromatic mono (meth) such as phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, and phenylphenoxyethyl (meth) acrylate.
• heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate
• benzyl (meth) acrylate phenyl (meth) acrylate, phenylbenzyl (meth
• Mono (meth) acrylate compounds such as acrylate compounds: Polyoxy such as (poly) oxyethylene chain, (poly) oxypropylene chain, and (poly) oxytetramethylene chain in the molecular structure of the various mono (meth) acrylate monomers.
• An aliphatic di (meth) acrylate compound such as glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate; 1,4-Cyclohexanedimethanol di (meth) acrylate, norbornandi (meth) acrylate, norbornan dimethanol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, etc.
• a chain-introduced polyoxyalkylene-modified di (meth) acrylate compound a lactone-modified di (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the various di (meth) acrylate compounds;
• An aliphatic tri (meth) acrylate compound such as (meth) acrylate and glycerin tri (meth) acrylate; a (poly) oxyethylene chain, a (poly) oxypropylene chain, etc. in the molecular structure of the aliphatic tri (meth) acrylate compound.
• a (meth) acrylate monomer in addition to the above-mentioned one, a (meth) acrylate monomer containing a phenol compound, a cyclic carbonate compound or a cyclic ether compound, and an unsaturated monocarboxylic acid as essential reaction raw materials. Can be used.
• phenolic compound examples include cresol, xylenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, 1,2,3-trihydroxybenzene, 1,2,4-.
• Trihydroxybenzene 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, hydrogenated bisphenol, hydrogenated biphenol, polyphenylene ether
• examples thereof include type diols, polynaphthylene ether type diols, phenol novolac resins, cresol novolac resins, bisphenol novolac type resins, naphthol novolac type resins, phenol aralkyl type resins, naphthol aralkyl type resins, cycloring structure-containing phenol resins and the like.
• cyclic carbonate compound examples include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. These cyclic carbonate compounds may be used alone or in combination of two or more.
• cyclic ether compound examples include ethylene oxide, propylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used alone or in combination of two or more.
• the same one as exemplified as the unsaturated monocarboxylic acid described above can be used.
• the content of the other (meth) acrylate monomer is preferably 90% by mass or less in the curable resin composition of the present invention.
• the curable resin composition of the present invention contains, if necessary, a curing agent, a curing accelerator, an ultraviolet absorber, an organic solvent, an inorganic filler, polymer fine particles, a pigment, a defoaming agent, a viscosity modifier, and leveling. It can also contain various additives such as an agent, a flame retardant, and a storage stabilizer.
• curing agent examples include polybasic acids, unsaturated monobasic acids, amine compounds, amide compounds, azo compounds, organic peroxides, polyol compounds, epoxy resins and the like.
• polybasic acid examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid.
• Tetrahydrophthalic acid Tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo [2 .2.1] Heptane-2,3-dicarboxylic acid, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, 4- (2,5-dioxotetra-3-yl) -1, 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid,
• polybasic acid for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used.
• polybasic acids can be used alone or in combination of two or more.
• the same ones as those exemplified as the above-mentioned unsaturated monobasic acid can be used, and the unsaturated monobasic acid may be used alone or in combination of two or more. You can also.
• amine compound examples include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivative and the like. These amine compounds can be used alone or in combination of two or more.
• amide compound examples include a polyamide resin synthesized from a dimer of dicyandiamide and linolenic acid and ethylenediamine. These amide compounds may be used alone or in combination of two or more.
• azo compound examples include azobisisobutyronitrile.
• organic peroxide examples include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, alkylperoxycarbonates and the like. These organic peroxides can be used alone or in combination of two or more.
• polyol compound examples include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1, 5-Pentanediol, Neopentylglycol, 1,6-hexanediol, Glycerin, Glycerin mono (meth) acrylate, Trimethylol ether, Trimethylolmethane mono (meth) acrylate, Trimethylolpropane, Trimethylolpropane mono (meth) acrylate , Pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate and other polyol monomers; , Hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, polyester polyol obtained by
• the same ones as those exemplified as the above-mentioned epoxy resin can be used, and the epoxy resin can be used alone or in combination of two or more.
• the curing accelerator promotes the curing reaction, and examples thereof include phosphorus compounds, amine compounds, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. These curing accelerators can be used alone or in combination of two or more.
• the amount of the curing accelerator added is preferably in the range of 0.01 to 10% by mass in the solid content of the curable resin composition, for example.
• UV absorber examples include 2- [4- ⁇ (2-hydroxy-3-dodecyloxypropyl) oxy ⁇ -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1. , 3,5-Triazine, 2- [4- ⁇ (2-Hydroxy-3-tridecyloxypropyl) oxy ⁇ -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, Triazine derivatives such as 3,5-triazine, 2- (2'-xanthencarboxy-5'-methylphenyl) benzotriazole, 2- (2'-o-nitrobenzyloxy-5'-methylphenyl) benzotriazole, 2 Examples thereof include -xanthenecarboxy-4-dodecyloxybenzophenone and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These UV absorbers can be used alone or in combination of two or more.
• organic solvent the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.
• examples of the inorganic filler include molten silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide and the like.
• pigment known and commonly used inorganic pigments and organic pigments can be used.
• inorganic pigment examples include white pigment, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, prussian blue, ultramarine, carbon black, graphite and the like. These inorganic pigments can be used alone or in combination of two or more.
• white pigment examples include titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide. And so on.
• organic pigments examples include quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanslon pigments, flavanthron pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, and the like.
• organic pigments examples include quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments. These organic pigments can be used alone or in combination of two or more.
• the flame retardant examples include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphate such as ammonium polyphosphate, and inorganic phosphorus compounds such as phosphoric acid amide; phosphoric acid ester compounds and phosphorus compounds.
• Organophosphorus compounds such as phosphorus compounds and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds and phenothiazine; silicone oils, silicone rubbers, Silicone-based flame retardants such as silicone resins; examples thereof include metal hydroxides, metal oxides, metal carbonate compounds, metal powders,
• the cured product of the present invention can be obtained by irradiating the curable resin composition with active energy rays.
• active energy ray include ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
• ultraviolet rays When ultraviolet rays are used as the active energy rays, they may be irradiated in an atmosphere of an inert gas such as nitrogen gas or in an air atmosphere in order to efficiently carry out the curing reaction by ultraviolet rays.
• an ultraviolet lamp is generally used from the viewpoint of practicality and economy. Specific examples thereof include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.
• Integrated light quantity of the active energy ray is not particularly limited, preferably from 0.1 ⁇ 50kJ / m 2, more preferably 0.5 ⁇ 10kJ / m 2.
• the integrated light amount is in the above range, it is preferable because the generation of the uncured portion can be prevented or suppressed.
• the irradiation of the active energy rays may be performed in one step or may be divided into two or more steps.
• the cured product of the present invention has high light sensitivity and excellent alkali developability, and has excellent heat resistance and heat-resistant yellowing, for example, a solder resist, an interlayer insulating material, and a package in semiconductor device applications. It can be suitably used as a package adhesive layer for materials, underfill materials, circuit elements, etc., and as an adhesive layer between an integrated circuit element and a circuit board. Further, it can be suitably used as a thin film transistor protective film, a liquid crystal color filter protective film, a color filter pigment resist, a black matrix resist, a spacer and the like in thin display applications typified by LCDs and OELDs. Among these, it can be particularly preferably used for solder resist applications.
• the resin material for solder resist of the present invention comprises the curable resin composition.
• the resist member of the present invention is, for example, a photomask in which the resin material for solder resist is applied onto a substrate, an organic solvent is volatile-dried in a temperature range of about 60 to 100 ° C., and then a desired pattern is formed. It can be obtained by exposing the unexposed portion with an alkaline aqueous solution, developing the unexposed portion with an alkaline aqueous solution, and further heating and curing the unexposed portion in a temperature range of about 140 to 200 ° C.
• Examples of the base material include metal foils such as copper foil and aluminum foil.
• the weight average molecular weight (Mw) is a value measured under the following conditions using a gel permission chromatograph (GPC).
• Example 1 Production of acid group-containing acrylate resin (1)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (1) is 58.6% by mass, the solid acid value is 82 mgKOH / g, the weight average molecular weight (Mw) is 22,470, and the double.
• the binding equivalent was 345.
• the double bond equivalent is a calculated value calculated from the amount of raw materials charged. Further, with respect to 1 mol of the epoxy group contained in the acrylic copolymer (A1) corresponding to the copolymer (A) specified in the present invention, the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 2 Production of acid group-containing acrylate resin (2)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (2) is 58.6% by mass, the solid acid value is 81 mgKOH / g, the weight average molecular weight (Mw) is 22,550, and the double.
• the binding equivalent was 345.
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 3 Production of acid group-containing acrylate resin (3)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (3) is 58.6% by mass, the solid acid value is 83 mgKOH / g, the weight average molecular weight (Mw) is 22,590, and the double.
• the binding equivalent was 345.
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 4 Production of acid group-containing acrylate resin (4)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (4) is 58.6% by mass, the solid acid value is 82 mgKOH / g, the weight average molecular weight (Mw) is 22,410, and the double.
• the binding equivalent was 345.
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 5 Production of acid group-containing acrylate resin (5)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (5) is 58.6% by mass, the solid acid value is 81 mgKOH / g, the weight average molecular weight (Mw) is 22,620, and the double.
• the binding equivalent was 345.
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 6 Production of acid group-containing acrylate resin (6)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (6) is 58.6% by mass, the solid acid value is 83 mgKOH / g, the weight average molecular weight (Mw) is 22,550, and the double.
• the binding equivalent was 345.
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 7 Production of acid group-containing acrylate resin (7)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• 72 parts by mass of glycidyl methacrylate, 18 parts by mass of methyl methacrylate, 10 parts by mass of benzyl methacrylate, 55.6 parts by mass of diethylene glycol monoethyl ether acetate, and 5 parts by mass of azobisisobutyronitrile were mixed in advance and over 3 hours. Dropped. Hold at 120 ° C.
• acrylic copolymer (A7) 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 parts by mass of triphenylphosphine were charged, and air was blown into the mixture, and the mixture was stirred at 120 ° C. for 10 parts. Reacted for time. Next, 38.3 parts by mass of hexahydroisobenzofuran-1,3-dione was added and reacted at 110 ° C. for 5 hours to obtain the desired acid group-containing acrylate resin (7).
• the non-volatile content of the acid group-containing acrylate resin (7) is 58.6% by mass, the solid acid value is 82 mgKOH / g, the weight average molecular weight (Mw) is 23,120, and the double.
• the binding equivalent was 345.
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 8 Production of acid group-containing acrylate resin (8)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (8) is 58.6% by mass, the solid acid value is 84 mgKOH / g, the weight average molecular weight (Mw) is 77,530, and the double.
• the binding equivalent was 345.
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 9 Production of acid group-containing acrylate resin (9)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (9) is 58.6% by mass, the solid acid value is 83 mgKOH / g, the weight average molecular weight (Mw) is 21,770, and the double.
• the binding equivalent was 345.
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 10 Production of acid group-containing acrylate resin (10)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (10) is 58.5% by mass, the solid acid value is 84 mgKOH / g, the weight average molecular weight (Mw) is 22,830, and the double.
• the binding equivalent was 344.
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 11 Production of acid group-containing acrylate resin (11) 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the binding equivalent was 345. Further, with respect to 1 mol of the epoxy group contained in the acrylic copolymer (A11) corresponding to the copolymer (A) specified in the present invention, the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the acrylic copolymer (A11) corresponding to the copolymer (A) specified in the present invention. The number of moles of succinic anhydride was 0.45 mol.
• Example 12 Production of acid group-containing acrylate resin (12)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• pentaerythritol tetrakis [3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] 0.5 parts by mass, methylhydroquinone 0.1 parts by mass, acrylic acid 36.5 parts by mass.
• a part, 0.6 parts by mass of triphenylphosphine was charged, and the reaction was carried out at 120 ° C. for 10 hours while blowing air and stirring.
• 38.3 parts by mass of hexahydroisobenzofuran-1,3-dione was added and reacted at 110 ° C. for 5 hours to obtain the desired acid group-containing acrylate resin (12).
• the non-volatile content of the acid group-containing acrylate resin (12) is 58.6% by mass, the solid acid value is 82 mgKOH / g, the weight average molecular weight (Mw) is 22,590, and the double.
• the binding equivalent was 345.
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 13 Production of acid group-containing acrylate resin (13) 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (13) is 58.6% by mass, the solid acid value is 83 mgKOH / g, the weight average molecular weight (Mw) is 22,720, and the double.
• the binding equivalent was 345.
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 14 Production of acid group-containing acrylate resin (14) 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (14) is 58.6% by mass, the solid acid value is 82 mgKOH / g, the weight average molecular weight (Mw) is 23,080, and the double.
• the binding equivalent was 345.
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 15 Production of acid group-containing acrylate resin (15)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (15) is 55.8% by mass, the solid acid value is 83 mgKOH / g, the weight average molecular weight (Mw) is 23,450, and the double.
• the binding equivalent was 319.
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 16 Production of acid group-containing acrylate resin (16)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (16) is 54.8% by mass, the solid acid value is 82 mgKOH / g, the weight average molecular weight (Mw) is 23,950, and the double.
• the binding equivalent was 293. Further, with respect to 1 mol of the epoxy group contained in the acrylic copolymer (A16) corresponding to the copolymer (A) specified in the present invention, the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 17 Production of acid group-containing acrylate resin (17)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (17) is 54.8% by mass, the solid acid value is 73 mgKOH / g, the weight average molecular weight (Mw) is 32,460, and the double.
• the binding equivalent was 382. Further, with respect to 1 mol of the epoxy group contained in the acrylic copolymer (A17) corresponding to the copolymer (A) specified in the present invention, the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 0.88.
• Example 18 Production of acid group-containing acrylate resin (18)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (18) is 59.1% by mass, the solid acid value is 90 mgKOH / g, the weight average molecular weight (Mw) is 20,330, and the double.
• the binding equivalent was 318.
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used.
• the number of moles was 1.11.
• Example 19 Production of acid group-containing acrylate resin (19)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of this acid group-containing acrylate resin (19) is 56.2% by mass, the solid acid value is 84 mgKOH / g, the weight average molecular weight (Mw) is 18,730, and the double.
• the binding equivalent was 489. Further, with respect to 1 mol of the epoxy group contained in the acrylic copolymer (A19) corresponding to the copolymer (A) specified in the present invention, the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 20 Production of acid group-containing acrylate resin (20)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of this acid group-containing acrylate resin (20) is 56% by mass, the solid content acid value is 85 mgKOH / g, the weight average molecular weight (Mw) is 17,210, and the double bond equivalent.
• Mw weight average molecular weight
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 21 Production of acid group-containing acrylate resin (21)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (21) is 64.2% by mass, the solid acid value is 85 mgKOH / g, the weight average molecular weight (Mw) is 21,250, and the double.
• the binding equivalent was 438.
• acrylic acid corresponding to the compound (B) specified in the present invention and acrylic acid corresponding to the compound (B) specified in the present invention and The total number of moles of the ⁇ -carboxy-polycaprolactone monoacrylate was 1.0.
• Example 22 Production of acid group-containing acrylate resin (22) 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (22) is 56.6% by mass, the solid acid value is 57 mgKOH / g, the weight average molecular weight (Mw) is 19,470, and the double.
• the binding equivalent was 317.
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 23 Production of acid group-containing acrylate resin (23) 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (23) is 54.8% by mass, the solid acid value is 117 mgKOH / g, the weight average molecular weight (Mw) is 23,510, and the double.
• the binding equivalent was 408. Further, with respect to 1 mol of the epoxy group contained in the acrylic copolymer (A23) corresponding to the copolymer (A) specified in the present invention, the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 24 Production of acid group-containing acrylate resin (24) 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of this acid group-containing acrylate resin (24) is 55.7% by mass, the solid acid value is 47 mgKOH / g, the weight average molecular weight (Mw) is 18,550, and the double.
• the binding equivalent was 306. Further, with respect to 1 mol of the epoxy group contained in the acrylic copolymer (A24) corresponding to the copolymer (A) specified in the present invention, the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 25 Production of acid group-containing acrylate resin (25) 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of this acid group-containing acrylate resin (25) is 54.8% by mass, the solid acid value is 134 mgKOH / g, the weight average molecular weight (Mw) is 23,510, and the double.
• the binding equivalent was 417.
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 26 Production of acid group-containing acrylate resin (26) 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of this acid group-containing acrylate resin (26) is 54.8% by mass, the solid acid value is 85 mgKOH / g, the weight average molecular weight (Mw) is 24,120, and the double.
• the bound equivalent was 305.
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0.
• Example 27 Production of acid group-containing acrylate resin (27)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used.
• the number of moles was 1.0.
• the number of moles of hexahydroisobenzofuran-1,3-dione was 0.49 mol.
• Example 28 Production of acid group-containing acrylate resin (28)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (28) is 57.5% by mass
• the solid acid value is 62 mgKOH / g
• the weight average molecular weight (Mw) is 16,890
• the double was 299. Further, with respect to 1 mol of the epoxy group contained in the acrylic copolymer (A28) corresponding to the copolymer (A) specified in the present invention, the acrylic acid corresponding to the compound (B) specified in the present invention can be used.
• the number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the acrylic copolymer (A28) corresponding to the copolymer (A) specified in the present invention.
• the number of moles of hexahydroisobenzofuran-1,3-dione was 0.32 mol.
• Example 29 Production of acid group-containing acrylate resin (29) 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the acrylic acid corresponding to the compound (B) specified in the present invention can be used.
• the number of moles was 1.0.
• the number of moles of 3-methyl-8-oxabicyclo [4.3.0] nonane-7,9-dione was 0.33 mol.
• Example 30 Production of acid group-containing acrylate resin (30)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• acrylic acid corresponding to the compound (B) specified in the present invention and acrylic acid corresponding to the compound (B) specified in the present invention and The total number of moles of the ⁇ -carboxy-polycaprolactone monoacrylate was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the acrylic copolymer (A30) corresponding to the copolymer (A) specified in the present invention. The number of moles of 3-methyl-8-oxabicyclo [4.3.0] nonane-7,9-dione was 0.42 mol.
• Example 31 Production of acid group-containing acrylate resin (31)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing acrylate resin (31) is 63.4% by mass, the solid acid value is 64 mgKOH / g, the weight average molecular weight (Mw) is 19,830, and the double.
• the binding equivalent was 454.
• acrylic acid corresponding to the compound (B) specified in the present invention and acrylic acid corresponding to the compound (B) specified in the present invention and The total number of moles of the ⁇ -carboxy-polycaprolactone monoacrylate was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the acrylic copolymer (A31) corresponding to the copolymer (A) specified in the present invention. The number of moles of 3-methyl-8-oxabicyclo [4.3.0] nonane-7,9-dione was 0.49 mol.
• Example 32 Production of acid group-containing methacrylate resin (1)
• 66.7 parts by mass of cyclohexanone was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• 60 parts by mass of methacrylic acid, 30 parts by mass of methyl methacrylate, 10 parts by mass of benzyl methacrylate, 55.6 parts by mass of cyclohexanone, and (2-ethylhexanoyl) (tert-butyl) peroxide ("Perbutyl O” manufactured by Nippon Oil & Fats Co., Ltd.
• the non-volatile content of the acid group-containing methacrylate resin (1) is 54.8% by mass
• the solid acid value is 102 mgKOH / g
• the weight average molecular weight (Mw) is 47,680
• the binding equivalent was 385.
• Example 33 Production of acid group-containing methacrylate resin (2)
• 66.7 parts by mass of diethylene glycol monoethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere.
• the non-volatile content of the acid group-containing methacrylate resin (2) is 59.8% by mass, the solid acid value is 82 mgKOH / g, the weight average molecular weight (Mw) is 20,790, and the double.
• the binding equivalent was 362. Further, for 1 mol of the epoxy group contained in the acrylic copolymer (A33) corresponding to the copolymer (A) specified in the present invention, methacrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0.
• a time esterification reaction was carried out. Then, 311 parts by mass of diethylene glycol monoethyl ether acetate and 160 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain the desired acid group-containing epoxy acrylate resin (1).
• the solid acid value of the acid group-containing epoxy acrylate resin (1) was 85 mgKOH / g.
• the non-volatile content of this acid group-containing acrylate resin (R1) is 58.6% by mass, the solid acid value is 82 mgKOH / g, the weight average molecular weight (Mw) is 21,210, and the double.
• the binding equivalent was 345.
• the non-volatile content of this acid group-containing acrylate resin (R2) is 58.6% by mass, the solid acid value is 83 mgKOH / g, the weight average molecular weight (Mw) is 25,210, and the double.
• the binding equivalent was 345.
• Example 34 Preparation of curable resin composition (1)
• 100 parts by mass of the acid group-containing acrylate resin (1) having a non-volatile content of 58.6% by mass obtained in Example 1 and a bisphenol A type epoxy resin (“EPICLON 850S” manufactured by DIC Co., Ltd., epoxy equivalent: 188 g / Equivalent) 16.1 parts by mass
• photopolymerizable initiator (“Omnirad 907” manufactured by IGM) 2.9 parts by mass
• 2-ethyl-4-methyl-imidazole 0.32 parts by mass and 0.35 parts by mass of titanium oxide (“R-820” manufactured by Ishihara Sangyo Co., Ltd.) were mixed to obtain a curable resin composition (1).
• Example 35 to 67 Preparation of curable resin compositions (2) to (34)
• the acid group-containing acrylate resins (2) to (31) obtained in Examples 2-33, the acid group-containing methacrylate resin (1) and (2). was used in the blending amounts shown in Tables 1 to 3, and curable resin compositions (2) to (34) were obtained in the same manner as in Example 34.
• Comparative Example 4 Preparation of curable resin composition (R2)
• the acid group-containing acrylate resin (R2) obtained in Comparative Example 2 was used in the blending amount shown in Table 2 instead of the acid group-containing acrylate resin (R1) used in Comparative Example 3.
• a curable resin composition (R2) was obtained.
• Table 1 shows the compositions and evaluation results of the curable resin compositions (1) to (34) prepared in Examples 34 to 67, and the curable resin compositions (R1) and (R2) prepared in Comparative Examples 3 and 4. Shown in 3 to 3.
• Example 68 Preparation of curable resin composition (35)
• Examples 69 to 101 Preparation of curable resin compositions (36) to (68)
• the acid group-containing acrylate resins (2) to (31) obtained in Examples 2-33, the acid group-containing methacrylate resin (1) and (2). was used in the blending amounts shown in Tables 4 to 6, and curable resin compositions (36) to (68) were obtained in the same manner as in Example 69.
• a 6 mm ⁇ 35 mm test piece was cut out from the cured product, and a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by Leometric Co., Ltd., tensile method: frequency 1 Hz, heating rate 3 ° C./min) was used.
• the temperature at which the change in viscoelasticity was maximized was evaluated as the glass transition temperature according to the following criteria. The higher the glass transition temperature, the better the heat resistance.
• Tg The glass transition temperature
• B Tg was 125 ° C. or higher and lower than 130 ° C.
• C Tg was 120 ° C. or higher and lower than 125 ° C.
• D Tg was 115 ° C. or higher and lower than 120 ° C.
• E Tg was less than 115 ° C.
• compositions and evaluation results of the curable resin compositions (35) to (68) obtained in Examples 68 to 101, and the curable resin compositions (R3) and (R4) obtained in Comparative Examples 5 and 6 are shown. It is shown in Tables 4-6.
• “Curing agent” in Tables 1 to 6 indicates a bisphenol A type epoxy resin (“EPICLON 850S” manufactured by DIC Corporation, epoxy equivalent: 188 g / equivalent).
• Examples 34 to 101 shown in Tables 1 to 6 are examples using the acid group-containing (meth) acrylate resin of the present invention.
• the cured product of the curable resin composition containing the acid group-containing (meth) acrylate resin of the present invention has a balance of light sensitivity and alkali developability, as well as heat resistance, heat-resistant yellowing and reflectivity of the obtained cured product. It was confirmed that they were well equipped.
• Comparative Examples 3 and 5 are examples in which the methacrylate compound (a1) having an aromatic ring specified in the present invention is not used. It was confirmed that this curable resin composition did not have both light sensitivity and alkali developability, as well as heat resistance, heat-resistant yellowing and reflectivity in the obtained cured product.
• Comparative Examples 4 and 6 are examples in which an acrylate compound having an aromatic ring is used instead of the methacrylate compound (a1) having an aromatic ring specified in the present invention. It was confirmed that this curable resin composition did not have both light sensitivity and alkali developability, as well as heat resistance, heat-resistant yellowing and reflectivity in the obtained cured product, as in Comparative Examples 3 and 5. ..

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