WO2020129666A1 - Résine (méth)acrylique contenant un groupe acide, composition de résine durcissable, produit durci, matériau isolant, matériau de résine pour réserves de soudure et élément de réserve - Google Patents

Résine (méth)acrylique contenant un groupe acide, composition de résine durcissable, produit durci, matériau isolant, matériau de résine pour réserves de soudure et élément de réserve Download PDF

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Publication number
WO2020129666A1
WO2020129666A1 PCT/JP2019/047582 JP2019047582W WO2020129666A1 WO 2020129666 A1 WO2020129666 A1 WO 2020129666A1 JP 2019047582 W JP2019047582 W JP 2019047582W WO 2020129666 A1 WO2020129666 A1 WO 2020129666A1
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meth
acid
acrylate
group
mass
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PCT/JP2019/047582
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English (en)
Japanese (ja)
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駿介 山田
裕美子 中村
亀山　裕史
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Dic株式会社
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Priority to JP2020537670A priority Critical patent/JP6797354B2/ja
Publication of WO2020129666A1 publication Critical patent/WO2020129666A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/14—Polyamide-imides

Definitions

  • the present invention has an acid group-containing (meth)acrylate resin having excellent alkali developability and excellent heat resistance in a cured product, a curable resin composition containing the same, and an insulation comprising the curable resin composition.
  • the present invention relates to a material, a resin material for a solder resist, and a resist member.
  • acid group-containing epoxy acrylate resins obtained by reacting an acid anhydride after acrylate conversion of epoxy resin with acrylic acid are widely used as resin materials for solder resists for printed wiring boards.
  • the required properties for the resin material for the solder resist are that it cures with a small exposure amount, has excellent alkali developability, and has excellent heat resistance and strength in the cured product, flexibility, elongation, dielectric properties, substrate adhesion, etc. And so on.
  • solder resist resin materials include active energy ray-curable products obtained by reacting a reaction product of a novolac type epoxy resin and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride.
  • a resin is known (for example, refer to Patent Document 1 below)
  • the heat resistance of the cured product does not satisfy the ever-increasing required properties and is not sufficient for the recent market demand. ..
  • the problem to be solved by the present invention is an acid group-containing (meth)acrylate resin having excellent alkali developability and excellent heat resistance in a cured product, a curable resin composition containing the same, and the curable resin.
  • An object is to provide an insulating material, a resin material for a solder resist, and a resist member made of the composition.
  • the present inventors have at least one amide bond, at least one imide bond, at least one ester bond, and at least one (meta ) It was found that the above problems can be solved by using an acid group-containing (meth)acrylate resin having an acryloyl group and at least one acid group, and completed the present invention.
  • the present invention has at least one amide bond, at least one imide bond, at least one ester bond, at least one (meth)acryloyl group, and at least one acid group.
  • the acid group-containing (meth)acrylate resin of the present invention has excellent alkali developability, and also has excellent heat resistance in a cured product, so that it can be used as an insulating material, a resin material for solder resist and a resist member. It can be preferably used.
  • the acid group-containing (meth)acrylate resin of the present invention has at least one amide bond, at least one imide bond, at least one ester bond, and at least one (meth)acryloyl group. However, it has at least one acid group.
  • (meth)acrylate means acrylate and/or methacrylate.
  • (meth)acryloyl means acryloyl and/or methacryloyl.
  • (meth)acrylic means acrylic and/or methacrylic.
  • the acid group-containing (meth)acrylate resin of the present invention has at least one amide bond, at least one imide bond, at least one ester bond, at least one (meth)acryloyl group, and at least one acid group.
  • the specific structure and manufacturing method are not particularly limited, and various materials can be used.
  • Examples of the acid group-containing (meth)acrylate resin having at least one amide bond, at least one imide bond, at least one ester bond, at least one (meth)acryloyl group, and at least one acid group include the following: Examples include structural formula (1), the following structural formula (2), the following structural formula (3), the following structural formula (4), and the following structural formula (5).
  • ring A is independently a benzene ring or a cyclo ring
  • X is any of (x-1) to (x-16)
  • Y is --OR 1 or *--X--Z, wherein Z is represented by the following structural formula (z-1) or (z-2), and R 1 is each independently And any one of the following structural formulas (1-1) to (1-9), and R 2 is any of the following structural formulas (2-1) to (2-9).
  • "*" in the said Y shows the bonding point with a carbon atom.
  • the ring A is a benzene ring or a cyclo ring
  • R 1 is any one of the following structural formulas (1-1) to (1-9)
  • R 2 is Is any one of the following structural formulas (2-1) to (2-9).
  • “*” indicates the point of attachment to the carbon atom.
  • the ring A is a benzene ring or a cyclo ring
  • R 1 is any one of the following structural formulas (1-1) to (1-9).
  • “*” indicates the point of attachment to the carbon atom.
  • R 3's each independently represent a hydrogen atom or a methyl group
  • R 4's independently represent the following structural formulas (1-a)- It is either represented by (1-z).
  • m is 1 or 2.
  • "*" in a formula shows the bond point with an oxygen atom.
  • each R 5 is independently a hydrogen atom or a methyl group, and l is an integer of 1 to 10.
  • "*" shows the bonding point with an oxygen atom.
  • the ring A is each independently a benzene ring or a cyclo ring
  • X is any one of the structural formulas (x-1) to (x-16)
  • Z is represented by the structural formula (z-1) or (z-2)
  • R 1 is any of the structural formulas (1-1) to (1-9). Yes. ]
  • each ring A is independently a benzene ring or a cyclo ring
  • each X is independently represented by the structural formulas (x-1) to (x-16).
  • Z is one of the structural formulas (z-1) and (z-2), and R 1 is one of the structural formulas (1-1) to (1-9).
  • R 2 is any one of the following structural formulas (2-1) to (2-9). ]
  • each ring A is independently a benzene ring or a cyclo ring
  • each X is independently represented by the structural formulas (x-1) to (x-16).
  • Y is each independently represented by —OR 1 or *—X—Z
  • Z is represented by the structural formula (z-1) or (z-2) above.
  • P is any of the following structural formulas (p-1) to (p-7)
  • R 1 in the Y is the structural formulas (1-1) to (1- It is any one of 9).
  • "*" in the said Y shows the bonding point with a carbon atom.
  • at least one of the Zs is represented by the structural formula (z-2). ]
  • R 6's each independently represent a hydrogen atom or a methyl group.
  • "*" shows the bonding point with an oxygen atom.
  • each ring A is independently a benzene ring or a cyclo ring
  • each X is independently represented by the structural formulas (x-1) to (x-16).
  • Y is each independently represented by —OR 1 or *—X—Z
  • Z is represented by the structural formula (z-1) or (z-2) above.
  • W is any of (w-1) to (w-4)
  • R 1 in Y is the structural formula (1-1) to (1-9). Is either represented.
  • "*" in the said Y shows the bonding point with a carbon atom.
  • at least one of the Zs is represented by the structural formula (z-2). ]
  • R 7's each independently represent a hydrogen atom or a methyl group.
  • "*" shows the bonding point with an oxygen atom.
  • R 1 since an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent alkali developability and excellent heat resistance is obtained, (1-1), (1 -3) and (1-5) are preferable.
  • R 2 since an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent alkali developability and excellent heat resistance is obtained, (2-1), (2 -2), (2-3), (2-4), (2-5), (2-6) and (2-7) are preferable.
  • Examples of the acid group-containing (meth)acrylate resin of the present invention include an amideimide resin (A) having an acid group and/or an acid anhydride group, a hydroxyl group-containing (meth)acrylate resin (B), and an epoxy group-containing (meth).
  • amideimide resin (A) having an acid group and/or an acid anhydride group a hydroxyl group-containing (meth)acrylate resin (B), and an epoxy group-containing (meth).
  • C acrylate compound
  • D polycarboxylic acid anhydride
  • the amide-imide resin (A) may have either an acid group or an acid anhydride group, or may have both. Among them, it is preferable to have an acid anhydride group from the viewpoint of reactivity and reaction control with the hydroxyl group-containing (meth)acrylate compound (B) and the epoxy group-containing (meth)acrylate compound (C). It is preferable to have both an acid group and an acid anhydride group.
  • Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group and the like.
  • Examples of the acid anhydride group include a carboxylic acid anhydride group, a sulfonic acid anhydride group, and a phosphoric acid anhydride group.
  • the amide imide resin (A) is not particularly limited in its specific structure, and general amide imide resins and the like can be widely used.
  • the polyisocyanate compound (a1) and the polycarboxylic acid anhydride (a2) may be used as essential reaction raw materials.
  • polyisocyanate compound (a1) examples include, butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and other aliphatic diisocyanate compounds; norbornane diisocyanate, Alicyclic diisocyanate compounds such as isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'- Aromatic diisocyanate compounds such as diisocyanato-3,3'-dimethylbiphenyl and o-tolidine diisocyanate; polymethylene polyphenyl polyis
  • polyisocyanate compounds (a1) can be used alone or in combination of two or more kinds. These polyisocyanate compounds (a1) have excellent alkali developability and can give an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent heat resistance. Is preferred.
  • each R 1 is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
  • Each R 2 is independently an alkyl group having 1 to 4 carbon atoms, or a bonding point connecting the structural site represented by the structural formula (6) and the methylene group marked with *. is there. l is 0 or an integer of 1 to 3, and m is an integer of 1 to 15. ]
  • the alicyclic diisocyanate compound or its modified product is preferable, and the alicyclic diisocyanate is preferable, in terms of the acid group-containing (meth)acrylate resin having excellent solvent solubility.
  • the aliphatic diisocyanate compound or a modified product thereof is preferable in that an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent alkali developability and excellent heat resistance can be obtained.
  • Group diisocyanates are preferred.
  • the ratio of the total mass of the alicyclic diisocyanate compound or a modified product thereof and the aliphatic diisocyanate compound or a modified product thereof to the total mass of the polyisocyanate compound (a1) is preferably 70% by mass or more, It is more preferably 90 mass% or more.
  • the mass ratio of both is preferably in the range of 20/80 to 80/20.
  • polycarboxylic acid anhydride (a2) examples include aliphatic polycarboxylic acid anhydride, alicyclic polycarboxylic acid anhydride, aromatic polycarboxylic acid anhydride and the like.
  • aliphatic polycarboxylic acid anhydrides examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, and itacone.
  • examples thereof include acids, glutaconic acid, and acid anhydrides of 1,2,3,4-butanetetracarboxylic acid.
  • the aliphatic hydrocarbon group may be linear or branched and may have an unsaturated bond in the structure.
  • the acid anhydride group is bonded to the alicyclic structure as an alicyclic polycarboxylic acid anhydride, the aromatic ring of the other structural site It does not matter whether it is present or not.
  • Examples of the alicyclic polycarboxylic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic 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-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene- Examples thereof include acid anhydrides of 1,2-dicarboxylic acid.
  • aromatic polycarboxylic acid anhydrides examples include phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, Examples thereof include acid anhydrides of benzophenone tetracarboxylic acid.
  • polycarboxylic acid anhydrides (a2) can be used alone or in combination of two or more kinds. Further, among these, since an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent alkali developability and excellent heat resistance is obtained, the alicyclic polycarboxylic acid anhydride And the aromatic polycarboxylic acid anhydrides are preferable. In addition, since an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent alkali developability and excellent heat resistance is obtained, a carboxyl group and an acid anhydride group are included in the molecular structure.
  • the content of the tricarboxylic acid anhydride in the polycarboxylic acid anhydride (a2) is preferably 70% by mass or more, and more preferably 90% by mass or more.
  • the amide imide resin (A) if necessary, other compounds may be used in combination as a reaction raw material in addition to the polyisocyanate compound (a1) and the polycarboxylic acid anhydride (a2).
  • the other compound when used in combination, the effects of the present invention are sufficiently exhibited, and therefore, the polyisocyanate compound (a1) and the polycarboxylic acid anhydride (a2) in the reaction raw material of the amide imide resin (A) are sufficiently exhibited.
  • the total content of () is preferably 80% by mass or more, and more preferably 85% by mass.
  • Examples of the other compounds include polycarboxylic acid and the like.
  • any compound can be used as long as it is a compound having two or more carboxyl groups in one molecule.
  • oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydro 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-
  • polycarboxylic 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.
  • polycarboxylic acids can be used alone or in combination of two or more kinds.
  • the copolymer of the conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule is, for example, a butadiene-acrylonitrile copolymer represented by the following structural formula (7-1).
  • the position of the carboxyl group may be located on either the side chain or the terminal of the molecule, but the terminal is preferred.
  • X is an integer of 1 to 50
  • Y is an integer of 1 to 50
  • Z is an integer of 1 to 20.
  • X is an integer of 1 to 50
  • Y is an integer of 1 to 50
  • Z is an integer of 1 to 20.
  • the acid value of the amide-imide resin (A) is a neutral condition because an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent alkali developability and excellent heat resistance can be obtained.
  • the measurement value under the condition that the acid anhydride group is not ring-opened is preferably in the range of 60 to 350 mgKOH/g, and measured under the condition that the acid anhydride group is ring-opened, such as in the presence of water. It is preferable that the value is in the range of 61 to 360 mgKOH/g.
  • the acid value is a value measured by the neutralization titration method of JIS K0070 (1992).
  • the production method is not particularly limited, and may be produced by any method. May be.
  • it can be produced by a method similar to that of a general amide-imide resin.
  • 0.8 to 3.5 mol of the polycarboxylic acid anhydride (a2) is used with respect to 1 mol of the isocyanate group contained in the polyisocyanate compound (a1), and the temperature condition is about 100 to 180° C. The method of stirring and mixing under the reaction is mentioned.
  • the reaction may be carried out in an organic solvent if necessary, and 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, propylene glycol monomethyl ether; alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether And glycol ether solvents 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 kinds. 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 becomes good.
  • Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene- 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-amin
  • hydroxyl group-containing (meth)acrylate compound (B) other specific structures are not particularly limited as long as it is a compound having a hydroxyl group and a (meth)acryloyl group in the molecular structure, and various compounds can be used. it can. Examples thereof include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate.
  • 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 each of the various hydroxyl group-containing (meth)acrylate compounds.
  • a modified poly)oxyalkylene a modified lactone obtained by introducing a (poly)lactone structure into the molecular structure of each of the various hydroxyl group-containing (meth)acrylate compounds.
  • These hydroxyl group-containing (meth)acrylate compounds may be used alone or in combination of two or more.
  • a (meth)acrylate compound having one hydroxyl group is preferable because the reaction can be easily controlled.
  • These hydroxyl group-containing (meth)acrylate compounds (B) can be used alone or in combination of two or more kinds.
  • the hydroxyl group-containing (meth)acrylate compound (B) has a molecular weight of an acid group-containing (meth)acrylate resin having excellent alkali developability and capable of forming a cured product having excellent heat resistance. , 1,000 or less is preferable. Further, when the hydroxyl group-containing (meth)acrylate compound (B) is an oxyalkylene modified product or a lactone modified product, the weight average molecular weight (Mw) is preferably 1,000 or less.
  • epoxy group-containing (meth)acrylate compound (C) other specific structures are not particularly limited as long as it has a (meth)acryloyl group and an epoxy group in the molecular structure, and various compounds are used. be able to. Examples thereof include glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; dihydroxybenzene diglycidyl ether and dihydroxy.
  • Examples thereof include mono(meth)acrylate compounds of diglycidyl ether compounds such as naphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether.
  • These epoxy group-containing (meth)acrylate compounds may be used alone or in combination of two or more kinds.
  • a (meth)acrylate compound having one epoxy group is preferable because the reaction can be easily controlled, and a cured product having excellent alkali developability and excellent heat resistance can be formed.
  • a glycidyl group-containing (meth)acrylate monomer is preferable because an acid group-containing (meth)acrylate resin can be obtained.
  • the molecular weight of the glycidyl group-containing (meth)acrylate monomer is preferably 500 or less. Furthermore, the ratio of the glycidyl group-containing (meth)acrylate monomer to the total mass of the epoxy group-containing (meth)acrylate compound (C) is preferably 70% by mass or more, and more preferably 90% by mass or more. ..
  • the polycarboxylic acid anhydride (D) may be the same as the above-mentioned polycarboxylic acid anhydride (a2), and the polycarboxylic acid anhydride (D) may be used alone or in two kinds. The above can also be used together. Further, since an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent alkali developability and excellent heat resistance is obtained, it is possible to obtain an aliphatic polycarboxylic acid anhydride or an alicyclic polycarboxylic acid. Carboxylic acid anhydrides are preferable, and aliphatic dicarboxylic acid anhydrides or alicyclic dicarboxylic acid anhydrides are more preferable.
  • the acid group-containing (meth)acrylate resin is the amide-imide resin (A), the hydroxyl group-containing (meth)acrylate compound (B), the epoxy group-containing (meth)acrylate compound (C) depending on desired resin performance and the like. ) And the polycarboxylic acid anhydride (D), other reaction raw materials may be used together.
  • the ratio of the total mass of the components (A) to (D) to the total mass of the reaction raw materials of the acid group-containing amide imide (meth)acrylate resin is 80% by mass. It is preferably not less than 90%, more preferably not less than 90% by mass.
  • 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.
  • an amide imide resin (A) having an acid group and/or an acid anhydride group a hydroxyl group-containing (meth)acrylate resin (B), an epoxy group-containing (meth)acrylate compound (C), and a polycarboxylic acid anhydride (D).
  • () is an essential reaction raw material, it may be produced by a method of reacting all of the reaction raw materials at once, or may be produced by a method of sequentially reacting the reaction raw materials.
  • the amide-imide resin (A) is reacted with the hydroxyl group-containing (meth)acrylate compound (B) (step 1), and the product of step 1 and the epoxy group-containing ( It is preferably produced by a method of reacting a (meth)acrylate compound (C) (step 2) and reacting the product of step 2 with the polycarboxylic acid anhydride (D) (step 3).
  • the step 1 is a reaction between the amide imide resin (A) and the hydroxyl group-containing (meth)acrylate compound (B).
  • the reaction is mainly the acid group and/or acid in the amide imide resin (A).
  • the anhydride group is reacted with the hydroxyl group in the hydroxyl group-containing (meth)acrylate compound (B). Since the hydroxyl group-containing (meth)acrylate compound (B) is particularly excellent in reactivity with the acid anhydride group, it is preferable that the amide imide resin (A) has an acid anhydride group as described above.
  • the content of the acid anhydride group in the amide imide resin (A) is the difference between the above-mentioned two measured values of the acid value, that is, the acid value under the condition where the acid anhydride group is ring-opened, It can be calculated from the difference from the acid value under the condition that the acid anhydride group is not opened.
  • the reaction ratio between the amide imide resin (A) and the hydroxyl group-containing (meth)acrylate compound (B) is such that when the amide imide resin (A) has an acid group and an acid anhydride group, and the amide imide resin (A) is When it has an acid anhydride group, the number of moles of the hydroxyl group of the hydroxyl group-containing (meth)acrylate compound (B) is 0.9 to 1.1 with respect to 1 mole of the acid anhydride group of the amide imide resin (A). It is preferable to use it within the range. When the amide imide resin (A) has an acid group, the number of moles of the hydroxyl group of the hydroxyl group-containing (meth)acrylate compound (B) is 0. 1 mole of the acid group of the amide imide resin (A). It is preferably used in the range of 1 to 0.5.
  • the reaction between the amide-imide resin (A) and the hydroxyl group-containing (meth)acrylate compound (B) is carried out, for example, by heating and stirring under a temperature condition of about 80 to 140° C. in the presence of a suitable esterification catalyst.
  • a suitable esterification catalyst include phosphorus compounds such as trimethylphosphine, tributylphosphine and triphenylphosphine, amine compounds such as triethylamine, tributylamine and dimethylbenzylamine, 2-methylimidazole, 2-heptadecylimidazole and 2-ethyl.
  • esterification catalysts can be used alone or in combination of two or more kinds.
  • the esterification catalyst is preferably added in an amount of 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of the reaction raw materials.
  • the reaction may be carried out in an organic solvent if necessary, and an acidic catalyst may be used if necessary.
  • the organic solvent the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.
  • the reaction may be continued as it is in the organic solvent used in the production of the amide imide resin (A).
  • 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, boron trifluoride, anhydrous aluminum chloride, Lewis acids such as zinc chloride. And so on. These acidic catalysts can be used alone or in combination of two or more kinds.
  • the step 2 is a reaction between the product of the step 1 and the epoxy group-containing (meth)acrylate compound (C).
  • the reaction is mainly to react the acid group in the product obtained in the step 1 with the epoxy group-containing (meth)acrylate compound.
  • the reaction ratio is such that the number of moles of the epoxy group contained in the epoxy group-containing (meth)acrylate compound (C) is 0.7 to 1.2 with respect to 1 mole of the acid group in the product obtained in step 1. It is preferable to use the above range, more preferably to the range of 0.9 to 1.1.
  • the reaction of step 2 can be carried out, for example, in the presence of a suitable esterification catalyst with heating and stirring under temperature conditions of about 90 to 140°C.
  • the esterification catalyst may not be added, or may be added appropriately. Further, the reaction may be carried out in an organic solvent, if necessary.
  • the esterification catalyst and the organic solvent may be the same as the above-mentioned esterification catalyst and the organic solvent, and they may be used alone or in combination of two or more kinds.
  • the step 3 is a reaction between the product of the step 2 and the polycarboxylic acid anhydride (D).
  • the reaction is mainly to react the hydroxyl group in the product obtained in the step 2 with the polycarboxylic acid anhydride (D).
  • a hydroxyl group generated by ring opening of the epoxy group in the epoxy group-containing (meth)acrylate compound (C) is present.
  • the reaction ratio of the polycarboxylic acid anhydride (D) is preferably adjusted so that the acid value of the product (meth)acrylate resin containing an acid group is about 60 to 120 mgKOH/g.
  • step 3 can be carried out, for example, in the presence of a suitable esterification catalyst while heating and stirring under a temperature condition of about 80 to 140°C.
  • the esterification catalyst may not be added, or may be added appropriately.
  • the reaction may be carried out in an organic solvent, if necessary.
  • the esterification catalyst and the organic solvent may be the same as the above-mentioned esterification catalyst and the organic solvent, and they may be used alone or in combination of two or more kinds.
  • the acid value of the acid group-containing (meth)acrylate resin of the present invention is such that an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent alkali developability and excellent heat resistance can be obtained. Therefore, the range of 50 to 120 mgKOH/g is preferable, and the range of 60 to 110 mgKOH/g is more preferable.
  • the acid value of the acid group-containing (meth)acrylate resin in the present invention is a value measured by the neutralization titration method of JIS K0070 (1992).
  • the weight average molecular weight (Mw) of the acid group-containing (meth)acrylate resin of the present invention is preferably in the range of 1,000 to 20,000.
  • a weight average molecular weight (Mw) shows the value measured by the gel permeation chromatography (GPC) method.
  • the acid group-containing (meth)acrylate resin of the present invention has a polymerizable (meth)acryloyl group in its molecular structure, it can be used as a curable resin composition by adding a photopolymerization initiator, for example. You can
  • the photopolymerization initiator may be appropriately selected and used depending on the type of active energy ray to be irradiated. Further, it may be used in combination with a photosensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound and a nitrile compound. Specific examples of the photopolymerization initiator include, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino).
  • Alkylphenone-based photopolymerization initiator such as 2-[[4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; 2,4,6-trimethylbenzoyl-diphenyl- Examples thereof include acylphosphine oxide-based photopolymerization initiators such as phosphine oxide; intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds. These may be used alone or in combination of two or more.
  • photopolymerization initiator examples include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2- Hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine Oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone and the like.
  • Examples of commercial products of the other photopolymerization initiators include “Omnirad-1173”, “Omnirad-184", “Omnirad-127”, “Omnirad-2959”, “Omnirad-369”, and “Omnirad-379”. , “Omnirad-907”, “Omnirad-4265”, “Omnirad-1000”, “Omnirad-651”, “Omnirad-TPO", “Omnirad-819", “Omnirad-2022”, “Omnirad-2100” and “Omnirad-2100".
  • Omnirad-754 "Omnirad-784", “Omnirad-500”, “Omnirad-81” (manufactured by IGM), "Kayacure-DETX”, “Kayacure-MBP”, “Kayacure-DMBI”, “Kayacure-EPA”.
  • photopolymerization initiators can be used alone or in combination of two or more kinds.
  • the amount of the photopolymerization initiator added is, for example, preferably in the range of 0.05 to 15% by mass, and in the range of 0.1 to 10% by mass, based on the total amount of the components other than the solvent of the curable resin composition. Is more preferable.
  • the curable resin composition of the present invention may contain other resin components other than the acid group-containing (meth)acrylate resin.
  • the other resin component include a resin (i) having an acid group and a polymerizable unsaturated bond, various (meth)acrylate monomers, and the like.
  • the resin (i) having an acid group and a polymerizable unsaturated bond may be any as long as it has an acid group and a polymerizable unsaturated bond in the resin, for example, an acid group and a polymerizable unsaturated bond Epoxy resin having, urethane resin having acid group and polymerizable unsaturated bond, acrylic resin having acid group and polymerizable unsaturated bond, amide imide resin having acid group and polymerizable unsaturated bond, acid group and polymerizable unsaturated Examples thereof include an acrylamide resin having a bond.
  • Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group and the like.
  • Examples of the epoxy resin having an acid group and a polymerizable unsaturated bond include, for example, an epoxy resin, an unsaturated monobasic acid, and an acid group-containing epoxy (meth)acrylate resin that uses polybasic acid anhydride as an essential 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, cresol novolac type epoxy resin, Bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-contracting novolac type epoxy resin, naphthol-cresol co-contracting novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition
  • examples thereof include reactive epoxy resins, biphenylaralkyl epoxy resins, fluorene epoxy resins, xanthene epoxy resins, dihydroxybenzene epoxy resins, trihydroxybenzene epoxy resins and the like. These epoxy resins can be used alone or in combination of two or more kinds.
  • the unsaturated monobasic acid means a compound having an acid group and a polymerizable unsaturated bond in one molecule.
  • the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and the like.
  • the unsaturated monobasic acid (D) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, ⁇ -cyanocinnamic acid, ⁇ -styrylacrylic acid and ⁇ -furfurylacrylic acid.
  • esterified products of unsaturated monobasic acids, acid halides, acid anhydrides and the like can also be used. These unsaturated monobasic acids can be used alone or in combination of two or more kinds.
  • polybasic acid anhydrides examples include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, and hexahydro.
  • examples thereof include phthalic anhydride, methylhexahydrophthalic anhydride, octenyl succinic anhydride and tetrapropenyl succinic anhydride.
  • These polybasic acid anhydrides can be used alone or in combination of two or more kinds. Further, among these, since a curable resin composition having excellent photosensitivity and alkali developability and capable of forming a cured product having excellent heat resistance is obtained, tetrahydrophthalic anhydride and succinic anhydride are preferable.
  • the same polyisocyanate compound (a1) as described above can be used as the polyisocyanate compound, and the polyisocyanate compound can be used alone or in combination of two or more kinds.
  • hydroxyl group-containing (meth)acrylate compound the same as the above-mentioned hydroxyl group-containing (meth)acrylate compound (B) can be used, and the hydroxyl group-containing (meth)acrylate compound may be used alone or in two kinds. The above can also be used together.
  • the method for producing the epoxy resin having the acid group and the polymerizable unsaturated bond is not particularly limited and may be produced by any method.
  • the production of the epoxy resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary.
  • organic solvent the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.
  • the same basic catalysts as described above can be used, and the basic catalyst can be used alone or in combination of two or more kinds.
  • the urethane resin having an acid group and a polymerizable unsaturated bond for example, a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound, a carboxyl group-containing polyol compound, and optionally a polybasic acid anhydride, the carboxyl group Those obtained by reacting with a polyol compound other than the containing polyol compound, 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 And the like.
  • the same polyisocyanate compound (a1) as described above can be used as the polyisocyanate compound, and the polyisocyanate compound can be used alone or in combination of two or more kinds.
  • hydroxyl group-containing (meth)acrylate compound the same as the above-mentioned hydroxyl group-containing (meth)acrylate compound (B) can be used, and the hydroxyl group-containing (meth)acrylate compound may be used alone or in two kinds. The above can also be used together.
  • carboxyl group-containing polyol compound examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid.
  • the carboxyl group-containing polyol compound may be used alone or in combination of two or more kinds.
  • polybasic acid anhydride the same polybasic acid anhydride as described above can be used, and the polybasic acid anhydride can be used alone or in combination of two or more kinds.
  • 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 biphenol and bisphenol; (Poly)oxyethylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains in the molecular structures of the various polyol compounds Modified (poly)oxyalkylene modified products; lactone modified products in which a (poly)lactone structure is introduced into the molecular structures of the various polyol compounds are included.
  • the polyol compounds other than the carboxyl group-containing polyol compound may be used alone or in combination of two or more kinds.
  • the method for producing the urethane resin having an acid group and a polymerizable unsaturated bond is not particularly limited and may be produced by any method.
  • the production of the urethane resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary.
  • organic solvent the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.
  • the same basic catalysts as described above can be used, and the basic catalyst can be used alone or in combination of two or more kinds.
  • the acrylic resin having an acid group and a polymerizable unsaturated bond for example, a (meth)acrylate compound ( ⁇ ) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, and a glycidyl group is polymerized as an essential component.
  • the acrylic resin intermediate may be a copolymer of the (meth)acrylate compound ( ⁇ ) and, if necessary, other polymerizable unsaturated group-containing compound.
  • the other polymerizable unsaturated group-containing compound include (meth)acrylates 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, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxy Examples thereof include 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. These may 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 contained in the (meth)acrylate compound ( ⁇ ), but from the viewpoint of reactivity, it is the following combination. Is preferred. That is, when a hydroxyl group-containing (meth)acrylate is used as the (meth)acrylate compound ( ⁇ ), an isocyanate group-containing (meth)acrylate is preferably used as the (meth)acrylate compound ( ⁇ ). When a carboxyl group-containing (meth)acrylate is used as the (meth)acrylate compound ( ⁇ ), it is preferable to use a glycidyl group-containing (meth)acrylate as the (meth)acrylate compound ( ⁇ ).
  • an isocyanate group-containing (meth)acrylate is used as the (meth)acrylate compound ( ⁇ )
  • a hydroxyl group-containing (meth)acrylate is preferably used as the (meth)acrylate compound ( ⁇ ).
  • a glycidyl group-containing (meth)acrylate is used as the (meth)acrylate compound ( ⁇ )
  • a carboxyl group-containing (meth)acrylate is preferably used as the (meth)acrylate compound ( ⁇ ).
  • the (meth)acrylate compound ( ⁇ ) can be used alone or in combination of two or more kinds.
  • polybasic acid anhydride the same polybasic acid anhydride as described above can be used, and the polybasic acid anhydride can be used alone or in combination of two or more kinds.
  • the method for producing the acrylic resin having an acid group and a polymerizable unsaturated bond is not particularly limited, and any method may be used.
  • the production of the acrylic resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary.
  • organic solvent the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.
  • the same basic catalysts as described above can be used, and the basic catalyst can be used alone or in combination of two or more kinds.
  • Examples of the amide imide resin having an acid group and a polymerizable unsaturated bond include an amide imide 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 include those obtained by reacting a compound with a compound having at least one reactive functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group.
  • the compound having a reactive functional group may or may not have a (meth)acryloyl group.
  • the amide-imide resin may have either an acid group or an acid anhydride group, or may have both. From the viewpoint of reactivity and reaction control with a hydroxyl group-containing (meth)acrylate compound or a (meth)acryloyl group-containing epoxy compound, it is preferable to have an acid anhydride group, and both an acid group and an acid anhydride group. It is more preferable to have The acid value of the amide-imide resin is preferably in the range of 60 to 350 mgKOH/g measured under neutral conditions, that is, under conditions where the acid anhydride group is not opened. On the other hand, the measured value under the condition that the acid anhydride group is ring-opened, such as in the presence of water, is preferably in the range of 61 to 360 mgKOH/g.
  • Examples of the amide-imide resin include those obtained by using a polyisocyanate compound and a polybasic acid anhydride as reaction raw materials.
  • the same polyisocyanate compound (a1) as described above can be used as the polyisocyanate compound, and the polyisocyanate compound can be used alone or in combination of two or more kinds.
  • polybasic acid anhydride the same polybasic acid anhydride as described above can be used, and the polybasic acid anhydride can be used alone or in combination of two or more kinds.
  • a polybasic acid may be used as a reaction raw material in combination with the amide-imide resin, if necessary.
  • any compound can be used as long as it is a compound having two or more carboxyl groups in one molecule.
  • oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydro 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,
  • 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.
  • These polybasic acids can be used alone or in combination of two or more kinds.
  • hydroxyl group-containing (meth)acrylate compound the same as the above-mentioned hydroxyl group-containing (meth)acrylate compound (B) can be used, and the hydroxyl group-containing (meth)acrylate compound may be used alone or in two kinds. The above can also be used together.
  • epoxy group-containing (meth)acrylate compound as the above-mentioned epoxy group-containing (meth)acrylate compound (C) can be used, and the epoxy group-containing (meth)acrylate compound can be used alone. It is also possible to use two or more kinds in combination.
  • the method for producing the amide-imide resin having the acid group and the polymerizable unsaturated bond is not particularly limited and may be produced by any method.
  • the amide-imide resin having an acid group and a polymerizable unsaturated bond may be produced in an organic solvent, if necessary, and a basic catalyst may be used, if necessary.
  • organic solvent the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.
  • the same basic catalysts as described above can be used, and the basic catalyst can be used alone or in combination of two or more kinds.
  • Examples of the acrylamide resin having an acid group and a polymerizable unsaturated bond include a phenolic hydroxyl group-containing compound, an alkylene oxide or 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, if necessary.
  • the above-mentioned phenolic hydroxyl group-containing compound means a compound having at least two phenolic hydroxyl groups in the molecule.
  • Examples of the compound having at least two phenolic hydroxyl groups in the molecule include compounds represented by the following structural formulas (8-1) to (8-4).
  • R 1 is any 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 each independently a hydrogen atom or a methyl group.
  • p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and further preferably 0.
  • q is an integer of 2 or more, preferably 2 or 3.
  • the position of the substituent on the aromatic ring in the above structural formula is arbitrary, and for example, in the naphthalene ring of the structural formula (8-2), the substituent may be substituted on any ring.
  • the ring may be substituted on any ring of the benzene ring present in one molecule, and in structural formula (8-4), it may be substituted on any ring of the benzene ring present in one molecule. It indicates that they may be substituted, and the number of substituents in one molecule is p and q.
  • phenolic hydroxyl group-containing compound for example, a compound having one phenolic hydroxyl group in the molecule and a compound represented by any of the following structural formulas (9-1) to (9-5) are essential.
  • An essential reaction between the reaction product used as the reaction raw material, the compound having at least two phenolic hydroxyl groups in the molecule, and the compound represented by any of the following structural formulas (9-1) to (9-5) A reaction product as a raw material can also be used.
  • a novolac type phenol resin using one or more compounds having one phenolic hydroxyl group in the molecule as a reaction raw material, and one or more compounds having at least two phenolic hydroxyl groups in the molecule It is also possible to use a novolac-type phenol resin as a reaction raw material.
  • h is 0 or 1.
  • R 3 is any 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 of 1 to 4.
  • Z is any 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.
  • Examples of the compound having one phenolic hydroxyl group in the molecule include compounds represented by the following structural formulas (2-1) to (2-4).
  • R 4 is any 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 5 are each independently a hydrogen atom or a methyl group.
  • p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and further preferably 0.
  • the position of the substituent on the aromatic ring in the above structural formula is arbitrary, and for example, in the naphthalene ring of the structural formula (10-2), the substituent may be substituted on any ring.
  • the ring may be substituted on any ring of the benzene ring present in one molecule, and in structural formula (10-4), the ring may be substituted on any ring of the benzene ring present in one molecule. It indicates that they may be replaced.
  • the compounds represented by the above structural formulas (8-1) to (8-4) can be used as the compound having at least two phenolic hydroxyl groups in the molecule.
  • phenolic hydroxyl group-containing compounds can be used alone or in combination of two or more kinds.
  • alkylene oxide examples include ethylene oxide, propylene oxide, butylene oxide, pentylene oxide and the like. Among these, ethylene oxide or propylene oxide is preferable because a curable resin composition having excellent alkali developability and capable of forming a cured product having excellent heat resistance can be obtained.
  • the alkylene oxides may be used alone or in combination of two or more.
  • alkylene carbonate examples include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate and the like.
  • ethylene carbonate or propylene carbonate is preferable because a curable resin composition having excellent alkali developability and capable of forming a cured product having excellent heat resistance can be obtained.
  • the alkylene carbonates may 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, N-methoxyethyl(meth)acrylamide. , N-ethoxyethyl (meth)acrylamide, N-butoxyethyl (meth)acrylamide and the like.
  • the N-alkoxyalkyl (meth)acrylamide compounds may be used alone or in combination of two or more.
  • polybasic acid anhydride the same polybasic acid anhydride as described above can be used, and the polybasic acid anhydride can be used alone or in combination of two or more kinds.
  • the unsaturated monobasic acid the same 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 kinds.
  • the method for producing the acrylamide resin having the acid group and the polymerizable unsaturated bond is not particularly limited and may be produced by any method.
  • the production of the acrylamide resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent, if necessary, and a basic catalyst and an acidic catalyst may be used, if necessary.
  • organic solvent the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.
  • the same basic catalysts as described above can be used, and the basic catalyst can be used alone or in combination of two or more kinds.
  • the same acidic catalyst as described above can be used, and the acidic catalyst can be used alone or in combination of two or more kinds.
  • the amount of the resin (i) having an acid group and a polymerizable unsaturated bond used 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, hexyl (meth)acrylate, 2 -Aliphatic mono(meth)acrylate compounds such as ethylhexyl(meth)acrylate and octyl(meth)acrylate; cycloaliphatic (meth)acrylate, isobornyl(meth)acrylate, adamantyl mono(meth)acrylate and other alicyclic mono(meth)acrylates Acrylate compounds; Heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)
  • (Meth)acrylate compounds such as aromatic mono(meth)acrylate compounds: (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxy in the molecular structure of the various mono(meth)acrylate monomers
  • An aliphatic poly(meth)acrylate compound of (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain, or the like in the molecular structure of the aliphatic poly(meth)acrylate compound A tetra- or higher functional (poly)oxyalkylene-modified poly(meth)acrylate compound having an oxyalkylene chain introduced; a tetra-functional or higher functional lactone having a (poly)lactone structure introduced into the molecular structure of the aliphatic poly(meth)acrylate compound Examples include modified poly(meth)acrylate compounds.
  • the various (meth)acrylate monomers may be used alone or in combination of two or more.
  • the curable resin composition of the present invention if necessary, a curing agent, a curing accelerator, an organic solvent, inorganic fine particles or polymer fine particles, a pigment, a defoaming agent, a viscosity modifier, a leveling agent, a flame retardant, It may also contain various additives such as a storage stabilizer.
  • Examples of the curing agent include epoxy resin.
  • Examples of the epoxy resin include, for example, 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, cresol novolac type epoxy resin.
  • Resin bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-contracting novolac type epoxy resin, naphthol-cresol co-contracting novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene- Examples thereof include phenol addition reaction type epoxy resin, biphenylaralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin and the like. These epoxy resins can be used alone or in combination of two or more kinds.
  • a curable resin composition having excellent alkali developability and capable of forming a cured product having excellent heat resistance and substrate adhesion since a curable resin composition having excellent alkali developability and capable of forming a cured product having excellent heat resistance and substrate adhesion, a phenol novolac type epoxy resin, Cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, and other novolac type epoxy resins are preferable, and the softening point is 20. Those in the range of to 120° C. are particularly preferable.
  • the curing accelerator is for promoting a curing reaction of the curing agent, and when an epoxy resin is used as the curing agent, a phosphorus compound, an amine compound, an imidazole, an organic acid metal salt, a Lewis acid, Examples thereof include amine complex salts. These curing accelerators can be used alone or in combination of two or more kinds. Further, the addition amount of the curing accelerator is preferably, for example, in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the curing agent.
  • organic solvent the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.
  • the cured product of the present invention can be obtained by irradiating the curable resin composition with an active energy ray.
  • the active energy rays include ionizing radiation such as ultraviolet rays, electron rays, ⁇ rays, ⁇ rays, and ⁇ rays.
  • the irradiation may be performed 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 the ultraviolet rays.
  • ultraviolet lamps are generally used from the viewpoint of practicality and economy. Specific examples thereof include a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, and an LED.
  • the cumulative light amount of the active energy rays is not particularly limited, but is preferably 10 to 5,000 mJ/cm 2 , and more preferably 50 to 1,000 mJ/cm 2 .
  • the integrated light amount is within the above range, it is possible to prevent or suppress the generation of an uncured portion, which is preferable.
  • the irradiation with the active energy rays may be performed in one step or in two or more steps.
  • the cured product of the present invention has excellent heat resistance, for example, in a semiconductor device application, a solder resist, an interlayer insulating material, a package material, an underfill material, a package adhesive layer such as a circuit element, or an integrated circuit. It can be suitably used as an adhesive layer between an 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 a thin display application represented by LCD and OELD. Among them, 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 on which a desired pattern is formed after applying the resin material for solder resist on a substrate and evaporating and drying an organic solvent in a temperature range of about 60 to 100°C. Through exposure with an active energy ray, the unexposed area is developed with an alkaline aqueous solution, and then heat-cured 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 acid value of the acid group-containing (meth)acrylate resin was measured by the neutralization titration method of JIS K0070 (1992).
  • the molecular weight of the acid group-containing (meth)acrylate resin was measured by GPC under the following conditions.
  • Measuring device "HLC-8220 GPC” manufactured by Tosoh Corporation, Column: Tosoh Co., Ltd. guard column “HXL-L” + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G3000HXL” manufactured by Tosoh Corporation + “TSK-GEL G4000HXL” manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: "GPC-8020 model II version 4.10" manufactured by Tosoh Corporation Measurement conditions: Column temperature 40°C Developing solvent Tetrahydrofuran Flow rate 1.0 ml/min Standard: The following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of “GPC-8020 Model II Version 4.10”.
  • the hydroxyl value of this pentaerythritol polyacrylate (A1) is 290 mgKOH/g
  • the content of pentaerythritol tetraacrylate (a1) calculated from the area ratio of the liquid chromatography chart is 16% by mass
  • the pentaerythritol triacrylate (a2) content is 50% by mass
  • the content of pentaerythritol diacrylate (a3) is 29% by mass
  • the content of pentaerythritol monoacrylate (a4) is 3% by mass
  • the content of the other high molecular weight component (a') is 2%. It was mass %.
  • the obtained aqueous layer was extracted with ethyl acetate and washed with a saturated aqueous solution of sodium hydrogen carbonate until the pH reached 7.
  • the organic layer was dehydrated with magnesium sulfate and then concentrated under reduced pressure at room temperature to obtain pentaerythritol diacrylate (A2).
  • dipentaerythritol acrylate (A3) was 140 mgKOH/g.
  • dipentaerythritol tetraacrylate (b1) calculated from the area ratio of the liquid chromatography chart is 28% by mass
  • the content of dipentaerythritol pentaacrylate (b2) is 42% by mass
  • dipentaerythritol hexaacrylate is 28% by mass
  • the content of (b3) was 22% by mass
  • the content of the high molecular weight component (b') was 8% by mass.
  • Example 1 Production of acid group-containing (meth)acrylate resin (1)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 276 parts by mass of diethylene glycol monomethyl ether acetate, 214 parts by mass of isophorone diisocyanate, 277 parts by mass of trimellitic anhydride, and 1.9 parts by mass of dibutylhydroxytoluene were added and dissolved.
  • the reaction was carried out at 160° C. for 5 hours in a nitrogen atmosphere, and it was confirmed that the isocyanate group content was 0.1% by mass or less.
  • hydroxyl group-containing ( It is abbreviated as "(meth)acrylate compound (1).) 85 parts by mass and 3.9 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours while blowing air. Then, 138 parts by mass of glycidyl methacrylate was added and reacted at 110° C. for 5 hours.
  • Example 2 Production of acid group-containing (meth)acrylate resin (2)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 211 parts by mass of diethylene glycol monomethyl ether acetate, 111 parts by mass of isophorone diisocyanate, 144 parts by mass of trimellitic anhydride, and 0.7 parts by mass of dibutylhydroxytoluene were added and dissolved.
  • the reaction was carried out at 160° C. for 5 hours in a nitrogen atmosphere, and it was confirmed that the isocyanate group content was 0.1% by mass or less.
  • Example 3 Production of acid group-containing (meth)acrylate resin (3)
  • a thermometer a stirrer, and a reflux condenser
  • 211 parts by mass of diethylene glycol monomethyl ether acetate a stirrer, and a reflux condenser
  • 211 parts by mass of diethylene glycol monomethyl ether acetate a stirrer, and a reflux condenser
  • 211 parts by mass of diethylene glycol monomethyl ether acetate 111 parts by mass of isophorone diisocyanate
  • 144 parts by mass of trimellitic anhydride 0.8 parts by mass of dibutylhydroxytoluene
  • the acid value of the solid content of the acid group-containing (meth)acrylate resin (3) was 79 mgKOH/g, and the weight average molecular weight was 1,690.
  • Example 4 Production of acid group-containing (meth)acrylate resin (4)
  • 341 parts by mass of diethylene glycol monomethyl ether acetate 341 parts by mass of diethylene glycol monomethyl ether acetate, 149 parts by mass of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, obtained in Synthesis Example 1
  • 44 parts by mass of pentaerythritol polyacrylate (A1), 0.7 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of methoquinone, and 0.6 parts by mass of triphenylphosphine were added and reacted at 120° C. for 6 hours while blowing air.
  • the acid value of the solid content of the acid group-containing (meth)acrylate resin (4) was 78 mgKOH/g, and the weight average molecular weight was 2,580.
  • Example 5 Production of acid group-containing (meth)acrylate resin (5)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 269 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 34 parts by mass of pentaerythritol diacrylate (A2) obtained in Synthesis Example 2, dibutyl. 0.7 parts by mass of hydroxytoluene, 0.2 parts by mass of metoquinone, and 0.6 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120° C. for 6 hours while blowing air.
  • the acid value of the solid content of the acid group-containing (meth)acrylate resin (5) was 92 mgKOH/g, and the weight average molecular weight was 2,590.
  • Example 6 Production of acid group-containing (meth)acrylate resin (6)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 345 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 110 parts by mass of dipentaerythritol polyacrylate (A3) obtained in Synthesis Example 3, 0.9 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of metoquinone, and 0.8 parts by mass of triphenylphosphine were added and the reaction was carried out at 120° C. for 6 hours while blowing air.
  • A3 dipentaerythritol polyacrylate
  • Example 7 Production of acid group-containing (meth)acrylate resin (7)
  • 236 parts by mass of diethylene glycol monomethyl ether acetate and 131 parts by mass of dicyclohexylmethane 4,4-diisocyanate (“Desmodur W” manufactured by Sumika Covestro Urethane Co., Ltd.) Parts, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 149 parts by mass and dibutylhydroxytoluene 0.6 parts by mass were added and dissolved.
  • the reaction was carried out at 160° C.
  • Example 8 Production of acid group-containing (meth)acrylate resin (8)
  • 395 parts by mass of diethylene glycol monomethyl ether acetate 395 parts by mass of diethylene glycol monomethyl ether acetate, 111 parts by mass of isophorone diisocyanate, 84 parts by mass of hexamethylene diisocyanate, 288 parts by mass of trimellitic anhydride, and dibutylhydroxytoluene 1. 0 part by mass was added and dissolved.
  • the reaction was carried out at 170° C. for 6 hours in a nitrogen atmosphere, and it was confirmed that the isocyanate group content was 0.1% by mass or less.
  • Example 9 Production of acid group-containing (meth)acrylate resin (9)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 205 parts by mass of diethylene glycol monomethyl ether acetate, trimethylhexamethylene diisocyanate (“VESTANAT TMDI” manufactured by EVONIK, isocyanate group content 39.9% by mass)
  • VESTANAT TMDI trimethylhexamethylene diisocyanate
  • Example 10 Production of acid group-containing (meth)acrylate resin (10)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 202 parts by mass of diethylene glycol monomethyl ether acetate, 97 parts by mass of hydrogenated xylylene diisocyanate (“Takenate 600” manufactured by Mitsui Chemicals, Inc.), and cyclohexane-1,3.
  • 149 parts by mass of 4-tricarboxylic acid-3,4-anhydride and 0.5 parts by mass of dibutylhydroxytoluene were added and dissolved.
  • the reaction was carried out at 160° C.
  • the acid value of the solid content of the acid group-containing (meth)acrylate resin (10) was 92 mgKOH/g, and the weight average molecular weight was 1790.
  • Example 11 Production of acid group-containing (meth)acrylate resin (11)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 203 parts by mass of diethylene glycol monomethyl ether acetate, 103 parts by mass of norbornene methane diisocyanate, 144 parts by mass of trimellitic anhydride, and 0.5 parts by mass of dibutylhydroxytoluene were added. Dissolved. The reaction was carried out at 160° C. for 5 hours in a nitrogen atmosphere, and it was confirmed that the isocyanate group content was 0.1% by mass or less.
  • Example 12 Production of acid group-containing (meth)acrylate resin (12)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 392 parts by mass of diethylene glycol monomethyl ether acetate, an isocyanurate modified product of isophorone diisocyanate (“VESTANAT T-1890/100” manufactured by EVONIK, isocyanate group content 17. (2 mass %) 244 mass parts, trimellitic anhydride 192 mass parts, and dibutyl hydroxytoluene 1.0 mass part were added and dissolved. The reaction was carried out at 160° C. for 5 hours in a nitrogen atmosphere, and it was confirmed that the isocyanate group content was 0.1% by mass or less.
  • VESTANAT T-1890/100 manufactured by EVONIK
  • Example 13 Production of acid group-containing (meth)acrylate resin (13)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 254 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 53 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, dibutyl. Hydroxytoluene (0.6 parts by mass), methoquinone (0.2 parts by mass) and triphenylphosphine (0.7 parts by mass) were added, and the mixture was reacted at 120° C. for 6 hours while blowing air.
  • the acid value of the solid content of the acid group-containing (meth)acrylate resin (13) was 95 mgKOH/g, and the weight average molecular weight was 20,50.
  • Example 14 Production of acid group-containing (meth)acrylate resin (14)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 271 parts by mass of dimethylacetamide, 168 parts by mass of trimellitic anhydride, 53 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, dibutylhydroxytoluene. 0.7 parts by mass, 0.2 parts by mass of metoquinone, and 0.7 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120° C. for 6 hours while blowing air.
  • the acid value of the solid content of the acid group-containing (meth)acrylate resin (14) was 94 mgKOH/g, and the weight average molecular weight was 2,450.
  • the acid value of the solid content of the acid group-containing acrylate resin (C1) was 85 mgKOH/g.
  • Example 15 Preparation of curable resin composition (1)
  • Curable resin composition (1) was obtained.
  • Examples 16 to 26 Preparation of curable resin compositions (2) to (14)
  • the acid group-containing (meth)acrylate resins (2) to (14) obtained in Examples 2 to 14 were used instead of the acid group-containing (meth)acrylate resin (1) used in Example 15, respectively.
  • Curable resin compositions (2) to (14) were obtained in the same manner as in Example 15.
  • Table 1 shows the compositions and evaluation results of the curable resin compositions (1) to (14) prepared in Examples 15 to 28 and the curable resin composition (C2) prepared in Comparative Example 2.
  • Example 29 Preparation of curable resin composition (15)
  • the acid group-containing (meth)acrylate resin (1) obtained in Example 1 an orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation) as a curing agent, and 2-methyl-1 as a photopolymerization initiator.
  • -(4-Methylthiophenyl)-2-morpholinopropan-1-one (“OMNIRAD-907” manufactured by IGM) and diethylene glycol monomethyl ether acetate as an organic solvent were mixed in a mass ratio shown in Table 2 to prepare a curable resin.
  • a composition (15) was obtained.
  • Examples 30 to 42 Preparation of curable resin compositions (16) to (28)
  • the acid group-containing (meth)acrylate resins (2) to (14) obtained in Examples 2 to 14 were used, respectively.
  • Curable resin compositions (16) to (28) were obtained in the same manner as in Example 29.
  • the test piece was cut into a size of 6 mm ⁇ 40 mm, and a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by Rheometric Co., tension method: frequency 1 Hz, temperature rising rate 3° C./min) was used.
  • DMA solid viscoelasticity measuring device “RSAII” manufactured by Rheometric Co., tension method: frequency 1 Hz, temperature rising rate 3° C./min
  • Tg glass transition temperature
  • Table 2 shows the compositions and evaluation results of the curable resin compositions (15) to (28) produced in Examples 29 to 42 and the curable resin composition (C3) produced in Comparative Example 3.
  • “Curing agent” in Tables 1 and 2 indicates an ortho-cresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation, epoxy equivalent: 214).
  • Organic solvent in Tables 1 and 2 indicates diethylene glycol monomethyl ether acetate.
  • Examples 15 to 42 shown in Tables 1 and 2 are examples of curable resin compositions using the acid group-containing (meth)acrylate resin of the present invention. It was confirmed that this curable resin composition had excellent alkali developability and that the cured product had excellent heat resistance.
  • Comparative Examples 2 and 3 are examples of curable resin compositions that do not use the acid group-containing (meth)acrylate resin of the present invention. It was confirmed that this curable resin composition was remarkably insufficient in heat resistance of the cured product.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Organic Insulating Materials (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

La présente invention concerne : une résine (méth)acrylique contenant un groupe acide qui est caractérisée en ce qu'elle comprend au moins une liaison amide, au moins une liaison imide, au moins une liaison ester, au moins un groupe (méth)acryloyle et au moins un groupe acide ; une composition de résine durcissable ; un produit durci ; un matériau isolant ; un matériau de résine pour des réserves de soudure ; et un élément de réserve. La résine (méth)acrylique contenant un groupe acide peut former un produit durci présentant une excellente résistance à la chaleur.
PCT/JP2019/047582 2018-12-19 2019-12-05 Résine (méth)acrylique contenant un groupe acide, composition de résine durcissable, produit durci, matériau isolant, matériau de résine pour réserves de soudure et élément de réserve WO2020129666A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022102388A1 (fr) * 2020-11-12 2022-05-19 根上工業株式会社 Composition contenant un uréthane-(méth)acrylate, composition de résine photodurcissable, produit durci de celle-ci, agent de revêtement dur et substrat portant une couche de revêtement dur

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000344889A (ja) * 1999-03-30 2000-12-12 Dainippon Ink & Chem Inc イミド（アミド）樹脂の製造方法及びその樹脂を使用したエネルギー線硬化型樹脂組成物
JP2015155500A (ja) * 2014-02-20 2015-08-27 Dic株式会社 硬化性アミドイミド樹脂およびアミドイミド樹脂の製造方法
WO2018230144A1 (fr) * 2017-06-14 2018-12-20 Dic株式会社 Résine de (méth)acrylate contenant un groupe acide, et matériau de type résine pour réserve de soudure
WO2018230428A1 (fr) * 2017-06-14 2018-12-20 Dic株式会社 Résine méthacrylate contenant un groupe acide et matière de type résine pour résines photosensibles de soudure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000344889A (ja) * 1999-03-30 2000-12-12 Dainippon Ink & Chem Inc イミド（アミド）樹脂の製造方法及びその樹脂を使用したエネルギー線硬化型樹脂組成物
JP2015155500A (ja) * 2014-02-20 2015-08-27 Dic株式会社 硬化性アミドイミド樹脂およびアミドイミド樹脂の製造方法
WO2018230144A1 (fr) * 2017-06-14 2018-12-20 Dic株式会社 Résine de (méth)acrylate contenant un groupe acide, et matériau de type résine pour réserve de soudure
WO2018230428A1 (fr) * 2017-06-14 2018-12-20 Dic株式会社 Résine méthacrylate contenant un groupe acide et matière de type résine pour résines photosensibles de soudure

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022102388A1 (fr) * 2020-11-12 2022-05-19 根上工業株式会社 Composition contenant un uréthane-(méth)acrylate, composition de résine photodurcissable, produit durci de celle-ci, agent de revêtement dur et substrat portant une couche de revêtement dur
JP2022077715A (ja) * 2020-11-12 2022-05-24 根上工業株式会社 ウレタン（メタ）アクリレート含有組成物、光硬化性樹脂組成物、その硬化物、ハードコート剤、及びハードコート層付き基材
JP7105502B2 (ja) 2020-11-12 2022-07-25 根上工業株式会社 ウレタン（メタ）アクリレート含有組成物、光硬化性樹脂組成物、その硬化物、ハードコート剤、及びハードコート層付き基材

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