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WO2017170049A1 - Composition durcissable et produit durci obtenu à partir de celle-ci - Google Patents

Composition durcissable et produit durci obtenu à partir de celle-ci Download PDF

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Publication number
WO2017170049A1
WO2017170049A1 PCT/JP2017/011480 JP2017011480W WO2017170049A1 WO 2017170049 A1 WO2017170049 A1 WO 2017170049A1 JP 2017011480 W JP2017011480 W JP 2017011480W WO 2017170049 A1 WO2017170049 A1 WO 2017170049A1
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compound
meth
group
curable composition
acid
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PCT/JP2017/011480
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English (en)
Japanese (ja)
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大西　美奈
一彦 大賀
快 鈴木
明子 佐藤
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昭和電工株式会社
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Priority to JP2018509130A priority Critical patent/JPWO2017170049A1/ja
Publication of WO2017170049A1 publication Critical patent/WO2017170049A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds

Definitions

  • the present invention relates to a curable composition and a cured product thereof.
  • Photosensitive resin compositions are used in the production of printed wiring boards and glass substrates.
  • a photoresist image made of a cured product obtained by exposing and curing the photosensitive resin composition is exposed to an acidic etching solution and a plating solution, and therefore has sufficient acid resistance. Need to be.
  • a protective mask made of a cured product obtained by exposing and curing the photosensitive resin composition, a transparent conductive film on the glass substrate In order to protect the flexible printed circuit board, the protective mask needs to have sufficient acid resistance.
  • Patent Documents 1 and 2 disclose a protective material having acid resistance, but since the acid resistance, flexibility, and adhesion to the protected object are insufficient, the protected object can be sufficiently protected. There was a problem that it was not possible.
  • this invention makes it a subject to solve the trouble which the above prior arts have, and to provide the curable composition which can form the hardened
  • Another object of the present invention is to provide a cured product having excellent acid resistance, flexibility and adhesion.
  • the thiol compound (B) includes a compound having two or more mercapto groups in one molecule and all mercapto groups bonded to secondary carbon atoms or tertiary carbon atoms.
  • R 1 in formula (1) represents an alkyl group having 1 to 10 carbon atoms
  • R 2 represents a hydrogen atom or a C 1 to 10 alkyl group carbon
  • m is 0 to 2 integer Indicates.
  • the thiol compound (B) is 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxy) Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, and at least one selected from trimethylolpropane tris (3-mercaptobutyrate) [1] to [4]
  • the curable composition according to any one of [4].
  • the ratio of the number of (meth) allyl groups in the (meth) allyl group-containing compound (A) to the number of mercapto groups in the thiol compound (B) is 0. Within the range of 25 or more and 4 or less, When the total content of the (meth) allyl group-containing compound (A), the thiol compound (B), and the compound (C) is 100 parts by mass, the content of the compound (C) is 10
  • the curability according to any one of [1] to [9], which is not less than 70 parts by mass and the content of the polymerization initiator (D) is not less than 0.01 parts by mass and not more than 10 parts by mass.
  • Composition. [11] A cured product of the curable composition according to any one of [1] to [10].
  • the curable composition of the present invention can form a cured product having excellent acid resistance, flexibility and adhesion. Moreover, the cured product of the present invention is excellent in acid resistance, flexibility, and adhesion.
  • the curable composition of this embodiment includes a (meth) allyl group-containing compound (A) having two or more (meth) allyl groups in one molecule and a thiol having two or more mercapto groups in one molecule.
  • the curable composition of the present embodiment can be easily cured in a short time by irradiation with active energy rays, and the cured product has excellent acid resistance, flexibility, and adhesion. Therefore, the curable composition of this embodiment can be suitably used as an etching protective material for protecting an acidic etching solution and a plating protective material for protecting an acidic plating solution. It can also be used as a casting material, paint, molding material, etc. in various other industrial fields.
  • (meth) allyl means methallyl (ie, 2-methyl-2-propenyl) and / or allyl (ie, 2-propenyl).
  • (meth) acrylate means methacrylate and / or acrylate, and “(meth) acryl” means methacryl and / or acrylic.
  • the (meth) allyl group-containing compound (A) may be a monomer, an oligomer or a polymer, and is preferably a compound having a number average molecular weight of 200 or more and 20000 or less from the viewpoint of viscosity.
  • the molecular weight of the oligomer or polymer in this invention is the number average molecular weight of polystyrene (PS) conversion measured by the gel permeation chromatography method (GPC method).
  • Examples of the (meth) allyl group-containing compound (A) include a compound (a-1) having at least one structure selected from an alicyclic structure, an aromatic ring structure, and a heterocyclic structure in the molecule and an acyclic compound ( a-2).
  • Examples of the alicyclic structure include alicyclic rings having 3 to 6 carbon atoms, preferably a cyclohexane ring and a cycloheptane ring.
  • Examples of the aromatic ring structure include aromatic rings having 6 to 10 carbon atoms, preferably a benzene ring and a naphthalene ring.
  • heterocyclic structure examples include a three-membered ring to a ten-membered ring having a nitrogen atom, an oxygen atom, or a sulfur atom, and examples thereof include a pyridine ring, a triazine ring, a ring derived from cyanuric acid, and a ring derived from isocyanuric acid.
  • the compound (a-1) includes diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl trimellitic acid, tetraallyl pyromellitic acid, bisphenol.
  • Allyloxycarbonyl group-containing compounds having an aromatic ring structure such as A diallyl ether, diallyl 1,2-cyclohexanedicarboxylate, diallyl 1,3-cyclohexanedicarboxylate, diallyl 1,4-cyclohexanedicarboxylate, 1,2,4 -Triallyl cyclohexanetricarboxylate, tetraallyl 1,2,4,5-cyclohexanetetracarboxylate, diallyl 5-alkyl-substituted cyclohexane-1,4-dicarboxylate, diallyl 5-halogen-substituted cyclohexane-1,4-dicarboxylate, 1, 3 Diallyl adamantane dicarboxylate, triallyl 1,3,5-adamantane tricarboxylate, hydrogenated bisphenol A diallyl ether, hydrogenated dimer acid (having 36 or 44 carbon atoms and an alicyclic structure) dially
  • compounds containing an aromatic ring such as dimethallyl phthalate, dimethallyl isophthalate, dimethallyl terephthalate, trimethallyl trimellirate, tetramethallyl pyromellitic acid, bisphenol A dimethallyl ether, 1,2-cyclohexanedicarboxylic acid, etc.
  • Dimethallyl acid dimethallyl 1,3-cyclohexanedicarboxylate, dimethallyl 1,4-cyclohexanedicarboxylate, trimethallyl 1,2,4-cyclohexanetricarboxylate, tetramethallyl 1,2,4,5-cyclohexanetetracarboxylate, 5-alkyl substituted Dimethallyl of cyclohexane-1,4-dicarboxylate, dimethallyl of 5-halogen-substituted cyclohexane-1,4-dicarboxylate, dimethallyl of 1,3-adamantane dicarboxylate, 1,3,5- Trimanallyl damantane tricarboxylate, dimethallyl 5-halogen-substituted cyclohexane-1,4-dicarboxylate, hydrogenated dimer acid (having 36 or 44 carbon atoms and an alicyclic structure) dimethallyl, tricycl
  • compound (a-1) bisphenol A diallyl ether, bisphenol A dimethallyl ether, bisphenol S diallyl ether, bisphenol S dimethallyl ether, 1,4-naphthalenedicarboxylic acid diallyl ether, 1,4-naphthalenedicarboxylic acid Dimethallyl ether, 1,5-naphthalenedicarboxylic acid diallyl ether, 1,5-naphthalenedicarboxylic acid dimethallyl ether, 2,6-naphthalenedicarboxylic acid diallyl ether, 2,6-naphthalenedicarboxylic acid dimethallyl ether, 2,7- Naphthalenedicarboxylic acid diallyl ether, 2,7-naphthalenedicarboxylic acid dimethallyl ether, diphenyl-m, m′-dicarboxylic acid diallyl ether, diphenyl-m, m′-dimethallyl ether Diphenyl-p, p
  • Compound (a-1) includes allyl methallyl phthalate, allyl methallyl isophthalate, diallyl methallyl trimellitic acid, allyl dimethallyl trimellitic acid, triallyl methallyl pyromellitic acid, diallyl dimetall pyromellitic acid Ester, pyromellitic acid allyltrimethallyl ester, bisphenol A allylmethallyl ether, bisphenol S allylmethallyl ether, 1,4-naphthalenedicarboxylic acid allylmethallyl ether, 1,5-naphthalenedicarboxylic acid allylmethallyl ether, 2,6-naphthalenedicarboxylic acid Acid allylmethallyl ether, 2,7-naphthalenedicarboxylic acid allylmethallyl ether, diphenyl-m
  • the compound (a-1) is preferable to the compound (a-2), and the (meth) allyl group-containing compound (A) is a monomer. In some cases, the same applies when the (meth) allyl group-containing compound (A) described later is an oligomer.
  • the (meth) allyl group-containing compound (A) described later is an oligomer.
  • preferred are allyloxycarbonyl group and N-allyl group. Compounds having at least one are preferred.
  • the (meth) allyl group-containing compound (A) having a bisphenol A type skeleton is particularly excellent in corrosion resistance against very strong acidity, and the commercially available product is represented by the following formula (2).
  • CM-BPADE manufactured by Chemidge.
  • examples of the (meth) allyl group-containing compound (A) include (meth) allyl ester resins.
  • the (meth) allyl ester resin is a compound having a (meth) allyloxycarbonyl group at the molecular end and a repeating unit in the molecule. For example, at least one selected from a transesterification reaction between a polybasic acid (meth) allyl ester compound and a polyhydric alcohol, a monool containing (meth) allyl allyl alcohol, a polyhydric alcohol and a polybasic acid, or a polybasic acid anhydride.
  • Condensation reaction with seed transesterification reaction between polyol having repeating unit and (meth) allyl ester compound of polybasic acid, and monool containing (meth) allylallyl alcohol, polyol having repeating unit and polybasic acid And a compound produced by various reactions of condensation reaction with at least one selected from polybasic acid anhydrides.
  • Specific examples of the (meth) allyl ester resin include, for example, oligomers having a structure represented by the following formulas (3), (4), and (6).
  • J R 3 in the formula (3) each independently represents a linear alkylene group or a branched alkylene group having 1 to 36 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms).
  • R 4 and R 5 each independently represent a hydrogen atom or a methyl group. Preferably, both R 4 and R 5 are hydrogen atoms.
  • Xs are each independently an organic group derived from a divalent carboxylic acid, preferably having an alkyl group having 1 to 4 carbon atoms as a substituent. It may be a phenylene group or a cyclohexylene group, more preferably a phenylene group or a cyclohexylene group having no substituent.
  • alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group.
  • the position at which the phenylene group or cyclohexylene group is bonded to the adjacent carbonyl carbon may be any of the 1,2-position, 1,3-position, and 1,4-position, but considering the ease of synthesis, the 1,3-position or 1-position , 4th position is preferred.
  • J in Formula (3) is an integer of 1 or more and 20 or less, preferably 1 or more and 18 or less, and more preferably 1 or more and 15 or less.
  • the molecular weight of the oligomer represented by the formula (3) is preferably 300 or more and 20000 or less, more preferably 800 or more and 18000 or less, and further preferably 1000 or more and 16000 or less.
  • A's are each independently an organic group derived from a divalent carboxylic acid, preferably having an alkyl group having 1 to 4 carbon atoms as a substituent.
  • the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group.
  • the position at which the phenylene group or cyclohexylene group is bonded to the adjacent carbonyl carbon may be any of the 1,2-position, 1,3-position, and 1,4-position, but considering the ease of synthesis, the 1,3-position or 1-position , 4th position is preferred.
  • k R 6 s each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec -Butyl group, isobutyl group, and tert-butyl group), or a group represented by the following formula (5).
  • R ⁇ 7 >, R ⁇ 9 > and k R ⁇ 8 > in Formula (4) show a hydrogen atom or a methyl group each independently.
  • R 7 , R 9 and k R 8 are all hydrogen atoms.
  • a in the formula (5) is the same as in the oligomer represented by the formula (4), and R 10 represents a hydrogen atom or a methyl group.
  • R 10 is a hydrogen atom.
  • K in Formula (4) is an integer of 3 or more and 70 or less, preferably 4 or more and 60 or less, more preferably 4 or more and 50 or less.
  • the molecular weight of the oligomer represented by the formula (4) is preferably 300 or more and 20000 or less, more preferably 500 or more and 18000 or less, and further preferably 700 or more and 16000 or less.
  • Z's are each independently an organic group derived from a divalent carboxylic acid, and preferably have an alkyl group having 1 to 4 carbon atoms as a substituent.
  • the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group.
  • R 11 in the formula (6) each independently represents a linear alkylene group having 1 to 36 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms). Or a branched alkylene group is shown.
  • R ⁇ 12 > and R ⁇ 13 > in Formula (6) show a hydrogen atom or a methyl group each independently. Preferably, both R 12 and R 13 are hydrogen atoms.
  • P in the formula (6) is an integer of 1 or more and 10 or less, preferably 1 or more and 9 or less, more preferably 1 or more and 8 or less.
  • Q in the formula (6) is an integer of 5 or more and 50 or less, preferably 5 or more and 45 or less, and more preferably 5 or more and 40 or less.
  • the molecular weight of the oligomer represented by formula (6) is preferably 300 or more and 20000 or less, more preferably 500 or more and 19000 or less, and further preferably 700 or more and 18000 or less.
  • Specific examples other than the (meth) allyl ester resin when the (meth) allyl group-containing compound (A) is an oligomer include polyene compounds derived from substituted or unsubstituted allyl alcohol, polyethylene glycol bis (allyl carbonate) Etc.
  • examples of the (meth) allyl group-containing compound (A) include compounds in which two or more allyl groups are introduced into the polymer skeleton.
  • polymer skeleton examples include a polyethylene skeleton, a polyurethane skeleton, a polyester skeleton, a polyamide skeleton, a polyimide skeleton, a polyoxyalkylene skeleton, and a polyphenylene skeleton. Only one type of (meth) allyl group-containing compound (A) may be used alone, or two or more types may be used in combination.
  • the iodine value of the mixture which mixed all the compounds which belong to the (meth) allyl group containing compound (A) used for the curable composition of this embodiment exists in the range of 20-240. More preferably, it is 30 or more and 210 or less. If the iodine value is in the range of 20 or more and 240 or less, the curable composition can be easily cured in a short time by irradiation with active energy rays.
  • the iodine value described in the present specification is a value obtained by converting the amount of halogen (unit: g) that reacts with 100 g of the target substance into grams of iodine.
  • the thiol compound (B) is preferably a compound having 2 to 6 mercapto groups in the molecule.
  • an aliphatic polythiol such as alkanedithiol having 2 to 20 carbon atoms, an aromatic polythiol such as xylylenedithiol, a polythiol or polyepoxide compound obtained by substituting a halogen atom of a halohydrin adduct of alcohol with a thiol group
  • a polythiol comprising an esterified product with thiocarboxylic acid is preferable from the viewpoint of storage stability and curability when
  • the thiol compound (B) is a compound having two or more mercapto groups in one molecule and all mercapto groups bonded to secondary carbon atoms or tertiary carbon atoms. That is, the thiol compound (B) has a mercapto group-containing group in which a substituent is bonded to a carbon atom at the ⁇ -position with respect to the mercapto group, and has two or more mercapto groups. At least one of the substituents is preferably an alkyl group.
  • Compounds with all mercapto groups bonded to secondary or tertiary carbon atoms have better water resistance than compounds with mercapto groups bonded to primary carbon atoms. Is also excellent with it.
  • a substituent is bonded to the carbon atom at the ⁇ -position with respect to the mercapto group means that the carbon at the ⁇ -position of the mercapto group is bonded to two or three carbon atoms. That at least one of the substituents is an alkyl group means that at least one of the groups other than the main chain among the groups bonded to the carbon atom at the ⁇ -position with respect to the mercapto group is an alkyl group.
  • the main chain refers to the longest-chain structural site other than the mercapto group and the hydrogen atom bonded to the ⁇ -position carbon atom.
  • R 1 in formula (1) represents an alkyl group having 1 to 10 carbon atoms
  • R 2 represents a hydrogen atom or a C 1 to 10 alkyl group carbon.
  • m in the following formula (1) represents an integer of 0 or more and 2 or less, preferably 0 or 1.
  • the alkyl group having 1 to 10 carbon atoms represented by R 1 and R 2 may be linear or branched. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-hexyl group, and an n-octyl group, preferably a methyl group Group or ethyl group.
  • the thiol compound (B) is not particularly limited as long as it is a compound having all mercapto groups bonded to secondary carbon atoms or tertiary carbon atoms and having two or more mercapto groups. It is preferably a polyfunctional thiol compound having two or more mercapto group-containing groups.
  • the thiol compound (B) when the thiol compound (B) is polyfunctional, it is possible to increase the sensitivity of active energy ray curability (photopolymerization) as compared with a monofunctional compound.
  • the mercapto group-containing group is more preferably a group having a carboxylic acid derivative structure represented by the following formula (7).
  • the thiol compound (B) is preferably an ester of a mercapto group-containing carboxylic acid represented by the following formula (8) and an alcohol.
  • the definitions of R 14 , R 15 , R 16 and R 17 in the above formulas (7) and (8) are the same as the definitions of R 1 and R 2 in the above formula (1), and the definitions of r and s Is the same as the definition of m in the above formula (1).
  • the alcohol to be esterified with the mercapto group-containing carboxylic acid represented by the above formula (8) is preferably a polyhydric alcohol. By using a polyhydric alcohol, the compound obtained by esterification can be made into a polyfunctional thiol compound.
  • polyhydric alcohol examples include alkylene glycol (wherein the alkylene group preferably has 2 to 10 carbon atoms, and its carbon chain may be linear or branched), diethylene glycol, glycerin, dipropylene glycol. , Trimethylolpropane, pentaerythritol, and dipentaerythritol.
  • alkylene glycol examples include ethylene glycol, trimethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, and tetramethylene glycol.
  • trimethylolpropane, pentaerythritol, and tris (2-hydroxyethyl) isocyanurate are easily available and are preferable from the viewpoint of the number of functional groups and vapor pressure.
  • the mercapto group-containing carboxylic acid of the above formula (8) include 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptobutanoic acid, 3-mercaptobutanoic acid, 4-mercaptobutanoic acid, 2-mercaptoisobutanoic acid, Examples include 2-mercaptoisopentanoic acid, 3-mercaptoisopentanoic acid, and 3-mercaptoisohexanoic acid.
  • Specific examples of the compound having two or more mercapto group-containing groups of the above formula (1) and having all mercapto groups bonded to secondary carbon atoms or tertiary carbon atoms include the following compounds: Can be mentioned.
  • Examples of the hydrocarbon dithiol include 2,5-hexanedithiol, 2,9-decanedithiol, 1,4-bis (1-mercaptoethyl) benzene, and the like.
  • Examples of the thiol compound (B) having an ester bond structure include di (1-mercaptoethyl ester) phthalate, di (2-mercaptopropyl ester) phthalate, di (3-mercaptobutyl ester) phthalate, ethylene glycol bis ( 3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), Trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropyl) Pionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercap
  • a thiol compound (B) may be used individually by 1 type, and may use 2 or more types together.
  • the molecular weight of the thiol compound (B) is not particularly limited, but is preferably 200 or more and 1000 or less from the viewpoint of improving the acid resistance of the cured product of the curable composition of the present embodiment.
  • the thiol compound (B) can also be easily obtained as a commercial product.
  • commercially available products include 1,4-bis (3-mercaptobutyryloxy) butane (a product manufactured by Showa Denko KK).
  • Karenz MT (trademark) BD1), pentaerythritol tetrakis (3-mercaptobutyrate) (trade name Karenz MT (trademark) PE1 manufactured by Showa Denko KK), 1,3,5-tris (3-mercaptobutyryloxy) Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (trade name Karenz MT (trademark) NR1 manufactured by Showa Denko KK), trimethylolpropane tris (3-mercapto Butyrate) (trade name TPMB manufactured by Showa Denko KK) and the like.
  • the preferred content of the thiol compound (B) in the curable composition of this embodiment is the number of (meth) allyl groups in the (meth) allyl group-containing compound (A) and the number of mercapto groups in the thiol compound (B). It can be expressed as a ratio. That is, the ratio of the number of (meth) allyl groups in the (meth) allyl group-containing compound (A) to the number of mercapto groups in the thiol compound (B) (number of allyl groups / number of mercapto groups) is determined by curability and acid resistance. From the viewpoint of property, it is preferably in the range of 0.25 to 4, and more preferably in the range of 0.6 to 4. It is good to determine content of the (meth) allyl group containing compound (A) and thiol compound (B) in a curable composition so that it may become such a ratio.
  • the number of (meth) allyl groups of the (meth) allyl group-containing compound (A) is the total number of (meth) allyl groups of all the compounds belonging to the (meth) allyl group-containing compound (A) (moles).
  • the number of mercapto groups in the thiol compound (B) means the total number (in moles) of mercapto groups in all the compounds belonging to the thiol compound (B).
  • blend mercapto group containing compounds other than a thiol compound (B) with the curable composition of this embodiment if it is the quantity of the range which does not impair the effect of invention.
  • the blending amount of the mercapto group-containing compound other than the thiol compound (B) is 20% by mass of the content of all mercapto group-containing compounds including the thiol compound (B) from the viewpoint of maintaining curability and acid resistance. The following is preferable.
  • the curable composition of this embodiment contains at least one compound (C) selected from epoxy (meth) acrylate, (poly) ester (meth) acrylate, and unsaturated polyester resin.
  • Epoxy (meth) acrylate means all compounds obtained by reacting polyepoxide with (meth) acrylic acid or its acid anhydride.
  • the number of (meth) acryloyl groups (average number of functional groups) possessed by the epoxy (meth) acrylate is preferably 1.5 or more. When the average number of functional groups is 1.5 or more, the crosslink density when the curable composition is cured is sufficiently high, so that the resulting cured product has good acid resistance.
  • epoxy (meth) acrylate may be used individually by 1 type, and may use 2 or more types together.
  • the polyepoxide is preferably a compound having an average of 1.5 or more, and preferably an average of 2 or more and 5 or less epoxy groups in one molecule.
  • Specific examples of polyepoxides include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, Examples include aliphatic polyepoxides such as 1,6-hexanediol diglycidyl ether and trimethylolpropane triglycidyl ether.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol S type epoxy resin, Bisphenol type epoxy resins such as hydrogenated bisphenol AD type epoxy resin and tetrabromobisphenol A type epoxy resin can also be mentioned.
  • ortho-cresol novolak type epoxy resin examples include novolak type epoxy resins such as group-containing novolak type epoxy resins and brominated phenol novolac type epoxy resins.
  • phenol aralkyl type epoxy resin commonly known as epoxidized xyloc resin
  • resorcin diglycidyl ether hydroquinone diglycidyl ether
  • catechol diglycidyl ether catechol diglycidyl ether
  • biphenyl type epoxy resin tetramethylbiphenyl type epoxy resin, etc.
  • Type epoxy resin triglycidyl isocyanurate, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl modified novolak type epoxy resin (phenolic nucleus linked by bismethylene group)
  • polyepoxides having an alicyclic structure, aromatic ring structure, or heterocyclic structure such as a methoxy group-containing phenol aralkyl resin. It is below.
  • the reaction between the polyepoxide and (meth) acrylic acid or its acid anhydride is usually performed at a temperature in the range of 50 ° C. to 150 ° C. for about 1 hour to 8 hours.
  • a catalyst is preferably used.
  • the catalyst include amines such as triethylamine, dimethylbutylamine and tri-n-butylamine, and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt and benzyltriethylammonium salt.
  • phosphines such as quaternary phosphonium salts and triphenylphosphine
  • imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole can also be mentioned as specific examples of the catalyst.
  • alcohol solvents such as methanol, propanol and ethyl cellosolve
  • ester solvents such as methyl cellosolve acetate
  • ketone solvents such as methyl ethyl ketone
  • Aromatic compound solvents such as benzene and toluene can be used as the reaction solvent.
  • hydroquinone, phenothiazine or the like may be present in the reaction system as a polymerization inhibitor.
  • the reaction in order to suppress the polymerization reaction of (meth) acrylic acid, the reaction may be performed under an air stream such as air, and in this case, in order to prevent the oxidation reaction by air, An antioxidant such as 6-di-t-butyl-methylphenol may be used in combination.
  • the epoxy (meth) acrylate is derived from an epoxy compound having at least one structure selected from an alicyclic structure, an aromatic ring structure, and a heterocyclic structure. Epoxy (meth) acrylate is preferred. Furthermore, epoxy (meth) acrylate derived from an epoxy compound having a bisphenol A type skeleton is particularly excellent in corrosion resistance against very strong acidity.
  • epoxy (meth) acrylates having a bisphenol A-type skeleton commercially available products include epoxy ester 3002M (N), epoxy ester 3002A (N), epoxy ester 3000MK, and epoxy ester manufactured by Kyoeisha Chemical Co., Ltd. 3000A, NK ester EA-1020, NK ester A-B126PE, NK ester ABE-300, NK ester A-BPE-4, NK ester A-BPE-500, NK oligo EA-5220, manufactured by Shin-Nakamura Chemical Co., Ltd. VR-77 manufactured by Showa Denko KK
  • (poly) ester (meth) acrylate means a saturated or unsaturated polyester having at least one (meth) acryloyl group in one molecule.
  • This (poly) ester (meth) acrylate is obtained by an ester reaction between a diol (optionally a triol) and a dibasic acid or an acid anhydride thereof (optionally a tribasic acid or an acid anhydride thereof). In that case, you may use together a monoepoxy compound and a polyepoxy compound.
  • (poly) ester (meth) acrylate may be used individually by 1 type, and may use 2 or more types together.
  • diol used as a raw material for polyester examples include 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, 1,5-pentanediol, 1,6-hexanediol, 3- Aliphatic diols typified by methyl-1,5-pentanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, Hydrogenated dimer diol (for example, having 36 or 44 carbon atoms), alicyclic diols typified by 1,4-cyclohexanedimethanol, 1,3-adamantanediol, tricyclodecanedimethanol, ethylene glycol, propylene Glycol, butylene glycol, neopentyl glycol, hexylene
  • triol used as a raw material for polyester examples include glycerin, trimethylolethane, 1,2,6-hexanetriol, trimethylolpropane, pentaerythritol, dipentalysitol, sorbidol, 1,3,5-adamantanetriol, 1 , 3,5-cyclohexanetriol, trimertriol (for example, 54 carbon atoms), and the like.
  • examples of the triol having a heterocyclic ring examples include tris (2-hydroxyethyl) isocyanurate, tris (3-hydroxypropyl) isocyanurate, tris (4-hydroxybutyl) isocyanurate and the like.
  • Examples of the tetraol used as a raw material for polyester include pentaerythritol, diglycerol, 1,2,3,4-butanetetraol, and the like.
  • Examples of the monoepoxy compound include ethylene oxide, propylene oxide, epichlorohydrin, styrene oxide, phenyldaricidyl ether, and the like.
  • Examples of the polyepoxy compound include the epoxy resins described in “Review Epoxy Resin” edited by the Epoxy Resin Technology Association.
  • dibasic acids and acid anhydrides used as raw materials for polyester include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, geltaric acid, hexahydrophthalic anhydride, 1,1,2- Dodecanoic acid and aliphatic or cycloaliphatic saturated dibasic acids that are esters thereof, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and ⁇ that is an ester thereof , ⁇ -unsaturated dibasic acid and its acid anhydride.
  • phthalic acid phthalic anhydride
  • isophthalic acid terephthalic acid
  • nitrophthalic acid tetrachlorophthalic acid
  • tetrahydrophthalic anhydride tetrabromophthalic acid
  • endomethylenetetrahydrophthalic acid halogenated phthalic anhydride
  • Aromatic dibasic acids and acid anhydrides thereof can also be mentioned.
  • tribasic acids and acid anhydrides used as polyester raw materials include, for example, trimellitic acid, aconitic acid, butanetricarboxylic acid, 6-carboxy-3-methyl-1,2,3,6-hexahydrophthal An acid and its acid anhydride are mentioned.
  • examples of the tetrabasic acid and its acid anhydride include pyromellitic acid, butanetetracarboxylic acid and its acid anhydride.
  • esterification of diol (optionally trivalent or higher alcohol) with (meth) acrylic acid and dibasic acid (trivalent or higher polybasic acid if necessary) A reaction method is common. However, a method by an esterification reaction of a compound having a (meth) acryloyl group and a hydroxy group and a dibasic acid (a tribasic or higher polybasic acid if necessary) may be used.
  • a (poly) ester (meth) acrylate having at least one structure selected from an alicyclic structure, an aromatic ring structure, and a heterocyclic structure is preferable, and is derived from bisphenol A.
  • (Poly) ester (meth) acrylate is more preferred.
  • Examples of the (poly) ester (meth) acrylate having a bisphenol A type skeleton available as a commercial product include Ebecryl 812 manufactured by Daicel Ornex Co., Ltd. represented by the following formula (9).
  • R 19 represents a hydrogen atom or a methyl group
  • R 20 and / or R 21 represents a group having a bisphenol A type skeleton.
  • the unsaturated polyester resin is an unsaturated polyester (prepolymer) obtained by polycondensation of an acid component composed of an ⁇ , ⁇ -unsaturated dibasic acid or an acid anhydride thereof and a polyhydric alcohol.
  • the method for producing the unsaturated polyester resin is not particularly limited. For example, there is a method in which a polybasic acid component and a polyhydric alcohol component are subjected to a polycondensation reaction, and in the polycondensation reaction, both components react. It is possible to proceed while removing the condensed water generated from time to time.
  • this unsaturated polyester resin contains (meth) acrylate, hydroxy group-containing (meth) acrylate obtained by reacting an epoxy compound containing an ⁇ , ⁇ -unsaturated carboxylic acid ester group with a terminal carboxyl group of the unsaturated polyester resin ( Also, (meth) acrylate obtained by reacting (meth) acrylate with the terminal carboxyl group of the unsaturated polyester resin, and (meth) acrylate obtained by reacting (meth) acrylic acid with the terminal hydroxy group of the unsaturated polyester resin included.
  • an unsaturated epoxy resin may be used individually by 1 type, and may use 2 or more types together.
  • the unsaturated polyester resin preferably has at least one structure selected from an alicyclic structure, an aromatic ring structure, and a heterocyclic structure, and more preferably has a bisphenol A type skeleton.
  • a bisphenol A type skeleton in addition to acid resistance, heat resistance and toughness can be imparted to the cured product, so that it is excellent in practicality when used as an industrial product.
  • An example of an unsaturated polyester resin having a bisphenol A type skeleton that is commercially available is Rigolac LP-1M manufactured by Showa Denko KK. This Rigolac LP-1M is a polymer represented by the following formula (10) and / or a polymer represented by the following formula (11). In the formulas (10) and (11), R 22 and R 23 represent a group having a bisphenol A type skeleton.
  • the molecular weight of a compound (C) is not specifically limited, It is preferable that it is 400 or more from a viewpoint of the acid resistance improvement of the hardened
  • the polymerization initiator (D) includes a photopolymerization initiator and a thermal polymerization initiator, and any compound can be used as long as it promotes the initiation of polymerization of the (meth) allyl group-containing compound (A). .
  • a polymerization initiator (D) may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.
  • the type of the photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals that contribute to the initiation of radical polymerization upon irradiation with active energy rays such as near infrared rays, visible rays, and ultraviolet rays.
  • photopolymerization initiator examples include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1,2-hydroxy-2-methyl-1-phenylpropane-1- ON, ⁇ -hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 2-hydroxy-2-methyl-1- (4-isopropylphenyl) propanone, 2-hydroxy-2-methyl-1 -(4-dodecylphenyl) propanone, 2-hydroxy-2-methyl-1-[(2-hydroxyethoxy) phenyl] propanone, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxy Benzofe 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenz
  • a metallocene compound can be used as a photopolymerization initiator.
  • the metallocene compound a metallocene compound in which the central metal is a transition element represented by Fe, Ti, V, Cr, Mn, Co, Ni, Mo, Ru, Rh, Lu, Ta, W, Os, Ir, or the like is used. Examples thereof include bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (pyrrol-1-yl) phenyl] titanium.
  • 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4 1,6-trimethylbenzophenone, 4-methylbenzophenone, ethoxyphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and 2-hydroxy-2-methylpropiophenone are preferably used.
  • 1-hydroxycyclohexyl phenyl ketone is available from BASF under the product name Irgacure 184, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide is available from BASF under the product name LUCIRIN TPO.
  • ethoxyphenyl (2,4,6-trimethylbenzoyl) phosphine oxide is available from BASF under the product name Irgacure TPO-L, and 2-hydroxy-2-methylpropiophenone is under the product name Darocur 1173. Available from BASF.
  • Particularly preferred photopolymerization initiators include diphenyl-2,4,6-trimethylbenzoylphosphine oxide, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-1- (4-isopropenylphenyl) -2-methyl.
  • the product name “ESACURE KTO 46” manufactured by Company A can be preferably used.
  • the thermal polymerization initiator is not particularly limited as long as it does not adversely affect physical properties such as acid resistance of the cured product, and known ones can be used.
  • the thermal polymerization initiator used in the present embodiment is soluble in other components present in the curable composition to be cured and generates free radicals at a temperature of 30 ° C. or higher and 120 ° C. or lower. What to do is desirable.
  • thermal polymerization initiator examples include organic compounds such as diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, and t-butyl perbenzoate.
  • organic compounds such as diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, and t-butyl perbenzoate.
  • a peroxide is mentioned, it is not limited to these.
  • diisopropyl peroxydicarbonate is preferable from the viewpoint of curability of the curable composition of the present embodiment.
  • peroxide-based polymerization initiators include dibenzoyl peroxide, t-butylpermaleate, di-t, t-hexyl peroxide, t-hexylperoxy-2-ethylhexanoate, t -Butyl hydroperoxide and the like.
  • examples of the redox polymerization initiator include a combination of persulfate and sodium bisulfite, a combination of peroxide and sodium ascorbate, and the like.
  • persulfate include potassium persulfate and ammonium persulfate.
  • the content of the polymerization initiator (D) in the curable composition of the present embodiment is determined from the total amount of the curable composition from the viewpoint of the curability of the curable composition.
  • An amount obtained by subtracting the content of a component that does not contribute to the reaction such as a solvent or an inorganic filler, for example, a total content of (meth) allyl group-containing compound (A), thiol compound (B), and compound (C) is 100 mass.
  • the content of the polymerization initiator (D) in the case of parts is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.5 parts by mass or more and 5.0 parts by mass or less. .
  • the curable composition of this embodiment may contain a polymerization inhibitor as necessary in order to suppress radical polymerization during storage and improve storage stability.
  • the type of the polymerization inhibitor is not particularly limited.
  • methylhydroquinone, pyrogallol, and tertiary butylhydroquinone are particularly preferable from the viewpoint of storage stability of the curable composition.
  • These polymerization inhibitors may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the polymerization inhibitor in the curable composition of the present embodiment is not particularly limited, but from the viewpoint of storage stability of the curable composition, the (meth) allyl group-containing compound (A) and the thiol compound.
  • the content of the polymerization inhibitor is preferably less than 0.1 parts by mass, and is 0.0001 parts by mass or more and 0.05 parts by mass or less. It is more preferable.
  • the curable composition of this embodiment comprises a (meth) allyl group-containing compound (A), a thiol compound (B), a compound (C), and a polymerization initiator.
  • a polymerization inhibitor which is an optional component, and may contain other components as long as it does not impair the purpose of the present invention. Good.
  • the curable composition of this embodiment does not need to contain a solvent as another component and may contain a solvent, it is preferable not to contain a solvent.
  • the components preferably contained as other components include color materials such as carbon materials, pigments, and dyes, and inorganic fillers.
  • the carbon material include carbon black, acetylene black, lamp black, and graphite.
  • the pigment include black pigments such as iron black, aniline black, cyanine black, and titanium black.
  • the curable composition of the present embodiment may contain organic pigments such as red, green, and blue.
  • organic pigments such as red, green, and blue.
  • commercially available gel nails or UV craft pigments may be used.
  • examples of such pigments include Pikaace coloring pigments (701, 731, 741, 755, 762), transparent pigments (900, 901, 910, 920, 921, 922, 924, 930, 932, 941, 942, 945, 947, 950, 955, 957, 960, 963, 968, 970, 980, 981, 982, 985) and the like.
  • the dye examples include direct dyes, acid dyes, basic dyes, mordant dyes, acid mordant dyes, vat dyes, disperse dyes, reactive dyes, fluorescent whitening dyes, and plastic dyes.
  • the dye means a substance having solubility in a solvent or compatibility with a resin and a property of coloring the dissolved or compatible substance.
  • a color material may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the coloring material in the curable composition of the present embodiment is not particularly limited. However, if the concentration is too high, the transmittance of the active energy ray is lowered and the curable composition causes poor curing. There is a fear. Therefore, the content of the color material in the curable composition is preferably 0.0001% by mass or more and 40% by mass or less.
  • the inorganic filler is not particularly limited as long as it is dispersed in the (meth) allyl group-containing compound (A), the thiol compound (B), and the compound (C) to form a paste.
  • examples of such inorganic fillers include silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), tantalum oxide (Ta 2 O 5 ), zirconia (ZrO 2 ), and silicon nitride (Si).
  • fine particle silica is used from the viewpoint of the viscosity controllability of the curable composition of the present embodiment and the sheet moldability of the cured product formed from the curable composition of the present embodiment. Is preferred.
  • the fine particle silica is available from Nippon Aerosil Co., Ltd. under the trade name Aerosil (trademark).
  • Aerosil (trademark) fine particle silica has the following names: Aerosil (trademark) OX50, RX50, RY50, 50, NAX50, NY50, NA50H, NA50Y, 90G, NX90G, 130, R972, RY200S, 150, R202, 200, R974 , R9200, RX200, R8200, RY200, R104, RA200H, RA200HS, NA200Y, R805, R711, R7200, 300, R976, R976S, RX300, R812, R812S, RY300, R106, 380, P25, T805, P90, NKT90, AluC , AluC805 and the like.
  • RX200 is more preferable from the viewpoint of dispersibility.
  • the content of the inorganic filler in the curable composition of the present embodiment is not particularly limited, but from the viewpoint of moldability of the cured product formed from the curable composition of the present embodiment, (meth) allyl
  • the content of the inorganic filler is preferably less than 10 parts by mass, and more preferably 2 parts by mass or more and 6 parts by mass or less.
  • the curable composition of this embodiment can contain the following (a) to (w) as other components in addition to the colorant. These other components may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.
  • e UV absorbers such as benzophenones, benzotriazoles, salicylic acid esters, metal complex salts, etc.
  • Stabilizers such as metal soaps, inorganic or organic salts of heavy metals (eg, zinc, tin, lead, cadmium), organic tin compounds, etc.
  • (G) pH adjusters such as aliphatic carboxylic acids such as acetic acid, acrylic acid, palmitic acid, oleic acid and mercaptocarboxylic acid, and aromatic organic acids such as phenol, naphthol, benzoic acid and salicylic acid
  • phthalic acid esters plasticizers such as phosphate esters, fatty acid esters, epoxidized soybean oil, castor oil, liquid paraffin, alkyl polycyclic aromatic hydrocarbons
  • Non-reactive diluents such as benzyl alcohol, tar and pitumen
  • Fillers such as acrylic resin powder and phenol resin powder
  • N Dehydrating agents such as silane coupling agents, monoisocyanate compounds, carbodiimide compounds
  • o antistatic agents
  • p antibacterial agents
  • q antifungal agents
  • r viscosity adjusting agents
  • s perfumes
  • T flame retardants
  • U Leveling agent
  • v Sensitizer
  • w Dispersant
  • the curable composition of this embodiment includes a (meth) allyl group-containing compound (A), a thiol compound (B), a compound (C), and a polymerization initiator (D). If necessary, it can be prepared by appropriately mixing a polymerization inhibitor and other components. At this time, the ratio of the number of (meth) allyl groups in the (meth) allyl group-containing compound (A) to the number of mercapto groups in the thiol compound (B) (number of allyl groups / number of mercapto groups) is 0.25 or more. It is good to mix so that it may become in the range of 4 or less (more preferably 0.6 or more and 4 or less).
  • the content of the compound (C) is 10 parts by mass. It is good to mix so that it may become in the range of 80 mass parts or less (more preferably 10 mass parts or more and 70 mass parts or less, More preferably 30 mass parts or more and 70 mass parts or less). Furthermore, when the amount obtained by subtracting the content of the polymerizable initiator (D) from the amount of the entire curable composition is 100 parts by mass, the content of the polymerization initiator (D) is 0.01 parts by mass or more and 10 parts by mass or more. It is good to mix so that it may become in the range below mass part (more preferably 0.5 mass part or more and 5.0 mass part or less).
  • the method for preparing the curable composition of the present embodiment is not particularly limited, and includes (meth) allyl group-containing compound (A), thiol compound (B), compound (C), polymerization initiator (D) and the like. Any method that can mix and disperse each raw material of the curable composition to be used. Examples of the method of mixing and dispersing include the following methods.
  • Each raw material is charged into a glass beaker, can, plastic cup, aluminum cup or the like and kneaded with a stir bar or spatula.
  • B Each raw material is kneaded with a double helical ribbon blade, a gate blade, or the like.
  • Each raw material is kneaded with a planetary mixer.
  • D Each raw material is kneaded by a bead mill.
  • E Each raw material is kneaded with three rolls.
  • Each raw material is kneaded by an extruder-type kneading extruder.
  • G Each raw material is kneaded by a rotating / revolving mixer.
  • each raw material can be performed in an arbitrary order, and all the raw materials may be added simultaneously or sequentially.
  • active energy ray illumination is performed through a filter that removes light having an absorption wavelength at which the photopolymerization initiator decomposes, prior to curing such as handling and mixing of the above raw materials.
  • the reaction can be performed under conditions where the polymerization initiator (D) does not act before the curing treatment, such as under or without irradiation with an active energy ray, or under a temperature at which the thermal polymerization initiator acts.
  • Curing method of curable composition By irradiating active energy rays or heating the curable composition of the present embodiment, the curable composition is cured to obtain a cured product.
  • active energy rays used at the time of curing include ultraviolet rays, electron beams, and X-rays, but ultraviolet rays are preferable because inexpensive devices can be used.
  • Various light sources can be used as the light source for curing the curable composition of the present embodiment with ultraviolet rays. Examples thereof include a black light, a UV-LED lamp, a high pressure mercury lamp, a pressurized mercury lamp, a metal halide lamp, a xenon lamp, and an electrodeless discharge lamp.
  • black light is a near-ultraviolet light having a wavelength of 300 nm or more and 430 nm or less (peak 350 nm) only when a near-ultraviolet phosphor is applied to a special outer glass cut from visible light and ultraviolet light having a wavelength of 300 nm or less. It is a lamp that radiates.
  • the UV-LED lamp is a lamp using a light emitting diode that emits ultraviolet rays.
  • metal halide lamps, high-pressure mercury lamps, and LED lamps (UV-LED lamps) are preferable from the viewpoint of curability.
  • the irradiation amount of the active energy ray may be an amount sufficient to cure the curable composition of the present embodiment, and the composition, usage amount, thickness, and cured product to be formed of the curable composition of the present embodiment.
  • the shape can be selected according to the shape. For example, when ultraviolet rays are radiated onto the coating film formed by coating the curable composition of the present embodiment is preferably 200 mJ / cm 2 or more 5000 mJ / cm 2 or less of the exposure amount, and more preferably 1000 mJ / cm it can be employed more than 3000 mJ / cm 2 or less of the exposure amount.
  • said exposure amount is a value when a measurement wavelength is 365 nm.
  • the application (coating) method in the case where the curable composition of the present embodiment is applied onto a substrate to form a coating film is not particularly limited.
  • natural coater curtain flow coater, comma coater, gravure coater, micro gravure coater, die coater, curtain coater, kiss roll, squeeze roll, reverse roll, air blade, knife belt coater, floating knife , A method using a knife over roll, a knife on blanket or the like.
  • a sheet-like cured product that is, a sheet material is obtained.
  • This sheet material may contain other components other than the cured product of the curable composition of the present embodiment, if necessary.
  • what is necessary is just to set the thickness of a sheet material suitably according to a use, but it is preferable that they are 0.1 mm or more and 10 mm or less, and it is more preferable that it is 0.3 mm or more and 8 mm or less from a viewpoint of a moldability.
  • this embodiment shows an example of this invention and this invention is not limited to this embodiment.
  • various changes or improvements can be added to the present embodiment, and forms to which such changes or improvements are added can also be included in the present invention.
  • (I) (Meth) allyl group-containing compound (A) The following four compounds (i-1) to (i-4) were used as the (meth) allyl group-containing compound (A).
  • the mixing ratio of the allyl group-containing compound represented by the formula (12) and the allyl group-containing compound represented by the formula (13) is 6: 4.
  • t and u in the formula (12) and the formula (13) are each independently an integer of 1 or more and 3 or less.
  • (Iii) Compound (C) The following four compounds (iii-1) to (iii-4) were used as the compound (C).
  • (Iii-1) Epoxy acrylate having a bisphenol A skeleton (VR77 manufactured by Showa Denko KK)
  • (Iii-2) Polyester acrylate having a bisphenol A type skeleton (Ebecryl 812 manufactured by Daicel Ornex Co., Ltd.)
  • (Iii-3) Unsaturated polyester resin having a bisphenol A type skeleton (trade name Rigolac LP-1M manufactured by Showa Denko KK)
  • (Iii-4) Epoxy acrylate represented by the following formula (14) (trade name: Epoxy ester 70PA manufactured by Kyoeisha Chemical Co., Ltd.)
  • Table 1 shows the (meth) allyl group-containing compound (A), thiol compound (B), compound (C) and / or (meth) acryloyloxy group-containing compound (c), and polymerization initiator (D). 2 were mixed at a mass ratio shown in 2, to prepare a curable composition.
  • “(A) / (B) functional group number ratio” is the number of (meth) allyl groups of the (meth) allyl group-containing compound (A) with respect to the number of mercapto groups of the thiol compound (B). Ratio (number of allyl groups / number of mercapto groups).
  • (C) mass ratio means (meth) allyl group-containing compound (A), thiol compound (B), compound (C) and / or (meth) acryloyloxy group-containing compound.
  • the total content with (c) is 1, the content of the compound (C) and / or the (meth) acryloyloxy group-containing compound (c) is shown.
  • test sheet thus obtained was subjected to a bending resistance test using a mandrel having a diameter of 2 mm in accordance with JIS K 5600. Flexibility and adhesion were evaluated in three stages of A, B, and C according to the following evaluation criteria.
  • A The test sheet is easily bent, and the flexibility of the cured product and the adhesion of the cured product to the copper / polyimide laminated substrate (coating object) are very excellent.
  • a test sheet similar to the above was immersed in an aqueous sulfuric acid solution having a concentration of 20% by mass and a temperature of 65 ° C. for 30 minutes.
  • the acid resistance 1 of the cured product was evaluated in three stages of A, B, and C according to the following evaluation criteria.
  • C The appearance of the cured product of the curable composition was changed, or the cured product was peeled from the copper / polyimide laminated substrate.
  • a test sheet similar to the above was immersed in a sulfuric acid aqueous solution having a concentration of 5% by mass and washed, and then immersed in an electroless tin plating solution 580M12Z manufactured by Ishihara Chemical Co., Ltd. at 60 ° C. for 4 minutes.
  • the test sheet was taken out from the electroless tin plating solution and repeatedly washed with warm water, and then subjected to a eutectic treatment at 120 ° C. for 90 minutes in a blow type constant temperature dryer.
  • the acid resistance 2 of the cured product was evaluated in three stages of A, B, and C according to the following evaluation criteria.
  • A The portion of the copper / polyimide laminated substrate that was not coated with the cured product could be plated without discoloring the portion of the copper coated with the cured product of the curable composition.
  • B Although it was possible to plate the portion of the copper / polyimide laminated substrate that was not coated with the cured product, the appearance of the copper or the cured product of the portion coated with the cured product was changed.
  • C The appearance of the cured product of the curable composition was changed, or plating was not possible because the cured product was peeled off from the copper / polyimide laminated substrate.
  • the curable compositions of Examples 1 to 16 were composed of (meth) allyl group-containing compound (A), thiol compound (B), and compound. Since (C) and the polymerization initiator (D) were contained, it was excellent in a softness
  • the cured product of the curable composition of Comparative Example 3 does not contain the (meth) allyl group-containing compound (A) and the thiol compound (B), the hardness of the cured product is too high and the adhesion is high. It was inferior. Therefore, when evaluating acid resistance, the cured product was peeled off from the copper / polyimide laminated substrate, and the acid resistance evaluation itself was not possible. Furthermore, since the cured product of the curable composition of Comparative Example 4 used a (meth) acryloyloxy group-containing compound (c) other than the compound (C) instead of the compound (C), it was the same as in Comparative Example 3. As a result.

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Abstract

L'invention concerne une composition durcissable qui permet de former un produit durci présentant d'excellentes propriétés de résistance aux acides, de flexibilité et d'adhérence. Cette composition durcissable contient un composé ( A) contenant un groupe méthallyle possédant au moins deux groupes méthallyle dans une molécule, un composé thiol (B) possédant au moins deux groupes mercapto dans une molécule, au moins un composé (C) choisi parmi des méthacrylates d'époxy, des polyester méthacrylates et des résines de polyester insaturées, et un initiateur de polymérisation (D).
PCT/JP2017/011480 2016-03-31 2017-03-22 Composition durcissable et produit durci obtenu à partir de celle-ci WO2017170049A1 (fr)

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WO2019102985A1 (fr) * 2017-11-24 2019-05-31 ミドリ安全株式会社 Gant, composition de moulage au trempé et procédé de fabrication de gant
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WO2020058880A1 (fr) * 2018-09-19 2020-03-26 3M Innovative Properties Company Composition comprenant un polythiol, un composé insaturé, et une charge et une composition en deux parties constituée à partir de ces derniers
US20220025122A1 (en) * 2018-09-19 2022-01-27 3M Innovative Properties Company Composition including a polythiol, an unsaturated compound, and a filler and a two-part composition made therefrom
CN114031775A (zh) * 2021-09-27 2022-02-11 武汉纺织大学 绿色无溶剂生物基抗菌胶粘剂及其制备方法
CN114031775B (zh) * 2021-09-27 2023-07-07 武汉纺织大学 绿色无溶剂生物基抗菌胶粘剂及其制备方法

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