WO2017150615A1 - Composition durcissable - Google Patents

Composition durcissable Download PDF

Info

Publication number
WO2017150615A1
WO2017150615A1 PCT/JP2017/008119 JP2017008119W WO2017150615A1 WO 2017150615 A1 WO2017150615 A1 WO 2017150615A1 JP 2017008119 W JP2017008119 W JP 2017008119W WO 2017150615 A1 WO2017150615 A1 WO 2017150615A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
compound
curable
curable composition
weight
Prior art date
Application number
PCT/JP2017/008119
Other languages
English (en)
Japanese (ja)
Inventor
坂根正憲
Original Assignee
株式会社ダイセル
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社ダイセル filed Critical 株式会社ダイセル
Publication of WO2017150615A1 publication Critical patent/WO2017150615A1/fr

Links

Classifications

    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof

Definitions

  • the present invention relates to a light or thermosetting composition.
  • This application claims the priority of Japanese Patent Application No. 2016-039842 for which it applied to Japan on March 2, 2016, and uses the content here.
  • Carbon fibers themselves are small and brittle, but can be reinforced by impregnating a matrix resin such as an epoxy resin or an acrylic resin and then curing the matrix resin.
  • the carbon fiber reinforced carbon fiber reinforced resin or carbon fiber reinforced plastic
  • a sizing agent is used for the purpose of improving the adhesion between the carbon fiber and the matrix resin and imparting excellent mechanical strength (toughness and scratch resistance) to the carbon fiber. .
  • a curable composition containing a compound having a (meth) acryloyloxy group as a radical curable group and a glycidyl group as a cationic curable group has been mainly used (Patent Document 1, etc.). .
  • an object of the present invention is to provide a curable composition that can form a cured product that is excellent in curability, toughness, and scratch resistance.
  • Another object of the present invention is to provide a carbon fiber sizing agent that has excellent curability and can impart excellent toughness and scratch resistance to carbon fibers.
  • a compound having a (meth) acryloyloxy group as a radical curable group and an alicyclic epoxy group as a cationic curable group in one molecule is excellent in curing. And can be cured quickly by light irradiation or heat treatment to form a cured product with excellent toughness and scratch resistance, and a curable composition containing the above compound for carbon fibers. It has been found that when used as a sizing agent, the carbon fiber can be provided with good toughness and scratch resistance with excellent workability. The present invention has been completed based on these findings.
  • this invention is a curable composition containing a curable compound, Comprising: The compound which has an alicyclic epoxy group and (meth) acryloyloxy group in 1 molecule as said curable compound is contained in a curable composition.
  • a curable composition containing 0.1 to 99.9% by weight of the total amount of the curable compound.
  • the present invention also provides the above curable composition, which is a light or thermosetting composition.
  • the compound having an alicyclic epoxy group and a (meth) acryloyloxy group in one molecule is represented by the following formula (a-1): (Wherein X represents a single bond or a linking group, and R 1 represents a hydrogen atom or a methyl group)
  • the curable composition is a compound represented by:
  • the present invention also provides the curable composition as described above, which is a sizing agent for carbon fiber.
  • a compound having an alicyclic epoxy group and a (meth) acryloyloxy group in one molecule is a compound containing one alicyclic epoxy group and one (meth) acryloyloxy group in one molecule.
  • a compound having an alicyclic epoxy group and a (meth) acryloyloxy group in one molecule is represented by formula (a) (wherein ring Z represents an alicyclic ring constituting an alicyclic epoxy group, and X represents a single bond. Or R 1 represents a hydrogen atom or a methyl group, and the curable composition according to [1] or [2].
  • Ring Z in formula (a) contains 3 to 20 membered cycloalkane ring, 3 to 20 membered cycloalkene ring, or bridged ring (preferably 2 to 4 3 to 10 membered rings)
  • the curable composition according to [4] which is a bridge ring).
  • the curable composition according to [1] or [2], wherein the compound having an alicyclic epoxy group and a (meth) acryloyloxy group in one molecule is a compound represented by the formula (a-1). object.
  • the curable compound further contains a cationic curable compound (excluding a compound containing a radical curable group) and / or a radical curable compound (excluding a compound containing a cation curable group), [1] The curable composition according to any one of [6].
  • the total content of the cationic curable compound and the radical curable compound is 0.1 to 99.9% by weight of the total amount of the curable compound contained in the curable composition (preferably 5 to 99% by weight,
  • the cationically curable compound is (3,4,3 ′, 4′-diepoxy) bicyclohexyl, bis (3,4-epoxycyclohexylmethyl) ether, 1,2-epoxy-1,2-bis (3 , 4-epoxycyclohexane-1-yl) ethane, 2,2-bis (3,4-epoxycyclohexane-1-yl) propane, 1,2-bis (3,4-epoxycyclohexane-1-yl) ethane,
  • the curable composition according to any one of [7] to [9] which is at least one compound selected from the compounds represented by formulas (b-1) to (b-10): [15]
  • the content of the cationic curable compound preferably an epoxy compound, more preferably an alicyclic epoxy compound, particularly preferably an alicyclic epoxy group-
  • the total amount of the curable compound contained in the curable composition is the total content of the compound having an alicyclic epoxy group and (meth) acryloyloxy group in one molecule, the cationic curable compound, and the radical curable compound.
  • Composition [18]
  • the content of components other than the curable compound, the polymerization initiator, the curing agent, and the curing accelerator is 0.05 to 10% by weight (preferably 0.1 to 5% by weight) of the total amount of the curable composition.
  • a carbon fiber reinforced resin is obtained by applying the curable composition according to any one of [1] to [18] to carbon fiber and then curing the applied curable composition. The manufacturing method of carbon fiber reinforced resin.
  • the curable composition of the present invention includes, as a curable compound, a compound having a (meth) acryloyloxy group as a radical curable group and an alicyclic epoxy group as a cationic curable group in one molecule in a specific range. Since it contains, it is excellent in sclerosis
  • inks for example, 3D printer ink
  • sealants for example, sealants for optical semiconductors
  • an insulating film forming material an adhesive sheet forming material for touch panels, a prepreg forming material, a sizing agent, a matrix resin for carbon fiber reinforced resin, and the like.
  • the curable composition of the present invention is used as a carbon fiber sizing agent or a carbon fiber reinforced resin matrix resin, excellent toughness and scratch resistance can be efficiently imparted to the carbon fiber.
  • the curable composition of the present invention is a curable composition containing a curable compound, and the curable compound includes a compound having an alicyclic epoxy group and a (meth) acryloyloxy group in one molecule (hereinafter, “ At least one of the component (A) ”and the“ alicyclic epoxy group-containing acrylate ”may be contained in an amount of 0.1 to 99.9% by weight of the total amount of the curable compound contained in the curable composition.
  • the curable composition of this invention may contain the below-mentioned component (B) and component (C) other than the said component (A) as a sclerosing
  • Component (A): Alicyclic epoxy group-containing acrylate is a compound having an alicyclic epoxy group as a cationic curable group and a (meth) acryloyloxy group as a radical curable group in one molecule.
  • the “alicyclic epoxy group” is “a group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring”.
  • (meth) acryloyloxy group” in the present specification refers to an acryloyloxy group and a methacryloyloxy group.
  • the alicyclic epoxy group-containing acrylate of the present invention is particularly preferably a compound containing one alicyclic epoxy group and one (meth) acryloyloxy group in one molecule.
  • an alicyclic epoxy group-containing acrylate represented by the following formula (a) A cyclic epoxy group-containing (meth) acrylate is preferred.
  • the ring Z shows the alicyclic ring which comprises an alicyclic epoxy group
  • X shows a single bond or a coupling group
  • R 1 represents a hydrogen atom or a methyl group.
  • Examples of the alicyclic ring include cycloalkane rings of about 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 8 members) such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane.
  • the alicyclic ring may be condensed with an aromatic or non-aromatic heterocyclic ring.
  • the alicyclic ring may have various substituents.
  • substituents include a halogen atom, an oxo group, a hydroxyl group, a substituted oxy group (for example, a C 1-4 alkoxy group, a C 6-10 aryloxy group, a C 7-16 aralkyloxy group, a C 1-4 acyloxy group).
  • carboxyl group substituted oxycarbonyl group (eg C 1-4 alkoxycarbonyl group, C 6-10 aryloxycarbonyl group, C 7-16 aralkyloxycarbonyl group etc.), substituted or unsubstituted carbamoyl group (eg C 1-4 alkyl substituted carbamoyl such as carbamoyl, methyl carbamoyl, C 6-10 aryl substituted carbamoyl group such as phenyl carbamoyl group), cyano group, nitro group, substituted or unsubstituted amino group (eg, methylamino, dimethylamino) , ethylamino, mono- or di-C 1-4 alkylamino group such as a diethylamino group; 1-pyrrolidinyl, Piperi Bruno, cyclic amino group of 5-8 membered, such as a morpholino group; acetylamino, propionylamino, C 1-10
  • the linking group in X is a divalent group having one or more atoms.
  • a divalent hydrocarbon group a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S -), An ester bond (-COO-), an amide bond (-CONH-), a carbonate bond (-OCOO-), and a group in which two or more selected from these are bonded.
  • Examples of the divalent hydrocarbon group include 1 to 20 carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group (preferably 1 to 10, particularly preferably 1 to An alkylene group of about 3); an alkenylene group of about 2 to 20 carbon atoms (preferably 2 to 10, particularly preferably 2 to 4) such as a vinylene group, a propenylene group, or a 1-butenylene group; an ethynylene group, a propynylene group, etc.
  • 1 to 20 carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group (preferably 1 to 10, particularly preferably 1 to An alkylene group of about 3); an alkenylene group of about 2 to 20 carbon atoms (preferably 2 to 10, particularly preferably 2 to 4) such as
  • alkynylene group having about 2 to 20 carbon atoms preferably 2 to 10, particularly preferably 2 to 3
  • 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2 -C3-20 (preferably 3-3) such as cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group, cyclohexylidene group, etc.
  • 1, particularly preferable examples thereof include such as 3-6) about a cycloalkylene group (including cycloalkylidene group).
  • a compound represented by the following formula (a-1) is preferable from the viewpoint of safety such as sensitization.
  • X and R 1 are the same as described above.
  • a commercially available product such as a trade name “E-DCPA” (a compound in which X in the following formula is a single bond; manufactured by Daicel Corporation) can be suitably used.
  • Component (B) in the present invention is a compound having one or more cationic curable groups in one molecule (excluding compounds containing radical curable groups). These can be used alone or in combination of two or more.
  • the cationic curable group include an epoxy group, an oxetane group, and a vinyl ether group.
  • a compound containing an epoxy group as a cationic curable group, that is, an epoxy compound is preferable from the viewpoint of the balance between the cationic curable property and the physical properties of the obtained cured product.
  • the epoxy compound is a compound having one or more epoxy groups (oxirane rings) in one molecule, such as an alicyclic epoxy compound; an aromatic epoxy compound (for example, bisphenol A type epoxy compound, bisphenol F type epoxy compound). Aromatic glycidyl ether epoxy compounds); aliphatic epoxy compounds; glycidyl ester epoxy compounds; glycidyl amine epoxy compounds; epoxy-modified siloxane compounds and the like.
  • an alicyclic epoxy compound in view of particularly excellent cationic curability.
  • the alicyclic epoxy compound includes the following compounds (i) to (iii).
  • (I) Compound having an alicyclic epoxy group (hereinafter sometimes referred to as “alicyclic epoxy group-containing compound”)
  • the above compound (i), that is, an alicyclic epoxy group-containing compound is particularly preferable.
  • the alicyclic epoxy group-containing compound among them, a compound having a cyclohexene oxide group is preferable in that a cured product particularly excellent in toughness and scratch resistance is obtained, and particularly represented by the following formula (b). Compounds are preferred.
  • Y shows a single bond or a coupling group.
  • the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of a carbon-carbon double bond is epoxidized, a carbonyl group (—CO—), an ether bond (—O—), Examples include an ester bond (—COO—), a carbonate group (—O—CO—O—), an amide group (—CONH—), and a group in which a plurality of these are linked.
  • the cyclohexene oxide group in the formula (b) may have a substituent such as a C 1-5 alkyl group.
  • divalent hydrocarbon group examples include the same examples as the divalent hydrocarbon group in X.
  • the divalent hydrocarbon group may be any of various substituents [eg, halogen atom, oxo group, hydroxyl group, carboxyl group, substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group. Group, epoxy group, heterocyclic group, etc.].
  • the hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis.
  • alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized include, for example, vinylene group, propenylene group, 1-butenylene group And straight-chain or branched alkenylene groups having 2 to 8 carbon atoms such as 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group and the like.
  • the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.
  • alicyclic epoxy group-containing compound examples include, for example, (3,4,3 ′, 4′-diepoxy) bicyclohexyl, bis (3,4-epoxycyclohexylmethyl) ether, 1,2-epoxy. -1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 2,2-bis (3,4-epoxycyclohexane-1-yl) propane, 1,2-bis (3,4-epoxy) And cyclohexane-1-yl) ethane and compounds represented by the following formulas (b-1) to (b-10). In the following formulas (b-5) and (b-7), n 1 and n 2 each represents an integer of 1 to 30.
  • L in the following formula (b-5) is an alkylene group having 1 to 8 carbon atoms, for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene group.
  • a linear or branched alkylene group such as a hexylene group, a heptylene group, and an octylene group.
  • linear or branched alkylene groups having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group are preferable.
  • N 3 to n 8 in the following formulas (b-9) and (b-10) each represents an integer of 1 to 30.
  • Examples of the compound (ii) in which the epoxy group is directly bonded to the alicyclic ring with a single bond include a compound represented by the following formula (b2).
  • R ′′ is a group obtained by removing p OH groups from the structural formula of the p-valent alcohol, and p and n each represent a natural number.
  • the p-valent alcohol [R ′′-(OH) p ] Includes, for example, polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol (alcohols having 1 to 15 carbon atoms, etc.).
  • p is preferably 1 to 6
  • n is preferably 1 to 30.
  • ns in the respective groups within [] (inside the outer parentheses) may be the same or different.
  • Examples of the (iii) hydrogenated aromatic glycidyl ether-based epoxy compound include 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2-bis [3,5- A compound obtained by hydrogenating a bisphenol A type epoxy compound such as dimethyl-4- (2,3-epoxypropoxy) cyclohexyl] propane (nuclear hydrogenated bisphenol A type epoxy compound); bis [o, o- (2,3 -Epoxypropoxy) cyclohexyl] methane, bis [o, p- (2,3-epoxypropoxy) cyclohexyl] methane, bis [p, p- (2,3-epoxypropoxy) cyclohexyl] methane, Bisphenol F type epoxy compounds such as bis [3,5-dimethyl-4- (2,3-epoxypropoxy) cyclohexyl] methane Compound (nuclear hydrogenated bisphenol F type epoxy compound); hydrogen
  • Component (C) in the present invention is a compound having one or more radical curable groups (for example, (meth) acryloyloxy group, vinyl group, vinyl ether group, etc.) in the molecule (compound containing a cationic curable group) Except). These can be used alone or in combination of two or more.
  • radical curable groups for example, (meth) acryloyloxy group, vinyl group, vinyl ether group, etc.
  • radical curable compound examples include (meth) acryl such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) acrylate.
  • Acid alkyl ester [eg (meth) acrylic acid C 1-10 alkyl ester, etc.]; benzyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, adamantyl (meth) acrylate, cyclopentenyl (meth) acrylate , Isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2- (dicyclopentenyloxy) ethyl (meth) acrylate, 2- (disicyl) (Meth) acrylic acid ester having a cyclic structure (aliphatic cyclic structure or aromatic cyclic structure) in the molecule such as pentanyloxy) ethyl (meth) acrylate; styrene, vinyltoluene, ⁇ -methylstyrene, vinylnaphthal
  • Styrenic compounds such as methyl vinyl ether, butyl vinyl ether, and phenyl vinyl ether, and derivatives thereof (for example, compounds in which substituents such as a hydroxyl group, a carboxyl group, a quaternary ammonium group, an amino group, and a heterocyclic group are bonded. And the like.
  • the curable composition of the present invention preferably contains one or more selected from a polymerization initiator, a curing agent, and a curing accelerator together with the above-described curable compound.
  • a polymerization initiator preferably contains a radical polymerization initiator and a cationic polymerization initiator) or a curing agent and a curing accelerator.
  • the polymerization initiator includes a radical photopolymerization initiator, a thermal radical polymerization initiator, a cationic photopolymerization initiator, and a thermal cationic polymerization initiator.
  • Photo radical polymerization initiator examples include benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyl disulfite, Orthobenzoyl methyl benzoate, ethyl 4-dimethylaminobenzoate (Nippon Kayaku Co., Ltd., trade name “Kayacure EPA”, etc.), 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd., trade name) “Kayacure DETX” etc.), 2-methyl-1- [4- (methyl) phenyl] -2-morpholinopropanone-1 (manufactured by BASF, trade name “Irgacure
  • thermal radical polymerization initiator examples include azo compounds such as azobisisobutyronitrile, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxydicarbonate, peroxyketal, and ketone peroxide.
  • Oxides (specifically, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoyl) peroxyhexane, t-butyl Peroxybenzoate, t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-dibutylperoxyhexane, 2,4-dichlorobenzoylper Oxide, 1,4-di (2- -Butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, methyl ethyl ketone peroxide, 1,1,3,3-tetramethylbutylperoxy-2- And organic peroxides such as ethylhexanoate).
  • the cationic photopolymerization initiator is a compound that generates an acid upon irradiation with light and initiates a curing reaction of the cationic curable compound contained in the curable composition, and includes a cation moiety that absorbs light and a source of acid generation. It consists of the anion part.
  • Examples of the cationic photopolymerization initiator include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, bromine salt compounds, and the like. Among them, it is preferable to use a sulfonium salt compound in that a cured product having excellent curability can be formed.
  • Examples of the cation moiety of the sulfonium salt compound include (4-hydroxyphenyl) methylbenzylsulfonium ion, triphenylsulfonium ion, diphenyl [4- (phenylthio) phenyl] sulfonium ion, and 4- (4-biphenylylthio) phenyl.
  • Examples thereof include arylsulfonium ions such as -4-biphenylylphenylsulfonium ion and tri-p-tolylsulfonium ion (particularly, triarylsulfonium ion).
  • Y represents a phenyl group or a biphenylyl group.
  • Phf represents at least one hydrogen atom
  • BF 4 ⁇ [(Rf) t PF 6-t ] - (Rf: an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, t: an integer of 0 to 5), AsF 6 ⁇ , SbF 6 ⁇ , SbF 5 OH ⁇ and the like. it can.
  • Examples of the cationic photopolymerization initiator include (4-hydroxyphenyl) methylbenzylsulfonium tetrakis (pentafluorophenyl) borate, 4- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) Borate, 4- (phenylthio) phenyldiphenylsulfonium phenyltris (pentafluorophenyl) borate, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluorophenyl) borate, diphenyl [4 -(Phenylthio) phenylsulfonium] hexafluoroantimonate, diphenyl [4- (phenylthio) pheny
  • Thermal cationic polymerization initiator is a compound that generates an acid by heat treatment and initiates a curing reaction of the cationic curable compound contained in the curable composition, and a cationic part that absorbs heat and a source of the acid It consists of an anion part.
  • thermal cationic polymerization initiator examples include iodonium salt compounds and sulfonium salt compounds.
  • Examples of the cationic part of the thermal cationic polymerization initiator include 4-hydroxyphenyl-methyl-benzylsulfonium ion, 4-hydroxyphenyl-methyl- (2-methylbenzyl) sulfonium ion, 4-hydroxyphenyl-methyl-1-naphthyl. Examples include methylsulfonium ion and p-methoxycarbonyloxyphenyl-benzyl-methylsulfonium ion.
  • Examples of the anion portion of the thermal cationic polymerization initiator include the same examples as the anion portion of the photocationic polymerization initiator.
  • thermal cationic polymerization initiator examples include 4-hydroxyphenyl-methyl-benzylsulfonium phenyltris (pentafluorophenyl) borate, 4-hydroxyphenyl-methyl- (2-methylbenzyl) sulfonium phenyltris (pentafluorophenyl) borate 4-hydroxyphenyl-methyl-1-naphthylmethylsulfonium, phenyltris (pentafluorophenyl) borate, p-methoxycarbonyloxyphenyl-benzyl-methylsulfonium, phenyltris (pentafluorophenyl) borate, and the like. These can be used alone or in combination of two or more.
  • the curing agent in the present invention is a compound that reacts with a compound having an epoxy group (particularly, an alicyclic epoxy group) to form a crosslinked structure by heat treatment.
  • a compound having an epoxy group particularly, an alicyclic epoxy group
  • an acid anhydride, an imidazole compound, an amine examples thereof include compounds, polyamide resins, polysulfide resins, and latent curing agents. These can be used alone or in combination of two or more.
  • Examples of the acid anhydride include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, hydrogenated methylnadic acid anhydride, methylheimic acid anhydride, Trialkyltetrahydrophthalic anhydride maleic acid adduct, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride, and derivatives thereof (for example, a substituent such as an alkyl group is bonded to the ring) Etc.).
  • an anhydride of a saturated monocyclic hydrocarbon dicarboxylic acid or a derivative thereof is particularly preferable from the viewpoint of transparency and light resistance of the cured product.
  • an acid anhydride that is liquid at 25 ° C. for example, hydrogenated methylnadic acid anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, Methyl endomethylenetetrahydrophthalic anhydride and the like are preferable, and hydrogenated methyl nadic acid anhydride is particularly preferable.
  • Examples of the acid anhydride include a product name “Licacid MH-700” (manufactured by Shin Nippon Rika Co., Ltd.), a product name “Rikacid MH-700F” (manufactured by Shin Nippon Rika Co., Ltd.) and a product name “HN-5500 ”(Manufactured by Hitachi Chemical Co., Ltd.) can be used.
  • imidazole compound examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium tolmellitate, and the like.
  • Examples of the amine compound include piperidine, N, N-dimethylpiperazine, triethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, diethylenetriamine, and diethylamino.
  • Examples include propylamine, xylenediamine, metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone.
  • latent curing agent e.g., boron trifluoride - amine complex, dicyandiamide, organic acid hydrazide, SbF 6 - aromatic sulfonium salts (e.g., trade name "San-Aid SI-100L”, “San-Aid SI-60L” , “Sun-Aid SI-80L”, “Sun-Aid SI-110”, “Sun-Aid SI-180”, Sanshin Chemical Industry Co., Ltd.) and the like.
  • SbF 6 - aromatic sulfonium salts e.g., trade name "San-Aid SI-100L", “San-Aid SI-60L” , “Sun-Aid SI-80L”, “Sun-Aid SI-110”, “Sun-Aid SI-180”, Sanshin Chemical Industry Co., Ltd.
  • the curing accelerator in the present invention is a compound that promotes the reaction between a curing agent and a compound having an epoxy group (particularly an alicyclic epoxy group), and exhibits an effect of quickly curing at a milder temperature.
  • curing accelerator examples include trade names “U-CAT SA 506”, “U-CAT SA 102”, “U-CAT 5003”, “U-CAT 18X”, “U-CAT 12XD” (developed product). (San Apro Co., Ltd.), TPP-K, TPP-MK (Hokuko Chemical Co., Ltd.), PX-4ET (Nippon Chemical Co., Ltd.), 2E4MZ ”(Manufactured by Shikoku Kasei Kogyo Co., Ltd.) can be used.
  • the curable composition of the present invention may contain one or more other components as necessary in addition to the above components.
  • other components include sensitizers, sensitizers, antioxidants, stabilizers, surfactants, solvents, leveling agents, silane coupling agents, fillers, polymerization inhibitors, light stabilizers, Examples thereof include a plasticizer, an antifoaming agent, a foaming agent, an ultraviolet absorber, an ion adsorbent, a pigment, a phosphor, and a release agent.
  • These contents are, for example, about 0.05 to 10% by weight, preferably 0.1 to 5% by weight, based on the total amount (100% by weight) of the curable composition. .
  • the curable composition of the present invention comprises a component (A) and, if necessary, a component (B), a component (C), a component (D), and other components, a self-revolving stirring deaerator, a homogenizer , A planetary mixer, a three-roll mill, a bead mill, and the like. Each component may be mixed simultaneously or sequentially.
  • the content of the component (A) (preferably the compound represented by the formula (a), particularly preferably the compound represented by the formula (a-1)) (the total amount when containing two or more) is the present invention.
  • 0.1 to 99.9% by weight of the total amount (100% by weight) of the curable compound contained in the curable composition preferably 1 to 95% by weight, more preferably 2 to 90% by weight, and particularly preferably 30 to 90% by weight, most preferably 60 to 90% by weight.
  • the curable composition of this invention contains a component (A) in the said range, it can be excellent in sclerosis
  • the content of the component (A) is less than the above range, the adhesion to the substrate tends to decrease, and if the content of the component (A) exceeds the above range, the toughness and scratch resistance are high. There is a tendency to decrease.
  • the curable composition of the present invention comprises component (A) and component (B) (preferably an epoxy compound, particularly preferably an alicyclic epoxy compound, most preferably an alicyclic epoxy group-containing compound) and / or component (C).
  • component (B) and component (C) preferably an epoxy compound, particularly preferably an alicyclic epoxy compound, most preferably an alicyclic epoxy group-containing compound
  • component (C) preferably an epoxy compound, particularly preferably an alicyclic epoxy compound, most preferably an alicyclic epoxy group-containing compound
  • component (C) preferably an epoxy compound, particularly preferably an alicyclic epoxy compound, most preferably an alicyclic epoxy group-containing compound
  • component (C) preferably an epoxy compound, particularly preferably an alicyclic epoxy compound, most preferably an alicyclic epoxy group-containing compound
  • component (C) preferably an epoxy compound, particularly preferably an alicyclic epoxy compound, most preferably an alicyclic epoxy group-containing compound
  • component (C) preferably an epoxy compound,
  • the weight ratio of the content of component (A) in the curable composition of the present invention and the total content of component (B) and component (C) [component (A) / (component (B) + component (C ))] Is, for example, 95/5 to 60/40, preferably 95/5 to 70/30, particularly preferably 90/10 to 75/25.
  • the curable composition of the present invention contains the component (A), the component (B), and the component (C) in the above range, a cured product having excellent curability and excellent toughness and scratch resistance is formed. Can do.
  • component (B) (preferably an epoxy compound, particularly preferably an alicyclic epoxy compound, most preferably an alicyclic epoxy group-containing compound) in the total amount (100% by weight) of the curable compound contained in the curable composition of the present invention. ) (When two or more types are contained, the total amount thereof) is, for example, 0.1 to 99.9% by weight, preferably 5 to 99% by weight, more preferably 10 to 90% by weight, and particularly preferably 10 to 90% by weight. 70% by weight, most preferably 10-40% by weight.
  • component (B) preferably an epoxy compound, particularly preferably an alicyclic epoxy compound, most preferably an alicyclic epoxy group-containing compound
  • component (C) contained in the curable composition of the present invention.
  • the proportion of component (B) in is, for example, 60% by weight or more, preferably 80% by weight or more, and particularly preferably 90% by weight or more.
  • the ratio of the total content of component (A), component (B) and component (C) in the total amount (100% by weight) of the curable compound contained in the curable composition of the present invention is, for example, 60% by weight or more, preferably Is 70% by weight or more, particularly preferably 80% by weight or more, most preferably 90% by weight or more, and particularly preferably 95% by weight or more.
  • the upper limit is 100% by weight.
  • the curable composition of this invention may contain curable compounds other than a component (A), a component (B), and a component (C), the content is curable compound whole quantity (100 % By weight), for example, 40% by weight or less, preferably 30% by weight or less, particularly preferably 20% by weight or less, most preferably 10% by weight or less, and particularly preferably 5% by weight or less.
  • the content of the radical polymerization initiator in the case where the curable composition of the present invention contains a polymerization initiator is the radical curable group contained in the curable composition of the present invention.
  • 0.1 to 10.0 parts by weight, preferably 0.1 to 5.0 parts by weight, per 100 parts by weight of the total amount of the compound having (preferably, the total amount of component (A) and component (C)) Particularly preferably 0.2 to 3.0 parts by weight, and most preferably 0.2 to 1.0 parts by weight.
  • all radical curable groups contained in the curable composition are contained. It is preferable to contain it in a proportion of 0.001 to 0.1 equivalent per equivalent of radical curable group (preferably (meth) acryloyloxy group) in the compound.
  • the content of the cationic polymerization initiator in the case where the curable composition of the present invention contains a polymerization initiator is the cationic curable group contained in the curable composition.
  • Particularly preferred is 0.2 to 3.0 parts by weight, and most preferred is 0.2 to 1.0 part by weight. More specifically, it has all the cationic curable groups contained in the curable composition.
  • cationically curable group preferably epoxy group
  • content of a cationic polymerization initiator is less than the said range, there exists a tendency for sclerosis
  • content of the cationic polymerization initiator exceeds the above range, particularly when the curable composition of the present invention is a photocurable composition, internal cured defects tend to occur easily in the obtained cured product. is there.
  • the content of the acid anhydride (the total amount when two or more types are contained) is the cation curable contained in the curable composition.
  • the cation curable contained in the curable composition For example, 50 to 200 parts by weight, preferably 100 to 145 parts by weight, more specifically, with respect to 100 parts by weight of the total amount of the compound having a group (preferably the total amount of component (A) and component (B))
  • the ratio of the acid anhydride group to 0.5 to 1.5 equivalents per equivalent of the cationically curable group (preferably epoxy group) in the compound having all the cationic curable groups contained in the curable composition It is preferable to contain.
  • the content of the acid anhydride is less than 50 parts by weight, the curing becomes insufficient and the toughness of the resulting cured product tends to decrease. On the other hand, if the content of the acid anhydride exceeds 200 parts by weight, the cured product may be colored to deteriorate the hue.
  • the content of the latent curing agent (the total amount when containing two or more types) is the cation contained in the curable composition.
  • Particularly preferred is 1 to 5 parts by weight.
  • the content of the latent curing agent is less than 0.1 parts by weight, curing becomes insufficient, and the toughness of the obtained cured product tends to decrease.
  • the content of the latent curing agent exceeds 5 parts by weight, the cured product may be colored to deteriorate the hue.
  • the curable composition of this invention contains a hardening
  • a hardening accelerator the total amount when it contains 2 or more types
  • content of the hardening accelerator is curable.
  • 0.05 to 5 parts by weight, preferably 0 with respect to 100 parts by weight of the total amount of compounds having a cationically curable group contained in the composition preferably the total amount of components (A) and (B)) 0.1 to 3 parts by weight, more preferably 0.2 to 3 parts by weight, particularly preferably 0.2 to 2.5 parts by weight, and most preferably 0.2 to 1.0 parts by weight.
  • the curing accelerator is contained in the range of 0.05 parts by weight or more, an excellent curing acceleration effect can be obtained.
  • a hardening accelerator is contained in 5 weight part or less, coloring of hardened
  • the curable composition of the present invention is excellent in curability and can quickly form a cured product by light irradiation or heat treatment.
  • a cured product can be formed by irradiating active energy rays such as ultraviolet rays.
  • active energy ray in addition to ultraviolet rays, for example, visible rays, infrared rays, X rays, ⁇ rays, ⁇ rays, ⁇ rays, electron rays, and the like can be used. Irradiation conditions can be appropriately changed according to the thickness of the applied curable composition.
  • the wavelength of the active energy ray is usually in the range of 200 to 600 nm, and a wavelength with high sensitivity can be appropriately selected and used according to the type of the photocationic polymerization initiator.
  • a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, or the like can be used as the ultraviolet irradiation source.
  • the irradiation amount is preferably within a range where the dose is 50 to 2000 mJ / cm 2 .
  • heat treatment may be performed as necessary.
  • unreacted substances in the curable composition can be reduced, and in the case of molding, distortion generated by the molding can be reduced.
  • the heating can be performed, for example, at an ambient temperature of 100 to 200 ° C. for 1 to 120 minutes.
  • a cured product can be formed by heat treatment.
  • the heat treatment temperature is, for example, 40 to 250 ° C.
  • the heat treatment time is, for example, 30 minutes to 12 hours. Further, the heat treatment may be performed at the same temperature, or may be performed by changing the temperature stepwise.
  • the cured product of the curable composition of the present invention is excellent in toughness and scratch resistance, and the pencil hardness (pencil hardness test; conforming to JIS K 5600-5-4) is, for example, H or more, preferably 2H or more.
  • the curable composition of the present invention is excellent in curability as described above, and can be quickly cured by light irradiation and / or heat treatment to form a cured product having excellent toughness and scratch resistance. . Therefore, the curable composition of the present invention is used for, for example, paints, inks (for example, 3D printer ink), adhesives, sealants (for example, optical semiconductor sealants), LSIs, and multilayer printed wiring boards.
  • Interlayer insulating film forming material adhesive sheet forming material for touch panel, prepreg forming material, sizing agent, matrix resin for carbon fiber reinforced resin, resist, sealant, optical material (for example, laminate, transparent substrate, transparent sheet, transparent film) , Optical elements (for example, optical lenses), stereolithography, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memory, etc., can be used in a wide range of applications.
  • the sizing agent of this invention consists of the above-mentioned curable composition containing a component (A) at least. Since the sizing agent of the present invention has the above-described configuration, it has excellent interfacial adhesion between the carbon fiber and the matrix resin, and by applying the sizing agent of the present invention to the carbon fiber and then curing, the toughness excellent in the carbon fiber. And scratch resistance can be efficiently imparted with excellent workability.
  • Example 1 A curable composition was prepared according to the formulation (unit: parts by weight) described in the following table.
  • the obtained curable composition was applied to a base material (aluminum plate treated with chromium phosphate) so as to have a film thickness of 10 ⁇ m, and was irradiated with ultraviolet rays (dose; 1100 mJ / cm 2) using a high-pressure mercury lamp. 2 ) to obtain a cured coating film (cured product).
  • the pencil hardness of the obtained cured coating film was evaluated by a method according to JIS K5600-5-4.
  • Examples 2-3 and Comparative Example 1 A curable composition was prepared in the same manner as in Example 1 except that the formulation shown in the following table was changed to obtain a cured coating film. In Examples 2 and 3, heat treatment was performed at 150 ° C. for 2 hours instead of ultraviolet irradiation.
  • EDCPA 3,4-epoxytricyclo [5.2.1.0 2,6 ] decan-9-yl acrylate represented by the following formula (a-1-1), trade name “E-DCPA”, Made by Daicel Corporation
  • GMA Glycidyl methacrylate
  • Blenmer G manufactured by NOF Corporation
  • Celoxide 2021P 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, trade name “Celoxide 2021P”, manufactured by Daicel Corporation ⁇ polymerization initiator>
  • Irgacure184 Photoradical polymerization initiator, 1-hydroxy-cyclohexyl phenyl ketone, trade name “Irgacure184”, BASF
  • CPI-101A Photocationic polymerization initiator, diphenyl [4- (phenylthio) phenyl] sulfonium hex
  • U-CAT 12XD Epoxy resin curing accelerator, special amine, manufactured by San Apro Co., Ltd. 2E4MZ: Epoxy resin curing accelerator, 2-ethyl-4-methylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.
  • the curable composition of the present invention is particularly excellent in curability, and can be quickly cured by light irradiation or heat treatment to form a cured product having excellent toughness and scratch resistance. Therefore, paints, inks, adhesives, sealants, interlayer insulating film forming materials used for LSIs and multilayer printed wiring boards, touch panel adhesive sheet forming materials, prepreg forming materials, sizing agents, matrix resins for carbon fiber reinforced resins, etc. Can be suitably used.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne une composition durcissable possédant une excellente aptitude au durcissement et pouvant former un produit durci d'une excellente dureté et d'une excellente résistance à l'abrasion. La composition durcissable de la présente invention contient un composé durcissable. Tout comme le composé durcissable, la composition durcissable contient de 0,1 à 99,9 % en poids d'un composé présentant un groupe époxy alicyclique et un groupe (méth)acryloyloxy par molécule du composé durcissable total qui est contenu dans la composition durcissable. Étant donné que le composé présente un groupe époxy alicyclique et un groupe (méth)acryloyloxy par molécule, le composé représenté par la formule (a-1) est préférable.
PCT/JP2017/008119 2016-03-02 2017-03-01 Composition durcissable WO2017150615A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-039842 2016-03-02
JP2016039842 2016-03-02

Publications (1)

Publication Number Publication Date
WO2017150615A1 true WO2017150615A1 (fr) 2017-09-08

Family

ID=59744155

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/008119 WO2017150615A1 (fr) 2016-03-02 2017-03-01 Composition durcissable

Country Status (1)

Country Link
WO (1) WO2017150615A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01123817A (ja) * 1987-11-09 1989-05-16 Kansai Paint Co Ltd 硬化性組成物
JPH10310681A (ja) * 1997-05-12 1998-11-24 Toyo Ink Mfg Co Ltd 放射線硬化性樹脂組成物およびその製造方法
JP2005226193A (ja) * 2004-02-13 2005-08-25 Mitsubishi Rayon Co Ltd 強化繊維用サイジング剤、炭素繊維束、熱可塑性樹脂組成物及びその成形品
JP2013092759A (ja) * 2011-10-07 2013-05-16 Sumitomo Chemical Co Ltd 着色感光性樹脂組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01123817A (ja) * 1987-11-09 1989-05-16 Kansai Paint Co Ltd 硬化性組成物
JPH10310681A (ja) * 1997-05-12 1998-11-24 Toyo Ink Mfg Co Ltd 放射線硬化性樹脂組成物およびその製造方法
JP2005226193A (ja) * 2004-02-13 2005-08-25 Mitsubishi Rayon Co Ltd 強化繊維用サイジング剤、炭素繊維束、熱可塑性樹脂組成物及びその成形品
JP2013092759A (ja) * 2011-10-07 2013-05-16 Sumitomo Chemical Co Ltd 着色感光性樹脂組成物

Similar Documents

Publication Publication Date Title
US20210206916A1 (en) Curable composition and cured product obtained by curing the same
WO2014061648A1 (fr) Composition de résine durcissable, et produit durci la contenant
WO2017159637A1 (fr) Composé d'époxy, composition durcissable, produit durci, procédé de production d'un composé époxy, et diluant reactif
JP2010018797A (ja) 光学部品用硬化性組成物、光学部品用接着剤及び有機エレクトロルミネッセンス素子用封止剤
JP2017228414A (ja) 有機エレクトロルミネッセンス表示素子用封止剤
JP7398960B2 (ja) ハードコート層形成用樹脂組成物
WO2014181787A1 (fr) Composition de resine epoxyde durcissable et son produit durci, compose diolefinique et son procede de production, et procede de production pour compose diepoxyde
JP5799177B2 (ja) 光後硬化性樹脂組成物
JP2023156307A (ja) 紫外線硬化性樹脂組成物、発光装置の製造方法、発光装置、及びタッチパネル
WO2014196515A1 (fr) Composition de résine époxy durcissable
US20190071409A1 (en) Epoxy compound, curable composition, cured product, method of producing epoxy compound, and reactive diluent
EP3375804B1 (fr) Composition de résine époxy contenant un groupe alcylène à longue chaîne
TWI821172B (zh) 偏光板用黏接劑組成物、偏光板用黏接劑及利用該黏接劑之偏光板
EP3663364A1 (fr) Composition de résine pour la formation d'une couche de revêtement dur
KR20220038275A (ko) 유기 el 표시 소자용 봉지제
JP5310690B2 (ja) エポキシ樹脂組成物及びエポキシ樹脂硬化体
WO2017150615A1 (fr) Composition durcissable
JP6691855B2 (ja) 硬化性組成物およびこれを硬化させた硬化物
JP6251894B2 (ja) エネルギー線感受性組成物
KR20220069877A (ko) 전자 디바이스용 광 경화성 수지 조성물
JP2005263965A (ja) 新規なエポキシ樹脂およびそれを含む硬化性樹脂組成物
JP4243980B2 (ja) ２，２−ビス（３，４−エポキシシクロヘキシル）−１，１，１，３，３，３−ヘキサフルオロプロパン及び該化合物を用いたエポキシ樹脂組成物
JP2015109202A (ja) 光半導体装置の製造方法
US11613661B2 (en) Curable resin composition and manufacturing method of three-dimensional object using the same
JP2001261741A (ja) 硬化組成物およびその被膜形成方法

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17760079

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 17760079

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP