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WO2020040052A1 - Composition de résine durcissable et produit durci obtenu à partir de celle-ci - Google Patents

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

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Publication number
WO2020040052A1
WO2020040052A1 PCT/JP2019/032144 JP2019032144W WO2020040052A1 WO 2020040052 A1 WO2020040052 A1 WO 2020040052A1 JP 2019032144 W JP2019032144 W JP 2019032144W WO 2020040052 A1 WO2020040052 A1 WO 2020040052A1
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Prior art keywords
acrylate
meth
resin composition
urethane
curable resin
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English (en)
Japanese (ja)
Inventor
三浦　賢治
和重 荻原
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Resonac Holdings Corp
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Showa Denko KK
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Priority to JP2020538356A priority Critical patent/JPWO2020040052A1/ja
Publication of WO2020040052A1 publication Critical patent/WO2020040052A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes

Definitions

  • the present invention relates to a curable resin composition and a cured product thereof.
  • Priority is claimed on Japanese Patent Application No. 2018-157549 filed on August 24, 2018, the content of which is incorporated herein by reference.
  • Pinyl ester resin and unsaturated polyester resin have excellent corrosion resistance, strength and toughness. For this reason, it has been used in molded products of various members such as corrosion-resistant tanks, pipes, transportation equipment, and variable pads. They have also been used in various fields such as lining materials and coating materials for these various members.
  • Patent Document 1 proposes a vinyl ester resin obtained by blending a side chain unsaturated bond type resin, an oligo (meth) acrylate, and a polymerizable monomer as required. It is reported that the vinyl ester resin has excellent adhesion, water resistance, and chemical resistance.
  • the vinyl ester resin has a problem that the molded product is easily damaged.
  • the present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a curable resin composition capable of securing impact resistance and securing strength at high temperatures, and a cured product thereof. .
  • the present inventors have intensively studied to solve the above problems.
  • the cured product has high impact resistance and high-temperature strength.
  • the present inventors have found that it has become possible to impart impact resistance to various members while obtaining a balance, and arrived at the present invention.
  • the present invention has been completed based on the above findings, and the gist is as follows.
  • the urethane (meth) acrylate (A) is an aliphatic polyester-based urethane (meth) acrylate
  • the aliphatic polyester-based urethane (meth) acrylate has a weight average molecular weight of 15,000 to 30,000
  • the other radically polymerizable unsaturated compound (B) contains at least one compound selected from the group consisting of a bisphenol-based vinyl ester resin (b1) and a novolak-based vinyl ester resin (b2). Curable resin composition.
  • the resin composition of the present invention contains urethane (meth) acrylate having a specific structure as an essential component, and is excellent in impact resistance particularly in various members such as an anticorrosive material, a waterproof material, a flooring material, and a variable pad.
  • the curable resin composition of the present embodiment (sometimes referred to as “resin composition of the present embodiment”) includes urethane (meth) acrylate (A), other radically polymerizable unsaturated compound (B), including.
  • the other radically polymerizable unsaturated compound (B) is a radically polymerizable unsaturated compound containing no urethane (meth) acrylate (A).
  • the urethane (meth) acrylate (A) is an aliphatic polyester-based urethane (meth) acrylate, and the aliphatic polyester-based urethane (meth) acrylate has a weight average molecular weight of 15,000 to 30,000. I do.
  • the other radically polymerizable unsaturated compound (B) contains at least one compound selected from the group consisting of a bisphenol-based vinyl ester resin (b1) and a novolak-based vinyl ester resin (b2). I do.
  • the other radically polymerizable unsaturated compound (B) preferably further contains styrene.
  • the other radically polymerizable unsaturated compound (B) may further contain a radically polymerizable unsaturated monomer other than styrene.
  • the resin composition of the present embodiment can further contain trimethylhydroquinone and a nitroso compound.
  • the resin composition of the present embodiment can further include a polymerization inhibitor, a radical polymerization initiator, and other additives.
  • (meth) acrylate refers to acrylate or methacrylate.
  • the urethane (meth) acrylate (A) used in the resin composition of the present embodiment is an aliphatic polyester-based urethane (meth) acrylate (sometimes referred to as “urethane (meth) acrylate (A) of the present embodiment”). is there. That is, the urethane (meth) acrylate (A) of the present embodiment includes a structure derived from a polyisocyanate, a structure derived from a polyester-based polyhydric alcohol, and a structure derived from a hydroxylalkyl (meth) acrylate.
  • the structure derived from a polyester-based polyhydric alcohol includes a structure derived from a dicarboxylic acid and a structure derived from a polyhydric alcohol.
  • the dicarboxylic acids, polyhydric alcohols, polyisocyanates, and hydroxylalkyl (meth) acrylates are all derivatives of aliphatic carbon.
  • the dicarboxylic acid is not particularly limited as long as it is an aliphatic dicarboxylic acid, but an aliphatic dicarboxylic acid having 2 to 10 carbon atoms is preferable in terms of availability.
  • aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid and isosebacic acid.
  • malonic acid, succinic acid Acids, glutaric acid, adipic acid are preferred. These may be used alone or in combination of two or more.
  • the polyhydric alcohol is not particularly limited as long as it is an aliphatic polyhydric alcohol, but an aliphatic polyhydric alcohol having 1 to 8 carbon atoms is preferable in terms of availability.
  • ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4 butanediol, 5-pentanediol, 1,6-hexanediol and neopentyl glycol are preferred. These may be used alone or in combination of two or more.
  • the polyisocyanate is not particularly limited as long as it is an aliphatic polyisocyanate, but an aliphatic polyisocyanate having 2 to 12 carbon atoms is preferable in terms of availability. Specific examples include hexamethylene diisocyanate, dimeryl isocyanate, and isophorone diisocyanate. Of these, isophorone diisocyanate is preferred. These may be used alone or in combination of two or more.
  • the hydroxylalkyl (meth) acrylate is preferably a hydroxylalkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms. Specific examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and the like, and hydroxyethyl (meth) acrylate is preferred from the viewpoint of easy availability. These may be used alone or in combination of two or more.
  • ⁇ Catalyst 1> When synthesizing the urethane (meth) acrylate (A) raw material polyurethane, for example, polyisocyanate and polyhydric alcohol can be synthesized using a catalyst. When synthesizing the urethane (meth) acrylate (A), a known catalyst such as dibutyltin dilaurate, tertiary amines, and phosphones can be added. The catalyst used in synthesizing each component may remain in the composition of the present embodiment.
  • urethane (meth) acrylate (A) used in the resin composition of the present embodiment includes, for example, the compound represented by the above formula (I).
  • R 1 is H.
  • R 2 is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms.
  • the alkylene group may be linear or branched, and may be a cycloalkylene group. Specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and the like.
  • An ethylene group and a propylene group are preferred.
  • R 3 is preferably an alkylene group having 2 to 12 carbon atoms, and more preferably an alkylene group having 4 to 12 carbon atoms.
  • the alkylene group may be linear or branched, may be a cycloalkylene group, or may contain a cycloalkylene group. Specific examples include ethylene, propylene, butylene, pentylene, hexylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, and cyclohexylene having 1 to 4 methyl substituents. And an alkylene group consisting of a cyclohexylene group having 1 to 4 methyl substituents and a methylene group.
  • a butylene group, a pentylene group, a cyclohexylene group having 1 to 4 methyl substituents, an alkylene group consisting of a cyclohexylene group having 1 to 4 methyl substituents and a methylene group are preferred.
  • R 4 is preferably an alkylene group having 2 to 10 carbon atoms, and more preferably an alkylene group having 4 to 10 carbon atoms.
  • the alkylene group may be linear or branched, and may be a cycloalkylene group.
  • R 5 is preferably an alkylene group having 1 to 8 carbon atoms, and more preferably an alkylene group having 2 to 6 carbon atoms.
  • the alkylene group may be linear or branched, and may be a cycloalkylene group.
  • a methylene group an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a methyl-substituted trimethylene group.
  • Ethylene, propylene and methyl-substituted trimethylene are preferred.
  • M and n are each independently preferably an integer of 2 to 80, more preferably an integer of 2 to 60.
  • urethane (meth) acrylate (A) used in the resin composition of the present embodiment include, in the above formula (1), R 1 to R 5 are the following alkylene groups:
  • the urethane (meth) acrylate (A) of the present embodiment has a weight average molecular weight of 15,000 to 30,000. It is preferably from 16,000 to 28,000, more preferably from 16,000 to 27,000. The weight average molecular weight is measured by the method described in Examples.
  • the content of the urethane (meth) acrylate (A) in the present embodiment is preferably from 5 to 40% by mass, more preferably from 10 to 35% by mass, based on the composition of the present embodiment.
  • the content of the urethane (meth) acrylate (A) is 5% by mass or more, a cured product excellent in impact resistance and flexibility is obtained, which is preferable.
  • the content of the urethane (meth) acrylate (A) is 40% by mass or less, the content of the other radically polymerizable unsaturated compound (B) in the resin composition of the present embodiment is easily secured, which is preferable. .
  • the mass ratio (A) / (B) of the urethane (meth) acrylate (A) of the present embodiment to another radically polymerizable unsaturated compound (B) described below is from 5/95.
  • the total amount (b1 + b2) of the bisphenol-based vinyl ester resin (b1) and the novolak-based vinyl ester resin (b2) is the content of the bisphenol-based vinyl ester resin (b1) when only the bisphenol-based vinyl ester resin (b1) is included.
  • radically polymerizable unsaturated compounds (B) of the present embodiment are bisphenol-based vinyl ester resin (b1), novolak-based vinyl ester resin (b2), or bisphenol-based vinyl ester resin (b1) and novolac-based vinyl ester It contains a mixture of resin (b2).
  • the bisphenol-based vinyl ester resin (b1) and the novolak-based vinyl ester resin (b2) indicate only the resin component and do not include a monomer component such as a reactive diluent.
  • a bisphenol-type epoxy resin or a modified product thereof can be used as the bisphenol-based vinyl ester resin (b1) according to the present embodiment.
  • a bisphenol-type epoxy resin or a modified product thereof can be used.
  • the bisphenol-type epoxy resin include those obtained by reacting bisphenols with epichlorohydrin and / or methyl epichlorohydrin.
  • those obtained by reacting a glycidyl ether of bisphenol A with a condensate of the above bisphenols with epichlorohydrin and / or methyl epichlorohydrin may, for example, be mentioned.
  • Examples of the bisphenols include bisphenol A, bisphenol F, bisphenol S and tetrabromobisphenol A.
  • Specific examples of the bisphenol-type epoxy resin include Araldite AER-2603 (a bisphenol A-type epoxy resin manufactured by Asahi Kasei E-Materials Co., Ltd.).
  • Examples of the modified bisphenol-type epoxy resin include those obtained by reacting a bisphenol-type epoxy resin with bisphenols. Further, a resin obtained by reacting a bisphenol-type epoxy resin with a compound selected from adipic acid, sebacic acid, dimer acid, and liquid nitrile rubber may be used.
  • Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S.
  • a catalyst such as triethylamine may be used.
  • a bisphenol-type epoxy resin modified material as a material of the bisphenol-based vinyl ester resin, a resin having a cured product having good flexibility and toughness can be obtained.
  • Novolak vinyl ester resin (b2) As the novolak-based vinyl ester resin (b2) according to the present embodiment, those derived from novolak-type glycidyl ether-type epoxy resin can be used. Those obtained by reacting a basic acid can be used. Examples of the novolak type glycidyl ether type epoxy resin include those obtained by reacting phenol novolak or cresol novolak with epichlorohydrin and / or methyl epichlorohydrin. A specific example is Epicron N-740 (phenol novolak type epoxy resin, manufactured by DIC Corporation).
  • Examples of a catalyst for synthesizing a vinyl ester by reacting a novolak glycidyl ether type epoxy resin with an unsaturated monobasic acid include compounds containing a tertiary nitrogen such as triethylamine, pyridine derivatives, imidazole derivatives, imidazole derivatives and the like. Amine salts such as tetramethylammonium chloride, tetradecyldimethylbenzylammonium chloride and triethylamine; and phosphorus compounds such as trimethylphosphine and triphenylphosphine.
  • the catalyst used in synthesizing each component may remain in the composition of the present embodiment.
  • unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, and cinnamic acid.
  • unsaturated monobasic acid instead of the unsaturated monobasic acid, a reaction product of a compound having one hydroxy group and one or more (meth) acryloyl groups and a polybasic anhydride may be used.
  • the polybasic acid in the above polybasic acid anhydride is used for increasing the molecular weight of the epoxy resin, and known polybasic acids can be used.
  • succinic acid glutaric acid, adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, ethylene glycol / 2 mol maleic anhydride adduct, polyethylene Glycol / 2 mol maleic anhydride adduct, propylene glycol / 2 mol maleic anhydride adduct, polypropylene glycol / 2 mol maleic anhydride adduct, dodecandioic acid, tridecandioic acid, octadecandioic acid, 1,16- (6 -Ethylhexadecane) dicarboxylic acid, 1,12- (6-ethyldodecane) dicarboxylic acid, carboxyl group-terminated butadiene-acrylonitrile copolymer (trade name: Hycar CTBN), and
  • the total amount of the urethane (meth) acrylate (A) of the present embodiment, the bisphenol-based vinyl ester resin (b1), and the novolak-based vinyl ester resin (b2) is based on The total amount of the ester resin (b1) and the novolac vinyl ester resin (b2) is preferably from 20 to 90% by mass, more preferably from 30 to 80% by mass.
  • the content of the bisphenol-based vinyl ester resin (b1) or the novolak-based vinyl ester resin (b2) is 20% by mass or more, the bisphenol-based vinyl ester resin (b1) or the novolak-based vinyl ester resin (b2) is included.
  • the total amount of the bisphenol-based vinyl ester resin (b1) and the novolak-based vinyl ester resin (b2) is 90% by mass or less, the content of the urethane (meth) acrylate (A) in the composition of the present embodiment is reduced. It is preferable because it can be easily secured.
  • the unsaturated polyester resin As long as the other radically polymerizable unsaturated compound (B) of the present embodiment is not a bisphenol-based vinyl ester resin (b1) or a novolak-based vinyl ester resin (b2), the unsaturated polyester resin is not impaired. May be included.
  • the unsaturated polyester resin mentioned here does not include a reactive diluent such as styrene.
  • the unsaturated polyester resin those obtained by subjecting an unsaturated dibasic acid and, if necessary, a dibasic acid component containing a saturated dibasic acid and a polyhydric alcohol component to an esterification reaction can be used. .
  • the unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, and itaconic anhydride, and these may be used alone or in combination of two or more. May be used.
  • saturated dibasic acids examples include adipic acid, suberic acid, azelaic acid, sebacic acid, and aliphatic dibasic acids such as isosebacic acid, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, and terephthalic acid.
  • polyhydric alcohol examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -Hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl -1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, 1,2-cyclohex Glycol, 1,3-cyclohexane glycol, 1,4-cyclo
  • a resin modified with a dicyclopentadiene-based compound may be used as long as the effects of the present invention are not impaired.
  • a modification method using a dicyclopentadiene-based compound for example, a method in which dicyclopentadiene and a maleic acid addition product (sidecanol monomalate) are obtained, and this is used as a monobasic acid to introduce a dicyclopentadiene skeleton. And other known methods.
  • the bisphenol-based vinyl ester resin (b1), the novolak-based vinyl ester resin (b2), and / or the unsaturated polyester resin used in the present embodiment may have an oxidatively polymerized group.
  • the method for introducing the oxidized polymer group is not particularly limited. For example, addition of an oxidized polymer group-containing polymer, condensation of a compound having a hydroxyl group and an allyl ether group, allyl glycidyl ether, 2,6-diglycidyl phenyl allyl ether A method of adding a reaction product of a compound having a hydroxyl group and an allyl ether group to an acid anhydride.
  • polyester (meth) acrylate resin Other radically polymerizable unsaturated compounds (B) of the present embodiment are polyester (meth) acrylates other than the bisphenol-based vinyl ester resin (b1) and the novolak-based vinyl ester resin (b2) as long as the effects of the present invention are not impaired. It may contain a resin.
  • the polyester (meth) acrylate resin for example, a resin obtained by reacting a polyvalent carboxylic acid with a polyhydric alcohol can be used.
  • the polyester (meth) acrylate resin a resin obtained by reacting (meth) acrylic acid with hydroxyl groups at both ends, such as polyethylene terephthalate, can be used.
  • (Meth) acrylate resin Other radically polymerizable unsaturated compounds (B) of the present embodiment, besides the bisphenol-based vinyl ester resin (b1) and the novolak-based vinyl ester resin (b2), are (meth) acrylate resins as long as the effects of the present invention are not impaired. May be included.
  • the (meth) acrylate resin include a poly (meth) acrylic resin having at least one substituent selected from a hydroxyl group, an isocyanato group, a carboxy group, and an epoxy group, and a monomer having the substituent and a (meth) acrylate resin.
  • A) A resin obtained by reacting a (meth) acrylic ester having a hydroxyl group with a substituent of a polymer with an acrylate can be used.
  • the other radically polymerizable unsaturated compound (B) of the present embodiment may further contain a radically polymerizable unsaturated monomer as a reactive diluent in addition to the above components.
  • a radically polymerizable unsaturated monomer examples include styrene, p-chlorostyrene, vinyltoluene, ⁇ -methylstyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyl acetate, diallyl phthalate, triallyl isocyanurate , (Meth) acrylate and the like.
  • (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl ( (Meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate , Ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol Chole mono
  • radically polymerizable unsaturated monomers may be used alone or in combination of two or more.
  • styrene, methyl (meth) acrylate, phenoxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate are preferred from the viewpoint of workability and curability.
  • styrene which has better workability and curability and is inexpensive, is desirable.
  • the amount of the radical polymerizable unsaturated monomer used is 20% by mass to 80% by mass based on the total amount of the urethane (meth) acrylate (A) of the present embodiment and the other radical polymerizable unsaturated compound (B).
  • the resin composition of the present embodiment further contains a nitroso compound.
  • the nitroso compound preferably contains a compound in which a nitroso group is bonded to a nitrogen atom, since a resin composition having better high-temperature stability can be obtained.
  • Examples of the nitroso compound having a nitroso group bonded to a nitrogen atom include N-nitroso-N-methylaniline represented by the following formula (1) and N-nitroso-N-phenylhydroxyl represented by the following formula (2) Amine ammonium, N, N-dinitrosopentamethylenetetramine represented by the following formula (3), N-nitrosodiphenylamine represented by the following formula (4), aluminum N-nitrosophenylhydroxylamine represented by the following formula (5), Examples include N-nitroso-N-cyclohexylaniline represented by the following formula (6).
  • nitroso compound among the above-mentioned nitroso compounds, one or more selected from N-nitroso-N-methylaniline, aluminum N-nitrosophenylhydroxylamine, and N-nitroso-N-cyclohexylaniline may be used. It is preferable to use N-nitroso-N-methylaniline for the following reasons.
  • N-nitroso-N-methylaniline As the nitroso compound, a resin composition having better high-temperature stability can be obtained. This effect is presumed to be due to the fact that the nitroso group contained in N-nitroso-N-methylaniline is released and traps radicals in the resin composition, thereby suppressing the gelation of the resin composition. You.
  • N-nitroso-N-methylaniline does not affect the curability of the resin composition and does not affect the curing delay of the resin composition.
  • N-nitroso-N-methylaniline is a liquid at ordinary temperature, so that it can be easily dissolved in the resin composition as compared with a solid (powder) at ordinary temperature and has good workability. It is.
  • the resin composition of this embodiment contains the nitroso compound in an amount of 0.005 to 5 parts by mass based on 100 parts by mass of the total amount of the urethane (meth) acrylate (A) and the other radically polymerizable unsaturated compound (B). Is preferred.
  • the content of the nitroso compound is 0.005 parts by mass or more, the effect of improving the high-temperature stability by including the nitroso compound is remarkably obtained. More preferably, the content of the nitroso compound is 0.05 parts by mass or more. Further, when the content of the nitroso compound is 5 parts by mass or less, the content of the resin component can be sufficiently increased, so that a resin composition having characteristics according to the intended use can be obtained.
  • the content of the nitroso compound is more preferably 1 part by mass or less because curing failure is less likely to occur and the resin composition has good curability.
  • ⁇ ⁇ ⁇ The presence of the nitroso compound in the resin composition of the present embodiment can be confirmed, for example, by a spectrum of the resin composition measured by nuclear magnetic resonance (1H-NMR) spectroscopy. Specifically, for example, in the case of N-nitroso-N-methylaniline, a peak derived from a methyl group-derived proton is detected at around 3.39 ppm.
  • the resin composition of the present embodiment may further contain a polymerization inhibitor.
  • a polymerization inhibitor include those commonly known and used, for example, piperidine derivatives such as 4H-2,2,6,6-tetramethylpiperidino-1-oxyl, hydroquinone, methylhydroquinone, trimethylhydroquinone, and trihydrobenzene.
  • piperidine derivatives such as 4H-2,2,6,6-tetramethylpiperidino-1-oxyl
  • hydroquinone methylhydroquinone
  • trimethylhydroquinone trihydrobenzene.
  • trimethylhydroquinone As the polymerization inhibitor, among the above, it is particularly preferable to use trimethylhydroquinone for the following reasons. Quinone compounds such as hydroquinone and trimethylhydroquinone have a retarding effect of slowing down the curing of the resin composition. Trimethylhydroquinone has a sufficient retarding effect and also has an effect of improving the high-temperature stability of the resin composition. This effect is presumed to be due to the fact that the three methyl groups of the trimethylhydroquinone serve as steric hindrance, so that the radicals in the resin composition trapped by the trimethylhydroquinone are difficult to leave.
  • Part or all of the polymerization inhibitor may be a residue of the polymerization inhibitor used when synthesizing the urethane (meth) acrylate (A) and the other radically polymerizable unsaturated compound (B).
  • the content of the polymerization inhibitor in the resin composition can be confirmed by, for example, a method of analyzing using a gas chromatography method.
  • the content of the polymerization inhibitor in the resin composition of the present embodiment is 100 parts by mass in total of urethane (meth) acrylate (A) and other radically polymerizable unsaturated compounds (B).
  • the amount is preferably 0.01 to 1 part by mass, more preferably 0.03 to 0.8 part by mass.
  • the content of the polymerization inhibitor in the resin composition of the present embodiment is 0.01 mass with respect to 100 mass parts of the total amount of the urethane (meth) acrylate (A) and the other radically polymerizable unsaturated compound (B).
  • the content of the polymerization inhibitor in the resin composition of the present embodiment is 1 part by mass or less based on 100 parts by mass of the total amount of the urethane (meth) acrylate (A) and the other radically polymerizable unsaturated compound (B). It is preferable that the resin composition of the present embodiment hardly causes poor curing.
  • the resin composition of the present embodiment preferably contains trimethylhydroquinone and a nitroso compound. By simultaneously containing trimethylhydroquinone and a nitroso compound, storage stability at high temperatures is improved.
  • the resin composition of the present embodiment may further include a radical polymerization initiator.
  • the radical polymerization initiator include an organic peroxide and a radical photopolymerization initiator.
  • organic peroxides include diacyl peroxides such as benzoyl peroxide, peroxyesters such as t-butylperoxybenzoate, hydroperoxides such as cumene hydroperoxide, and dialkyl peroxides such as dicumyl peroxide.
  • Ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, peroxyketals, alkyl peresters, percarbonates and the like.
  • photoradical polymerization initiator examples include benzoin ethers such as benzoin alkyl ether, benzophenones such as benzophenone, benzyl and methyl orthobenzoyl benzoate, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, and 2-hydroxy-2-methyl.
  • Acetophenones such as propiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone and 1,1-dichloroacetophenone; and thioxanthones such as 2-chlorothioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone. Including.
  • methyl ethyl ketone peroxide methyl ethyl ketone peroxide, benzoyl peroxide, t-butyl peroxybenzoate, and cumene hydroperoxide are desirable from the viewpoints of cost, availability, stability, and curability.
  • These radical polymerization initiators may be used alone or in a combination of two or more.
  • the content is 100 parts by mass in total of the total amount of the urethane (meth) acrylate (A) and the other radically polymerizable unsaturated compound (B).
  • the amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and still more preferably 0.5 to 5 parts by mass.
  • the resin composition of the present embodiment can include other additives as necessary.
  • the additives include a curing accelerator, a curing accelerator, a filler, a thixotropic agent, a wax, a coloring agent, a drying agent, and the like. These additives may be used alone or in combination of a plurality of types.
  • a known curing accelerator such as a cobalt metal salt can be used.
  • the cobalt metal salt used as the curing accelerator is not particularly limited, and includes, for example, cobalt naphthenate, cobalt octylate, cobalt hydroxide and the like, and uses cobalt naphthenate and / or cobalt octylate Is preferred.
  • the content of the curing accelerator is 0.02 to 10 parts by mass, preferably 0.1 to 3.0 parts by mass, based on 100 parts by mass of the resin composition.
  • the content of the curing accelerator is 0.02 parts by mass or more, the curing time is sufficiently shortened, and poor curing can be prevented, which is preferable.
  • the content of the curing accelerator is 10 parts by mass or less, it is preferable to prevent the curing time from being excessively accelerated and the pot life from being insufficient or the storage stability from being poor.
  • Examples of the curing accelerator include amines. Specifically, aniline, diethanolaniline, p-toluidine, m-toluidine, N-ethyl-m-toluidine, triethanolamine, diethylenetriamine, pyridine, piperidine, phenylimorpholine, N, N- Amines such as substituted aniline, N, N-substituted-p-toluidine, 4- (N, N-substituted amino) benzaldehyde and the like can be used. Examples of N, N-substituted anilines include N, N-dimethylaniline, N, N-diethylaniline, N, N-bis (hydroxyethyl) aniline.
  • N, N-substituted-p-toluidine examples include N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxypropyl) -Contains p-toluidine.
  • 4- (N, N-substituted amino) benzaldehyde examples include 4- (N, N-dimethylamino) benzaldehyde, 4- [N, N-bis (2-hydroxyethyl) amino] benzaldehyde, 4- (N- Methyl-N-hydroxyethylamino) benzaldehyde.
  • curing accelerator examples include ⁇ -diketones such as acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetylbutyllactone, and dimethylacetoacetamide.
  • ⁇ -diketones such as acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetylbutyllactone, and dimethylacetoacetamide.
  • the above-mentioned curing accelerators may be used alone or in combination of two or more.
  • the resin composition of the present embodiment may include a filler for the purpose of improving workability and adjusting physical properties.
  • the filler include an inorganic filler and an organic filler.
  • the inorganic filler include cement, river gravel, river sand, sea gravel, sea sand, mountain gravel, crushed stone, crushed sand, sand containing silica as a main component, ceramics, artificial aggregates such as glass chips, talc, and water.
  • Known materials such as aluminum oxide, calcium carbonate and cement can be used. These may be used alone or in combination.
  • the resin composition of the present embodiment can include a thixotropic agent from the viewpoint of adjusting the mixing property and the fluidity of the adhesive composition.
  • a thixotropic agent an inorganic thixotropic agent such as fumed silica and talc may be used, or an organic thixotropic agent such as a special amide type may be used.
  • the thixotropic agent only one type may be used, or a plurality of types may be used in combination.
  • the resin composition of the present embodiment may contain wax for the purpose of improving the drying property.
  • the wax include paraffin waxes and polar waxes. These waxes may be used alone or in combination of two or more. Known paraffin waxes having various melting points can be used.
  • the polar waxes those having both a polar group and a non-polar group in the structure can be used, and specifically, NPS-8070, NPS-9125 (manufactured by Nippon Seiro Co., Ltd.), Emanon 3199 And 3299 (manufactured by Kao Corporation).
  • an inorganic pigment such as titanium oxide can be used.
  • ⁇ desiccant ⁇ Molecular sieves or the like can be used as the desiccant.
  • the production method of the resin composition of the present embodiment includes, for example, the urethane (meth) acrylate (A) of the present embodiment, the other radically polymerizable unsaturated compound (B) of the present embodiment, and Can be manufactured by mixing the additives to be used with a known method.
  • the additives include a polymerization inhibitor, a radical polymerization initiator, and other additives.
  • the radically polymerizable unsaturated compound (B) preferably contains styrene.
  • One example of the method for producing the urethane (meth) acrylate (A) of the present embodiment is, for example, a method in which a dicarboxylic acid that is a derivative of aliphatic carbon and a polyhydric alcohol that is a derivative of aliphatic carbon are mixed using a known method.
  • a step of producing the aliphatic polyester-based polyhydric alcohol of the present embodiment Mixing a polyester polyhydric alcohol of the present embodiment and an isocyanate that is a derivative of an aliphatic carbon using a known method, to produce an aliphatic polyester urethane containing isocyanate groups at both ends,
  • the aliphatic polyester-based urethane containing polyisocyanato groups at both ends and hydroxylalkyl (meth) acrylate are mixed using a known method, and the aliphatic polyester-based urethane (meth) acrylate of the present embodiment (of the present embodiment) Producing urethane (meth) acrylate (A)).
  • the method for producing the resin composition of the present embodiment include, for example, the urethane (meth) acrylate (A) of the present embodiment, the other radically polymerizable unsaturated compound (B) of the present embodiment, It can be produced by mixing a nitroso compound, trimethylhydroquinone, a radical polymerization initiator contained as necessary, and other additives using a known method.
  • the nitroso compound is added in an amount of 0.005 to 100 parts by mass of the urethane (meth) acrylate (A) and the other radically polymerizable unsaturated compound (B) in total. It is preferable to mix up to 5 parts by mass.
  • the radically polymerizable unsaturated compound (B) preferably contains styrene.
  • the curable resin composition containing the radical polymerization initiator can be cured by heating or the like.
  • the cured product preferably has a compressive yield stress at 65 ° C of 3 MPa or more and a Charpy impact value at 23 ° C of 5 kJ / m 2 or more.
  • the compression yield stress and the Charpy impact value are evaluated by the evaluation methods described below.
  • urethane acrylate (a1) The aliphatic polyester-based urethane acrylate obtained in this synthesis example was used as urethane acrylate (a1). 650 g of styrene was added to 650 g of the obtained urethane methacrylate (a1) to prepare a styrene-containing urethane methacrylate (a1) composition.
  • urethane acrylate (a2) The aliphatic polyester-based urethane acrylate obtained in this synthesis example was used as urethane acrylate (a2). 650 g of styrene was added to 650 g of the obtained urethane methacrylate (a2) to prepare a styrene-containing urethane methacrylate (a2) composition.
  • Method for evaluating weight average molecular weight of urethane (meth) acrylate (a1) and urethane (meth) acrylate (a2) It is measured under gel permeation chromatography (GPC) under the following conditions and calculated in terms of polystyrene.
  • Apparatus Showa Denko KK, high-speed GPC system GPC SYSTEM-21 Column: Showex KF-802 (2), manufactured by Showa Denko KK Oven temperature: 40 ° C Eluent: tetrahydrofuran Sample concentration: 0.2% by mass Flow rate: 1 ml / min Detector: differential refraction.
  • the reaction mixture was cooled to 90 ° C., and 430 g of methacrylic acid, 9 g of tetradecyldimethylbenzylammonium chloride, 0.9 g of hydroquinone, and 1000 g of styrene were added to the reaction product, and the mixture was reacted at 90 ° C. for 20 hours while blowing air thereinto.
  • a bisphenol-based vinyl ester resin (b1) diluted with styrene was obtained.
  • 1912 g of styrene was further added to the bisphenol-based vinyl ester resin (b1) diluted with styrene to prepare a styrene-containing bisphenol-based vinyl ester resin (b1) composition.
  • the mixture was mixed with a stirrer to obtain the curable resin compositions of Examples 1 to 9 and Comparative Examples 1 and 2.
  • the parts by mass of each component in Table 1 are based on 100 parts by mass of the total amount of the urethane (meth) acrylate (A) and the other radically polymerizable unsaturated compound (B).
  • the curable resin compositions of Examples 1 to 9 and Comparative Examples 1 and 2 were cured by the following curing method to obtain cured products.
  • "Production method of cured product” To the curable resin compositions of Examples 1 to 9 and Comparative Examples 1 and 2, 0.3 parts by mass of cobalt octylate having a metal content of 8% was added as an accelerator and mixed with a stirrer. Next, 1.0 part by mass of a methyl ethyl ketone peroxide-based radical polymerization initiator was added and mixed with a stirrer. After pouring into a dedicated mold and curing at 23 ° C. for 12 hours, after-curing was performed at 80 ° C. for 180 minutes. The obtained cured product was evaluated for impact resistance and strength at high temperature by the following method. Table 1 shows the results.
  • the test was performed according to JIS K7111.
  • the test specimen is a resin casting having a length of 90.0 ⁇ 1.0 mm and a width and thickness of 15.0 ⁇ 0.2 mm. In addition, U-shaped notch processing was performed.
  • the test temperature was 23 ° C.
  • the testing machine was manufactured by Zwick GmbH & Co. "HIT25P” manufactured by KG was used.
  • the test was performed according to JIS K7181.
  • the test specimen is a resin casting having a length of 25.4 ⁇ 0.3 mm and a width and thickness of 12.7 ⁇ 0.3 mm.
  • the test speed was 1 mm / min and the test temperature was 65 ° C.
  • the tester used was "59R5583" manufactured by INSTRON.
  • Examples 5 to 7 containing urethane (meth) acrylate (a2) and bisphenol-based vinyl ester resin (b1) are Comparative Examples 1 and 2 containing no urethane (meth) acrylate (A).
  • the compression yield value at 65 ° C. was not so high as compared with that at 3 ° C., it was at least 3 MPa, and at the same time, the Charpy impact value at 23 ° C. was high, at 5 kJ / m 2 or more.
  • Comparative Example 2 which contained neither the bisphenol-based vinyl ester resin (b1) nor the novolac-based vinyl ester resin (b2), had a Charpy impact value at 23 ° C of 100 kJ / m 2 or more, but a low compression yield value at 65 ° C. And 3 MPa or less.
  • Example 10 to 15 The styrene-containing urethane (meth) acrylate (a1) composition obtained in the synthesis example and the styrene-containing bisphenol-based vinyl ester resin (b1) composition were used.
  • the urethane (meth) acrylate (a1), the bisphenol-based vinyl ester resin (b1), the styrene, the nitroso compound, and the other additives were added to the mass shown in Table 2 so that the mass ratio shown in Table 2 was obtained.
  • the mixture was mixed at a ratio using a stirrer to obtain curable resin compositions of Examples 10 to 13. Parts by mass of each component in Table 2 are based on 100 parts by mass of the total amount of the urethane (meth) acrylate (A) and the other radically polymerizable unsaturated compound (B).
  • the circular can is placed in a thermostatic drier within 6 hours after the completion of the production. It was left still. Tilt the round can every day (every 24 hours) after the end of production, and check by hearing whether or not the test specimen has gelled (state in which fluidity is lost), and measure the number of days until the test specimen gels did.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne une composition de résine durcissable et un produit durci qui permettent d'obtenir un équilibre entre résistance au choc et résistance à haute température. Cette composition de résine durcissable contient un uréthane (méth)acrylate (A) et un autre composé insaturé polymérisable par voie radicalaire (B). L'uréthane (méth)acrylate (A) est un polyester aliphatique uréthane (méth)acrylate et la masse moléculaire moyenne en poids du polyester aliphatique uréthane (méth)acrylate est de 15 000 à 30 000. L'autre composé insaturé polymérisable par voie radicalaire (B) est au moins un composé choisi dans le groupe constitué par les résines à base d'ester vinylique de bisphénol (b1) et les résines à base d'ester vinylique de novolaque (b2).
PCT/JP2019/032144 2018-08-24 2019-08-16 Composition de résine durcissable et produit durci obtenu à partir de celle-ci Ceased WO2020040052A1 (fr)

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Publication number Priority date Publication date Assignee Title
JPWO2022196328A1 (fr) * 2021-03-18 2022-09-22
JP7811399B2 (ja) 2021-03-18 2026-02-05 ナミックス株式会社 樹脂組成物、導電性接着剤、硬化物及び半導体装置

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JP2002187920A (ja) * 2000-12-20 2002-07-05 Nippon Kayaku Co Ltd 樹脂組成物、レンズ用樹脂組成物及びその硬化物
WO2013069441A1 (fr) * 2011-11-07 2013-05-16 昭和電工株式会社 Composition de résine pour des récipients sous pression et récipient sous pression
JP2013138194A (ja) * 2011-12-01 2013-07-11 Denki Kagaku Kogyo Kk 被加工部材の仮固定方法

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JPS58208315A (ja) * 1982-05-28 1983-12-05 Mitsubishi Gas Chem Co Inc 不飽和エポキシエステル樹脂組成物
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JPS62218409A (ja) * 1986-03-20 1987-09-25 Sumitomo Bakelite Co Ltd 光硬化性樹脂組成物
JP2002187920A (ja) * 2000-12-20 2002-07-05 Nippon Kayaku Co Ltd 樹脂組成物、レンズ用樹脂組成物及びその硬化物
WO2013069441A1 (fr) * 2011-11-07 2013-05-16 昭和電工株式会社 Composition de résine pour des récipients sous pression et récipient sous pression
JP2013138194A (ja) * 2011-12-01 2013-07-11 Denki Kagaku Kogyo Kk 被加工部材の仮固定方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022196328A1 (fr) * 2021-03-18 2022-09-22
WO2022196328A1 (fr) * 2021-03-18 2022-09-22 ナミックス株式会社 Composition de résine, adhésif électroconducteur, objet durci, et dispositif semi-conducteur
JP7811399B2 (ja) 2021-03-18 2026-02-05 ナミックス株式会社 樹脂組成物、導電性接着剤、硬化物及び半導体装置

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