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WO2018012205A1 - Composition de résine durcissable par voie radicalaire, et produit durci associé - Google Patents

Composition de résine durcissable par voie radicalaire, et produit durci associé Download PDF

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Publication number
WO2018012205A1
WO2018012205A1 PCT/JP2017/022482 JP2017022482W WO2018012205A1 WO 2018012205 A1 WO2018012205 A1 WO 2018012205A1 JP 2017022482 W JP2017022482 W JP 2017022482W WO 2018012205 A1 WO2018012205 A1 WO 2018012205A1
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WIPO (PCT)
Prior art keywords
mass
resin composition
bromine
vinyl ester
radical polymerizable
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2017/022482
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English (en)
Japanese (ja)
Inventor
村上　修一
梶野　正彦
塚本　貴史
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Japan Composite Co Ltd
Original Assignee
Japan Composite Co Ltd
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 Japan Composite Co Ltd filed Critical Japan Composite Co Ltd
Priority to JP2018527464A priority Critical patent/JP7019572B2/ja
Priority to CN201780024654.XA priority patent/CN109071738B/zh
Publication of WO2018012205A1 publication Critical patent/WO2018012205A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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

Definitions

  • the present invention relates to a radical curable resin composition and a cured product thereof.
  • the radical curable resin can be handled in a liquid state, has good workability, and the cured product has excellent performance such as durability, water resistance, strength, etc., and thus is suitably used for various applications. .
  • the cured product has excellent performance such as durability, water resistance, strength, etc., and thus is suitably used for various applications.
  • radical curable resins Construction materials and molded bodies are widely used. In recent years, studies for achieving low thermal expansion have been made from the current situation where high performance is required (see, for example, Patent Documents 1 and 2).
  • radical curable resins are widely used in various fields because they are excellent in various physical properties.
  • the physical properties required in various fields have become increasingly strict.
  • a higher level of dimensional stability is required than before, and excellent heat resistance is also required.
  • the current situation is that conventional radical curable resins cannot sufficiently meet these requirements.
  • the present invention has been made in view of the above situation, and achieves low thermal expansion, has high dimensional stability, and can provide a cured product having excellent heat resistance and flame retardancy. It aims at providing the resin composition and its hardened
  • the inventor paid attention to the fact that a resin composition containing a radically polymerizable oligomer and a radically polymerizable monomer has good handleability and workability, and that a cured product has various physical properties. And while advancing diligently, making a bromine-containing vinyl ester as a radically polymerizable oligomer essential, and a resin composition containing a radically polymerizable monomer and a liquid rubber in a predetermined ratio, respectively, can achieve low thermal expansion, It has been found that it provides a cured product having high dimensional stability and excellent heat resistance.
  • Such a cured product is also useful in various fields in that it has excellent toughness, flame retardancy, and surface smoothness, and can exhibit various physical properties in a balanced manner while achieving low thermal expansion. .
  • the inventors have conceived that the above problems can be solved brilliantly, and have completed the present invention.
  • the first present invention is a radical curable resin composition
  • a radical curable resin composition comprising a radical polymerizable oligomer (A), a radical polymerizable monomer (B), and a liquid rubber (C), wherein the radical polymerizable oligomer (A ) Contains a bromine-containing vinyl ester, and the content ratio of the bromine-containing vinyl ester, the radical polymerizable monomer (B) and the liquid rubber (C) includes the radical polymerizable oligomer (A) and the radical polymerizable monomer. 30 to 65% by mass, 25 to 50% by mass, and 10 to 30% by mass with respect to 100% by mass of the total amount of the body (B) and all the thermoplastic resins and elastomers including the liquid rubber (C), respectively. It is a radical curable resin composition.
  • the radical curable resin composition further includes a thermoplastic resin and / or an elastomer (D) other than the liquid rubber (C), and the thermoplastic resin and / or the elastomer (D) includes polyvinyl acetate and polystyrene. And at least one selected from the group consisting of (meth) acrylate polymers.
  • the second aspect of the present invention is a radically curable resin composition
  • the radical polymerizable oligomer (A) contains a bromine-containing vinyl ester
  • the thermoplastic resin and / or elastomer (E) is a liquid rubber (C) and a thermoplastic resin other than the liquid rubber (C) and / or Containing the elastomer (D), the bromine-containing vinyl ester, the radical polymerizable monomer (B), and the thermoplastic resin and / or the elastomer (E) are contained in a proportion of the radical polymerizable oligomer (A), 30 to 65% by mass and 25 to 50% by mass, respectively, with respect to 100% by mass of the total amount of the radical polymerizable monomer (B) and the thermoplastic resin and / or elasto
  • thermoplastic resin and / or elastomer (D) is preferably at least one selected from the group consisting of polyvinyl acetate, polystyrene, and (meth) acrylate polymers.
  • the bromine-containing vinyl ester preferably has a glass transition temperature of 130 to 170 ° C. when the resin cured product contains 30% by mass of styrene.
  • the liquid rubber (C) preferably has a number average molecular weight of 60,000 or less.
  • the radical polymerizable monomer (B) preferably contains a compound having two or more polymerizable groups.
  • the radical polymerizable oligomer (A) further contains a bromine-free vinyl ester having a glass transition temperature of 130 to 170 ° C. and / or 30% by weight of styrene. It is preferable to include an unsaturated polyester having a glass transition temperature of 130 to 250 ° C. of the cured resin.
  • the present invention is also a cured product obtained by curing the radical curable resin composition.
  • the term “the present invention” simply means the matters common to the first and second present inventions.
  • the radical curable resin composition of the present invention is configured as described above, the cured product achieves low thermal expansion, and has high dimensional stability, heat resistance, toughness, flame retardancy, and surface smoothness. Various physical properties such as can be exhibited in a well-balanced manner. Moreover, since it is liquid at normal temperature (25 degreeC), handling property and workability
  • operativity are favorable. Therefore, for example, in addition to lining materials, adhesives, electrical insulating paints, etc., it contributes greatly in various fields such as building materials, housings, machine parts, electronic / electric parts, vehicle parts, ship parts, aircraft parts, etc. Is.
  • the radical curable resin composition of the present invention (also simply referred to as “resin composition”) includes a radical polymerizable oligomer (A), a radical polymerizable monomer (B), and a liquid rubber (C) ( Hereinafter, it is also abbreviated as “component (A)”.) If necessary, one or more other components may be further contained, and one or two or more of each component may be used.
  • a mixture of the radical polymerizable oligomer (A) and the radical polymerizable monomer (B) is also collectively referred to as “radical polymerizable resin” or “radical curable resin”.
  • the “total amount of the radical polymerizable oligomer (A), the radical polymerizable monomer (B), and all the thermoplastic resins and elastomers including the liquid rubber (C)” refers to the radical polymerizable oligomer ( A), a radical polymerizable monomer (B), a liquid rubber (C), and a component (D) described later (a thermoplastic resin and / or an elastomer (D) other than the liquid rubber (C)). In the case, it means the total amount of the component (D).
  • the radically polymerizable oligomer (A) essentially contains a bromine-containing vinyl ester (also referred to as brominated vinyl ester).
  • the content of the bromine-containing vinyl ester is the components (A), (B) and (C) (however, when the component (D) described later is further included, the components (A), (B), (C) and ( The total amount of D)) is 30 to 65% by mass. By being within this range, it is possible to sufficiently exhibit the effects of the present invention.
  • the lower limit of the content ratio of the bromine-containing vinyl ester is preferably 35% by mass or more, more preferably 38% by mass or more, and the upper limit is preferably 63% by mass or less. Is 60% by mass or less.
  • the components (A), (B) and (C) (however, when the component (D) described later is further included, the components (A), (B), (C) and (D))
  • the bromine atom content with respect to the total amount of 100% by mass is 10% by mass or more.
  • cured material further improves. More preferably, it is 12 mass% or more, More preferably, it is 14 mass% or more.
  • the upper limit is preferably 45% by mass or less. More preferably, it is 40 mass% or less, More preferably, it is 35 mass% or less.
  • the bromine content can be determined by the method described in Examples described later.
  • the bromine-containing vinyl ester preferably occupies 50 to 100% by mass, more preferably 60 to 100% by mass, and still more preferably 60 to 99% by mass in the total amount of 100% by mass of the radical polymerizable oligomer (A). Particularly preferred is 60 to 90% by mass.
  • a bromine free vinyl ester and unsaturated polyester are preferable.
  • An unsaturated polyester having a temperature of ⁇ 250 ° C. is more preferable, and a form containing at least one of these is one of the preferred forms of the present invention.
  • each radical polymerizable oligomer will be further described.
  • the bromine-containing vinyl ester is a compound in which a bromine atom is introduced into the main chain and / or side chain of the vinyl ester, and among them, a compound in which a bromine atom is introduced into the main chain of the vinyl ester is preferable.
  • the bromine-containing vinyl ester preferably has a glass transition temperature (also referred to as Tg) of 130 to 170 ° C. of a cured resin product containing 30% by mass of styrene.
  • Tg glass transition temperature
  • the resulting cured product can be further reduced in thermal expansion and further improved in heat resistance and surface smoothness.
  • the Tg of the cured product is more preferably 135 ° C. or higher, further preferably 140 ° C. or higher, more preferably 165 ° C. or lower, and further preferably 160 ° C. or lower.
  • the Tg of the cured resin containing 30% by mass of styrene means the Tg of the cured product when the resin is composed of 70% by mass of a bromine-containing vinyl ester and 30% by mass of styrene. It can obtain
  • the bromine-containing vinyl ester is, for example, a compound obtained by reaction of an epoxy compound containing bromine (also referred to as brominated epoxy compound or bromine-containing epoxy compound) with an unsaturated monobasic acid, or brominated with a bromine-containing epoxy compound.
  • an epoxy compound containing bromine also referred to as brominated epoxy compound or bromine-containing epoxy compound
  • bromine-containing epoxy compound A compound obtained by reacting an epoxy compound having a high molecular weight with bisphenol A and an unsaturated monobasic acid is preferred. You may use 1 type, or 2 or more types for each raw material used by this reaction. Moreover, you may use together the epoxy compound which does not contain a bromine as needed.
  • the amount of each raw material is set so that the equivalent of the carboxyl group of the unsaturated monobasic acid to the epoxy group of the epoxy compound is 0.9 to 1.2. It is preferable to do.
  • the reaction temperature for the above reaction is not particularly limited, but is preferably 80 to 130 ° C.
  • a reaction catalyst, a polymerization inhibitor or the like may be appropriately used in the presence of air as necessary.
  • the above reaction is preferably carried out in substantially the same manner as the vinyl ester synthesis reaction method described in, for example, Japanese Patent No. 4768161 [0028] to [0035].
  • numerator is suitable.
  • bisphenol type epoxy compound, novolak type epoxy compound, aliphatic type epoxy compound, alicyclic epoxy compound, monocyclic epoxy compound, amine type epoxy compound, etc. such as mechanical strength, corrosion resistance, heat resistance, etc.
  • a bisphenol type epoxy compound is preferable.
  • Examples of the bisphenol type epoxy compound include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol AD type epoxy compound, and a bisphenol S type epoxy compound.
  • Examples of novolak type epoxy compounds include phenol novolac type epoxy compounds and cresol novolac type epoxy compounds.
  • Examples of the aliphatic epoxy compound include a hydrogenated bisphenol A type epoxy compound and a propylene glycol polyglycidyl ether compound.
  • Examples of the alicyclic epoxy compound include alicyclic diepoxy acetal, dicyclopentadiene dioxide, vinyl hexene dioxide, vinyl hexene dioxide, and glycidyl methacrylate.
  • a phenol compound such as bisphenol A, or an epoxy compound modified with a dibasic acid such as adipic acid, sebacic acid, dimer acid, or liquid nitrile rubber can also be used.
  • brominated epoxy compound for example, a compound in which one or more bromine atoms are introduced into the above-described epoxy compound is preferable, among which a brominated bisphenol type epoxy compound or a brominated novolak type epoxy compound is more preferable. More preferred is a brominated bisphenol type epoxy compound, and particularly preferred is the following general formula (1):
  • Y represents —C (CH 3 ) 2 —, —CH 2 —, —O—, —S— or —S (O) 2 —
  • a compound in which Y represents —C (CH 3 ) 2 — that is, a brominated bisphenol A type epoxy compound
  • a, b is more preferable.
  • C and d are all 2 compounds (that is, tetrabromobisphenol A type epoxy compound).
  • An epoxy compound containing a bisphenol skeleton and a brominated bisphenol skeleton in one molecule can also be used as the brominated bisphenol type epoxy compound.
  • Examples of the unsaturated monobasic acid include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and sorbic acid; dibasic acid anhydrides and alcohols having at least one unsaturated group in the molecule; And the like.
  • Examples of the dibasic acid anhydride include aliphatic or aromatic dicarboxylic acids such as maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.
  • Acrylic acid and methacrylic acid are preferable from the viewpoint of achieving low thermal expansion more preferably methacrylic acid.
  • bromine-containing vinyl esters particularly preferred is a compound obtained by reacting an epoxy compound containing a compound represented by the above general formula (1) (in particular, a tetrabromobisphenol A type epoxy compound is preferred) with acrylic acid. It is. Since such a compound has many crosslinking points, the cured product Tg can satisfy the preferred range described above. Therefore, in the obtained cured product, low thermal expansion can be further achieved, and heat resistance and surface smoothness are further improved.
  • the number average molecular weight of the bromine-containing vinyl ester is not particularly limited, but is preferably 300 to 2000, for example. Thereby, in the hardened
  • the resin composition preferably contains a bromine-free vinyl ester in addition to the bromine-containing vinyl ester.
  • a bromine-free vinyl ester is a vinyl ester containing no bromine atom.
  • the bromine-free vinyl ester preferably has a glass transition temperature (Tg) of 130 to 170 ° C. of the resin cured product containing 30% by mass of styrene. That is, when the resin is composed of 70% by mass of a bromine-free vinyl ester and 30% by mass of styrene, the Tg of the cured product is preferably 130 to 170 ° C. When such a bromine-free vinyl ester is used, the resulting cured product can be further reduced in thermal expansion and further improved in heat resistance and surface smoothness. From the viewpoint of more manifesting this effect, the Tg of the cured product is more preferably 135 ° C. or higher, further preferably 140 ° C. or higher, more preferably 165 ° C. or lower, and further preferably 160 ° C. or lower.
  • Tg glass transition temperature
  • the bromine-free vinyl ester can be obtained, for example, by a reaction between an epoxy compound and an unsaturated monobasic acid in the same manner as the bromine-containing vinyl ester described above except that a brominated epoxy compound is not used.
  • Preferred conditions for the reaction and preferred examples of the epoxy compound used are as described above.
  • the number average molecular weight of the bromine-free vinyl ester is not particularly limited, but is preferably 200 to 2000, for example. More preferably, it is 300 to 1000.
  • the resin composition preferably contains an unsaturated polyester in addition to the bromine-containing vinyl ester.
  • the unsaturated polyester preferably has a glass transition temperature (Tg) of 130 ° C. to 250 ° C. of the cured resin product containing 30% by mass of styrene.
  • Tg glass transition temperature
  • the resulting cured product can be further reduced in thermal expansion and further improved in heat resistance and surface smoothness.
  • the Tg of the cured product is more preferably 140 ° C. or higher.
  • the unsaturated polyester is, for example, a compound obtained by a condensation reaction between a polybasic acid and a polyhydric alcohol.
  • Each raw material used in this reaction may be used alone or in combination of two or more. Further, it may be modified with dicyclopentadiene (DCPD).
  • DCPD dicyclopentadiene
  • the amount ratio (the total amount of polybasic acid / polyhydric alcohol and epoxy compound) of these may be 10/8 to 10/12 (mol%). Is preferred.
  • the said reaction is not specifically limited, What is necessary is just to perform by a normal synthesis means. In general, the reaction is carried out under an inert gas atmosphere under heating, and the reaction proceeds while removing by-product water. Further, in an inert gas atmosphere, heating to a temperature range of 120 to 250 ° C.
  • the desired acid You may dehydrate-condense until it becomes a value or a viscosity (molecular weight).
  • the temperature range is more preferably 150 to 220 ° C.
  • the polybasic acid preferably contains an ⁇ , ⁇ -unsaturated dibasic acid.
  • the ⁇ , ⁇ -unsaturated dibasic acid include maleic anhydride, maleic acid, fumaric acid, itaconic acid and the like. Of these, maleic anhydride, maleic acid and / or fumaric acid are preferred. Further, it may contain a saturated polybasic acid, and examples of the saturated polybasic acid include malonic acid, succinic acid, adipic acid, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, and heptic acid. Can be mentioned.
  • Examples of the polyhydric alcohol include glycol (also referred to as diol) and an epoxy compound.
  • Examples of the glycol include alkyl-substituted alkylene glycols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, and neopentyl glycol; diethylene glycol, dipropylene glycol, triethylene glycol Condensates of alkylene glycols such as bisphenol A, hydrogenated bisphenol A, alkylene oxide adducts of bisphenol A, bisphenols such as alkylene oxide adducts of hydrogenated bisphenol A; trimethylolpropane monoallyl ether, pentaerythritol diallyl Allyl group-containing alcohols such as ethers; Trivalent or higher alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol;
  • the number average molecular weight of the unsaturated polyester is not particularly limited, but is preferably 600 to 10,000, for example. More preferably, it is 1000 to 5000.
  • the unsaturated polyester preferably has an ester acid value of 1 to 50 mgKOH / g. More preferably, it is 5 to 30 mg KOH / g.
  • an ester acid value can be calculated
  • the content of the radically polymerizable monomer (B) is such that the components (A), (B) and (C) (provided that the component (D) described later is further included)
  • the total amount of (A), (B), (C) and (D)) is 25 to 50% by mass with respect to 100% by mass.
  • a low thermal expansion coefficient can be achieved, a high degree of dimensional stability can be achieved, and a cured product with excellent heat resistance, toughness, flame retardancy, and surface smoothness can be provided, and resin Handling property and workability when using the composition are improved.
  • the amount of residual monomer is reduced, and it becomes possible to suppress the emission from the molded product.
  • the radical polymerizable monomer is not particularly limited, and is a compound having one polymerizable group in one molecule (also referred to as a monofunctional compound) or a compound having two or more polymerizable groups (polyfunctional compound). Any of these may also be used suitably. Among them, it is preferable to use at least a polyfunctional compound from the viewpoints of further improving the toughness and heat resistance of the cured product and further reducing the coefficient of thermal expansion. Thus, the form in which the radical polymerizable monomer includes a compound having two or more polymerizable groups is one of the preferred forms of the present invention. Moreover, it is also preferable to contain styrene as described later, and it is most preferable to use styrene and a polyfunctional compound in combination. Hereinafter, these radical polymerizable monomers will be further described.
  • the monofunctional compound is not particularly limited.
  • aromatic monomers such as styrene, ⁇ -methylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, and vinyltoluene
  • non-functional such as (meth) acrylic acid Saturated monocarboxylic acids
  • vinyl esters such as vinyl acetate and vinyl adipate
  • monofunctional (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and benzyl (meth) acrylate; Can be mentioned.
  • a monomer containing an aromatic ring is preferable from the viewpoint of excellent polymerization reactivity and compatibility. More preferred is styrene, vinyltoluene and / or benzyl (meth) acrylate, and even more preferred is styrene.
  • cured material which is further excellent by heat resistance, toughness, a flame retardance, etc. is obtained.
  • aromatic monomers such as divinylbenzene, diallyl phthalate, and diallyl benzene phosphonate
  • aromatic monomers such as divinylbenzene, diallyl phthalate, and diallyl benzene phosphonate
  • the content ratio of the liquid rubber (C) is the components (A), (B) and (C) (provided that the component (D)
  • the total amount of A), (B), (C), and (D)) is 10 to 30% by mass with respect to 100% by mass.
  • the lower limit of the content ratio of the component (C) is preferably 11% by mass or more, and the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less. It is.
  • the liquid rubber (C) preferably has a number average molecular weight of 60,000 or less. Thereby, it is excellent in compatibility with other components, the toughness and surface smoothness of the cured product are further improved, and the resin composition is more excellent in storage stability and handleability. More preferably, it is 50,000 or less.
  • the lower limit of the number average molecular weight is not particularly limited, but is preferably 50 or more, for example. Especially, it is preferable that it is 500 or more from a viewpoint of the toughness improvement of hardened
  • the liquid rubber (C) preferably has an 80 ° C. viscosity of 15 Pa ⁇ s or less. More preferably, it is 13 Pa.s or less, More preferably, it is 10 Pa.s or less.
  • the 80 degreeC viscosity of a compound can be calculated
  • the liquid rubber (C) is preferably one that becomes liquid at room temperature (25 ° C.), for example, liquid polyisoprene, liquid polyisobutylene, liquid polybutadiene, liquid butadiene rubber, liquid butyl rubber, liquid styrene butadiene rubber, Examples thereof include liquid nitrile butadiene rubber, liquid acrylonitrile rubber, liquid chloroprene rubber, liquid polysulfide, liquid phenol resin, liquid epoxy resin, and liquid xylene resin. Among these, liquid polyisoprene, liquid polybutadiene, liquid acrylic lithyl rubber, and liquid xylene resin are preferable.
  • liquid polybutadienes compounds having hydroxyl groups and / or carboxylic acid groups at both ends are preferred.
  • the liquid rubber (C) a compound obtained by acid-modifying the liquid rubber or a compound obtained by polymerizing an acid component on the liquid rubber is also preferable. Examples thereof include carboxyl group-terminated butadiene acrylonitrile rubber, maleic acid-modified isoprene, and acrylonitrile / butadiene / methacrylic acid copolymer.
  • the resin composition of the present invention may also contain one or more thermoplastic resins and / or elastomers (D) (also referred to as component (D)) other than the liquid rubber (C).
  • the elastomer includes rubber and thermoplastic elastomer.
  • the composition containing liquid rubber (C) and a thermoplastic resin and / or elastomer (D) is also called a thermoplastic resin and / or elastomer (E).
  • the content rate is 50 mass% or less among 100 mass% of total amounts of a component (C) and (D).
  • the component (C) is 50% by mass or more in the total amount of 100% by mass of the components (C) and (D). More preferably, it is 75 mass% or more, More preferably, it is 90 mass% or more.
  • the resin composition of the present invention preferably contains a liquid rubber (C) and a thermoplastic resin and / or an elastomer (D).
  • the resin composition of the present invention contains the liquid rubber (C) and the thermoplastic resin and / or the elastomer (D), the radically polymerizable oligomer (A) and the radically polymerizable monomer (B).
  • Compatibility is improved, and separation due to aging of these mixtures can be more sufficiently suppressed.
  • the addition amount of liquid rubber (C) may be reduced.
  • the second present invention is a radical curable resin composition comprising a radical polymerizable oligomer (A), a radical polymerizable monomer (B), and a thermoplastic resin and / or an elastomer (E).
  • the radical polymerizable oligomer (A) contains a bromine-containing vinyl ester
  • the thermoplastic resin and / or elastomer (E) is a liquid rubber (C) and a thermoplastic resin other than the liquid rubber (C) and / or Or the elastomer (D), and the bromine-containing vinyl ester
  • the radical polymerizable monomer (B), and the thermoplastic resin and / or elastomer (E) are contained in the radical polymerizable oligomer (A).
  • thermoplastic resin and / or elastomer (E) The content of the thermoplastic resin and / or elastomer (E) in the second aspect of the present invention is as follows: radical polymerizable oligomer (A), radical polymerizable monomer (B), thermoplastic resin and / or elastomer (E ) With respect to a total amount of 100% by mass, and preferably 10 to 25% by mass, more preferably 10 to 20% by mass.
  • thermoplastic resin and / or elastomer is not particularly limited.
  • polystyrene, polyethylene, polyvinyl acetate, cross-linked polystyrene, polyvinyl acetate-polystyrene block copolymer, polyphase structure polymer such as acrylic / styrene, cross-linked / non-cross-linked From the viewpoint of more fully exhibiting the effects of the present invention, a compound having excellent compatibility with the above-described radical polymerizable oligomer (A) is used. It is preferable. Specifically, at least one compound selected from the group consisting of polyvinyl acetate, polystyrene, and (meth) acrylate polymers is preferable.
  • the polystyrene may be a styrene polymer. Below, a polyvinyl acetate and a (meth) acrylate type polymer are further demonstrated.
  • Polyvinyl acetate- Polyvinyl acetate is not particularly limited.
  • vinyl acetate homopolymer ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-acrylate copolymer, vinyl acetate-acrylate copolymer Examples thereof include copolymers such as coalescence.
  • the modified polyvinyl acetate which carried out the modification process may be sufficient.
  • vinyl acetate homopolymer and acid-modified polyvinyl acetate also referred to as acid-modified polyvinyl acetate
  • Polyvinyl acetate which is dissolved in styrene and has improved workability is also preferably used.
  • (meth) acrylate polymer examples include acrylic resin, methyl methacrylate butadiene styrene copolymer, styrene methyl methacrylate maleic anhydride copolymer, and ethylene acrylate copolymer.
  • alkyl acrylate, alkyl methacrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, cyclohexyl, etc.); Hydroxy-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate; Epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether; acrylic acid and methacrylic acid Carboxy groups such as itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene sulfonic acid or salts thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.)
  • Dialnal BR-77 T
  • Dialnal BR-106 T
  • Dialnal MB-7601 Dialnal MB-7602
  • Dialnal MB-7603 All manufactured by Mitsubishi Rayon Co., Ltd.
  • the resin composition of the present invention is a composition comprising only components (A), (B) and (C) (however, when component (D) is further included, components (A), (B) and (C) And (D) is preferably a composition having a viscosity at 25 ° C. of 50 to 3000 mPa ⁇ s. Thereby, workability
  • viscosity is more preferably 50 mPa ⁇ s or more, still more preferably 100 mPa ⁇ s or more, and the upper limit is more preferably 6000 mPa ⁇ s or less, and still more preferably 1000 mPa ⁇ s or less.
  • the 25 ° C. viscosity of the composition can be determined by, for example, a Brookfield viscometer.
  • the resin composition of the present invention is preferably used by being cured as a resin component of a molding material.
  • the resin composition can be used as a molding material substantially as it is or as a coating film-forming component. You can do it.
  • a molding material containing these is excellent in moldability and excellent in physical properties and flame retardancy. This is one of the preferred embodiments of the present invention.
  • the inorganic filler is not particularly limited.
  • aluminum hydroxide for example, aluminum hydroxide, calcium carbonate, barium sulfate, alumina, metal powder, kaolin, talc, milled fiber, quartz sand, diatomaceous earth, crystalline silica, fused silica, glass powder, clay, etc. And can be selected in a timely manner according to the intended use.
  • aluminum hydroxide is preferable in that it has excellent moldability and also has an effect of improving flame retardancy.
  • the inorganic filler is preferably blended in the range of 30 to 400 parts by mass with respect to 100 parts by mass of the radical polymerizable resin.
  • the material of the fiber reinforcing material is not particularly limited, for example, inorganic fibers such as glass fiber and carbon fiber; polyvinyl alcohol-based, polyester-based, polyamide-based (including wholly aromatic-based), fluororesin-based, phenol-based various organic materials Fibers can be appropriately selected and used.
  • the shape of the fiber reinforcement may be any shape such as cross; mat shape such as chopped strand mat, preformable mat, continuous strand mat, surfacing mat; chop shape; roving shape; nonwoven fabric shape; paper shape; There is no problem.
  • the fiber reinforcing material is pre-determined according to the shape of the target molded article, and used by impregnating the radical curable resin composition before curing, or chopping into the radical curable resin composition.
  • the reinforcing fibers can be mixed to obtain a molding material, which can be used for molding into a desired shape.
  • the fiber reinforcement is preferably used in the range of 20 to 300 parts by mass with respect to 100 parts by mass of the radical polymerizable resin. If the amount is less than 20 parts by mass, the molded product may have insufficient strength. If the amount exceeds 300 parts by mass, the water resistance and chemical resistance of the molded product may be deteriorated. A more preferable amount of the fiber reinforcing material is 30 to 250 parts by mass.
  • a thermal polymerization initiator, a photopolymerization initiator, a photosensitizer, etc. are blended and heated, or ultraviolet rays, electron beams, radiation, etc. It is sufficient to irradiate the active energy ray.
  • thermal polymerization initiator known ones can be used. Specifically, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxyneodikenate, lauryl peroxide, benzoylper Oxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexanone, cyclohexanone peroxide, t-butylperoxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-teto Methyl butyl hydroperoxide, cum
  • a curing accelerator it is also effective to mix a curing accelerator during thermal polymerization.
  • the curing accelerator include metal soaps such as cobalt naphthenate and cobalt octylate; tertiary amines; and the like. These may be appropriately selected depending on the combination with the thermal polymerization initiator used.
  • the amount of the thermal polymerization initiator used is preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the radical polymerizable resin.
  • photopolymerization initiators are not particularly limited and can be used.
  • the amount of the photopolymerization initiator used is preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the radical polymerizable resin.
  • it is also effective to use a known photosensitizer in combination.
  • the molding material may be irradiated with active energy rays such as ultraviolet rays, electron beams, and radiation using a known apparatus.
  • active energy rays such as ultraviolet rays, electron beams, and radiation
  • the ultraviolet irradiation device a device equipped with a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp, or the like can be used.
  • the electron beam irradiation apparatus include a scanning electro curtain type, a curtain type, a laminar type, an area beam type, a broad beam type, and a pulse beam type.
  • a phosphorus-containing compound, a nitrogen-containing compound, red phosphorus, antimony oxide, a boron compound, or the like is used as a flame retardant or flame retardant. It is also possible to mix as an auxiliary agent. Furthermore, pigments, colorants, flame retardants, antifoaming agents, wetting agents, dispersants, rust inhibitors, antistatic agents, ultraviolet absorbers, antioxidants, and the like can be blended as necessary.
  • the radical curable resin composition of the present invention can achieve a low coefficient of thermal expansion, has a high degree of dimensional stability, and can give a cured product having excellent heat resistance, toughness, flame retardancy, and surface smoothness. . Therefore, it can be effectively used in various fields such as adhesives and electrical insulating paints, and the resin composition can be used as it is or in combination with the above-mentioned inorganic fillers, fiber reinforcements, etc. It can be used for a wide range of parts such as casting materials, mechanical parts, electronic / electrical parts, vehicles, ships, aircrafts, etc.
  • a cured product obtained by curing such a radical curable resin composition (also referred to as a cured product of the resin composition) is also included in the present invention.
  • a hardening method of the said resin composition it is suitable to mix and harden a hardening
  • the combination of the curing accelerator and the curing agent include cobalt octenoate and cumene hydroperoxide.
  • the curing temperature is preferably 50 to 190 ° C., more preferably 80 to 180 ° C.
  • the curing time is preferably 1 to 180 minutes, more preferably 10 to 100 minutes. By curing under such conditions, the curing is completed and the unreacted radical polymerizable monomer (B) is consumed.
  • the cured product preferably has a linear expansion coefficient of 40 ⁇ 10 ⁇ 6 / K or less when it is a cured product containing an inorganic filler. More preferably, it is 39 ⁇ 10 ⁇ 6 / K or less, further preferably 38 ⁇ 10 ⁇ 6 / K or less, and particularly preferably 37 ⁇ 10 ⁇ 6 / K or less.
  • a low expansion coefficient can be achieved in this way, so that a cured product having excellent physical properties such as dimensional stability and smoothness and a high appearance can be provided.
  • cured material can be calculated
  • Examples of the shape of the cured product include a coating film shape and a molded product (also referred to as a molded product) shape. Below, the method of obtaining these is further demonstrated.
  • the method for forming the coating film is not particularly limited.
  • a curing agent is mixed with the resin composition, applied to a substrate, and then cured to form a coating film.
  • Method When a mat-like fiber reinforcing material is used, a curing agent is mixed into the resin composition, the fiber reinforcing material is impregnated by hand layup or the like to form a coating material, and a coating is formed by curing. Method; and the like.
  • the base material is not particularly limited, and examples thereof include inorganic base materials such as glass, slate, concrete, mortar, ceramic, and stone materials; metals made of aluminum, iron, zinc, tin, copper, titanium, stainless steel, tinplate, tin, and the like.
  • Metal base material such as plate, metal plated with zinc, copper, chromium, etc., metal treated with chromic acid, phosphoric acid, etc .; polyethylene, polyvinyl chloride, ABS (acrylonitrile-butadiene-styrene), FRP ( Textile reinforced plastic), polyethylene terephthalate, polycarbonate, polymethyl methacrylate, polystyrene, polypropylene, polyester, polyolefin, acrylic resin, epoxy resin, nylon resin and other plastic substrates; synthetic leather; cypress, cedar, pine, plywood, etc. ; Organic materials such as fiber and paper; etc. And the like. These substrates may be coated with a commonly used primer or a coating material such as an undercoat, an intermediate coat, or a top coat such as a metallic base before the resin composition is coated.
  • a commonly used primer or a coating material such as an undercoat, an intermediate coat, or a top coat such as a metallic base before the resin composition is coated.
  • the resin composition As a method of applying the resin composition to the substrate, it may be appropriately set depending on the application, etc., but as the coating method, for example, dip coating, brush coating, roll brush coating, spray coating, roll coating, spin coating, Examples include dip coating, spin coating, bar coating, flow coating, electrostatic coating, die coating, film lamination, and gel coating.
  • the coating method for example, dip coating, brush coating, roll brush coating, spray coating, roll coating, spin coating, Examples include dip coating, spin coating, bar coating, flow coating, electrostatic coating, die coating, film lamination, and gel coating.
  • the method for obtaining the molded product is not particularly limited.
  • a normal casting method, compression molding method, centrifugal molding method, injection molding method, transfer molding method, injection molding method An extrusion method or the like can be employed.
  • the radical polymerizable resin was cured by further heating at 175 ° C. for 30 minutes to obtain a cured resin product of 65 mm ⁇ 140 mm (thickness 3 mm).
  • a test piece of 5 mm ⁇ 5 mm ⁇ 3 mm was cut from the cured resin, and Tg was measured with a thermomechanical analyzer (manufactured by Hitachi High-Tech Science Co., Ltd., EXSTAR TMA SS7100). The temperature was raised from room temperature to 230 ° C. at a rate of temperature increase of 5 ° C./min, and the glass transition point (Tg) was determined from the inflection point of the measured linear expansion coefficient ( ⁇ ).
  • bromine content of brominated epoxy compounds (tetrabromobisphenol A type epoxy resin used in Synthesis Examples 1 to 4) and tetrabromobisphenol A (used in Synthesis Example 4), which are raw materials for bromine content, are the test tables for each product. From the values, they were 48.0% and 58.8%, respectively. From this bromine content and the amount of each raw material used during the synthesis, the bromine content in the radical polymerizable resin comprising the radical polymerizable oligomer (A) (bromine-containing vinyl ester) and 30% styrene (in each synthesis example) And bromine content (described in Table 1 or 2) with respect to 100% by mass of the total amount of components (A) to (D).
  • the compound (or mixture) to be measured for the molecular weight of the compound was dissolved in a THF (tetrahydrofuran) solvent, and the molecular weight was determined by GPC (gel permeation chromatography). At that time, a calibration curve was prepared using a commercially available monodisperse standard polystyrene, and obtained based on the following conversion method.
  • HLC-8320GPC manufactured by Tosoh Corporation
  • detector differential refractometer column: TSKgelSuperH2000, TSKgelSuperH2500, TSKgelSuperH3000 (manufactured by Tosoh Corporation)
  • Column temperature 40 ° C
  • Mobile phase THF
  • Polystyrene conversion Polystyrene conversion (general-purpose calibration method)
  • Linear expansion coefficient ( ⁇ ) To 100 parts of the resin composition, 150 parts of aluminum hydroxide (Showa Denko, Heidilite H-320) and 1.0 part of 80% cumene hydroperoxide (Nippon Yushi Co., Ltd., Park Mill H-80) are added and mixed. Thereafter, vacuum degassing was performed to prepare a compound. The compound is added to the above 1. Was cured by the same method as above to obtain a compound cured product having a thickness of 3 mm. The glass transition point (Tg) was measured with a thermomechanical analyzer using a test piece obtained by cutting from the cured product.
  • Tg glass transition point
  • Heat resistance evaluation 1 part by weight of 80% cumene hydroperoxide as a curing agent was added to 100 parts of the resin composition and mixed. Above 1. In the same manner as above, casting was performed to obtain a cured resin composition of 65 mm ⁇ 140 mm (thickness 3 mm). A glass transition point (Tg) was measured by a thermomechanical analyzer using a test piece obtained by cutting from the cured product. This Tg was used as an index of heat resistance.
  • Synthesis Example 1 Synthesis of Brominated Vinyl Ester Resin (1) Tetrabromobisphenol A type epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd.) was placed in a reaction vessel (flask) equipped with a stirrer, reflux condenser, gas inlet tube and thermometer. "Epototo (R) YDB-400, epoxy equivalent 400) 1200 parts, 260 parts of methacrylic acid, 2.9 parts of triethylamine, and 0.3 parts of hydroquinone were charged and reacted at 110 ° C for 8 hours while introducing air. As a result, a brominated vinyl ester having an acid value of 2.0 mgKOH / g was obtained.
  • Synthesis Example 2 Brominated vinyl ester resin (2)
  • a bromine-containing vinyl ester resin (2) (bromine content 27.6%) containing 30% by mass of vinyl toluene was obtained by the same method except that styrene was changed to vinyl toluene.
  • the glass transition temperature of the cured resin was 147 ° C.
  • Synthesis Example 3 Brominated vinyl ester resin (3)
  • a bromine-containing vinyl ester resin (3) (bromine content 27.6%) containing 30% by mass of vinyl toluene was obtained by the same method except that styrene was changed to benzyl methacrylate.
  • the glass transition temperature of the cured resin was 140 ° C.
  • Synthesis Example 4 Synthesis of Brominated Vinyl Ester Resin (4)
  • BPA bisphenol A
  • tetrabromobisphenol A Tosoh Corporation
  • bisphenol A type epoxy resin Mitsubishi (R) R-139S
  • epoxy equivalent 400 tetrabromobisphenol A type epoxy resin
  • new 804 parts of "Epototo (R) YDB-400” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 400
  • 5.2 parts of triethylamine, and 0.52 parts of hydroquinone were charged and reacted at 110 ° C.
  • Synthesis Example 5 Synthesis of bromine-free vinyl ester resin (1)
  • 793 parts of epoxy resin (“Epomic® R-139S” manufactured by Mitsui Chemicals)
  • methacrylic acid A vinyl ester having an acid value of 5.6 mg KOH / g was obtained by charging 387 parts, 1 part of hydroquinone and 6 parts of triethylamine and reacting at 110 ° C. for 4 hours while introducing air.
  • styrene By adding 505 parts of styrene to the obtained vinyl ester, a bromine-free vinyl ester resin (1) (bromine content 0%) containing 30% by mass of styrene was obtained.
  • the glass transition temperature of the cured resin was 146 ° C.
  • Synthesis Example 6 Synthesis of unsaturated polyester resin (1)
  • a reaction vessel flask equipped with a stirrer, reflux condenser, gas introduction tube, and thermometer
  • 1026 parts of propylene glycol, 503 parts of dipropylene glycol, maleic anhydride 1470 parts and 0.6 part of hydroquinone were charged, the inside of the container was purged with nitrogen, and a dehydration condensation reaction was carried out at 200 ° C. for 9 hours to obtain an unsaturated polyester having an acid value of 10 mgKOH / g.
  • an unsaturated polyester resin (1) containing 30% by mass of styrene was obtained.
  • the glass transition temperature of the cured resin was 190 ° C.
  • Example 1 Brominated vinyl ester resin (1) 55 parts, unsaturated polyester resin (1) 25 parts, trimethylolpropane trimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), liquid rubber (1) (manufactured by Nippon Zeon Co., Ltd., acrylonitrile butadiene rubber) , "Nipol (R) 1312") 15 parts was mixed to prepare a resin composition. Using this resin composition, the above 5. A cured resin composition is produced by the method described in 6 above, and the above 6. Compound cured products were prepared by the method described in 1. and various physical properties were evaluated by the methods described above. The results are shown in Table 1.
  • the blending ratio (% by mass) is component (A), (B) and (C) (however, when component (D) is included, component (A), (B), (C) And (D)) are the content ratios of the bromine-containing vinyl ester, component (B) and component (C), respectively, when the total amount is 100% by mass.
  • Liquid rubber (1) manufactured by Nippon Zeon Co., Ltd., acrylonitrile butadiene rubber, “Nipol (R) 1312”, Mn: 2500, Mw: 6700, 80 ° C. viscosity: 2.5 Pa ⁇ s
  • Liquid rubber (2) manufactured by Kuraray Co., Ltd., liquid polyisoprene rubber, “Kuraprene (registered trademark) LIR-30”, Mn: 40000, Mw: 49000, 80 ° C.
  • Polyvinyl acetate manufactured by Wacker, acid-modified vinyl acetate, “C-305”, Mn: 20000, Mw: 50000
  • Polystyrene manufactured by DIC, polystyrene, "Dick Styrene GPPS CR-3500”
  • Xylene resin manufactured by Fudou, “Nikanol (registered trademark) H”, Mn: 60, Mw: 720, 80 ° C. viscosity: 0.4 Pa ⁇ s
  • each of the resin compositions obtained in Examples 1 to 12 contains a bromine-containing vinyl ester, a radical polymerizable monomer (B), and a liquid rubber (C), the contents of which are specified in the present invention.
  • the resin composition is in the range. All of the compound cured products obtained using this resin composition had a low coefficient of linear expansion and excellent dimensional stability. In addition, the flame retardancy, water resistance and surface smoothness were good, and the glass transition point of the cured resin composition was high, indicating good heat resistance.
  • Comparative Examples 1 to 3 were examples in which the liquid rubber (C) was not used. In this case, the compound cured product had a high linear expansion coefficient and was inferior in dimensional stability. In Comparative Example 3, the glass transition point of the cured resin composition was further low and the heat resistance was poor. Comparative Examples 4 and 5 are examples in which the liquid rubber (C) is used, but the content is outside the range defined in the present invention. Among these, in the comparative example 4, the linear expansion coefficient of the compound hardened
  • Comparative Examples 6 to 8 are examples in which the liquid rubber (C) was not included, but other components were used in place of the liquid rubber (C). Among these, in Comparative Example 6 using polyvinyl acetate, whitening of the appearance remarkably occurred in the water resistance test, and the water resistance was poor. In Comparative Example 7 using polystyrene, as in Comparative Example 5, since the separation of component (C) occurred remarkably during the preparation of the cured product, the cured product was uneven and surface irregularities were severe, and physical properties could not be evaluated. It was. In Comparative Example 8 using xylene resin, the surface smoothness of the cured product was poor and the flame retardancy did not meet the V-0 standard.
  • Comparative Example 9 is an example in which the content of the radical polymerizable monomer (B) exceeds the range specified in the present invention. In this case, as in Comparative Examples 5 and 7, the component (C ) was remarkably separated, the cured product was non-uniform and surface irregularities were severe, and the physical properties could not be evaluated.
  • Comparative Example 10 was an example in which no bromine-containing vinyl ester was used, but in this case, the flame retardancy was inferior and the linear expansion coefficient ⁇ was also higher than in Examples 1-12.
  • the cured product achieves low thermal expansion, and has high dimensional stability, heat resistance, toughness, flame resistance, water resistance, surface smoothness, etc. It was found that various physical properties of can be exhibited in a well-balanced manner.
  • the composition ratio defined in the present invention bromine-containing vinyl ester, radical polymerizable monomer (B), and content ratio of liquid rubber (C) are components (A), (B) and (C). (However, when the component (D) is included, 30 to 65% by mass and 25 to 50% by mass, respectively, with respect to 100% by mass of the total amount of the components (A), (B), (C) and (D)).

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  • Health & Medical Sciences (AREA)
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Abstract

L'invention a pour objet de fournir une composition de résine durcissable par voie radicalaire qui permet d'obtenir une faible dilatation thermique et présente une grande stabilité dimensionnelle, et qui simultanément permet de procurer un produit durci excellent en termes de résistance à la chaleur et de propriétés ignifuges. L'invention fournit également le produit durci associé à cette composition. Plus précisément, l'invention concerne une composition de résine durcissable par voie radicalaire qui contient un oligomère polymérisable par voie radicalaire (A), un monomère polymérisable par voie radicalaire (B) et un caoutchouc liquide (C). L'oligomère polymérisable par voie radicalaire (A) contient un vinylester comprenant un brome. Les teneurs en vinylester comprenant un brome, en monomère polymérisable par voie radicalaire (B) et en caoutchouc liquide (C) sont respectivement comprises entre 30 et 65% en masse, 25 et 50% en masse et 10 et 30% en masse pour 100% en masse de la quantité totale de l'ensemble d'une résine thermoplastique contenant l'oligomère polymérisable par voie radicalaire (A), le monomère polymérisable par voie radicalaire (B) et le caoutchouc liquide (C), et d'un élastomère. En outre, l'invention concerne une composition de résine durcissable par voie radicalaire qui contient l'oligomère polymérisable par voie radicalaire (A), le monomère polymérisable par voie radicalaire (B) et une résine thermoplastique et/ou un élastomère (E). L'oligomère polymérisable par voie radicalaire (A) contient un vinylester comprenant un brome. La résine thermoplastique et/ou l'élastomère (E) contient le caoutchouc liquide (C), et une résine thermoplastique et/ou un élastomère (D) autre que le caoutchouc liquide (C). Les teneurs en vinylester comprenant un brome, en monomère polymérisable par voie radicalaire (B), et en résine thermoplastique et/ou un élastomère (E), sont respectivement comprises entre 30 et 65% en masse, 25 et 50% en masse et 10 et 30% en masse pour 100% en masse de la quantité totale d'oligomère polymérisable par voie radicalaire (A), de monomère polymérisable par voie radicalaire (B) et de résine thermoplastique et/ou d'élastomère (E).
PCT/JP2017/022482 2016-07-11 2017-06-19 Composition de résine durcissable par voie radicalaire, et produit durci associé Ceased WO2018012205A1 (fr)

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WO2019198641A1 (fr) * 2018-04-12 2019-10-17 ジャパンコンポジット株式会社 Composition de résine de polyester insaturé, matériau de moulage, article moulé, et boîtier de bloc-batterie de véhicule électrique
WO2020080412A1 (fr) * 2018-10-19 2020-04-23 ジャパンコンポジット株式会社 Composition de résine de polyester insaturé, matériau de moulage, article moulé et boîtier de bloc-batterie de véhicules électriques
JP7572884B2 (ja) 2021-03-18 2024-10-24 フクビ化学工業株式会社 繊維強化樹脂成形体およびその製造方法

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WO2019198641A1 (fr) * 2018-04-12 2019-10-17 ジャパンコンポジット株式会社 Composition de résine de polyester insaturé, matériau de moulage, article moulé, et boîtier de bloc-batterie de véhicule électrique
CN111936537A (zh) * 2018-04-12 2020-11-13 日本复合材料株式会社 不饱和聚酯树脂组合物、成型材料、成型品、及电动车辆的电池组壳体
JPWO2019198641A1 (ja) * 2018-04-12 2021-03-25 ジャパンコンポジット株式会社 不飽和ポリエステル樹脂組成物、成形材料、成形品、および、電動車両のバッテリーパック筐体
US12037436B2 (en) 2018-04-12 2024-07-16 Japan Composite Co., Ltd. Unsaturated polyester resin composition, molding material, molded article, and battery pack housing for electric vehicles
JP7162056B2 (ja) 2018-04-12 2022-10-27 ジャパンコンポジット株式会社 不飽和ポリエステル樹脂組成物、成形材料、成形品、および、電動車両のバッテリーパック筐体
KR20210042152A (ko) * 2018-10-19 2021-04-16 재팬 콤퍼짓 가부시키가이샤 불포화 폴리에스터 수지 조성물, 성형 재료, 성형품, 및 전동 차량의 배터리 팩 하우징
CN112703214B (zh) * 2018-10-19 2023-08-04 日本复合材料株式会社 不饱和聚酯树脂组合物、成型材料、成型品、及电动车辆的电池组壳体
JPWO2020080412A1 (ja) * 2018-10-19 2021-09-30 ジャパンコンポジット株式会社 不飽和ポリエステル樹脂組成物、成形材料、成形品、および、電動車両のバッテリーパック筐体
WO2020080412A1 (fr) * 2018-10-19 2020-04-23 ジャパンコンポジット株式会社 Composition de résine de polyester insaturé, matériau de moulage, article moulé et boîtier de bloc-batterie de véhicules électriques
CN112703214A (zh) * 2018-10-19 2021-04-23 日本复合材料株式会社 不饱和聚酯树脂组合物、成型材料、成型品、及电动车辆的电池组壳体
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