WO2022210869A1 - Procédé de production d'un composite de produit semi-durci, procédé de production d'un composite de produit durci, et composite de produit semi-durci - Google Patents

Procédé de production d'un composite de produit semi-durci, procédé de production d'un composite de produit durci, et composite de produit semi-durci Download PDF

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WO2022210869A1
WO2022210869A1 PCT/JP2022/015943 JP2022015943W WO2022210869A1 WO 2022210869 A1 WO2022210869 A1 WO 2022210869A1 JP 2022015943 W JP2022015943 W JP 2022015943W WO 2022210869 A1 WO2022210869 A1 WO 2022210869A1
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polymerization initiator
polymerizable component
semi
polymerization
curable composition
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Japanese (ja)
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絵梨 金子
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デンカ株式会社
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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
    • C08F2/00—Processes of polymerisation

Definitions

  • the present invention relates to a method for producing a semi-cured composite, a method for producing a cured composite, and a semi-cured composite.
  • the composite as described above is used by adhering it to an adherend such as an electronic component, it is desirable that the state of high adhesion can be maintained for a long time because of its excellent handleability.
  • the composite when the resin is in a semi-cured state and within a predetermined viscosity range, excellent adhesiveness is achieved. In conventional composites, it was difficult to keep the viscosity within the desired range because the viscosity of the semi-cured resin tended to increase rapidly.
  • One aspect of the present invention is a semi-cured composite in which a porous body is impregnated with a semi-cured product of a curable composition, and a semi-cured composite that can maintain the semi-cured product in a desired viscosity range.
  • the object is to provide a method for manufacturing a body.
  • the present inventors contain a first polymerizable component and a second polymerizable component as polymerizable components, and contain a polymerization initiator that initiates the polymerization of each polymerizable component under conditions different from each other.
  • a curable composition it was found that a semi-cured composite in which the semi-cured product of the curable composition is adjusted to a desired viscosity range (for example, a viscosity range for excellent adhesion) can be produced.
  • One aspect of the present invention provides a first polymerizable component, a first polymerization initiator that initiates polymerization of the first polymerizable component, a second polymerizable component, and a first polymerization initiator. a step of impregnating the porous body with a curable composition containing a second polymerization initiator that initiates polymerization of the second polymerizable component under different conditions; and a step of polymerizing with a polymerization initiator, wherein one of the first polymerization initiator and the second polymerization initiator is a photopolymerization initiator, and the other is a thermal polymerization initiator.
  • a method for manufacturing a body is provided.
  • Another aspect of the present invention includes a first polymerizable component, a first polymerization initiator that initiates polymerization of the first polymerizable component, a second polymerizable component, and a first polymerization initiator
  • the described method for producing a cured composite wherein one of the initiator and the second polymerization initiator is a photopolymerization initiator and the other is a thermal polymerization initiator.
  • Another aspect of the present invention is a semi-cured composite comprising a porous body and a semi-cured curable composition impregnated in the porous body, wherein the curable composition is a first a polymerizable component, a first polymerization initiator for initiating polymerization of the first polymerizable component, a second polymerizable component, and a second polymerizable component under conditions different from those of the first polymerization initiator; and a second polymerization initiator that initiates polymerization, and the semi-cured product contains the polymer of the first polymerizable component, the second polymerizable component, and the second polymerization initiator.
  • one of the first polymerization initiator and the second polymerization initiator is a photopolymerization initiator, and the other is a thermal polymerization initiator to provide a semi-cured composite.
  • the first polymerization initiator may be a photopolymerization initiator
  • the second polymerization initiator may be a thermal polymerization initiator
  • a semi-cured composite in which a porous body is impregnated with a semi-cured product of a curable composition, a semi-cured composite that can maintain the semi-cured product in a desired viscosity range It is possible to provide a method for manufacturing an object composite.
  • 1 is a graph showing an example of viscosity behavior of a curable composition when a first polymerization initiator is a photopolymerization initiator and a second polymerization initiator is a thermal polymerization initiator.
  • 1 is a graph showing an example of viscosity behavior of a curable composition when a first polymerization initiator is a thermal polymerization initiator and a second polymerization initiator is a photopolymerization initiator.
  • 4 is a graph showing another example of viscosity behavior of a curable composition when the first polymerization initiator is a thermal polymerization initiator and the second polymerization initiator is a photopolymerization initiator.
  • (meth)acryl means acrylic or its corresponding methacryl, and similar expressions such as “(meth)acrylate” also apply.
  • a method for producing a semi-cured composite comprises a first polymerizable component, a first polymerization initiator that initiates polymerization of the first polymerizable component, a second polymerizable component, A step of impregnating a porous body with a curable composition containing a second polymerization initiator that initiates polymerization of the second polymerizable component under conditions different from the first polymerization initiator (hereinafter referred to as impregnation and a step of polymerizing the first polymerizable component with a first polymerization initiator (hereinafter also referred to as a semi-curing step) S2.
  • a porous body has a structure in which a plurality of fine pores (hereinafter also referred to as “pores”) are formed. At least some of the pores in the porous body may be connected to each other to form continuous pores.
  • the porous body may be made of an inorganic compound, preferably a sintered body of an inorganic compound.
  • the sintered body of an inorganic compound may be a sintered body of an insulator.
  • the insulator in the insulator sintered body preferably contains non-oxides such as carbide, nitride, diamond and graphite, and more preferably contains nitride.
  • the carbide may be silicon carbide or the like.
  • the nitride may contain at least one nitride selected from the group consisting of boron nitride, aluminum nitride and silicon nitride, preferably boron nitride.
  • the porous body may preferably be formed of a sintered body of an insulator containing boron nitride, more preferably a sintered body of boron nitride.
  • the boron nitride sintered body may be formed by sintering together primary particles of boron nitride.
  • boron nitride both amorphous boron nitride and hexagonal boron nitride can be used.
  • the thermal conductivity of the porous material may be, for example, 30 W/(m ⁇ K) or more, 50 W/(m ⁇ K) or more, or 60 W/(m ⁇ K) or more.
  • the porous material is made of an inorganic compound having excellent thermal conductivity, the heat resistance of the resulting semi-cured composite can be reduced.
  • the thermal conductivity of the porous body is measured by a laser flash method on a sample of the porous body having a length of 10 mm, a width of 10 mm and a thickness of 1 mm.
  • the average pore diameter of the pores in the porous body may be, for example, 0.5 ⁇ m or more, and from the viewpoint that the curable composition described later can be suitably filled in the pores, it is preferably 0.6 ⁇ m or more, more preferably It is 0.8 ⁇ m or more, more preferably 1 ⁇ m or more.
  • the average pore diameter of the pores is preferably 3.5 ⁇ m or less, 3.0 ⁇ m or less, 2.5 ⁇ m or less, 2.0 ⁇ m or less, or 1.5 ⁇ m or less from the viewpoint of improving the insulation of the semi-cured composite. be.
  • the average pore diameter of the pores in the porous body is the pore diameter distribution (horizontal axis: pore diameter, vertical axis: cumulative pore volume) measured using a mercury porosimeter, and the cumulative pore volume is the total pore volume. Defined as the pore size reaching 50%.
  • the mercury porosimeter for example, a mercury porosimeter manufactured by Shimadzu Corporation can be used, and the pressure is increased from 0.03 atmosphere to 4000 atmospheres for measurement.
  • the ratio of pores in the porous body is preferably 10% by volume or more, 20% by volume or more, or 30% by volume or more, preferably 70% by volume or less, more preferably 60% by volume or less, from the viewpoint of improving the insulation and thermal conductivity of the semi-cured composite , more preferably 50% by volume or less.
  • the porous body may be produced by sintering raw materials, etc., or a commercially available product may be used.
  • the porous body is a sintered body of an inorganic compound
  • the porous body can be obtained by sintering powder containing the inorganic compound. That is, in one embodiment, the impregnation step S1 includes a step of sintering a powder containing an inorganic compound (hereinafter also referred to as an inorganic compound powder) to obtain a sintered body of the inorganic compound, which is a porous body.
  • the sintered body of the inorganic compound may be prepared by subjecting the slurry containing the powder of the inorganic compound to a spheroidization treatment with a spray dryer or the like, further shaping the sintered body, and then sintering it to prepare a sintered body that is a porous body.
  • a mold may be used, or a cold isostatic pressing (CIP) method may be used.
  • a sintering aid may be used during sintering.
  • the sintering aid may be, for example, yttria oxide, oxides of rare earth elements such as alumina oxide and magnesium oxide, alkali metal carbonates such as lithium carbonate and sodium carbonate, and boric acid.
  • the amount of the sintering aid added is, for example, 0.01 parts by mass or more, or 0.1 parts by mass with respect to a total of 100 parts by mass of the inorganic compound and the sintering aid. or more.
  • the amount of the sintering aid added may be 20 parts by mass or less, 15 parts by mass or less, or 10 parts by mass or less with respect to a total of 100 parts by mass of the inorganic compound and the sintering aid.
  • the sintering temperature of the inorganic compound may be, for example, 1600°C or higher, or 1700°C or higher.
  • the sintering temperature of the inorganic compound may be, for example, 2200° C. or lower, or 2000° C. or lower.
  • the sintering time of the inorganic compound may be, for example, 1 hour or more and 30 hours or less.
  • the atmosphere during sintering may be, for example, an inert gas atmosphere such as nitrogen, helium, and argon.
  • a batch type furnace and a continuous type furnace can be used.
  • Batch type furnaces include, for example, muffle furnaces, tubular furnaces, atmosphere furnaces, and the like.
  • continuous furnaces include rotary kilns, screw conveyor furnaces, tunnel furnaces, belt furnaces, pusher furnaces, and koto-shaped continuous furnaces.
  • the porous body may be formed by cutting or the like into a desired shape and thickness before the impregnation step S1, if necessary.
  • the porous body to be subjected to the impregnation step S1 may be, for example, sheet-like.
  • the sheet-like porous body may be formed into a sheet with a desired thickness during the above sintering, or a sintered body having a thickness greater than the desired thickness is produced, and the desired thickness is obtained from the sintered body. It may be produced by cutting a thick sheet.
  • the thickness of the porous body is such that when the first polymerizable component or the second polymerizable component is polymerized by light (ultraviolet) irradiation (details will be described later), the thickness of the porous body is It is preferably 2 mm or less, 1 mm or less, or 0.5 mm or less from the viewpoint that the interior is also sufficiently irradiated with light (ultraviolet rays) and the polymerization proceeds more favorably.
  • the thickness of the porous body (sheet-like porous body) may be, for example, 0.1 mm or more or 0.2 mm or more.
  • a solution containing a curable composition is prepared in an impregnation device, and the porous body is immersed in the solution to impregnate the pores of the porous body with the curable composition.
  • the curable composition contains a first polymerizable component and a second polymerizable component as polymerizable components.
  • the first polymerizable component and the second polymerizable component may be the same or different from each other.
  • the polymerizable components used as the first polymerizable component and the second polymerizable component are not particularly limited as long as they are components that can be generally used in curable compositions.
  • These polymerizable components include, for example, epoxy compounds, (meth) acrylic compounds, oxetane compounds, vinyl compounds, phenol compounds, maleimide compounds, cyanate compounds, and at least one selected from the group consisting of silicone compounds. good.
  • epoxy compounds include bifunctional epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol A/F type epoxy resins; novolak type epoxy resins such as phenol novolak type epoxy resins and cresol novolak type epoxy resins; Polyfunctional epoxy resins such as phenolmethane type epoxy resins; Glycidylamine type epoxy resins such as N,N-diglycidylaniline and N,N-diglycidyl-o-toluidine; Heterocyclic ring-containing epoxy resins such as triglycidyl isocyanurate; Alicyclic epoxy resins such as bisphenol A-type epoxy resins and hydrogenated bisphenol F-type epoxy resins; aromatic ring-containing epoxy resins such as 1,6-bis(2,3-epoxypropan-1-yloxy)naphthalene; dicyclo So-called epoxy resins such as pentadiene type epoxy resins can be mentioned.
  • An epoxy compound may be used individually by 1 type or in combination of
  • the (meth)acrylic compound may be (meth)acrylic acid or (meth)acrylate.
  • the (meth)acrylate may be a monofunctional (meth)acrylate having one (meth)acryloyl group, or may be a polyfunctional (meth)acrylate having two or more (meth)acryloyl groups.
  • Monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.
  • n-octyl (meth)acrylate isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, 2-hydroxyethyl ( meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenylglycidyl (meth)acrylate Acrylates, dimethylaminomethyl (meth)acrylate, phenyl cellosolve (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, biphenyl (meth)acryl
  • Polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate.
  • the compounds shown above may be used singly or in combination of two or more.
  • the oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- ⁇ [(3-ethyloxetan-3-yl)methoxy]methyl ⁇ oxetane, 1,4-bis ⁇ [(3-ethyl -3-oxetanyl)methoxy]methyl ⁇ benzene, 4,4′-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl, 1,4-benzenedicarboxylate bis[(3-ethyl-3-oxetanyl) ] methyl ester, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, di[1-ethyl(3-oxetanyl)]methyl ether, 3-ethyl- 3- ⁇ [3-(triethoxysilyl)prop
  • vinyl compounds include ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, and isopropenyl.
  • ether-propylene carbonate dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, Vinyl ether group-containing compounds such as hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, and trimethylolpropane trivinyl ether; styrene compounds such as styrene, methylstyrene, and ethylstyrene; A vinyl compound may be used individually by 1 type or in combination of 2 or more types.
  • Phenol compounds include phenol novolak resin, alkylphenol borak resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene-modified phenol resin, polyvinylphenols, bisphenol F, bisphenol S type phenol resin, poly So-called phenolic resins such as p-hydroxystyrene, condensates of naphthol and aldehydes, and condensates of dihydroxynaphthalene and aldehydes. Phenol compounds may be used alone or in combination of two or more.
  • Maleimide compounds include 4,4′-diphenylmethanebismaleimide, polyphenylmethanemaleimide, m-phenylenebismaleimide, 2,2′-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3′-dimethyl -5,5′-diethyl-4,4′-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 4,4′-diphenyletherbismaleimide, 4,4′-diphenylsulfonebismaleimide, 1, 3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene and the like. These maleimide compounds may be used singly or in combination of two or more.
  • cyanate compounds include novolac type cyanate resins; bisphenol type cyanate resins such as bisphenol A type cyanate resins, bisphenol E type cyanate resins, and tetramethylbisphenol F type cyanate resins; Naphthol aralkyl type cyanate resins; dicyclopentadiene type cyanate resins; and biphenylene skeleton-containing phenol aralkyl type cyanate resins.
  • a cyanate compound may be used individually by 1 type or in combination of 2 or more types.
  • silicone compounds include methyl-based straight silicone resin (polydimethylsiloxane), methylphenyl-based straight silicone resin (polydimethylsiloxane in which some of the methyl groups are substituted with phenyl groups), acrylic resin-modified silicone resin, and polyester resin-modified silicone resin. , epoxy resin-modified silicone resins, alkyd resin-modified silicone resins and rubber-based silicone resins. These silicone compounds may be used alone or in combination of two or more.
  • the content of the first polymerizable component is based on the total amount of the curable composition, from the viewpoint of maintaining the desired viscosity in the semi-cured state and imparting handling, adhesiveness, and adhesion to the semi-cured composite, It is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more.
  • the content of the first polymerizable component is preferably 60% by mass or less, more preferably 50% by mass or less, based on the total amount of the curable composition, from the viewpoint of imparting adhesiveness and adhesion to the semi-cured resin. More preferably, it is 40% by mass or less.
  • the content of the second polymerizable component is preferably 40% by mass or more, more preferably 50% by mass, based on the total amount of the curable composition, from the viewpoint of the melt viscosity of the resin in the semi-cured composite when heated. % or more, more preferably 60 mass % or more.
  • the content of the second polymerizable component is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass, based on the total amount of the curable composition, from the viewpoint of handling of the semi-cured composite. % by mass or less.
  • the ratio of the content of the first polymerizable component to the content of the second polymerizable component in the curable composition is 0 by mass ratio. .1 or more, 0.25 or more, or 0.4 or more, and may be 1.5 or less, 1.0 or less, or 0.7 or less.
  • the curable composition comprises a first polymerization initiator that initiates polymerization of the first polymerizable component and a second polymerization initiator that initiates polymerization of the second polymerizable component under conditions different from those of the first polymerization initiator. and a polymerization initiator, wherein one of the first polymerization initiator and the second polymerization initiator is a photopolymerization initiator, and the other is a thermal polymerization initiator.
  • the second polymerization initiator can be produced under conditions different from those of the first polymerization initiator. Polymerization of the polymerizable component can be initiated.
  • the semi-curing step S2 it is possible to suppress the initiation of polymerization of the second polymerizable component while polymerizing the first polymerizable component.
  • the first polymerization initiator may be a photopolymerization initiator and the second polymerization initiator may be a thermal polymerization initiator.
  • the polymerization initiator of may be a thermal polymerization initiator, and the second polymerization initiator may be a photopolymerization initiator.
  • the first polymerization initiator is preferably a photopolymerization initiator, and the second 2 is a thermal polymerization initiator.
  • the photopolymerization initiator may be at least one selected from the group consisting of radical photopolymerization initiators, cationic photopolymerization initiators, and anionic photopolymerization initiators.
  • photoradical polymerization initiators include, but are not limited to, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis-(2, Acylphosphine oxide compounds such as 6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; Thioxanthone compounds such as thioxanthone, diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone, and 2-isopropylthioxanthone; 2,2-dimethoxy-1 , 2-diphenylethan-1-one, benzoin ketals such as benzyl dimethyl ketal; 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2- ⁇ -hydroxyketones such as hydroxyeth,
  • the substituents on the aryl groups of the two triarylimidazole moieties may be identical to give symmetrical compounds or different to give asymmetrical compounds. good too. Also.
  • a thioxanthone compound and a tertiary amine may be combined, such as a combination of diethylthioxanthone and dimethylaminobenzoic acid.
  • photoradical polymerization initiators include, in addition to the above, 2,2-dimethoxy-2-phenylacetophenone, N-phenylglycine, coumarin, xanthone, fluorenone, fluorene, 3-methylacetophenone, 1-(4-isopropylphenyl )-2-hydroxy-2-methylpropan-1-one and the like.
  • radical photopolymerization initiator the above compounds may be used singly or in combination of two or more.
  • a photoradical polymerization initiator can also be used in combination with a suitable sensitizer.
  • the photocationic polymerization initiator is not particularly limited as long as it generates an acid upon exposure to light.
  • photocationic polymerization initiators include B(C 6 F 5 ) 4 -salts, PF 6 -salts , AsF 6 -salts , SbF 6 - salts of onium compounds such as sulfonium, phosphonium, diazonium, iodonium, ammonium and pyridinium.
  • the photocationic polymerization initiator may be used alone or in combination of two or more of these compounds.
  • Photoanionic polymerization initiators include acetophenone o-benzoyloxime, nifedipine, 2-(9-oxoxanthen-2-yl)propionic acid 1,5,7-triazabicyclo[4,4,0]deca-5- Ene, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidium 2-(3-benzoylphenyl)propionate, 1,2-dicyclohexyl -4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate and the like.
  • the thermal polymerization initiator may be at least one selected from the group consisting of thermal radical polymerization initiators, thermal cationic polymerization initiators, and thermal anionic polymerization initiators.
  • the thermal radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals upon heating and initiates a chain polymerization reaction.
  • thermal radical polymerization initiators include organic peroxides, azo compounds, benzoin compounds, benzoin ether compounds, acetophenone compounds, benzopinacol and the like, and benzopinacol is preferably used.
  • a thermal radical polymerization initiator may use these compounds individually by 1 type or in combination of 2 or more types.
  • organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methyl cyclohexanone peroxide; 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-Butylperoxy)-2-methylcyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1- Peroxyketals such as bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane; hydroperoxides such as p-menthane hydroperoxide; ⁇ , ⁇ '-bis(t-butylperoxy)diisopropylbenzene , dialkyl peroxide such as dicumyl peroxide, t-butyl cumyl peroxide
  • Organic peroxides include Kayamec RTMA, M, R, L, LH, SP-30C, Perkadox CH-50L, BC-FF, Kadox B-40ES, Perkadox 14, Trigonox RTM22-70E, 23-C70, 121, 121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kayaester RTMP-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl RTMB, Parkadox 16, Kayacarbon RTMBIC-75, AIC-75 (manufactured by Kayaku Nourion Co., Ltd.); Permek RTMN, H, S, F, D, G, Perhexa RTMH, HC, TMH, C, V, 22, MC, Percure RTMAH, AL, HB, Perbutyl Commercially available products such as RTMH, C, ND, L, Permil RTMH, D, Perroyl RTMIB, IPP
  • Azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(4-methoxy-2′-dimethylvaleronitrile ) and the like.
  • azo compound commercially available products such as VA-044, V-70, VPE-0201, and VSP-1001 (manufactured by Wako Pure Chemical Industries, Ltd.) may be used.
  • the thermal radical polymerization initiator is preferably at least one selected from the group consisting of diacyl peroxides, peroxyesters, and azo compounds, from the viewpoints of curability of the semi-cured product and heat resistance of the semi-cured product. is.
  • the thermal radical polymerization initiator may be uniformly dispersed by reducing the particle size.
  • the average particle diameter of the thermal radical polymerization initiator is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, from the viewpoint of appropriately using the semi-cured composite for various uses.
  • the lower limit of the average particle size of the thermal radical polymerization initiator is not limited, it is, for example, 0.1 ⁇ m or more.
  • the average particle size of the thermal radical polymerization initiator can be measured with a laser diffraction/scattering particle size distribution analyzer (dry type) (for example, LMS-30 manufactured by Seishin Enterprise Co., Ltd.).
  • the thermal cationic polymerization initiator is not particularly limited as long as it generates cationic species such as Bronsted acids and Lewis acids.
  • Thermal cationic polymerization initiators include, for example, onium salts such as sulfonium salts, phosphonium salts, quaternary ammonium salts, aryldiazonium salts, and aryliodonium salts, organosilanes, heteropolyacids, allene-ion complexes, and boron trifluoride amine complexes. etc.
  • the use of such a thermal cationic polymerization initiator tends to improve the dimensional accuracy and degree of cure.
  • these compounds may be used singly or in combination of two or more.
  • sulfonium salts for example, San-Aid SI-L85, SI-L110, SI-L145, SI-L160, SI-H15, SI-H20, SI-H25, SI-H40, SI-H50, SI-60L , SI-80L, SI-100L, SI-80, SI-100 (manufactured by Sanshin Chemical Industry Co., Ltd.), CP-77 (manufactured by ADEKA Corporation) and the like can be used.
  • SI-Aid SI-L85, SI-L110, SI-L145, SI-L160, SI-H15, SI-H20, SI-H25, SI-H40, SI-H50, SI-60L , SI-80L, SI-100L, SI-80, SI-100 manufactured by Sanshin Chemical Industry Co., Ltd.
  • CP-77 manufactured by ADEKA Corporation
  • Phosphonium salts include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoro antimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, benzyl-3-methyl-4-hydroxy-5-tert-butylphenylmethylsulfonium hexafluoroantimonate, 4-methoxybenzyl-4-hydroxypheny
  • quaternary ammonium salt commercially available products such as CXC-1616 (manufactured by KING INDUSTRY) can be used.
  • Organosilanes include monofunctional silane compounds such as methoxytrimethylsilane, ethoxytriethylsilane, propoxytripropylsilane, butoxytributylsilane, methoxytrioctylsilane, methoxytriphenylsilane, methoxytribenzylsilane, and triphenylhydroxysilane; Silane, dimethoxydiethylsilane, diethoxydibutylsilane, dipropoxydipropylsilane, dimethoxydilaurylsilane, dimethoxydiphenylsilane, dimethoxydibenzylsilane, methoxybenzyloxydipropylsilane, methoxy-2-ethylhexyloxydipropylsilane, diphenylsilanediol Bifunctional silane compounds such as trimethoxymethylsilane, triethoxyethylsilane
  • SH6018 manufactured by Toray Silicone Co., Ltd.: hydroxyl equivalent weight 400, molecular weight 1600 methiphenyl polysiloxane
  • Possible silicone resins may also be used.
  • the organosilane is preferably triphenylsilanol, or a silicone resin available as SH6018, due to its reactivity and availability.
  • the thermal anionic polymerization initiator a known one that can be used as an anionic polymerization initiator for the polymerizable component can be employed, and is a compound that generates a base capable of anionically polymerizing the anionically polymerizable compound by heat.
  • the thermal anionic polymerization initiator includes known aliphatic amine compounds, aromatic amine compounds, secondary or tertiary amine compounds, imidazole compounds, polymercaptan compounds, and boron trifluoride.
  • -Amine complexes, dicyandiamide, organic acid hydrazides, etc. can be used, and encapsulated imidazole compounds that exhibit good latency against temperature can also be preferably used.
  • the content of the first polymerization initiator, based on the total amount of the curable composition may be 0.01% by mass or more, 0.1% by mass or more, or 1% by mass or more, 15% by mass or less, 10 % by mass or less, 5% by mass or less, or 3% by mass or less.
  • the content of the second polymerization initiator, based on the total amount of the curable composition may be 0.01% by mass or more, 0.1% by mass or more, or 1% by mass or more, 15% by mass or less, 10 % by mass or less, 5% by mass or less, 3% by mass or less, 1% by mass or less, or 0.5% by mass or less.
  • the curable composition may further contain other components in addition to the above-described first polymerizable component, second polymerizable component, first polymerization initiator, and second polymerization initiator.
  • Other components may further include, for example, silane coupling agents, adhesion imparting agents, antioxidants, photosensitizers, and additives that inhibit polymerization inhibition (phosphorus compounds, thiol compounds, etc.).
  • the total content of other components may be 10% by mass or less, 5% by mass or less, or 3% by mass or less based on the total amount of the curable composition.
  • the impregnation step S1 may be performed under either reduced pressure or pressurized conditions, or may be performed in combination with impregnation under reduced pressure conditions and impregnation under pressurized conditions.
  • the pressure in the impregnation device when the impregnation step S1 is performed under reduced pressure conditions may be, for example, 1000 Pa or less, 500 Pa or less, 100 Pa or less, 50 Pa or less, or 20 Pa or less.
  • the pressure in the impregnation device when the impregnation step S1 is performed under pressurized conditions may be, for example, 1 MPa or higher, 3 MPa or higher, 10 MPa or higher, or 30 MPa or higher.
  • the thinner the porous body the easier it is to impregnate the porous body with the curable composition without under reduced pressure and pressure impregnation conditions. For this reason, whether or not to carry out under reduced pressure conditions or under increased pressure conditions may be appropriately determined according to the thickness, the viscosity of the resin to be used, and the like.
  • the curable composition may be heated when the porous body is impregnated with the curable composition.
  • the temperature for heating the curable composition for impregnation can be set as appropriate, but when the first polymerization initiator is a thermal polymerization initiator, the reaction initiation temperature of the first polymerization initiator is exceeded. It may be the temperature. In this case, the upper limit of the temperature for heating the curable composition may be equal to or lower than the reaction initiation temperature of the first polymerization initiator +20°C.
  • the reaction initiation temperature of the thermal polymerization initiator is determined by reacting the polymerizable component corresponding to the first polymerizable component or the second polymerizable component with the thermal polymerization initiator, using a differential scanning calorimeter (DSC). It can be confirmed by measuring the temperature history.
  • DSC differential scanning calorimeter
  • the porous body is immersed in the solution containing the curable composition and held for a predetermined time.
  • the predetermined time is not particularly limited, and may be, for example, 5 minutes or longer, 30 minutes or longer, 1 hour or longer, 5 hours or longer, 10 hours or longer, 100 hours or longer, or 150 hours or longer.
  • the first polymerizable component in the curable composition is polymerized with the first polymerization initiator.
  • the first polymerizable component is a photopolymerization initiator
  • the first polymerizable component can be polymerized by irradiating light (ultraviolet rays) from an ultraviolet irradiation device (high-pressure mercury lamp, ultraviolet irradiation LED).
  • an ultraviolet irradiation device high-pressure mercury lamp, ultraviolet irradiation LED.
  • the amount and time of light (ultraviolet) irradiation can be set as appropriate.
  • the porous body impregnated with the curable composition is heated at a temperature at which the first polymerization initiator reacts (hereinafter also referred to as temperature T1). can polymerize the first polymerizable component.
  • the temperature T1 is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher.
  • the temperature T1 is preferably 180° C. or lower, more preferably 150° C. or lower, and even more preferably 120° C. or lower, from the viewpoint of reducing the change in viscosity over time.
  • the temperature T1 refers to the atmospheric temperature when heating the porous body impregnated with the curable composition.
  • the heating time in this case may be 1 hour or more, 3 hours or more, or 5 hours or more, and may be 12 hours or less, 10 hours or less, or 8 hours or less.
  • a semi-cured composite can be produced by the steps described above. That is, a semi-cured composite according to one embodiment includes the porous body described above and the semi-cured material of the curable composition impregnated in the porous body.
  • the proportion of the porous material in the semi-cured composite is preferably 30% by volume or more based on the total volume of the semi-cured composite, from the viewpoint of improving the insulation and thermal conductivity of the semi-cured composite. , more preferably 40% by volume or more, and still more preferably 50% by volume or more.
  • the proportion of the porous material in the semi-cured composite is, for example, 90% by volume or less, 80% by volume or less, 70% by volume or less, or 60% by volume or less based on the total volume of the semi-cured composite. you can
  • the semi-cured product contains a polymer of the first polymerizable component, a second polymerizable component, and a second polymerization initiator. That is, it can be said that the semi-cured product contains a polymer of the first polymerizable component and an unpolymerized product of the second polymerizable component.
  • the curable composition preferably contains a photopolymerization initiator as the first polymerization initiator. Therefore, the semi-cured product preferably contains a polymer obtained by photopolymerizing the first polymerizable component as the polymer of the first polymerizable component. In this case, the semi-cured product can be said to contain a polymer obtained by photopolymerizing the first polymerizable component, the second polymerizable component, and a thermal polymerization initiator.
  • the semi-cured product may not contain the first polymerizable component (all of the first polymerizable component may be polymerized), and the semi-cured product may contain one of the first polymerizable components.
  • the moieties may be included without polymerization. That is, in the semi-cured composite according to one embodiment, part of the first polymerizable component remains in the semi-cured composite as a minor component. By intentionally allowing a part of the first polymerizable component to remain in the semi-cured composite as a minor component, it is possible to suppress the initiation of polymerization of the second polymerizable component in the semi-curing step S2. .
  • the fact that the semi-cured product contains a part of the first polymerizable component can be confirmed by analyzing the semi-cured product composite using FT-IR or NMR and determining the functional group contained in the first polymerizable component. It can be confirmed by analysis. At this time, a solvent such as acetone may be used to extract and concentrate the first polymerizable component before analysis. Alternatively, the decomposition product of the semi-cured composite is analyzed using pyrolysis gas chromatography to confirm that the semi-cured composite contains part of the first polymerizable component. can be done.
  • the semi-cured product contains the first polymerizable component
  • its content is less than the second polymerizable component.
  • the content of the first polymerizable component contained in the semi-cured product is 5 parts by mass or less with respect to a total of 100 parts by mass of the content of the first polymerizable component and the content of the second polymerizable component. , 3 parts by mass or less, or 1 part by mass or less, or 0.5 mass % or more.
  • the content is determined by analyzing the semi-cured composite by FT-IR to examine the types of functional groups possessed by the first polymerizable component and the second polymerizable component, and then by NMR to determine the structure of the functional group, and by checking the ratio of the peaks obtained.
  • the curable composition since the second polymerizable component is contained in a non-polymerized state, the curable composition has better adhesion to adherends than a completely cured cured product.
  • the semi-cured composite can easily maintain a desired viscosity for excellent adhesion to adherends unless the second polymerizable component is polymerized. This makes it possible to obtain a semi-cured composite excellent in handleability (details of the viscosity behavior of the curable composition will be described later).
  • the semi-cured composite can be used by forming it into a sheet or the like and adhering it to an adherend.
  • a semi-cured composite is obtained by the method described above, and the resin (curable composition or semi-cured material) adhering to the outer periphery of the composite is removed to obtain a sheet-like semi-cured composite.
  • the sheet-like semi-cured composite is placed on an adherend and pressed, for example, under reaction conditions of the second polymerization initiator, thereby bonding the semi-cured composite to the adherend while forming a semi-cured composite.
  • the cured product can be cured to form a cured product composite (details will be described later).
  • a cured composite can be produced by polymerizing the second polymerizable component of the semi-cured composite described above. That is, the method for producing a cured product composite according to one embodiment includes a first polymerizable component, a first polymerization initiator that initiates polymerization of the first polymerizable component, and a second polymerizable component.
  • the second polymerizable component in the semi-cured product is polymerized with the second polymerization initiator.
  • the second polymerization initiator is a thermal polymerization initiator (the first polymerization initiator is a photopolymerization initiator)
  • the porous body impregnated with the curable composition is treated with the second By heating at a temperature at which the polymerization initiator reacts (hereinafter also referred to as temperature T2), the second polymerizable component can be polymerized.
  • the temperature T2 may be, for example, 100°C or higher or 120°C or higher, and may be 150°C or higher, 180°C or higher, or 200°C or higher from the viewpoint of polymerizing the second polymerizable component in a short time.
  • the temperature T2 may be 260° C. or lower, 240° C. or lower, or 220° C. or lower from the viewpoint of volatilization of low molecular weight components contained in the curable composition and thermal stability of the composition.
  • the temperature T2 refers to the ambient temperature when heating the semi-cured composite. Heating in the curing step may be performed by changing the temperature T2 stepwise (for example, stepwise increasing).
  • the heating time at temperature T2 may be 1 hour or more, 5 hours or more, or 10 hours or more, and may be 30 hours or less, 25 hours or less, or 20 hours or less.
  • FIG. 1 shows an example of the viscosity behavior of the curable composition when the first polymerization initiator is a photopolymerization initiator and the second polymerization initiator is a thermal polymerization initiator.
  • the first polymerizable component is polymerized by irradiation with light (ultraviolet rays), and the viscosity of the curable composition increases as the polymerization progresses over time. Then, when most of the polymerization of the first polymerizable component is completed, the viscosity of the curable composition becomes substantially constant within a specific range.
  • the viscosity range of 10 2 to 10 6 Pa s it is preferable that there is no time region where the viscosity increase per hour is 50000 Pa s or more, and the viscosity increase per hour is 150000 Pa s or more. It is more preferable that there is no time region where Further, when the viscosity of the curable composition immediately after stopping the light irradiation for polymerizing the first polymerizable component is taken as 1, the viscosity of the curable composition after holding for 1 hour is preferably less than 10. Yes, more preferably less than 100.
  • the viscosity of the curable composition is reduced due to the viscosity reduction (softening) of the second polymerizable component due to heating, and then the second polymerizable component is polymerized by heating.
  • the viscosity of the curable composition increases as the polymerization progresses over time.
  • the second polymerization initiator is a photopolymerization initiator (the first polymerization initiator is a thermal polymerization initiator)
  • the first polymerization initiator is a thermal polymerization initiator
  • light UV rays
  • the amount and time of light (ultraviolet) irradiation can be set as appropriate.
  • FIG. 2 shows an example of the viscosity behavior of the curable composition when the first polymerization initiator is a thermal polymerization initiator and the second polymerization initiator is a photopolymerization initiator.
  • the first polymerizable component is polymerized by heating, and the viscosity of the curable composition increases as the polymerization progresses over time. Then, when most of the polymerization of the first polymerizable component is completed, the viscosity of the curable composition becomes substantially constant within a specific range.
  • the viscosity range of 10 2 to 10 6 Pa s it is preferable that there is no time region where the viscosity increase per hour is 50000 Pa s or more, and the viscosity increase per hour is 150000 Pa s or more. It is more preferable that there is no time region where Subsequently, in the curing step S3, the second polymerizable component is polymerized by irradiation with light (ultraviolet rays), and the viscosity of the curable composition increases as the polymerization progresses over time.
  • the step of heating the curable composition immediately before the curing step S3 or simultaneously with the curing step S3 may be performed.
  • the heating step S4 reduces the viscosity of the curable composition due to the viscosity reduction (softening) of the second polymerizable component, which makes it easier to adhere the semi-cured composite to the adherend.
  • FIG. 3 Another example of the viscosity behavior of the curable composition when the first polymerization initiator is a thermal polymerization initiator and the second polymerization initiator is a photopolymerization initiator (heating step S4 immediately before curing step S3 is shown in FIG.
  • the first polymerizable component is polymerized by heating, and the viscosity of the curable composition increases as the polymerization progresses over time. Then, when most of the polymerization of the first polymerizable component is completed, the viscosity of the curable composition becomes substantially constant within a specific range.
  • the viscosity of the curable composition decreases due to the viscosity decrease (softening) of the second polymerizable component.
  • the second polymerizable component is polymerized by irradiation with light (ultraviolet rays), and the viscosity of the curable composition increases as the polymerization progresses over time.
  • a cured composite can be produced by the above-described steps. That is, a cured product composite according to one embodiment includes the above-described porous body and a cured product of the above-described curable composition impregnated in the porous body.
  • the cured product in the cured product composite contains a polymer of the first polymerizable component and a polymer of the second polymerizable component.
  • the cured product may not contain the first polymerizable component and the second polymerizable component (all of the first polymerizable component and the second polymerizable component may be polymerized), and cured A part of the first polymerizable component and/or the second polymerizable component may remain in the product as a minor component.
  • thermosetting compositions according to Examples and Comparative Examples were prepared.
  • thermosetting compositions according to Examples and Comparative Examples are irradiated with ultraviolet rays for 15 minutes under conditions of a light intensity of 8 mW/cm 2 using an ultraviolet irradiation device (manufactured by Hamamatsu Photonics Co., Ltd.) equipped with a high-pressure mercury lamp.
  • the first polymerization component was polymerized at , followed by a 1 hour hold. Subsequently, the temperature was raised at a rate of temperature increase of 1° C./min, and cured by heating for 5 hours under the conditions of 150° C. and atmospheric pressure.
  • the viscosity of the thermosetting composition was measured at a shear rate of 10 (1/sec) using a rotary viscometer during the period from the irradiation of the ultraviolet rays to the heating.
  • the obtained viscosity behavior was evaluated according to the following two criteria.
  • Viscosity increase per hour in the viscosity range of 10 2 to 10 6 Pa s does not apply
  • the mixed powder was filled in a mold and press-molded at a pressure of 5 MPa to obtain a compact.
  • a cold isostatic press (CIP) device manufactured by Kobe Steel, Ltd., trade name: ADW800
  • the compact was compressed by applying a pressure of 20 to 100 MPa.
  • the compressed molded body is held at 2000 ° C. for 10 hours using a batch-type high-frequency furnace (manufactured by Fuji Dempa Kogyo Co., Ltd., product name: FTH-300-1H) to obtain a porous body (50 mm ⁇ 50 mm ⁇ 50 mm approximately cubic shape) was produced.
  • the firing was carried out by adjusting the inside of the furnace to a nitrogen atmosphere while flowing nitrogen into the furnace at a flow rate of 10 L/min in a standard state.
  • the sliced porous body is impregnated with the curable compositions according to Examples 1 to 5 by the following method. let me
  • the porous body and the thermosetting composition contained in a container were placed in a vacuum heating impregnation device (manufactured by Kyoshin Engineering Co., Ltd., trade name: G-555AT-R).
  • a vacuum heating impregnation device manufactured by Kyoshin Engineering Co., Ltd., trade name: G-555AT-R.
  • the temperature was 50°C and the pressure was 15 Pa
  • the curable composition of Example 5 was used, the temperature was 90°C and the pressure was 15 Pa.
  • the inside of each device was degassed for 10 minutes under the conditions of . After degassing, the porous body was immersed in the curable composition for 40 minutes under the same conditions to impregnate the porous body with the curable composition.
  • the container containing the porous body and the curable composition was taken out, placed in a pressure heating impregnation device (manufactured by Kyoshin Engineering Co., Ltd., product name: HP-4030AA-H45), and the contents of Examples 1 to 4 were obtained.
  • a pressure heating impregnation device manufactured by Kyoshin Engineering Co., Ltd., product name: HP-4030AA-H45
  • the curable composition under the conditions of a temperature of 50 ° C. and a pressure of 3.5 MPa
  • the curable composition of Example 5 Under the conditions of a temperature of 90 ° C. and a pressure of 3.5 MPa, By holding each for 120 minutes, the curable composition was further impregnated into the porous body (at this point, polymerization of the polymerizable component (semi-curing of the curable composition) had not progressed).
  • the porous body impregnated with the curable composition was removed from the apparatus and irradiated with ultraviolet rays for 10 minutes using an ultraviolet irradiation apparatus (manufactured by Hamamatsu Photonics Co., Ltd.) under conditions where the light amount was 8 mW/cm 2 .
  • an ultraviolet irradiation apparatus manufactured by Hamamatsu Photonics Co., Ltd.

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Abstract

L'invention concerne un procédé de production d'un composite de produit semi-durci pourvu d'une étape d'imprégnation d'un corps poreux avec une composition durcissable contenant un premier composant polymérisable, un premier initiateur de polymérisation qui initie la polymérisation du premier composant polymérisable, un second composant polymérisable, et un second initiateur de polymérisation qui initie la polymérisation du second composant polymérisable dans différentes conditions à partir du premier initiateur de polymérisation, et une étape de polymérisation du premier composant polymérisable par le premier initiateur de polymérisation, l'un ou l'autre du premier initiateur de polymérisation et du second initiateur de polymérisation étant un initiateur de photopolymérisation et l'autre étant un initiateur de polymérisation thermique.
PCT/JP2022/015943 2021-03-31 2022-03-30 Procédé de production d'un composite de produit semi-durci, procédé de production d'un composite de produit durci, et composite de produit semi-durci WO2022210869A1 (fr)

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Citations (6)

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Publication number Priority date Publication date Assignee Title
JPS59204519A (ja) * 1983-05-09 1984-11-19 Nippon Sheet Glass Co Ltd 合成樹脂平面レンズの製造方法
JP2011074196A (ja) * 2009-09-30 2011-04-14 Sekisui Chem Co Ltd プロトン伝導性材料、プロトン伝導性電解質膜、プロトン伝導性電解質層付プロトン伝導性電解質膜、膜−電極接合体及び固体高分子形燃料電池
WO2016039059A1 (fr) * 2014-09-11 2016-03-17 富士フイルム株式会社 Composition pour la formation de membrane polymère fonctionnelle, membrane polymère fonctionnelle et son procédé de fabrication, module de membrane de séparation, et échangeur d'ions
JP2018517648A (ja) * 2015-03-03 2018-07-05 スリーエム イノベイティブ プロパティズ カンパニー ゲル組成物、形状化ゲル物品及び焼結物品の製造方法
JP2019523309A (ja) * 2016-05-19 2019-08-22 シクパ ホルディング ソシエテ アノニムＳｉｃｐａ Ｈｏｌｄｉｎｇ Ｓａ 多孔性材料を含浸させるための方法及び配合物
WO2021200871A1 (fr) * 2020-03-31 2021-10-07 デンカ株式会社 Complexe de produit semi-durci et son procédé de production, complexe de produit durci et son procédé de production, et composition thermodurcissable utilisée pour imprégner un corps poreux

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59204519A (ja) * 1983-05-09 1984-11-19 Nippon Sheet Glass Co Ltd 合成樹脂平面レンズの製造方法
JP2011074196A (ja) * 2009-09-30 2011-04-14 Sekisui Chem Co Ltd プロトン伝導性材料、プロトン伝導性電解質膜、プロトン伝導性電解質層付プロトン伝導性電解質膜、膜−電極接合体及び固体高分子形燃料電池
WO2016039059A1 (fr) * 2014-09-11 2016-03-17 富士フイルム株式会社 Composition pour la formation de membrane polymère fonctionnelle, membrane polymère fonctionnelle et son procédé de fabrication, module de membrane de séparation, et échangeur d'ions
JP2018517648A (ja) * 2015-03-03 2018-07-05 スリーエム イノベイティブ プロパティズ カンパニー ゲル組成物、形状化ゲル物品及び焼結物品の製造方法
JP2019523309A (ja) * 2016-05-19 2019-08-22 シクパ ホルディング ソシエテ アノニムＳｉｃｐａ Ｈｏｌｄｉｎｇ Ｓａ 多孔性材料を含浸させるための方法及び配合物
WO2021200871A1 (fr) * 2020-03-31 2021-10-07 デンカ株式会社 Complexe de produit semi-durci et son procédé de production, complexe de produit durci et son procédé de production, et composition thermodurcissable utilisée pour imprégner un corps poreux

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