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WO1999024509A1 - Durcisseur, composition reticulable et composition de resine expansible contenant toutes deux ledit durcisseur, mousse fabriquee a partir de ladite composition de resine expansible et procede de fabrication correspondant - Google Patents

Durcisseur, composition reticulable et composition de resine expansible contenant toutes deux ledit durcisseur, mousse fabriquee a partir de ladite composition de resine expansible et procede de fabrication correspondant Download PDF

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Publication number
WO1999024509A1
WO1999024509A1 PCT/JP1998/004988 JP9804988W WO9924509A1 WO 1999024509 A1 WO1999024509 A1 WO 1999024509A1 JP 9804988 W JP9804988 W JP 9804988W WO 9924509 A1 WO9924509 A1 WO 9924509A1
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group
component
carbon
compound
organic
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English (en)
Japanese (ja)
Inventor
Naoaki Nakanishi
Katsuya Ouchi
Shintaro Komitsu
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Kaneka Corp
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Kaneka Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences

Definitions

  • the present invention relates to a curing agent, a curable composition and a foamable resin composition using the curing agent, and a foam using the foamable resin composition and a method for producing the same.
  • An object of the present invention is to provide an organic curing agent containing a silyl group at a lip opening, a curable composition using the curing agent, and a method of producing a foam by foaming and curing under heating at ordinary temperature or relatively low temperature.
  • the present invention relates to a foamable resin composition, a foam using the composition, and a method for producing the foam. Background art
  • the above-mentioned polyorganosiloxane generally has poor compatibility with an organic polymer, and cures a polyorganohydrogensiloxane and an organic polymer containing a carbon-carbon double bond (hereinafter also referred to as an alkenyl group).
  • an organic polymer cures a polyorganohydrogensiloxane and an organic polymer containing a carbon-carbon double bond (hereinafter also referred to as an alkenyl group).
  • an alkenyl group an organic polymer containing a carbon-carbon double bond
  • the foaming agent have a high expansion ratio and a high closed cell rate. ing.
  • an organic hardener having a hydrosilyl group in the molecule has been proposed (JP-A-3-95266).
  • the curing agents generally have good compatibility with organic polymers containing alkenyl groups.
  • this curing agent is not sufficiently compatible with an organic compound having a highly polar alkenyl group such as a phenol compound. Therefore, even if an attempt was made to cure these curing agents and an organic compound having a highly polar alkenyl group, there was a problem that it was difficult to obtain a transparent and uniform cured product due to phase separation.
  • the present invention has been made in view of the above problems, and the first invention is to provide a curing agent having sufficient compatibility with an organic compound containing a particularly high-polarity carbon-carbon double bond. Is what you do.
  • the present invention provides a curable composition using the curing agent according to the first aspect described above.
  • the curable composition provides a highly transparent and uniform cured product.
  • the third invention is capable of foaming and hardening under heating at room temperature or relatively low temperature, and is particularly suitable for foaming even when an organic compound containing a highly polar carbon-carbon double bond is used.
  • An object of the present invention is to provide a foamable resin composition capable of obtaining a foam having a high magnification and a high independent cell rate, a foam using the composition, and a method for producing the foam. Disclosure of the invention
  • the present inventors have made intensive studies and found that a compound having a specific structure has good compatibility with an organic compound having at least one carbon-carbon double bond in a molecule.
  • the present inventors have found that each of the above-mentioned problems can be solved by using the compound as a hardening agent, and have reached the present invention.
  • the curing agent according to the first invention has one of the following structures.
  • the first curing agent is an organic curing agent having one or more phenolic hydroxyl groups and two or more hydrosilyl groups in the molecule,
  • R 1 represents a group selected from a hydrogen atom and a monovalent organic group having 1 to 20 carbon atoms, and each R ′ may be the same or different.
  • i ⁇ 2, j ⁇ 0. p ⁇ l, and i, j and p are numbers satisfying 3 ⁇ (i + j) xp ⁇ 50.
  • R 1 is the same as above
  • R 2 is a hydrogen atom, —S i (CH 3 ) -S i (CH 3 ) 2 H and a monovalent organic compound having 1 to 20 carbon atoms.
  • R 3 represents a carbon number of 1 to 1 or more containing an alkenyl group.
  • 25 represents a monovalent organic group, and when m is 2 or more, each R 3 is the same and May also be different.
  • R 4 represents a monovalent group selected from a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and a monovalent organic group having 1 to 25 carbon atoms, and when p is 2, each R 4 is the same Or different.
  • j and / or 1 are preferably 0.
  • i is a number satisfying 3 ⁇ i ⁇ 7
  • Z or k is a number satisfying 2 ⁇ k ⁇ l0.
  • the following general formula (4) or general formula (5) is preferably 0.
  • R 5 represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms containing at least one alkenyl group, and each R 5 is the same.
  • X is — CH 2 —,-C (CH 3 ) 2 —,-CH (CH 3 ) one, one C (CF 3 ) z- . — CO —, One S ⁇ 2 —, one hundred one, or:
  • the second curing agent according to the present invention comprises the following components (i), (ii) and (iii);
  • the number of silicon atoms in one molecule is from 3 to 10 ⁇ ), a chain-like or mono- or cyclic organohydrogensiloxane,
  • the third curing agent is characterized in that it has a structure represented by the following formula (6) or (7).
  • R 5 and R 7 each have 0 to 6 carbon atoms Monovalent substituent, R 'has a molecular weight indicates 1 0 0-1 0 0 0 0 Poriokishiaru Killen chain, R 9, R 10 represents hydrogen or a hydrocarbon group with carbon number 1-2 0 . the m, n pieces, one, k-number of R 6, n pieces. p number of R 7 may be different even those same respectively.
  • X represents a divalent substituent having 0 to 10 carbon atoms containing only C, H. N, ⁇ , S, and halogen as constituent elements.
  • the curable composition according to the second invention comprises: (A) an organic compound containing at least one carbon-carbon double bond in the molecule; and (B) an organic compound having a hydrosilyl group.
  • the foamable resin composition according to the third invention further comprises (D) a foaming agent and / or a compound having a ⁇ H group as essential components in addition to the components (A) and (B), and preferably comprises ( C) It further contains a hydrosilylation catalyst.
  • the molecular skeleton of the organic compound as the component (A) is charcoal. It is preferable that it is composed of only one or more elements selected from the group consisting of oxygen, hydrogen, nitrogen, zeolite, and halogen.
  • R 1 1 represents H or CH 3, R 12, R 13 , R 1 6, R 17.
  • R 18, R 2 2 is 0 carbon atoms
  • R 14 , R 15 , R 19 , R 2 °, R 21 .R 23 .R 24 represent a monovalent substituent having 0 to 6 carbon atoms
  • X 1 and X 2 each represent a divalent substituent having 0 to 10 carbon atoms
  • n and m are integers of 0 to 300
  • 1 is 1 to 1
  • P.Q represents an integer of 0 to 3
  • n, m.1 is an integer of 0 to 300
  • s is an integer of 1 to 300
  • p, Q, and r are integers of 0 to 3
  • in the formula (10), n and m are integers of 0 to 4.
  • the carbon-carbon double bond of the organic compound as the component (A) is preferably an average of 2 or more per molecule.
  • Examples of the foaming agent as the component (D) include compounds selected from hydrocarbons, ethers, fluorinated fluorocarbons, and fluorinated carbons, and mixtures thereof.
  • Examples of the compound having an OH group include one or more of alcohol, carboxylic acid, and water.
  • the curing agent according to the first invention is characterized by having good compatibility with an organic compound containing at least one carbon-carbon double bond in a molecule.
  • organic compound refers to a compound that does not substantially contain a siloxane bond in the molecular skeleton
  • good compatibility means that the compound dissolves uniformly when mixed with the above organic compound and stirred. It shall mean that no turbidity or phase separation is observed by visual observation. Alternatively, it means that no turbidity or phase separation is observed even after centrifugation at 100 rpm for about 10 minutes after mixing and stirring. Due to the good compatibility, the cured product obtained by using this has excellent appearance such as mechanical properties and transparency, and the foam has a high closed cell ratio, resulting in excellent heat insulation performance. It will be.
  • R 3 represents 1 to 3 carbon atoms containing at least one alkenyl group.
  • 25 represents a monovalent organic group, and when m is 2 or more, each R 3 may be the same or different, and R 4 is a halogen atom, an alkoxy group having 1 to 6 carbon atoms, Represents a monovalent group selected from monovalent organic groups having 1 to 25 carbon atoms, and P is 2 , Each R 4 may be the same or different.
  • R ′ of the cyclic polysiloxane represented by the general formula (1) and the chain polysiloxane represented by the general formula (2) is selected from a hydrogen atom and a monovalent organic group having 1 to 20 carbon atoms.
  • the monovalent organic group include an alkoxy group, a halogenated alkyl group, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, and an aryl group.
  • a substituted alkyl group represented by trifluoropropyl group, methyl group, ethyl group, and CH 2 CH 2 R R is a halogen atom, a cyano group, a phenyl group, an alkoxy group, an alkyl carboxy group
  • a monovalent organic group such as an alkoxycarbonyl group.
  • R is a halogen atom, a phenyl group, an alkylcarbonyl Represents a monovalent organic group such as an alkoxy group or an alkoxycarbonyl group.
  • a substituted alkyl group represented by CH 2 CH 2 CH 2 R where R is a halogen atom, a hydroxyl group, an alkoxy group, etc.
  • a phenyl group are preferred in view of industrial availability and chemical stability.
  • R 2 of the linear polysiloxane represented by the general formula (2) is a hydrogen atom, —Si (CH 3 ) 3 , one Si (CH 3 ) 2 H, and a group having 1 to 20 carbon atoms. It is a group selected from monovalent organic groups. Examples of the monovalent organic group include a methyl group and ethyl. Group, propyl group, butyl group, phenyl group or a substituted alkyl group represented by one (CH 2 CH 2 ⁇ ) ⁇ CH 3 (where n represents a positive number of 0 or 20 or less) No.
  • i 2 or more.
  • a number, j is 0 or a positive number
  • p is a number of 1 or more
  • i, j and P are numbers satisfying 3 ⁇ (i + j) Xp ⁇ 50
  • k is a number of 2 or more.
  • the number, 1 is 0 or a positive number
  • q is a number of 1 or more
  • k and 1 may be numbers that satisfy (k + 1) X q ⁇ 50, but are generally available industrially.
  • the curing agent has 3 ⁇ i ⁇ 7 and no or 2 ⁇ k ⁇ 10 from the viewpoint that the obtained curing agent has low viscosity and good handleability.
  • cyclic polysiloxane represented by the general formula (1) include the following formula:
  • R 3 of the compound having one or more alkenyl groups and one or more phenolic hydroxyl groups in the molecule represented by the above-mentioned HN general formula (3) include:
  • R 2 5 is a hydrogen atom or a Ariru group, and one of R 2 s at least are Ariru group formula (1 2), X,. - C
  • an aryl group or a group represented by the above general formula (11) or (12) is preferred because it is commercially available generally or has good reactivity with a hydrosilyl group.
  • R 4 of the compound having one or more alkenyl groups and one or more phenolic hydroxyl groups in the molecule represented by the general formula (3) include a chlorine atom, A methoxy group, a methyl group, a hydroxycarbonyl group, an alkoxycarbonyl group, or the following general formula (13) or (14)
  • X is — CH 2 —, —C (CH 3 ) 2 —, one CH (CH 3 ; one C (CF 3 ) 2 —, one CO—, one S ⁇ 2 —, One-one, or the formula;
  • a methoxy group or a group represented by the above general formula (13) or (14) is preferable because it is generally available industrially.
  • substituents When two or more of these substituents are substituted, they may be the same or different.
  • R 5 represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms containing at least one alkenyl group, and each R 5 is the same.
  • X is — CH 2 —, one C (CH 3 ) 2 —, one CH (CH 3 ) —,-C (CF 3 ) 2 —, one CO—, one S 0 2 —, 110, or expression;
  • the curing agent of the present invention can be obtained by reacting the above components (a) and (b).
  • the hydrosilylation catalyst used in this case include: Platinum simple substance, solid platinum supported on a carrier such as alumina, silica, carbon black, etc., chloroplatinic acid, complexes of chloroplatinic acid with alcohols, aldehydes, ketones, etc.
  • P d C l 2 '2 H 2 ⁇ among these the N i C 1 2, T i C 1 4 , and the like are chloroplatinic acid in terms of catalytic activity, a platinum - Orefi down complex And platinum-vinylsiloxane complexes, etc. These catalysts may be used alone or in combination of two or more.
  • the addition amount of the catalyst is not particularly limited, relative to the hydrosilyl group 1 mol, preferably 1 0 -' ⁇ 1 0 _ 8 mols, more preferably 1 0-2 ⁇ 1 0 6 model range of Le It is.
  • Phosphinic compounds and phosphine complexes as cocatalysts with the above catalysts Can be used.
  • Examples of the phosphine complex include C r (CO) 5 PP h 3 , C r (C ⁇ ) 4 (PP h 3 ) 2 (cis and trans isomers), C r (CO) 3 (PP h 3 ) 3 (fac and me r isomers), Mo and V analogues of those C r compounds, F e (CO) 4 PP h 3, F e (CO) 3 (PP h 3) 2, and these F e compound R u and s s analogs, C o C (PP h 3 ), R h C 1 (PP h 3 ) 3 , R h C l (CO) (PP h 3 ) 3 , I r C l (CO) (PP h) 2, N i C l 2 (PP h) 2, P d C 1 2 (PP h) P t C l 2 (PP h) 2, and C 1 A u (PP h 3 ) is.
  • metal complexes such as the above-mentioned metal complexes containing phosphines other than triphenyl phosphine can also be effective cocatalysts. Furthermore, it can be a P (0 P h) Hosufai bets such as 3, etc., A s P h 3 arsine and S b P h 3 stibine effective complex containing cocatalysts such as such as.
  • the amount of the cocatalyst added is not particularly limited.
  • a solvent is not particularly necessary, but if the starting material is solid or of high viscosity and it is difficult to perform operations such as stirring, use an inert organic solvent as appropriate.
  • organic solvents include aromatic solvents such as benzene, toluene, and xylene, aliphatic hydrocarbon solvents such as hexane and octane, and ether solvents such as ethyl ether, butyl ether, and tetrahydrofuran.
  • the solvent examples include halogenated hydrocarbon solvents such as ton-based solvents, chloroform, methylene chloride and trichloroethylene, and ester solvents such as ethyl acetate.
  • the amount of the solvent used is not particularly limited, but is preferably 100 parts by weight or less based on 100 parts by weight of the total amount of the reactants used from the viewpoint of economy.
  • a method of charging the three components at a time, (b) the component (a) and the hydrosilylation catalyst The method of adding, the method of adding the component (b) to the component (a) and the hydrosilylation catalyst, the method of adding the component (a) to the component (b) and the catalyst, the method of adding each component simultaneously, and the like can be considered. However, there is no particular limitation.
  • the polyvalent hydrogen silicon compound (a) is always present in excess with respect to the component (b)
  • the mixture of the hydrid silylation catalyst is
  • the mixing ratio of component (a) to component (b) may be set so that the molar ratio of the hydrosilyl group to the alkenyl group is such that the silyl group at the mouth is excessive. It is preferable to set the number of hydrosilyl groups exceeding one on average in one molecule of the obtained curing agent from the viewpoint of curability when used as a curing agent.
  • the curing agent of the present invention is also obtained by a method of reacting the component (b) with an excess of the component (a) and then removing the unreacted component (a) by distillation, adsorption, precipitation, extraction, or the like. be able to.
  • the reaction temperature is 0 to 200: preferably 50 to 150. If the reaction temperature is lower than 0, the catalytic activity is not sufficient, and the reaction rate is reduced. On the other hand, when it is higher than 150, the catalyst is often deactivated.
  • the curing agent of the present invention is obtained by reacting the component (a) with the component (b), the unreacted hydrosilyl group and possibly a transition metal catalyst are present in the curing agent.
  • the viscosity or gelation may occur due to the gradual reaction between the hydrosilyl groups or between the hydrosilyl groups and the water in the system.
  • an additive for deactivating the catalyst may be added after synthesizing the curing agent by a hydrosilylation reaction.
  • additives used include acetylene alcohols such as dimethyl malate, benzothiazole, 2-hydroxy-2-methyl-1-butyne and the like.
  • additive amount of agent in particular to be used is preferably in the range of 1-10 2 moles of catalyst 1 mol used in the reaction from the viewpoint of satisfying both the curability of the storage stability and the curing agent, good Ri preferably 1 330 mol.
  • the hydrosilylation catalyst may be removed from the curing agent to avoid the above problems.
  • the removal method include a method of stirring the reaction solution with silica, silica gel, alumina, an ion exchange resin, activated carbon, or the like, a method of performing a column treatment, a method of washing with a neutral or weakly acidic aqueous solution, and the like.
  • the second curing agent comprises the following components (i), (ii) and (iiii):
  • hydrosilyl derived from the U) component This is a compound in which the group substantially remains.
  • linear or cyclic organohydrogensiloxane as the component (i) include the following general formulas (16) and (17)
  • R 26 is a hydrogen atom and a carbon atom having 1 to 20 carbon atoms. Represents a group selected from monovalent organic groups, and may contain one or more aromatic substituents, and each R 26 may be the same or different.
  • R 26 represents a hydrogen atom and a carbon atom having 1 to 20 carbon atoms. Represents a group selected from monovalent organic groups, which may contain one or more aromatic substituents, and each R 26 may be the same or different.
  • the number of hydrosilyl groups per one molecule of the chain and cyclic siloxane is preferably 2 or more and 10 or less, more preferably 2 or more and 6 or less. If the number of hydrosilyl groups per molecule is less than 2, Finally, the physical strength of the obtained foam is reduced, and as a result, the shrinkage becomes difficult to suppress.Conversely, if the number exceeds 10, the foam may crack as well as shrink. .
  • compositions include polymethylhydrogensiloxane, polyethylhydrogensiloxane, polyphenylhydrogensiloxane, etc., and 1,3,5-trimethylcyclotrisiloxane, 1,1, Examples thereof include 3,5,7-tetramethylcyclotetrasiloxane, 1.3,5,7,9-pentamethylcyclopentylsiloxane, and mixtures thereof.
  • the functional group capable of reacting with the hydrosilyl group of the component includes a carbon-carbon double bond such as a vinyl group, an aryl group, an acryl group and a methacryl group, and a ⁇ H group and a carboxyl group.
  • a carbon-carbon double bond such as a vinyl group, an aryl group, an acryl group and a methacryl group, and a ⁇ H group and a carboxyl group.
  • Compounds may be mentioned, and two or more of these may be present in one molecule.
  • the carbon-carbon double bond may be present anywhere in the molecule, but is preferably present on the side chain or terminal from the viewpoint of reactivity.
  • the number of functional groups that can react with the hydrosilyl group in one molecule is preferably 2 or more and 4 or less, more preferably 2 or more and 3 or less. If the number of functional groups capable of reacting with the hydrosilyl group in one molecule exceeds 4, the gelling may occur during the reaction between the component (i) and the component (ii), which is not preferable.
  • the skeleton of the component is not particularly limited, and examples thereof include ordinary organic monomer skeletons or organic polymer skeletons, and inorganic compounds such as water.
  • organic monomer skeleton examples include hydrocarbons, aromatic hydrocarbons, phenols, bisphenols, epoxy resin monomers, and isocyanates. Or a mixture thereof.
  • Organic polymers include polyethers, polyesters, polycarbonates, saturated hydrocarbons, polyacrylic esters, polyamides, diaryl phthalates, phenol-formaldehydes (phenolic resins), polyurethanes, and polyureas. And skeletons of melamine-based polymers and epoxy resins.
  • the component include ⁇ , ⁇ -alkadiene such as 1,9-decadiene, divinylbenzene, diarylbenzene, 1.4-butanediol and aryl ether, furanic anhydride and its aryl ester, ⁇ , ⁇ '—Diarylbisphenol A, 2,2'-Diarylbisphenol A, ethylenedalicol or diethylenedalicol and their aryl ethers, aryl-terminated polypropylene oxide and polyethylene oxide, anhydrous furan Examples include an acid mono-ethylene glycol polymer or an allylic ester of phthalic anhydride-diethylene glycol polymer, 9-decen-1-ol, and ethylene glycol monoallyl ether.
  • ⁇ ⁇ -alkadiene
  • 1,9-decadiene divinylbenzene
  • diarylbenzene diarylbenzene
  • 1.4-butanediol and aryl ether furanic anhydride and its aryl
  • the molecular weight of the component (ii) is not particularly limited, those having a molecular weight of about 100,000 or less can be appropriately used, and those having a molecular weight of 100,000 or less are preferable.
  • Examples of the functional group capable of reacting with the hydrosilyl group include a carbon-carbon double bond such as a vinyl group, an aryl group, an acryl group and a methacryl group, and a ⁇ H group and a carboxyl group.
  • the carbon-carbon double bond may be present anywhere in the molecule, but is preferably present on the side chain or terminal from the viewpoint of reactivity.
  • Examples of the skeleton of the component (iii) include the organic monomers and amino or organic polymers listed as the skeleton of the component (ii).
  • Specific examples of the component include ⁇ -olefins such as 1-hexene, 1-octene and 1-decene, and 1-propanol, 1-octanol, ethylene glycol monoethyl ether and the like.
  • carboxylic acids such as 2-ethylhexanoic acid
  • (meth) acrylics such as butyl acrylate, methyl methacrylate, styrene, 4-methylstyrene, 2,4-dimethylstyrene, ⁇ -methylstyrene , 4-bromostyrene, 2-vinyl naphthalene, arylbenzene, arylazole, arylphenyl ether, ⁇ -arylphenol, ⁇ -isopropenylphenol, and other aromatic compounds, one end of which is an aryl group, ⁇ group, Polyoxy substituted with an acrylic group, a carboxyl group, or another organic group that does not react with the hydrosilyl group Examples include alkylene, polyester, and acrylic polymers.
  • the molecular weight of the component (iiii) is not particularly limited, but a molecular weight of about 100,000 or less can be used as appropriate, and a molecular weight of 100,000 or less is preferable.
  • the compatibility is not sufficient. If the ratio exceeds 0.5, on the other hand, the viscosity increases due to the increase in the molecular weight, etc., during the reaction between the components U) and (ii). Therefore, it is not preferable. On the other hand, if 2 is smaller than 0.001, the compatibility of the system is not sufficient, and as a result, the cells of the foam are roughened. When the value exceeds 0.8, the effect of suppressing shrinkage, which is the object of the present invention, tends to decrease.
  • the above-mentioned hydrosilylation catalyst or the like can be appropriately used.
  • the compound obtained by reacting component (i), component (ii), and component ii) has the ability to form a mixture of components having various structures because component (ii) is polyfunctional. And a mixture containing a compound represented by the following formula. In addition, these mixtures can be used as they are without purification.
  • n represents an integer of 1 or more and 100 or less, preferably 40 or less.
  • the third curing agent is a compound having a structure represented by the following formula (6) or (7).
  • R s and R 7 are monovalent substituents having 0 to 6 carbon atoms
  • R 8 is a polyoxyalkylene chain having a molecular weight of 100 to 100,000
  • R 9 and R ia are hydrogen or.
  • n pieces, p number of R 7 may also be different from those same respectively.
  • X represents a divalent substituent having 0 to 10 carbon atoms containing only C, H, N.II, S, and halogen as constituent elements.
  • a double bond for example, an aryl group
  • a ⁇ H group Such as a method of reacting a polyoxyalkylene compound having a functional group capable of reacting with a hydrosilyl group and an aromatic ring-containing organic group with a polyorganohydrogensiloxane; A method of synthesizing polyorganooctahydrogensiloxane using a silicon compound having an organic group, or a redistribution reaction between the silicon compound and polyorganosiloxane can be used.
  • a polyether compound such as 1 ⁇ (m + n) x1 ⁇ 80, m, n ⁇ 0, 1 ⁇ 1) and styrene, 4-methylstyrene, 2,4-methylstyrene, ⁇ -Methylstyrene, 4-bromostyrene, 2-vinylnaphthalene, arylbenzene, arylanisole, arylphenylether, ⁇ -arylphenol, ⁇ -isopropenylmaenoyl, phenol, vinylcresol, benzyl alcohol, phenylethyl alcohol Benzoic acid, 4-hydroxybenzoic acid, and the like.
  • a reaction product of the linear or cyclic polyorganohydrogensiloxane represented by the above formulas (18) and (19) and the above-mentioned aromatic ring-containing compound
  • polyorganohydrogensiloxane represented by the formula (18) include polymethylhydrogensiloxane, polyethylhydrogensiloxane, polyphenylhydrogensiloxane, and methylhydrogensiloxane-dimethylsiloxane copolymer. And methylhydrogensiloxane-getylsiloxane copolymer, methylhydrogensiloxane-methylphenylsiloxane copolymer, and ethylhydrogensiloxane-dimethylsiloxane copolymer.
  • siloxane unit in the cyclosiloxane represented by the formula (19) include methylhydrogensiloxane, ethylhydrogensiloxane, phenylhydrogensiloxane, dimethylsiloxane, dimethylsiloxane, methylfuninylsiloxane. And those obtained by copolymerizing them to form a cyclic body.
  • ⁇ (I + k) / (m + n + l + k) ⁇ 100 (%) is called a denaturation rate.
  • the above modification rate is generally preferably 5 to 90%, particularly preferably 5 to 25%, although it depends on the composition and mixing ratio of other components.
  • the values given here are average values. If the modification ratio is lower than 5%, the compatibility with the organic compound having a carbon-carbon double bond is deteriorated, the foam-regulating property is reduced, and the cells of the foam are not made fine, and in some cases, the foam is formed. Bubbles may be generated on the way, and a sufficient expansion ratio may not be obtained. Conversely, if the modification ratio is higher than 90%, the hydrosilyl group equivalent becomes large. To obtain a foam by using this compound alone as a curing agent, a large amount is required, and a foam having a low expansion ratio is required. It is not preferable because only these can be obtained.
  • the ratio of the aromatic ring-containing organic groups bonded to the modification ratio is arbitrarily set within a range that does not adversely affect the compatibility of the mixture during foam production. Can be adjusted.
  • the ratio of the oxyethylene unit is large, and the ratio of the oxyethylene unit to all the oxyalkylene units is 50 to 100% by several units. If the ratio of the oxyalkylene unit is smaller than this, sufficient foam control properties cannot be obtained.
  • the molecular weight of the oxyalkylene chain is not particularly limited, but is preferably from 100 to 300, more preferably from 200 to 100, in terms of number average molecular weight. If the number average molecular weight is less than 100, sufficient foam control properties cannot be obtained, and if the number average molecular weight is more than 300, the density of the hydrosilyl group decreases. For this purpose, a large amount must be used, and therefore, only a foam having a low expansion ratio can be obtained, which is not preferable.
  • One of the above-mentioned first to third curing agents may be used alone, or two or more thereof may be used in combination.
  • the number of hydrosilyl groups in the curing agent of the present invention is preferably at least one in one molecule on average, as long as the force compatibility is not impaired.
  • a carbon sieve When an organic compound having an elemental carbon double bond is cured, if the number of the hydrosilyl groups is less than 2, curing is slow and poor curing often occurs.
  • the curing agent of the present invention is applied to a foamable resin composition, the curing agent and the ⁇ H group-containing compound undergo dehydrocondensation and participate in foaming. Although it depends on the desired expansion ratio, it is generally preferred that the number be three or more.
  • the upper limit of the number is preferably 80 or less, more preferably 50 or less, in view of the availability of the compound and the balance between foaming and curing.
  • the various curing agents described in the first invention can be used, and the preferable molecular structure and the like of the first invention can be applied.
  • curing agent as the component (B), other curing agents having a hydrosilyl group may be used in combination as long as the compatibility with the component (A) is not affected.
  • the organic compound containing at least one carbon-carbon double bond in the molecule which is the component (A) of the present invention, has a particular structure if it has substantially no siloxane bond in the skeleton.
  • various components such as low molecular weight compounds and polymers Those having a child structure are used.
  • component (A) When the molecular structure of component (A) is considered as being divided into a skeleton portion and an alkenyl group having a carbon-carbon double bond bonded to the skeleton by a covalent bond, carbon-carbon
  • the alkenyl group having a double bond may be present anywhere in the molecule, but is preferably present on the side chain or terminal from the viewpoint of reactivity.
  • component (A) examples include low molecular weight compounds such as ester compounds of diarylphthalate ⁇ , ether compounds such as ethylene glycol diaryl ether, and 2,6-diarylphenol. And phenol compounds such as 2,2'-diarylbisphenol A.
  • polystyrene examples include those in which an alkenyl group is introduced into the terminal or main chain of various polymers.
  • various polymers include polyoxyethylene, polyoxypropylene, polyoxytetramethylene, and polyoxyethylene-poly.
  • Polyether polymers such as oxypropylene copolymers; polyester polymers obtained by condensation of dibasic acids such as adipic acid with glycols or ring-opening polymerization of lactones; ethylene-propylene copolymers , Polyisobutylene, copolymer of isobutylene and isoprene, polycloprene, polyisoprene, copolymer of isoprene and butadiene, acrylonitrile, styrene, etc., polybutadiene, butadiene and styrene, acrylonitrile, etc.
  • Copolymer polyisoprene, polybutadiene, A polyolefin-based polymer obtained by hydrogenating a copolymer of isoprene or butadiene with acrylonitrile, styrene, etc .; a polyacrylic acid ester obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate; Of acrylates such as ethyl acrylate and butyl acrylate with vinyl acetate, acrylonitrile, methyl methacrylate, styrene, etc.
  • Acrylic ester copolymers graft polymers obtained by polymerizing vinyl monomers in the above organic polymers, polysulfide polymers, nylon 6 and hexame by ring-opening polymerization of ⁇ -aminoprolactam Nylon 66 by condensation polymerization of tylenediamine and adipic acid, Nylon 610 by condensation polymerization of hexamethylenediamine and sebacic acid, Nylon 11 by condensation polymerization of ⁇ -aminoundecanoic acid, ⁇ -amino Manufactured by condensation polymerization from nylon 12 by ring-opening polymerization of radiolactam, polyamide polymers such as copolymerized nylon containing two or more of the above-mentioned nylons, such as bisphenol and carbonyl chloride Phenolic polymers such as polycarbonate polymers, diaryl phthalate polymers, novolak resins and resole resins It is.
  • ester-based compounds and (B) have the advantage that they have good compatibility with the highly polar compounds of the organic curing agent containing a hydrosilyl group.
  • Preferred are ether compounds, phenol compounds, polyester polymers, acrylate ester polymers, acrylate ester copolymers, polyether polymers, polycarbonate polymers, and phenol polymers.
  • a compound containing at least one phenol group in the molecule is particularly preferred.
  • preferred constructions include the following general formulas (8) to (10).
  • R 11 represents H or CH 3
  • R 12 , R 13 , R 16 , R 17 , R 18 , and R 2 Z each have 0 carbon atoms.
  • R 24 is indicates a monovalent substituent having 0-6 carbon atoms
  • X 1 and X 2 each represent a divalent substituent having 0 to 10 carbon atoms
  • nm is an integer of 0 to 300
  • I is 1
  • Q represents an integer of 0 to 3
  • n, m, 1 are integers of 0 to 300
  • s is an integer of 1 to 300.
  • Integers, p, q, and r represent integers of 0 to 3.
  • n and m represent integers of 0 to 4.
  • an organic compound containing at least one alkenyl group in the molecule of the component (A) various methods can be used, and examples thereof include a hydroxyl group, an alkoxide group, and a carboxyl group.
  • Examples of organic compounds having both an active group and an alkenyl group that are reactive with the above functional groups include acrylic acid, methacrylic acid, vinyl acetic acid, acrylic acid mouthride, and acrylic acid promylate.
  • an alkenyl group during polymerization.
  • a radical reaction such as a vinyl monomer having an alkenyl group with low radical reactivity in an molecule such as aryl methacrylate or aryl acrylate, or aryl mercaptan is performed.
  • a radical chain transfer agent having an alkenyl group with low reactivity
  • the main chain of the polymer can be improved.
  • an alkenyl group can be introduced at the terminal.
  • the alkenyl group of the component (A) be present at the molecular terminal, since the effective network chain length of the cured product becomes longer.
  • Another method is to introduce an alkenyl group using a transesterification method.
  • the alcohol residue in the ester portion of the polyester resin acrylate resin is transesterified with an alkenyl group-containing alcohol or an alkenyl group-containing phenol derivative using a transesterification catalyst.
  • the alkenyl group-containing alcohol and the alkenyl group-containing phenol derivative used for exchange with the alcohol residue have at least one alkenyl group such as aryl alcohol diaryl glycol and bisphenol A, and have at least one alkenyl group. Any alcohol or phenol derivative having one OH group may be used.
  • a catalyst may or may not be used, but if used, an acid, titanium-based, aluminum-based or tin-based catalyst is preferred. Specific examples include dicarboxylic acids such as bisphenol A, bis (meth) acrylates, and the like.
  • the component (A) of the present invention is preferably a compound containing one or more phenolic hydroxyl groups in the molecule as described above.
  • a method for producing this compound include phenol and phenol. Novolac and / or resole type phenols using cresol, xylenol, resorcin, catechol, pyrogallol, etc., and bisphenol compounds such as bisphenol A, bisphenol F, bisphenol S and tetrabromobisphenol A
  • Examples of such a method include a method in which an alkenyl group is introduced by reacting an organic compound having both an alkenyl group and an active group having reactivity with a phenolic hydroxyl group.
  • phenols such as ⁇ , O'-diarylbisphenol A, 2,2'-diarylbisphenol A, and aryl chloride, acrylyl bromide, etc. are reacted in the presence of a base catalyst.
  • Reaction such as bisphenol A
  • phenols are reacted with allylic glycidyl ether glycidyl methacrylate in the presence of an epoxidation catalyst
  • isocyanates such as 4,4′-methylenebis (phenyl isocyanate) and tolylene 1,2,6-diisocyanate.
  • a method of reacting the compound with aryl alcohol or arylamine in the presence of a urethanation catalyst a method of reacting the compound with aryl alcohol or arylamine in the presence of a urethanation catalyst.
  • a main chain skeleton having a functional group such as a ⁇ H group, an alkoxide group, a carboxyl group, or an epoxy group at the terminal, main chain or side chain is synthesized in advance, and the method exemplified in the above-described method To introduce an alkenyl group.
  • a method of synthesizing a phenol resin skeleton using a part or all of a compound having an alkenyl group is a method in which an aromatic compound having a double bond and phenols are reacted with, for example, formaldehyde diisocyanate. Specifically, aryl phenol and another phenol are reacted with an acid or a base. This is a method in which polycondensation is carried out with formaldehyde in the presence. Further, an aryl ether compound obtained by Michael addition of aryl alcohol, aryl glycol, or the like to a bis (meth) acrylate can also be used.
  • the molecular weight of the component (A) is preferably from i000 to 500,000, and more preferably from 100 to 200,000, from the viewpoint of the properties of the cured product and the compatibility with the component (B). preferable.
  • the number of carbon-carbon double bonds in the organic compound (A) is preferably more than 1.0 on average per molecule, and more preferably 2 or more and 5 or less. Is preferred. When the number of carbon-carbon double bonds in one molecule of the component (A) is 1 or less, even if it reacts with the component (B), only a graft structure is formed and not a bridge structure. is there.
  • the molar ratio of the component (B) to the component (A) is preferably from 0.2 to 50, more preferably from 0.4 to 25, in terms of a molar ratio of the hydro ⁇ silyl group to the alkenyl group.
  • the cured composition of the present invention is insufficiently cured to obtain only a cured product with low tackiness and low strength. Since a large amount of active hydrosilyl groups remains in the cured product, cracks and voids are generated, and a uniform and strong cured product tends not to be obtained.
  • hydrosilylation catalyst as the component (C) of the present invention, any catalyst can be used without particular limitation.
  • the same catalyst as described for the hydrosilyl group-containing organic curing agent of the first invention can be used.
  • These catalysts may be used alone or in combination of two or more.
  • chloroplatinic acid, a platinum one-year-old olefin complex, a platinum-vinylsiloxane complex, and the like are preferable.
  • No particular limitation is imposed on the amount of catalyst 1 0 for the alkenyl group to 1 mol of the component (A) - is preferably used 1 to 1 0 _ 8 mols. And it is preferably used in 1 0 3 to 1 0 _ 6 model ranges Le.
  • the above-mentioned filler include, for example, glass fiber, carbon fiber, myriki, graphite, diatomaceous earth, terra alba, fume silica, precipitated silica, silicate anhydride, alumina, carbon black, calcium carbonate, clay, Silver, titanium oxide, magnesium carbonate, barium sulfate, quartz, aluminum fine powder, flint powder, zinc dust, inorganic balloons, rubber granules, wood powder, phenolic resin, melamine resin, vinyl chloride resin, etc. .
  • anti-aging agent As the above-mentioned anti-aging agent, generally used anti-aging agents such as citric acid, phosphoric acid and sulfur-based anti-aging agents are used.
  • sulfur-based antioxidants examples include mercaptans and salts of mercaptan.
  • radical inhibitor examples include 2,2'-methylene-bis (4-methyl-6-6-1-butylphenol) and tetrakis (methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl).
  • Phenyl radical inhibitors such as methane, phenyl, 0-naphthylamine, ⁇ -naphthylamine, ⁇ ', ⁇ '-secondary butyl- ⁇ -phenylenediamine, phenothiazine, ⁇ , N'-diphenyl- ⁇ -Amine-based radical inhibitors such as phenylenediamine.
  • UV absorber examples include 2 (2'-hydroxy-3 ', 5'-dibutylphenyl) benzotriazole and bis (2,2,6,6-tetramethyl-4-piperidine). ) Sebacate and the like.
  • adhesion improver examples include commonly used adhesives and aminosilas. Silane coupling agents such as epoxy compounds and epoxysilane compounds, and other compounds can be used. Specific examples of such adhesion improvers include phenolic resins, epoxy resins, aminopropyl trimethoxysilane, N-(/ 3-aminoethyl) aminopropylmethyldimethoxysilane, bear mouth-indene resin, rosin Examples thereof include ester resins, terpene-phenol resins, ⁇ -methylstyrene-vinyltoluene copolymers, polymethylmethylstyrene, alkyl titanates, and aromatic polyisocyanates.
  • the flame retardants include halogen-based agents such as tetrabromobisphenol, epoxy, tetrabromobisphenol, decabromodiphenyl oxide, triethyl phosphate, tricresyl phosphate, trichloro (phosphoryl) phosphate, and tris.
  • Phosphorus flame retardants such as (methyl propyl) phosphate, tris (dichloro propyl) phosphate, ammonium polyphosphate, and red phosphorus; and inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, antimony trioxide, and antimony pentoxide. And the like. These flame retardants may be used alone or in combination of two or more.
  • the properties of the cured product depend on the main chain skeleton, molecular weight, etc. of the polymer of the component (A) and (B) to be used, but it is possible to produce from a rubbery to a resinous one.
  • the curing conditions are not particularly limited. Generally, the curing is performed at 0 to 200 t: for 10 seconds to 4 hours, preferably at 30 to 150 at 10 seconds to 4 hours. Particularly, at a high temperature of 80 to 150 t :, a material which cures in a short time of about 10 seconds to 1 hour can be obtained.
  • the method of compounding the composition from the viewpoint of workability, after preparing two or more types of compositions each containing (A) and (B) components of the curable composition as substantial components, It is desirable to cure them by mixing them.
  • the method of adding the component (C), which is a catalyst is not particularly limited, and a method which is easy to work may be selected.
  • the method may be used by mixing with either the component (A) or the component (B). It may be added simultaneously with the mixing of the components (A) and (B) or after the mixing is completed.
  • a curable composition of the present invention As a specific method of producing a cured product, a curable composition of the present invention, a catalyst, and, if necessary, two or more separate liquids in which the additive is mixed in an appropriate combination in advance or in an appropriate number are used. It is desirable to mix, extrude or pour the mixture immediately before use.
  • the mixing method is not particularly limited, but a method usually used for urethane resin, epoxy resin, and phenol resin such as hand mixing, an electric mixer, a static mixer, and collision mixing can be used.
  • the foamable resin composition according to the third invention comprises the curable composition according to the second invention further comprising (D) a foaming agent and / or a compound having a ⁇ H group as essential components. .
  • the component (A) and the component (B) are cured by performing an addition-type cross-linking reaction by a hydrosilylation reaction that generates a Si—C bond having excellent weather resistance.
  • the blowing agent vaporizes or decomposes due to the heat of reaction between the components (A) and (B), or reacts with the components (B) and (D) to generate hydrogen gas. Foam and foam formed It is.
  • the foaming resin composition of the present invention by using an organic compound containing no siloxane unit in the molecular skeleton as the component (A), the foaming resin composition has a higher compressive strength and a lower foam strength than the silicone foam disclosed in the above prior art. Products with improved paintability, adhesion, contamination, dust adhesion, etc. can be obtained.
  • component (B) by changing the component (B) in various ways, one having a wide range of physical properties such as hard to semi-hard and soft can be obtained.
  • a foam having a high expansion ratio and a high closed cell rate can be obtained.
  • the various curing agents described in the first invention can be used, and the preferred molecular structure, the combination with other curing agents, and the like are also important. And those described in the second invention can be applied.
  • the organic compound containing at least one carbon-carbon double bond in the molecule, which is the component (A) of the present invention, is not particularly limited. Those having various molecular structures such as coalescence can be used.
  • the skeleton of the component (A) take advantage of its good compatibility with the component (B), such as a polysiloxane-organic block copolymer or a polysiloxane-organograft copolymer.
  • the component (B) such as a polysiloxane-organic block copolymer or a polysiloxane-organograft copolymer.
  • the monomer skeleton may be, for example, a phenol-based, bisphenol-based, or
  • the polyether-based polymer skeleton is suitably used for obtaining a soft foam.
  • examples thereof include polyoxyethylene, polyoxypropylene, polyoxytetramethylene, and polyoxyethylene-polyoxypropylene copolymer.
  • the organic compound of component (A) can be uniformly mixed with other components, and has fluidity at a temperature of 100 or less so that a foam can be obtained by spraying, pouring, or the like.
  • the structure may be linear or branched, and the molecular weight is not particularly limited. Any structure of about 100 to 100,000 can be suitably used. Those having a value of from 00 to 200, 000 are particularly preferred. If the molecular weight is less than 500, characteristics due to the use of an organic polymer, such as imparting flexibility, are unlikely to be exhibited, and if the molecular weight exceeds 100,000, crosslinking by reaction between a alkenyl group and a hydrosilyl group. Effect tends to hardly be exhibited.
  • the foaming agent of the component (D) and the compound having an OH group will be described.
  • the foaming agent and the compound having a ⁇ H group may be used alone or in combination.
  • the type of the foaming agent is not particularly limited.
  • it can be used by selecting from those usually used for organic foams such as polyurethane, phenol, polystyrene, and polyolefin.
  • a method in which a volatile compound is added in advance to the composition as a foaming agent and foaming is performed by heat generation or reduced pressure is preferable.
  • blowing agent is a volatile compound
  • its boiling point is preferably 100 and less, It is more preferably at most 80 ° C, particularly preferably at most 50. Considering the equipment to be used and the ease of handling, those having a boiling point of about ⁇ 30 to about 35 are preferred.
  • the solubility of the foaming agent in the component (A) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and more preferably 15 parts by weight, based on 100 parts by weight of the component (A) in 23X. The above is more preferred. If the solubility is less than 5 parts by weight, the cells of the foam become rough, which is not preferable, and it is difficult to obtain a foam having a desired multiplication factor.
  • the solubility of the blowing agent in the component (A) can be determined, for example, by the following method. That is, if the boiling point of the blowing agent is 23 or more, the weight of the component (A) and the weight after dissolving the blowing agent may be measured, and the difference may be obtained. twenty three. If it is difficult to measure by the above method due to the reason that it is less than C, etc., weigh the component (A) and the foaming agent into a pressure-resistant container with a known volume, and dissolve it from the volume and pressure of the void in the pressure-resistant container. The amount of the blowing agent that has not been obtained can be determined, and the solubility can be determined based on this.
  • the type of the foaming agent is not particularly limited.However, from the viewpoint of workability and safety, compounds selected from hydrocarbons, ketone compounds, organic compounds such as fluorocarbons and ethers, carbon dioxide, nitrogen, air, etc. are used alone or in combination. It is preferable to use two or more kinds in combination.
  • the hydrocarbons include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2, 3-dimethylbutane, cyclopentane, cyclobutane, cyclopentane, cyclohexane and the like.
  • propane, n-butane, isobutane, n-pentane, and cyclopentane are preferred from the viewpoint of easy handling.
  • Examples of ketone compounds include acetone, methylethyl ketone, methyl isopropyl ketone, and the like.
  • chlorofluorocarbons examples include trifluoromethane (R11), dichlorodifluoromethane (R12), trifluoromethane (R13), bromotrifluoromethane (R13B1), and tetrafluoromethane (R14).
  • chlorofluorocarbon a so-called alternative fluorocarbon, rather than chlorofluorocarbon (CFC), and to use fluorocarbon (HFC).
  • HCFC chlorofluorocarbon
  • CFC chlorofluorocarbon
  • fluorocarbon fluorocarbon
  • tetrafluoroethane, difluoroethane, okofuropropane, hexafluoropropane, pentafluoropropane, okofurocyclobutane, hexafluorobutane, pentafluorobutane Is particularly excellent.
  • ethers include dimethyl ether, getyl ether, ethyl methyl ether, dipropyl ether, diisopropyl ether, butyl methyl ether, butyl ethyl ether, tert-butyl methyl ether, tert-butyl ethyl ether, 1.1-dimethylpropyl methyl ether, Methyl pentafluoroethyl ether, 2,2,2-trifluoroethyl ether, methyl (trifluoromethyl) tetrafluoroethyl ether and the like.
  • the foaming agent preferably used includes, for example, hydrocarbons and fluorocarbons depending on the structure of the component (A), and among them, 23 to 100 parts by weight of the component (A) is preferred.
  • HFCFC Fluorocarbon
  • HCFC Fluorocarbon with 1 to 3 carbon atoms
  • Carbonization with 3 to 6 carbon atoms One or more selected from hydrogen, ketone compounds having 3 to 5 carbon atoms, and ethers having 2 to 6 carbon atoms are particularly preferably used.
  • hydrocarbons, fluorinated carbon fluoride (HFCFC) and fluorinated carbon (HFC) are preferred.
  • Inorganic blowing agents such as inorganic blowing agents, azodicarbonamide, azobisisobutyronitrile, barium azodicarboxylate, dinitrosopentamethylenetetramine, para-toluenesulfonyl hydrazide, etc., containing isocyanate and active hydrogen groups It is also possible to use a combination of generation of carbon dioxide by reaction with the compound, mechanical stirring, and the like.
  • the type of the compound having an H group used in the present invention is not particularly limited, but is not the OH group-containing (poly) siloxane used frequently in the conventional silicone foam, but has good compatibility with other components. It is preferable that a siloxane bond is not contained in the molecular skeleton. Specifically, it is preferable to use one or both of an organic compound in which the ⁇ H group is directly bonded to a carbon atom and water, whereby the effect of using an organic compound having a carbon-carbon double bond is preferred. Becomes more noticeable.
  • Compounds in which the H group is directly bonded to a carbon atom include alcohols, carboxylic acids, and the like.
  • Alcohols include methanol, ethanol, n-propanol, iso-propanol, n-butanol. Iso-butanol, tert-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Monovalent alcohols such as monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, ethylene glycol monophenyl ether, ethylene glycol monoallyl ether, glycerin diaryl ether, ethylene glycol, propylene glycol, 1,4-butylene glycol 1,3-butylene glycol, 2,3-butylene glycol, ethylene glycol, triethylene glycol, neopentyl glycol, 1.6-hexyl Polyhydric alcohols such as methylene glycol, 1,9-nonamethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorb
  • Polyether polyols such as copolymers and polytetramethylene glycol (including those containing three or more ⁇ H groups in one molecule using sorbitol, sucrose, tetraethylenediamine, ethylenediamine, etc. as initiators), Adipate polyol, Polyol polyols such as polyprolactone polyols and polycarbonate polyols, epoxy-modified polyols, polyetherester polyols, phenolic polyols such as benzylic ether phenol polyols, and fluorine polyols such as Lumiflon (made by Asahi Glass Co., Ltd.).
  • HE-10, HE-20, HP110 and HP-20 all acrylate acrylate oligomers having terminal ⁇ H groups
  • PP series polypropylene glycol methacrylate
  • Blemmer PE series polyethylene glycol monomethacrylate
  • Blemmer PEP series polyethylene glycol polypropylene acrylate copolymer
  • alcohols having 3 or more carbon atoms are desirable because they do not adversely affect the coalescence, enlargement, and breakage of bubbles due to evaporation and vaporization due to heat generated during the curing reaction.
  • n-propanol, n-butanol, ethylene glycol monomethyl ether, diethylene glycol, etc. because of the ease of reaction with the hydrosilyl group and the fact that cross-linking does not occur even if dehydrocondensation proceeds, and the odor during handling.
  • Primary alcohols such as monomethyl ether and ethylene glycol monophenyl ether are particularly preferred.
  • carboxylic acids include acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, hexanoic acid, 2-ethylhexanoic acid, malonic acid, succinic acid, adipic acid, meso— 1, 2,3,4-Tetracarboxylic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid and the like.
  • monovalent carboxylic acids are preferred because they are easy to react with a silyl group at the mouth and do not cause cross-linking even when dehydrocondensation proceeds, and 2-ethylhexanoic acid is more preferred from the viewpoint of odor during handling. Is particularly preferred.
  • the hydroxyl equivalent becomes large, the volume of the OH group-containing compound to be added becomes large and the expansion ratio does not increase, so that the hydroxyl equivalent is 1 to 33 mmo 1 /
  • the compound of formula (1) is preferred, and the compound of (2.5 to 25 mmo) Zg is more preferred in terms of reactivity.
  • ⁇ H compounds in combination for adjusting the foaming speed.
  • Preferred examples of the combination include a primary alcohol such as n-propanol and a secondary alcohol such as iso-propanol, a carboxylic acid and a primary alcohol, or a combination of a carboxylic acid and water.
  • divalent or higher polyvalent ⁇ H compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, and glycerin, ethylene glycol monoallyl ether, glycerin monoallyl ether, and glycerin Has both a carbon-carbon double bond capable of hydrosilylation and a ⁇ H group in the molecule of phenyl ether, erythritol diaryl ether, erythritol triaryl ether, pendecylenic acid, etc.
  • Compounds can also be used.
  • component (D) which has two or more ⁇ H groups in one molecule
  • component (D) which has two or more ⁇ H groups in one molecule
  • the reaction between component (B) and component (D) generates hydrogen gas and creates a crosslinked structure. It is possible to use a small amount to assist in setting the curing time. It is not desirable to use a large amount because it cures before sufficient foaming occurs. Further, a compound having a carbon-carbon double bond and an OH group in one molecule can be used as a dual-purpose substance of the component (A) and the component (D).
  • the mixing ratio of the three components (A), (B) and (D) is appropriately selected depending on the structure of each component, the desired expansion ratio, and the desired physical properties, and is not particularly limited.
  • a catalyst is suitably used for the dehydrocondensation of the component (B) and the component (D) and the addition reaction (hydrosilylation reaction) of the component (A) and the component (B). be able to.
  • hydrosilylation catalyst and cocatalyst described in the first and second inventions can be applied to the present invention.
  • the foamable resin composition of the present invention further comprises a filler, an antioxidant, a radical inhibitor, an ultraviolet absorber, an adhesion improver, a flame retardant, a polydimethylsiloxane-polyalkylene oxide-based surfactant or an organic interface.
  • Foam stabilizers such as activators (polyethylene glycol alkyl phenyl ether, etc.), acids or basic compounds (additives for adjusting the reaction between the hydrosilyl group and the ⁇ H group, and suppress the condensation reaction with acid And accelerates with a base.), Storage stability improver, ozone deterioration inhibitor, light stabilizer, thickener, plasticizer, coupling agent, antioxidant, heat stabilizer, conductivity imparting agent, antistatic agent , A radiation blocking agent, a nucleating agent, a phosphorus-based peroxide decomposer, a lubricant, a pigment, a metal deactivator, a physical property modifier, and the like may be added as long as the object and effects of the present invention are not impaired. Kill.
  • a foam is produced by mixing the above-mentioned foamable resin composition of the present invention with a catalyst and other additives as necessary, followed by foaming and curing.
  • the temperature for foaming and curing is preferably 100 t: or less, and more preferably near room temperature in consideration of application to in-situ foaming.
  • a high temperature exceeding 100 t : the rate of the addition-type crosslinking (curing) reaction between the component (A) and the component (B) becomes too high, and the reaction occurs between the component (B) and the component (D). It is difficult to balance with hydrogen gas foaming.
  • the production of the foam according to the present invention may be performed by mixing the foamable resin composition of the present invention with a catalyst, and further, if necessary, an appropriate combination of additives and mixing two liquids or more separate mixtures in advance.
  • Can be mixed immediately before use, applied directly to the substrate surface, and foamed in situ, or a similar mixture can be mixed immediately before use and injected and foamed.
  • a mixing method a method such as hand mixing, an electric mixer, a static mixer, or collision mixing can be used.
  • a static mixer or collision mixing In particular, in the case of foaming in situ, it is preferable to use a static mixer or collision mixing.
  • the method of combining the foamable resin composition of the present invention and the catalyst in the case where two or more separate mixtures in which additives are mixed beforehand as needed, or more, is as follows.
  • the combination is not limited to these as long as the generation and hardening of hydrogen do not proceed before all the components are mixed. That is,
  • component (A) A mixture of component (A), component (D) and component (C), and only component (B) Or two liquids, or
  • foam molding the foam there is no particular limitation on the method of molding the foam, and it is used for the production of polyurethane foam, phenolic foam, silicone foam, etc., such as extrusion foaming, continuous foaming, cast molding, discontinuous molding, or in-situ foaming.
  • foam molding methods can be used as appropriate.
  • Examples of the continuous foaming method include a slab foaming method in which foam is freely foamed on a paper or a plastic film continuously fed out onto a belt conveyor, and a double competition in which a sheet, a veneer plate, a metal plate, and the like are molded and laminated together.
  • the key method is used.
  • the casting molding method is a method in which a foam having a desired shape is discharged and foamed, cured and cured to form a molded article conforming to the inner surface shape of the mold.
  • the discontinuous molding method is used for molding a sandwich panel or the like.
  • On-site construction methods include the one-pack simple spray method, the two-pack spray method, the two-pack injection method and the two-pack coating method, and are mainly used for building insulation.
  • the foam according to the present invention is a foam although there is no particular limitation on the expansion ratio per unit volume, expressed as (volume of foam) / (volume of foam-volume of voids in foam). It is preferable to have a foaming ratio of 2 times or more, especially 4 times or more, in which useful features are remarkable.
  • the foamable resin composition of the present invention foams under heating at room temperature or at a relatively low temperature, it can be foamed in-situ, has low toxicity without containing isocyanate, and has a low expansion ratio. Increasing the value has the effect of reducing the price per unit volume.
  • the production method of the present invention characterized by using the foamable resin composition, the weather resistance, the coating property, and the adhesiveness are good, and the harmful gas at the time of combustion is harmful.
  • a foam having an excellent characteristic of no generation of a foam is obtained.
  • the composition of the component (A) molecular weight between the skeleton and the cross-linking point
  • the mixing ratio of each component it is possible to manufacture from a rigid foam to a flexible foam, and the expansion ratio can be set from low to high.
  • 1,3,5,7-tetramethylcyclotetrasiloxane (KF 9 manufactured by Shin-Etsu Chemical Co., Ltd.) was placed in a 3 L four-necked round bottom flask equipped with a thermometer, stirrer element, dropping funnel, and condenser. 90 2) 1504 g and 500 ml of toluene were added. Under stirring at room temperature, a xylene solution of platinum-vinylsiloxane complex (47.2 IX1 (6.210 " 6 mo1 in terms of platinum atom)) was dissolved in toluene (20 ml) and added.
  • a one-liter four-necked flask was equipped with a stirring rod, a dropping funnel, a cooling tube with a three-way cock at the top, and a thermometer.
  • This flask was charged with 120 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 241 ⁇ 1) of a xylene solution of a platinum-vinylsiloxane complex, and 120 ml of toluene.
  • the mixture was heated to 80 "C, and 67.0 g (0.50 mo1) of polyphenylphenol was added dropwise from the dropping funnel over 20 minutes. The mixture was stirred at 80 as it was for 2 hours.
  • 1, 3, 5, 5 and 7 tetramethylcyclotetrasiloxane in a four-neck flask connected to a dropping funnel, a cooling tube with a three-way cock connected to the top, a thermometer, and a mechanical lubricator. And heated to 40 t: while flowing an oxygen-nitrogen mixed gas (oxygen content 1%) from a three-way cock.
  • Pt Vinyl siloxane (3% xylene solution) 6.5 mg was added, and ⁇ , O '— diarylbisphenol A3 0.8 g was added dropwise from a dropping port.
  • 8. lg of a polyethylene oxide polymer substituted with a methyl group (number average molecular weight: 400). At 40 degrees
  • a 1-liter four-necked flask was equipped with a stirring rod, a dropping funnel, a cooling tube with a three-way cock on top, and a thermometer.
  • the flask was charged with 120 g of 1,3,5,7-tetramethylcyclotetrasiloxane and 24 1 l of a xylene solution of a platinum-vinylsiloxane complex.
  • the mixture was heated to 40 and 11.8 g (0.10 mo 1) of ⁇ -methylstyrene was added dropwise from the dropping funnel over 5 minutes.
  • the reaction mixture was confirmed by 1 H-NMR to confirm that the peak of the pinyl group had disappeared.
  • 10 g of activated carbon was added, and the mixture was stirred at room temperature for 1 hour.
  • the mixture was filtered to obtain a cyclotetrasiloxane modified with a phenethyl group and a polyoxyalkylene group as a viscous liquid.
  • the measured Si H value of this polysiloxane was 8.3 mmol / l.
  • Synthesis Example 4 instead of 1,3,5,7-tetramethylcyclotetrasiloxane, 120 g of polyorganohydrogensiloxane (KF-99 manufactured by Shin-Etsu Chemical Co., Ltd.), toluene 1 After 24 m, a platinum-vinylsiloxane complex xylene solution 2411 was added. The mixture was heated to 80, and as in Synthesis Example 5, 11.8 g of ⁇ -methylstyrene and 70 g of ethylenoxide polymer were added dropwise from the dropping funnel over 10 minutes. And stirred for 2 hours.
  • KF-99 manufactured by Shin-Etsu Chemical Co., Ltd.
  • the reaction mixture was analyzed by 1 H-NMR to confirm that the vinyl group peak had disappeared. After confirming and cooling, 10 g of activated carbon was added and the mixture was stirred at room temperature for 1 hour. The mixture was filtered, and the filtrate was concentrated to obtain a methylhydrodiene polysiloxane modified with a phenethyl group and a polyoxyalkylene group as a viscous liquid. When the SiH value of this polysiloxane was measured, it was 8.3 mmol / g.
  • Example 2 The same operation as in Example 1 was performed except that 7.9 g of the compound synthesized in Synthesis Example 2 was used instead of 7.9 g of the compound synthesized in Synthesis Example 1. As a result, the mixture became cloudy and did not dissolve. Also, what is obtained by heating is non-uniform. Did not give a good cured product.
  • Example 2 The same operation as in Example 2 was performed, except that 7.9 g of the compound synthesized in Synthesis Example 2 was used instead of 7.9 g of the compound synthesized in Synthesis Example 1. As a result, the mixture became cloudy and did not dissolve. The product obtained by heating was not uniform and did not give a good cured product.
  • Example 2 The same operation as in Example 1 was performed using 7.9 g of the compound synthesized in Synthesis Example 1 and 9.2 g of the compound synthesized in Synthesis Example 9. The compatibility of the mixture was good, and a uniform and transparent cured product was obtained by heating.
  • Example 3 the same operation as in Example 3 was performed, except that 9.2 g of the compound synthesized in Synthesis Example 10 was used instead of the compound synthesized in Synthesis Example 9. The compatibility of the mixture was good, and a uniform transparent cured product was obtained by heating.
  • Example 2 A similar operation was performed according to Example 1, except that 7.7 g of the compound synthesized in Synthesis Example 3 was used instead of the compound synthesized in Synthesis Example 1. The compatibility of the mixture was good, and a uniform and transparent cured product was obtained by heating.
  • Example 2 A similar operation was performed according to Example 1, except that 7.9 g of the compound synthesized in Synthesis Example 4 was used instead of the compound synthesized in Synthesis Example 1. The compatibility of the mixture was good, and a uniform and transparent cured product was obtained by heating.
  • Example 1 instead of the compound synthesized in Synthesis Example 1, The same operation was performed using 7.2 g of the synthesized compound. The compatibility of the mixture was good, and a uniform and transparent cured product was obtained by heating.
  • Example 1 the same operation was performed using 7.2 g of the compound synthesized in Synthesis Example 6 instead of the compound synthesized in Synthesis Example 1.
  • the compatibility of the mixture was good, and a uniform and transparent cured product was obtained by heating.
  • Example 7 A similar operation was performed according to Example 1, except that 6.6 g of the compound synthesized in Synthesis Example 7 was used instead of the compound synthesized in Synthesis Example 1. As a result, the mixture became cloudy and did not dissolve. The product obtained by heating was non-uniform and did not give a good cured product.
  • Example 7 A similar operation was performed according to Example 1, except that 6.3 g of the compound synthesized in Synthesis Example 7 was used instead of the compound synthesized in Synthesis Example 1. As a result, the mixture became cloudy and did not dissolve. The product obtained by heating was not uniform and did not give a good cured product.
  • Example 2 A similar operation was performed according to Example 1, except that 3.9 g of polymethylhydrogensiloxane (KF-99) was used instead of the compound synthesized in Synthesis Example 1. As a result, the mixture became cloudy and did not dissolve. The product obtained by heating was not uniform and did not give a good cured product.
  • KF-99 polymethylhydrogensiloxane
  • Example 9 A similar operation was performed according to Example 1, except that 3.9 g of 1,3,5,7-tetramethylcyclotetrasiloxane (KF-9902) was used instead of the compound synthesized in Synthesis Example 1. went. As a result, the mixture became cloudy and did not dissolve. Ma The product obtained by heating was not uniform and did not give a good cured product.
  • KF-9902 1,3,5,7-tetramethylcyclotetrasiloxane
  • Example 2 According to the same manner as that of Example 1, the same operation was carried out using 7.9 g of the compound synthesized in Synthesis Example 1 and 240 g of terminal aryl esterified polypropylene oxide (number average molecular weight: about 800,000). The compatibility of the mixture was good, and a uniform transparent cured product was obtained by heating.
  • 2,2'-Diarylbisphenol A 10.8 g (vinyl group 7.00 mo 1), the compound containing a hydrosilyl group prepared in Synthesis Example 1 9 ⁇ 20 g (SiH 0.070 mol) and 1.5 g of n-butane were mixed to obtain a homogeneous liquid.
  • 43 mg of a xylene solution of platinum-vinylsiloxane (3.0% by weight of platinum atoms) was added, and the mixture was vigorously stirred and mixed for 10 seconds to foam while generating heat, and a rigid foam was obtained.
  • the foam was allowed to stand at 23 for 24 hours, and the dimensional change immediately after the completion of foaming was expressed as a percentage (hereinafter referred to as shrinkage) and was 5% or less.
  • shrinkage a percentage
  • a cube was cut out from the obtained foam, the weight was measured, and the density was determined. The result was 27.5 kg Zm 3 .
  • the closed cell ratio was measured according to ASTM-D2856, and was found to be 85%.
  • 2,2'-diarylbisphenol A10.8 g 2,2'-diarylbisphenol A 5.39 g (vinyl group 0.035 mol)
  • a mixture of 5.39 g of bisphenol A diaryl ether (0.035 mol of Bier group) was used.
  • the resulting foam had a shrinkage of 5% or less, a density of 22.8 kg / m 3 and a closed cell rate of 82%.
  • Example 11 except that 9.64 g of the compound containing a hydrosilyl group produced in Synthesis Example 3 was used instead of 9.20 g of the compound containing a hydrosilyl group produced in Synthesis Example 1. The same operation as described above was performed. The density of the obtained foam was 27.8 kgZm 3 , and the closed cell ratio was 70%.
  • Example 11 The same operation as in Example 11 was performed, except that 3.6 g (0.025 mo 1) of 2-ethylhexanoic acid was used instead of 1.5 g of n-butane.
  • the foam had a density of 45.9 kgZm 3 and a closed cell ratio of 61%.
  • Example 11 The same operation as in Example 11 was carried out except that 8.43 g of the modified siloxane produced in Synthesis Example 5 was used instead of the compound containing a hydrosilyl group produced in Synthesis Example 4.
  • the contraction rate of the obtained foam was 30%, but the density was 50 k / m and the closed cell rate was 60%.
  • Example 11 The same operation as in Example 11 was performed except that 9.2 g of the modified siloxane prepared in Synthesis Example 6 was used instead of the compound containing a hydrosilyl group prepared in Synthesis Example 4. Although the shrinkage of the obtained foam was 30%, the density was 50 kg / m 3 and the closed cell ratio was 60%.
  • a mixture was prepared by mixing 280 g of the polypropylene oxide used in Example 9, 9.20 g of the compound containing a hydrosilyl group produced in Synthesis Example 4, and HFC245fa10.Og. And A platinum-vinylsiloxane solution was added and vigorously stirred and mixed for 10 seconds in the same manner as in Example 11 to generate heat while generating heat. Thus, a soft foam was obtained. The density of the obtained foam was 200 kg Zm 3 .
  • Example 10 35 g of the terminal allyl esterified nodiethylene glycol fluorate copolymer used in Example 10; 9.20 g of the compound having a hydr ⁇ silyl group produced in Synthesis Example 4; and 8.0 g of HFC245-fa was mixed to make a homogeneous solution.
  • a platinum-vinylsiloxane solution was added, and the mixture was vigorously stirred and mixed for 10 seconds. When the mixture was foamed while generating heat, a soft foam was obtained. The density of the obtained foam was 70 kg Zm 3 .
  • Example 11 The same procedure as in Example 11, except that 1,3,5,7-tetramethylcyclotetrasiloxane (4.20 g) was used instead of the compound containing a hydrosilyl group produced in Synthesis Example 1. The operation was performed. As a result, the aryl compound and the SiH compound were not compatible with each other and did not form a foam.
  • Example 11 The same operation as in Example 11 was performed except that 7.29 g of the modified polymethylhydrogensiloxane prepared in Synthesis Example 7 was used instead of the compound containing a hydrosilyl group prepared in Synthesis Example 1. .
  • the obtained foam had a weight of 80 kgm 3 and a closed cell ratio of 30%.
  • Example 11 The same operation as in Example 11 was performed except that 7.53 g of the modified polymethylhydrogensiloxane produced in Synthesis Example 8 was used instead of the compound containing a hydrosilyl group produced in Synthesis Example 1.
  • the density of the obtained foam was determined, it was 33 kgZm 3 .
  • the closed cell rate was measured, it was 10%.
  • a curing agent having sufficient compatibility with a highly polar organic compound having a carbon-carbon double bond, and a curable composition and a foaming resin composition using the curing agent. it can.
  • the curable composition using the curing agent of the present invention is excellent in mechanical strength and excellent in appearance such as transparency, its use is not particularly limited, and can be used for general and wide use.
  • Examples include sealing materials for electrical and electronic components, undercoats for automobiles, coating agents such as waterproof coatings for construction, gasket materials, sealing materials, rubber and resins.
  • Examples include molding materials, various paints such as liquids and powders, adhesives, and property modifiers, and resin modifiers such as compatibilizers.
  • a foam that can be foamed and cured under heating at room temperature or relatively low temperature has a high expansion ratio, and has a high closed cell ratio can be obtained. Therefore, a high foaming ratio can reduce the price per unit volume, and a high closed cell rate can provide a foam with good heat insulation performance, so soundproofing, heat insulation, water stoppage, airtightness, vibration suppression, It can be widely applied to various uses such as protection, cushion, and decoration.
  • cushioning materials for vehicles include, but are not limited to, cushioning materials for vehicles, ceiling materials, door trim materials, floor cushion vibration-absorbing sound absorbing materials, power cooler heat insulating materials, damper air sealing materials, Waterproof material, gasket, air filter, center villa garnish, headliner, quarter trim, dust cover, safety foam in fuel tank, oil Filters, flexible containers, crash pads, sun visors, head restraints, insulators, dashboards, door panels, pillars, console boxes, energy-absorbing bumpers, refrigerated vehicles 'cooled vehicles' tank trucks.
  • Refrigerators for home appliances Freezers Insulation materials such as electronic jars, anti-condensation materials for room coolers, puffs for sports equipment, medical products and cosmetics, W-pads, slippers, sandals, sword mountains, toys, etc. For daily necessities.
  • the foamable resin composition of the present invention a foam using the same, and a method for producing the same can be used for molding an article shape in a casting method, producing a model sample from a mold, producing a decorative article, and the like. Things.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)

Abstract

On utilise avec un composé organique possédant une double liaison carbone-carbone, un durcisseur possédant une compatibilité suffisante avec ledit composé. Une composition réticulable contenant le durcisseur permet de produire un article réticulé doté d'excellentes caractéristiques mécaniques et parfaitement transparent. Une composition de résine expansible produit par ajout d'un agent moussant à la composition réticulable, peut mousser et subir une réticulation à température ordinaire ou par chauffage à une température relativement basse. Il est notamment possible de produire une mousse dotée d'un coefficient d'expansion élevé et présentant un pourcentage élevé en cellules fermées, même lorsque la composition de résine expansible contient un composé organique fortement polaire possédant une double liaison carbone-carbone.
PCT/JP1998/004988 1997-11-06 1998-11-05 Durcisseur, composition reticulable et composition de resine expansible contenant toutes deux ledit durcisseur, mousse fabriquee a partir de ladite composition de resine expansible et procede de fabrication correspondant Ceased WO1999024509A1 (fr)

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JP30433197 1997-11-06
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JP2001325972A (ja) * 2000-05-17 2001-11-22 Three Bond Co Ltd 燃料電池用硬化性組成物
JP2002080733A (ja) * 2000-04-21 2002-03-19 Kanegafuchi Chem Ind Co Ltd 光学材料用組成物、光学用材料、その製造方法およびそれを用いた液晶表示装置およびｌｅｄ
JP2002235005A (ja) * 2001-02-09 2002-08-23 Kanegafuchi Chem Ind Co Ltd 光学用材料用組成物、光学用材料およびその製造方法
JP2002235006A (ja) * 2001-02-13 2002-08-23 Kanegafuchi Chem Ind Co Ltd 光学用材料用組成物、光学用材料およびその製造方法
JP2003261770A (ja) * 2002-03-08 2003-09-19 Kanegafuchi Chem Ind Co Ltd 封止剤、半導体等の封止方法、半導体装置の製造方法、および半導体装置
JP2005343984A (ja) * 2004-06-02 2005-12-15 Kaneka Corp 硬化性組成物及び該硬化性組成物により封止された半導体装置
JP2006335947A (ja) * 2005-06-03 2006-12-14 Kaneka Corp ＳｉＨ基含有化合物、その製造方法、並びに、ＳｉＨ基含有化合物を用いた硬化性組成物、その硬化物
JP2007291276A (ja) * 2006-04-26 2007-11-08 Kaneka Corp 複合成形体
WO2008136351A1 (fr) * 2007-04-26 2008-11-13 Hitachi Chemical Company, Ltd. Composition de résine thermodurcissable et élément optique utilisant un produit durci de la composition de résine thermodurcissable
WO2008146759A1 (fr) * 2007-05-25 2008-12-04 Kaneka Corporation Composition durcissable et produit durci
US7470457B2 (en) 2000-04-21 2008-12-30 Kaneka Corporation Curable composition, composition for optical material, optical material, liquid-crystal display device, transparent conductive film, and process for producing the same
JP2009126892A (ja) * 2007-11-20 2009-06-11 Kaneka Corp 硬化性組成物
WO2014073605A1 (fr) * 2012-11-07 2014-05-15 東レ・ダウコーニング株式会社 Polyorganosiloxane dénaturé par du phénol et à teneur réduite en platine, son procédé de production et modificateur de résine organique en contenant
JP2017520519A (ja) * 2014-05-08 2017-07-27 モメンティブ パフォーマンス マテリアルズ インコーポレイテッド ジアルキルコバルト触媒並びにヒドロシリル化および脱水素シリル化のためのそれらの使用
JP2022502525A (ja) * 2019-09-02 2022-01-11 エルジー・ケム・リミテッド コポリカーボネートおよびこれを含むポリカーボネート組成物

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JPH0395266A (ja) * 1989-05-29 1991-04-19 Kanegafuchi Chem Ind Co Ltd 硬化剤、その製造方法及び該硬化剤を用いた硬化性組成物
JPH08337670A (ja) * 1995-06-12 1996-12-24 Toshiba Silicone Co Ltd 発泡性ポリオルガノシロキサン組成物および難燃性発泡体
JPH09302095A (ja) * 1996-05-10 1997-11-25 Kanegafuchi Chem Ind Co Ltd 硬化性組成物、成形体及び製造方法
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US7470457B2 (en) 2000-04-21 2008-12-30 Kaneka Corporation Curable composition, composition for optical material, optical material, liquid-crystal display device, transparent conductive film, and process for producing the same
JP2002080733A (ja) * 2000-04-21 2002-03-19 Kanegafuchi Chem Ind Co Ltd 光学材料用組成物、光学用材料、その製造方法およびそれを用いた液晶表示装置およびｌｅｄ
JP2001325972A (ja) * 2000-05-17 2001-11-22 Three Bond Co Ltd 燃料電池用硬化性組成物
JP2002235005A (ja) * 2001-02-09 2002-08-23 Kanegafuchi Chem Ind Co Ltd 光学用材料用組成物、光学用材料およびその製造方法
JP2002235006A (ja) * 2001-02-13 2002-08-23 Kanegafuchi Chem Ind Co Ltd 光学用材料用組成物、光学用材料およびその製造方法
JP2003261770A (ja) * 2002-03-08 2003-09-19 Kanegafuchi Chem Ind Co Ltd 封止剤、半導体等の封止方法、半導体装置の製造方法、および半導体装置
JP2005343984A (ja) * 2004-06-02 2005-12-15 Kaneka Corp 硬化性組成物及び該硬化性組成物により封止された半導体装置
JP2006335947A (ja) * 2005-06-03 2006-12-14 Kaneka Corp ＳｉＨ基含有化合物、その製造方法、並びに、ＳｉＨ基含有化合物を用いた硬化性組成物、その硬化物
JP2007291276A (ja) * 2006-04-26 2007-11-08 Kaneka Corp 複合成形体
JPWO2008136351A1 (ja) * 2007-04-26 2010-07-29 日立化成工業株式会社 熱硬化性樹脂組成物及びその硬化物を用いた光学部材
WO2008136351A1 (fr) * 2007-04-26 2008-11-13 Hitachi Chemical Company, Ltd. Composition de résine thermodurcissable et élément optique utilisant un produit durci de la composition de résine thermodurcissable
JP5368302B2 (ja) * 2007-05-25 2013-12-18 株式会社カネカ 硬化性組成物及びその硬化物
WO2008146759A1 (fr) * 2007-05-25 2008-12-04 Kaneka Corporation Composition durcissable et produit durci
JP2009126892A (ja) * 2007-11-20 2009-06-11 Kaneka Corp 硬化性組成物
WO2014073605A1 (fr) * 2012-11-07 2014-05-15 東レ・ダウコーニング株式会社 Polyorganosiloxane dénaturé par du phénol et à teneur réduite en platine, son procédé de production et modificateur de résine organique en contenant
JPWO2014073605A1 (ja) * 2012-11-07 2016-09-08 東レ・ダウコーニング株式会社 白金含有量が低減されたフェノール変性ポリオルガノシロキサン、その製造方法、及びそれを含む有機樹脂改質剤
US9512276B2 (en) 2012-11-07 2016-12-06 Dow Corning Toray Co., Ltd. Phenol-modified polyorganosiloxane with reduced platinum content, method for preparing the same, and modifier for organic resin containing the same
JP2017520519A (ja) * 2014-05-08 2017-07-27 モメンティブ パフォーマンス マテリアルズ インコーポレイテッド ジアルキルコバルト触媒並びにヒドロシリル化および脱水素シリル化のためのそれらの使用
JP2022502525A (ja) * 2019-09-02 2022-01-11 エルジー・ケム・リミテッド コポリカーボネートおよびこれを含むポリカーボネート組成物
US11572439B2 (en) 2019-09-02 2023-02-07 Lg Chem, Ltd. Copolycarbonate and polycarbonate composition comprising the same

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