WO1999024509A1 - Hardener, curable composition and foamable resin composition both containing the hardener, and foam made from the foamable resin composition and process for producing the same - Google Patents

Hardener, curable composition and foamable resin composition both containing the hardener, and foam made from the foamable resin composition and process for producing the same 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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PCT/JP1998/004988
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French (fr)
Japanese (ja)
Inventor
Naoaki Nakanishi
Katsuya Ouchi
Shintaro Komitsu
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Kaneka Corporation
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Priority to JP2000520511A priority Critical patent/JP3831834B2/en
Publication of WO1999024509A1 publication Critical patent/WO1999024509A1/en

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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.

Abstract

For an organic compound having a carbon-carbon double bond, a hardener having sufficient compatibility therewith is used. A curable composition containing the hardener gives a cured article excellent in mechanical properties and appearance including transparency. A foamable resin composition produced by adding a foaming agent to the curable composition can foam and cure at ordinary temperature or with heating at a relatively low temperature. In particular, even when the foamable resin composition contains a highly polar organic compound having a carbon-carbon double bond, a foam having a high expansion ratio and a high percentage of closed cells can be obtained.

Description

明 細 書 硬化剤、 該硬化剤を用いた硬化性組成物及び発泡性樹脂組成物、 及び 該発泡性樹脂組成物を用いた発泡体とその製造方法 技術分野  TECHNICAL FIELD 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.
本発明はヒド口シリル基を含有する有機系硬化剤及び該硬化剤を用いた 硬化性組成物、 及び、 常温あるいは比較的低温の加熱下において、 発泡， 硬化することにより発泡体を生成することを特徵とする発泡性樹脂組成物、 その組成物を用いた発泡体、 及びその製造方法に関する。 背景技術  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
従来、 硬化してゴム状物質を生成する硬化性液状組成物としては、 各種 のものが開発されている。 中でも、 深部硬化性に優れた硬化系として、 1 分子中に平均 2個又はそれ以上のビニル基を末端もしくは分子鎖中にもつ ポリオルガノシロキサンを、 珪素原子に結合する水素原子を 1分子中に 2 個以上有するポリオルガノハイ ドロジェンシロキサンで架橋するものが開 発され、 その優れた耐候性、 耐水性、 耐熱性を利用して、 シーリング剤、 ポッティ ング剤として使用されている。  Conventionally, various curable liquid compositions that cure to form a rubber-like substance have been developed. Above all, as a curing system with excellent deep curability, polyorganosiloxanes having an average of two or more vinyl groups in the terminal or in the molecular chain in one molecule, and hydrogen atoms bonding to silicon atoms in one molecule A crosslinkable polyorganohydrogensiloxane having two or more has been developed, and is used as a sealing agent and potting agent by utilizing its excellent weather resistance, water resistance and heat resistance.
しかし、 この系はコス トが高い、 接着性が悪い， カビが発生しやす い等の点からその用途に制限を受けている。 更に、 上記のポリオルガ ノ シロキサンは一般に有機系重合体に対する相溶性が悪く 、 ポリオル ガノハイ ドロジェンシロキサンと炭素一炭素二重結合 （以下、 ァルケ ニル基ともいう） を含有する有機重合体とを硬化させよう としても、 相分離によ りポリオルガノハイ ドロジェンシロキサンの加水分解及び 脱水素縮合反応が助長され、 ボイ ド発生のために充分な機械特性が得 られないという問題があった。 However, this system is limited in its use due to its high cost, poor adhesion, and easy mold generation. Furthermore, 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). In some cases, the hydrolysis of polyorganohydrogensiloxane and the There was a problem that the dehydrocondensation reaction was promoted and sufficient mechanical properties could not be obtained due to generation of voids.
また， 断熱材等の用途に用いられる発泡剤については、 重要な特性 として熱伝導率が低いことが要求されており、 このため、 高発泡倍率 でしかも高独立気泡率であることが特に望まれている。  In addition, low thermal conductivity is required as an important property of foaming agents used for applications such as heat insulating materials. Therefore, it is particularly desirable that the foaming agent have a high expansion ratio and a high closed cell rate. ing.
上記の問題を解決するため、 分子中にヒ ドロシリル基を有する有機系硬 化剤が提案されている （特開平 3 — 9 5 2 6 6号公報）。 該硬化剤はァルケ 二ル基を含有する有機重合体と一般に相溶性が良好である。 ところが、 こ の硬化剤も、 例えばフエノール系化合物のような極性の高いアルケニル基 を含有する有機系化合物とは十分な相溶性を有さない。 そのため、 これら の硬化剤と極性の高いアルケニル基を含有する有機系化合物とを硬化させ ようとしても， 相分離により、 透明で均一な硬化物が得られ難いという問 題があった。  In order to solve the above problem, 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. However, 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.
一方、 炭素一炭素二重結合を有する有機重合体とヒ ドロシリル基を有す る化合物を主成分として、 低毒性で発泡倍率が高い発泡体が得られること が見いだされている （特開平 8— 8 1 5 1 9 4号公報）。  On the other hand, it has been found that a foam having low toxicity and a high expansion ratio can be obtained by using an organic polymer having a carbon-carbon double bond and a compound having a hydrosilyl group as main components (Japanese Unexamined Patent Publication No. No. 8,151,944).
ところが、 上記炭素一炭素二重結合を有する有機重合体とヒ ドロシ リル基を有する化合物から発泡体を得る場合にも、 例えばフエノール 系化合物のような極性の高い炭素 -炭素二重結合を含有する有機系化 合物を用いた場合には一般にヒ ドロシリル基を有する化合物との相溶 性が悪く ， 高発泡倍率で、 しかも高独立気泡率である発泡体は得られ ないという問題があった。  However, when a foam is obtained from the above-mentioned organic polymer having a carbon-carbon double bond and a compound having a hydrosilyl group, it also contains a highly polar carbon-carbon double bond such as a phenolic compound. When an organic compound is used, there is a problem that the compatibility with the compound having a hydrosilyl group is generally poor, and a foam having a high expansion ratio and a high closed cell rate cannot be obtained.
本発明は上記問題に鑑みてなされたものであり 、 第一の発明は、 特 に極性の高い炭素一炭素二重結合を含有する有機系化合物とも十分な 相溶性を有する硬化剤を提供しょう とするものである。 また、 第二の発明では、 上記した第一の発明に係る硬化剤を用いて なり . 透明性が高く均一な硬化物を与える硬化性組成物を提供する。 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. In a second aspect, 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.
さ らに、 第三の発明は， 常温あるいは比較的低温の加熱下において 発泡硬化させることができ、 かつ特に極性の高い炭素一炭素二重結合 を含有する有機系化合物を用いた場合にも発泡倍率が高く、 しかも独 立気泡率が高い発泡体が得られる発泡性樹脂組成物、 その組成物を用 いた発泡体、 及びその製造方法を提供することを目的とする。 発明の開示  Further, 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
かかる課題を解決するために本発明者らは鋭意研究の結果、 特定の 構造を有する化合物が、 分子中に少なく とも 1個の炭素一炭素二重結 合を有する有機化合物との相溶性が良好なこと、 及びこの化合物を硬 化剤として用いることにより、 上記各課題を解決できることを見出し、 本発明に至った。  In order to solve such a problem, 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.
まず、 第一の発明に係る硬化剤は、 以下のいずれかの構造を有するもの とする。  First, the curing agent according to the first invention has one of the following structures.
第一の硬化剤は、 分子内に 1個以上のフエノール性水酸基及び 2個以上 のヒドロシリル基を有する有機系硬化剤であり、  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,
( a ) 下記一般式 （ 1 )  (a) The following general formula (1)
( 1 )
Figure imgf000005_0001
(式 （ 1 ) 中、 R1 は、 水素原子及び炭素数が 1〜 2 0の一価の有機基より 選ばれる基を表し、 それぞれの R' は同じであっても異なっていてもよい。 i ≥2 , j ≥ 0. p≥ lであり、 かつ i , j及び pは、 3≤ ( i + j ) x p ≤ 5 0を満足する数である。） (1)
Figure imgf000005_0001
(In the formula (1), 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.)
で表される環状オリゴシロキサン， 及び Z又は下記一般式 （ 2) A cyclic oligosiloxane represented by the formula: and Z or the following general formula (2)
Figure imgf000006_0001
Figure imgf000006_0001
(式 （ 2 ) 中、 R1は上記に同じ、 R2は、 水素原子、 — S i (CH3) 一 S i ( C H3) 2H及び炭素数が 1〜 2 0の一価の有機基より選ばれる基を 表し、 それぞれの は同じであっても異なっていてもよい。 k≥2、 1 ≥ 0、 q≥ lであり、 かつ k, l 及び Qは、 2≤ (k + l ) X q 5 0を満足 する数である。） (In the formula (2), 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. Represents a group selected from groups, each of which may be the same or different, k≥2, 1≥0, q≥l, and k, l and Q are 2≤ (k + l ) A number that satisfies Xq50.)
で表される鎖状ポリシロキサン、 と， A linear polysiloxane represented by
( b ) 下記一般式 （ 3 )  (b) The following general formula (3)
Figure imgf000006_0002
Figure imgf000006_0002
(式 （ 3 ) 中、 m及び nは、 それぞれ独立に 1〜 3の数を表し、 pは 0〜 2の数を表す。 R3は、 1個以上のアルケニル基を含有する炭素数 1〜 2 5 の一価の有機基を表し， mが 2以上の場合， それぞれの R3は同じであって も異なっていてもよい。 R4は、 ハロゲン原子、 炭素数 1〜 6のアルコキシ 基、 炭素数 1〜 2 5の一価の有機基より選ばれる一価の基を表し、 pが 2 の場合、 それぞれの R 4は同じであっても異なっていてもよい。） (In the formula (3), m and n each independently represent a number of 1 to 3, p represents a number of 0 to 2. 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. )
で表される分子内に 1個以上のアルケニル基及び 1個以上のフエノール性 水酸基を有する化合物とを反応させて得られるものである。 Is obtained by reacting a compound having one or more alkenyl groups and one or more phenolic hydroxyl groups in the molecule represented by
上記式 （ 1 ) 及び （ 2 ) においては、 j 及び/又は 1が 0であるのが好 ましい。 その場合において、 前記 i力 3≤ i≤ 7を満足する数であり、 及び Z又は前記 kが、 2≤k≤ l 0を満足する数であるのがより好ましい。 また、 （ b) 成分としては、 下記一般式 （4) 又は一般式 （ 5 )  In the above formulas (1) and (2), j and / or 1 are preferably 0. In this case, it is more preferable that i is a number satisfying 3 ≤ i ≤ 7, and Z or k is a number satisfying 2 ≤ k ≤ l0. In addition, as the component (b), the following general formula (4) or general formula (5)
Figure imgf000007_0001
Figure imgf000007_0001
Figure imgf000007_0002
Figure imgf000007_0002
(式 （ 4) 及び （ 5 ) 中、 R5は， 水素原子あるいは 1個以上のアルケニル 基を含有する炭素数 1〜 1 0の一価の有機基を表し、 それぞれの R 5は同じ であっても異なっていてもよい。 式 （ 5〉 中、 Xは、 — CH2—、 - C ( C H3) 2—、 - C H (CH3) 一、 一 C (C F3) z -. — C O—、 一 S〇2—、 一〇一， あるいは次式 ：
Figure imgf000008_0001
(In the formulas (4) and (5), 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. In the formula (5), X is — CH 2 —,-C (CH 3 ) 2 —,-CH (CH 3 ) one, one C (CF 3 ) z- . — CO —, One S〇 2 —, one hundred one, or:
Figure imgf000008_0001
で表される基より選ばれる二価の置換基を示す。） And a divalent substituent selected from the groups represented by )
で表される、 分子内に 1個以上のアルケニル基及び 1個以上のフエノール 性水酸基を有する化合物が特に好適に用いられる。 Compounds having at least one alkenyl group and at least one phenolic hydroxyl group in the molecule represented by are particularly preferably used.
本発明に係る第二の硬化剤は、 次の成分 （i) , (ii) 及び （iii) ； The second curing agent according to the present invention comprises the following components (i), (ii) and (iii);
(i) 1分子中のケィ素原子の数が 3〜 1 0個であ ^) , 鎖状及びノ又は 環状のオルガノハイ ドロジェンシロキサン、 (i) the number of silicon atoms in one molecule is from 3 to 10 ^), a chain-like or mono- or cyclic organohydrogensiloxane,
(ii) (i) 成分のヒ ドロシリル基と反応しうる官能基を 1分子中に 2 個以上有する化合物、  (ii) a compound having at least two functional groups per molecule capable of reacting with the hydrosilyl group of the component (i);
(iii) (ii) 成分のヒ ドロシリル基と反応しうる官能基を 1分子中に 1 偭含有する有機化合物  (iii) (ii) An organic compound containing 1% of a functional group capable of reacting with the hydrosilyl group of the component in one molecule.
を反応させて得られ， しかも （i) 成分由来のヒ ドロシリル基が実質上 残存した化合物である。 And a compound in which the hydrosilyl group derived from the component (i) substantially remains.
また、 第三の硬化剤は、 次の式 （ 6 ) 又は式 （ 7 ) で示される構造を有 することを特徵とする。  The third curing agent is characterized in that it has a structure represented by the following formula (6) or (7).
Ry-
Figure imgf000008_0002
R y-
Figure imgf000008_0002
(式 （ 6 ) 中、 m≥2 , n≥ 0 1 . k , q≥ 1 , pは 0〜 5の整 ¾c、 1 0≤ (m+ n + l + k) X q≤ 8 0であり . R5 , R7 は、 炭素数 0〜 6の 1価の置換基、 R' は， 分子量が 1 0 0 ~ 1 0 , 0 0 0のポリオキシアル キレン鎖を示し、 R9 , R10 は、 水素又は炭素数 1〜 2 0の炭化水素基を 示す。 m個， n個， 1個， k個の R6 ， n個. p個の R7 は、 それぞれ同 じものでも異なるものでもよい。 Xは、 構成元素として C, H. N , 〇， S , ハロゲンのみを含む炭素数 0〜 1 0の 2価の置換基を示す。） (In Equation (6), m≥2, n≥01.k, q≥1, and p are integers c from 0 to 5, and 10≤ (m + n + l + k) Xq≤80. 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, 〇, S, and halogen as constituent elements. )
Figure imgf000009_0001
Figure imgf000009_0001
(式 （ 7 ) 中、 m≥ 2、 n≥ 0、 1 , k . q≥ 1 , pは 0〜 5の整数、 3 ≤ (m + n + 1 + k ) x q≤2 0であり、 RS , R7 , R8. Xは、 式 （ 6 ) と 同じ。） (Where m≥2, n≥0, 1, k.q≥1, p is an integer from 0 to 5, 3≤ (m + n + 1 + k) xq≤20, and R S , R 7 , R 8. X is the same as in equation (6).)
次に、 第二の発明に係る硬化性組成物は、 （A) 分子中に少なく とも 1個 の炭素一炭素二重結合を含有する有機化合物と、 （B) ヒ ドロシリル基を有 する有機系硬化剤とを必須成分として含有し、 好ましくは、 （C) ヒ ドロシ リル化触媒をさらに含有し、 その （B) 成分として、 上記第一の発明の有 機系硬化剤のいずれか 1種又は 2種以上を含有するものである。  Next, 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. A curing agent as an essential component, and preferably further comprises (C) a hydrosilylation catalyst, and as the component (B), any one of the organic curing agents of the first invention or It contains two or more types.
第三の発明に係る発泡性樹脂組成物は、 上記 （A) 成分及び （B) 成分 に加えて （D) 発泡剤及び 又は〇 H基を有する化合物をさらに必須成分 として含有し、 好ましくは （C) ヒ ドロシリル化触媒をさらに含有するも のである。  The foamable resin composition according to the third invention further comprises (D) a foaming agent and / or a compound having a 〇H group as essential components in addition to the components (A) and (B), and preferably comprises ( C) It further contains a hydrosilylation catalyst.
第二及び第三の発明における （A) 成分の有機化合物の分子骨格は、 炭 素、 酸素、 水素、 窒素、 ィォゥ、 ハロゲンのうちのいずれか 1種以上の元 素のみからなるのが好ましい。 In the second and third inventions, 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.
より具体的には、 （A) 成分の有機化合物としては， 下記一般式 （ 8 ) 〜 式 （ 1 0 )  More specifically, as the organic compound of the component (A), the following general formulas (8) to (10)
Figure imgf000010_0001
Figure imgf000010_0001
Figure imgf000010_0002
Figure imgf000010_0002
H?C ( 1 0 )H ? C (1 0)
Figure imgf000010_0003
Figure imgf000010_0003
(式 （ 8 ) 〜式 （ 1 0 ) において、 R 1 1は、 H又は CH3 を示し、 R 12, R 13, R 1 6, R17. R18, R 2 2は， 炭素数 0〜 6の 2価の置換基を示し、 R 14, R 1 5, R 1 9, R 2°, R 21. R23. R24は， 炭素数 0〜 6の 1価の置換基を示 し、 X1, X2 は、 炭素数 0〜 1 0の 2価の置換基を示す。 また、 式 （ 8 ) に おいて、 n, mは、 0〜 3 0 0の整数、 1 は， 1〜 3 0 0の整数、 P . Qは、 0〜 3の整数を示し、 式 （ 9 ) において、 n , m. 1は、 0〜 3 0 0の整数、 s は、 1〜 3 0 0の整数、 p， Q , r は、 0〜 3の整数を示し、 式 （ 1 0 ) に おいて、 n , mは、 0 ~ 4の整数を示す。） In (Equation (8) to Formula (1 0), 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, and in the formula (8), n and m are integers of 0 to 300, and 1 is 1 to 1 An integer of 300, P.Q represents an integer of 0 to 3, and in the formula (9), 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, and in the formula (10), n and m are integers of 0 to 4. )
のうちのいずれか 1種以上の構造を分子骨格として有するものが好適に用 いられる。 Those having at least one of these structures as a molecular skeleton are preferably used.
上記 （A ) 成分の有機化合物の炭素一炭素二重結合は、 1分子あたり平 均 2偭以上であるのが好ましい。  The carbon-carbon double bond of the organic compound as the component (A) is preferably an average of 2 or more per molecule.
上記 （D ) 成分の発泡剤の例としては、 炭化水素、 エーテル類、 ハイ ド 口クロ口フルォロカーボン、 又はハイ ド口フルォロカ一ボンから選ばれる 化合物、 あるいはそれらの混合物が挙げられる。 また、 O H基を有する化 合物の例としては、 アルコール、 カルボン酸、 及び水のうちの 1種以上が 挙げられる。  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.
上記発泡性樹脂組成物を常温あるいは比較的低温の加熱下において発泡 硬化させることにより， 発泡倍率が高く、 しかも独立気泡率が高い発泡体 が得られる。 発明を実施するための最良の形態  By foaming and curing the foamable resin composition under heating at room temperature or at a relatively low temperature, a foam having a high expansion ratio and a high closed cell ratio can be obtained. BEST MODE FOR CARRYING OUT THE INVENTION
上記第一〜第三の発明を以下， 詳細に説明する。  The first to third inventions will be described in detail below.
1 . 硬化剤  1. Curing agent
第一の発明に係る硬化剤は、 分子中に少なく とも 1個の炭素—炭素二重 結合を含有する有機化合物との相溶性が良好なことを特徵とする。 ここで、 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. here,
「有機化合物」 とは、 分子骨格中に実質的にシロキサン結合を含まない化 合物をいい、 「相溶性が良好」 とは、 上記有機化合物と混合撹拌した際に均 —状態に溶解し、 肉眼による観察で白濁や相分離が認められないことをい うものとする。 もしくは、 混合撹拌後、 1 0 0 0回転 分で 1 0分間程度 遠心分離しても白濁や相分離が認められないことをいうものとする。 相溶性が良好であることにより、 これを用いて得られる硬化物は機械的 特性及び透明性等の外観に優れたものとなり， また発泡体は独立気泡率が 高く、 その結果断熱性能等に優れたものとなる。 The term “organic compound” refers to a compound that does not substantially contain a siloxane bond in the molecular skeleton, and the term “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.
その具体的な構造として、 第一の硬化剤は， （ a) 下記一般式 （ 1 )  The specific structure of the first curing agent is as follows: (a) The following general formula (1)
Figure imgf000012_0001
Figure imgf000012_0001
で表される環状オリゴシロキサン及びノ又は下記一般式 （ 2 ) And a cyclic oligosiloxane represented by the general formula (2):
H R1 HR 1
—— 0- Si—— Ω ■Si— O- -R' (2)  —— 0- Si—— Ω ■ Si— O- -R '(2)
R k R q で表される鎖状ポリシロキサンと、  A chain polysiloxane represented by R k R q,
(b) 下記一般式 （ 3 )  (b) The following general formula (3)
(3)
Figure imgf000012_0002
(3)
Figure imgf000012_0002
(式 （ 3 ) 中、 m及び ηは、 それぞれ独立に 1 ~ 3の数を表し、 ρは 0〜 2の数を表す。 R3は、 1個以上のアルケニル基を含有する炭素数 1〜 2 5 の一価の有機基を表し、 mが 2以上の場合、 それぞれの R3は同じであって も異なっていてもよい。 R4は、 ハロゲン原子、 炭素数 1〜 6のアルコキシ 基、 炭素数 1〜 2 5の一価の有機基より選ばれる一価の基を表し、 Pが 2 の場合、 それぞれの R4は同じであっても異なっていてもよい。） (In the formula (3), m and η each independently represent a number of 1 to 3, ρ represents a number of 0 to 2. 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. )
で表される分子内に 1個以上のアルケニル基及び 1個以上のフエノール性 水酸基を有する化合物とを反応させて得られる化合物である。 Is a compound obtained by reacting a compound having one or more alkenyl groups and one or more phenolic hydroxyl groups in the molecule represented by
上記一般式 （ 1 ) で表される環状ポリ シロキサン及び一般式 （ 2 ) で表 される鎖状ポリシロキサンの R' は、 水素原及び炭素数が 1 ~ 2 0の一価の 有機基より選ばれる基であり、 一価の有機基の例としてはアルコキシ基、 ハロゲン化アルキル基、 アルキル基、 シクロアルキル基， アルケニル基、 シクロアルケニル基、 あるいはァリール基等が挙げられる。 これらのうち、 ト リ フルォロプロピル基， メチル基， ェチル基、 一 CH2C H2Rで表され る置換アルキル基 （ここでいう Rは、 ハロゲン原子、 シァノ基、 フエニル 基、 アルコキシ基、 アルキルカルボ二ル基， アルコキシカルボニル基等の 一価の有機基を表す。）、 - C H'2CH (CH3) Rで表される置換アルキル 基 （ここでいう Rは、 ハロゲン原子、 フエニル基、 アルキルカルボニル基， アルコキシカルボニル基等の一価の有機基を表す。）、 — CH2CH2CH2R で表される置換アルキル基 （ここでいう Rは、 ハロゲン原子、 水酸基， ァ ルコキシ基等の一価の有機基を表す。）、 フエニル基が工業的に一般に入手 容易なこと、 及び化学的安定性の点から好ましい。 これらのうち、 メチル 基、 トリフルォロプロピル基、 フエニル基， 2-フエニルェチル基、 あるい は一 CH2CH2CHZ (〇 CH2C H2) nO C H3 (ここでいう nは、 0又は 2 0以下の正の数を表す。） で表される置換アルキル基がさらに好ましく > 最 も好ましいのはメチル基である。 なお、 それぞれの Rは同一であっても異 なっていてもよい。 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. Examples of 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. Among these, 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) Or a monovalent organic group such as an alkoxycarbonyl group.), -CH ' 2 CH (CH 3 ) R, a substituted alkyl group represented by R (where 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.) And a phenyl group are preferred in view of industrial availability and chemical stability. Of these, a methyl group, a trifluoropropyl group, a phenyl group, a 2-phenylethyl group, or one CH 2 CH 2 CH Z (〇CH 2 CH 2 ) n OCH 3 (where n is 0 or A substituted alkyl group represented by the following formula is more preferred.> The most preferred is a methyl group. Note that each R may be the same or different.
前記一般式 （ 2) で表される鎖状ポリ シロキサンの R2は、 水素原子、 ― S i ( C H3) 3、 一 S i ( C H3) 2H , 及び炭素数が 1〜 2 0の一価の有機 基より選ばれる基であり、 一価の有機基の例としては、 メチル基、 ェチル 基、 プロピル基、 ブチル基、 フエニル基、 あるいは一 （CH2CH2〇） „C H3 (ここでいう nは 0又は 2 0以下の正の数を表す） で表される置換アル キル基が挙げられる。 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 〇) 〇CH 3 (where n represents a positive number of 0 or 20 or less) No.
前記一般式 （ 1 ) で表される環状ポリシロキサンの i 、 j 、 P , 及び前 記一般式 （ 2 ) で表される鎖状ポリシロキサンの k , 1 、 qのうち、 iは 2以上の数、 j は 0又は正の数、 pは 1以上の数であり、 かつ i 、 j 及び Pは 3≤ ( i + j ) X p≤ 5 0を満足する数であり、 kは 2以上の数、 1 は 0又は正の数、 qは 1以上の数であり、 かつ k及び 1 は (k + 1 ) X q≤ 5 0を満足する数であればよいが、 工業的に一般に入手が容易であ る点から j = 1 =0 であることが好ましい。 さらに > 得られる硬化剤が低 粘度で取り扱い性がよい等の点から、 3≤ i ≤ 7及びノ又は 2≤ k≤ 1 0 であることが好ましい。  Among i, j, P of the cyclic polysiloxane represented by the general formula (1) and k, 1, and q of the chain polysiloxane represented by the general formula (2), i is 2 or more. A number, j is 0 or a positive number, p is a number of 1 or more, and i, j and P are numbers satisfying 3≤ (i + j) Xp≤50, and 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, and k and 1 may be numbers that satisfy (k + 1) X q ≤ 50, but are generally available industrially. From the standpoint of easiness, it is preferable that j = 1 = 0. Further, it is preferable that 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.
前記一般式 （ 1 ) で表される環状ポリシロキサンの具体例としては、 次 式： Specific examples of the cyclic polysiloxane represented by the general formula (1) include the following formula:
Figure imgf000015_0001
で表される化合物が挙げられる 前記一般式 （ 2 ) で表される鎖状ポリシロキサンの具体例としては、 式
Figure imgf000015_0001
Compounds represented by Specific examples of the linear polysiloxane represented by the general formula (2) include the following:
0寸 Si(CH3)3 0 inch Si (CH 3 ) 3
/ 10 / Ten
Figure imgf000016_0001
Figure imgf000016_0001
で表される化合物が挙げられる 前記 HN一般式 （ 3 ) で表される分子内に 1個以上のアルケニル基及び 1個 以上のフエノール性水酸基を有する化合物の R 3の例としては、 式 Compounds represented by Examples of 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:
CH=CH CM2CH-CH2 CH2
Figure imgf000017_0001
し CH = CH CM2CH-CH2 CH 2
Figure imgf000017_0001
I
0 0 0 0
0——CH。- CH=CH2 , —— C一〇一 CH2CH=CH2 0— C— CH=CH, 0——CH. -CH = CH 2 , —— C-one CH 2 CH = CH 2 0— C— CH = CH,
〇 CH 〇 〇 CH 〇
〇—— C——C=CH2 —— O— C— O— CH.CH=CH2
Figure imgf000017_0002
〇—— C——C = CH 2 —— O— C— O— CH.CH = CH 2
Figure imgf000017_0002
0 0
11 H  11 H
c- ■N— CH2CH=CH2 c- ■ N— CH 2 CH = CH 2
OO
H CH2-CH=CH2 H CH 2 -CH = CH 2
O— C— — CH2CH=CH2 N O— C— — CH 2 CH = CH 2 N
CH2-CH=CH2 ， O O CH3 CH 2 -CH = CH 2 , OO CH 3
II II I II II I
NH-C— CH=CH2 , — H-C— C=CH2 , NH-C— CH = CH 2 , — HC— C = CH 2 ,
-O—
Figure imgf000017_0003
-O—
Figure imgf000017_0003
で表される基が挙げられる あるいは下記一般式 （ 1 1 ) 又は （ 1 2 ) Group represented by Or the following general formula (11) or (12)
Figure imgf000018_0001
Figure imgf000018_0001
(式 （ 1 1 ) 及び （ 1 2 ) 中， R 2 5は水素原子あるいはァリル基であり、 かつ少なく とも一つの R 2 sはァリル基である。 式 （ 1 2 ) 中、 Xは， — C(In the formula (1 1) and (1 2), 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
H2— — C ( C H3) ，一、 一 C H ( C H3) ― C (C F - C O 一， - S O 一〇—、 あるいは式 ： H 2 — — C (CH 3 ), one, one CH (CH 3 ) — C (CF—CO one, —SO one——or the formula:
Figure imgf000018_0002
Figure imgf000018_0002
で表される基である。） Is a group represented by )
で表される基が挙げられる。 And the group represented by
これらのうち、 ァリル基あるいは上記一般式 （ 1 1 ) 又は （ 1 2 ) で表 される基が、 工業的に一般に入手可能なこと， あるいはヒ ドロシリル基と の反応性が良好なことから好ましい。  Of these, 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.
上記一般式 （ 3 ) で表される分子内に 1個以上のアルケニル基及び 1個 以上のフエノール性水酸基を有する化合物の R 4の例としては、 塩素原子， メ トキシ基、 メチル基、 ヒ ドロキシカルボニル基、 アルコキシカルボニル 基、 あるいは下記一般式 （ 1 3) 又は （ 1 4) Examples of 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)
Figure imgf000019_0001
Figure imgf000019_0001
(式 （ 1 4) 中、 Xは、 — CH2—、 - C ( C H3) 2—、 一 CH (CH3; 一 C (C F3) 2—、 一 C O—、 一 S〇2—、 一〇一、 あるいは式； (In the formula (1 4), X is — CH 2 —, —C (CH 3 ) 2 —, one CH (CH 3 ; one C (CF 3 ) 2 —, one CO—, one S〇 2 —, One-one, or the formula;
Figure imgf000019_0002
で表される基を示す。）
Figure imgf000019_0002
Represents a group represented by )
で表される基が挙げられる。 And the group represented by
これらのうちメ トキシ基， あるいは上記一般式 （ 1 3 ) 又は （ 1 4 ) で 表される基が， 工業的に一般に入手可能なことから好ましい。 これらの置 換基が 2個以上置換している場合はそれぞれ同一であっても異なっていて もよい。  Of these, a methoxy group or a group represented by the above general formula (13) or (14) is preferable because it is generally available industrially. When two or more of these substituents are substituted, they may be the same or different.
上記一般式 （ 3 ) で表される分子内に 1個以上のアルケニル基及び 1個 以上のフエノール性水酸基を有する化合物の具体例としては， 式； Specific examples 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 compound represented by the following formula:
Figure imgf000020_0001
Figure imgf000020_0001
Figure imgf000020_0002
Figure imgf000020_0002
で表される化合物が挙げられる 以上 （b) 成分について述べたが、 中でも、 下記一般式 （4) 又は （ 5) Compounds represented by Although the component (b) has been described above, the following general formula (4) or (5)
Figure imgf000021_0001
Figure imgf000021_0001
(式 （ 4) 及び （ 5 ) 中， R5は、 水素原子あるいは 1個以上のアルケニル 基を含有する炭素数 1〜 1 0の一価の有機基を表し、 それぞれの R 5 は同じ であっても異なっていてもよい。 Xは、 — CH2—、 一 C (C H3) 2—、 一 CH (CH3) —、 - C (C F3) 2—、 一 C O—， 一 S 02—、 一〇一、 ある いは式 ； (In the formulas (4) and (5), 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;
Figure imgf000021_0002
で表される基より選ばれる二価の置換基を示す。）
Figure imgf000021_0002
And a divalent substituent selected from the groups represented by )
で表される、 分子内に 1個以上のアルケニル基及び 1個以上のフエノール 性水酸基を有する化合物が好適に用いられる。 Compounds having at least one alkenyl group and at least one phenolic hydroxyl group in the molecule represented by
本発明の硬化剤は、 上記 （ a ) 成分と （ b ) 成分とを反応させて得るこ とができるが、 その際用いられるヒ ドロシリル化触媒の具体例としては、 白金の単体、 アルミナ、 シリカ， カーボンブラック等の担体に固体白金を 担持させたもの， 塩化白金酸、 塩化白金酸とアルコール、 アルデヒ ド、 ケ トン等との錯体、 白金一才レフイ ン錯体 （例えば， P t (CH2 =CH2) 2 ( P P h 3) 2， P t ( C H2= C H2) 2C I 2)、 白金一ビニルシロキサン錯体 (例えば、 P t (V i M e2S i〇 S i M e2V i ) n, P t [(Me V i S i O) J „ ), 白金—ホスフィ ン錯体 （例えば、 P t (P P h3) 4、 P t (P B u3) 4)、 白金一ホスファイ ト錯体 （例えば、 P t [ P (O P h ) 3] い P t [ P (〇 B u) 3] 4) (式中、 M eはメチル基、 B uはブチル基， V i はビニル基、 P hはフエ二ル基を表わし、 n、 mは整数を表わす。）、 ジカ ルポニルジクロ口白金、 カールシュテト （Karstedt) 触媒、 また、 ァシュ ビ一 （Ashby) の米国特許第 3 1 5 9 6 0 1号及び第 3 1 5 9 6 6 2号明細 書中に記載された白金—炭化水素複合体、 ならびにラモロー （Lamoreaux) の米国特許第 3 2 2 0 9 7 2号明細書中に記載された白金アルコラ一ト触 媒が挙げられる。 さらに、 モディ ック （Modic) の米国特許第 3 5 1 6 9 4 6号明細書中に記載された塩化白金一才レフィ ン複合体も本発明において 有用である。 また， 白金化合物以外の触媒の例としては、 R h C l ( P P h3) 3、 R h C l 3, R h / A i 203< R u C l 3、 I r C l 3、 F e C lい A 1 C 13、 P d C l 2 ' 2 H2〇、 N i C 12, T i C 14等が挙げられる。 こ れらの中では、 触媒活性の点から塩化白金酸、 白金—ォレフィ ン錯体、 白 金一ビニルシロキサン錯体等が好ましい。 また、 これらの触媒は単独で使 用してもよく、 2種以上併用してもよい。 The curing agent of the present invention can be obtained by reacting the above components (a) and (b). Specific examples of 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 t (CH 2 = CH 2 ) 2 (PP h 3 ) 2 , P t (CH 2 = CH 2 ) 2 C I 2 ), a platinum-vinylsiloxane complex (for example, P t (V i Me 2 S i〇 S i Me 2 V i) n , P t [(Me V i S i O) J „), platinum-phosphine complex (for example, P t (PP h 3 ) 4, P t (PB u 3 4 ), a platinum monophosphite complex (for example, Pt [P (OPh) 3 ] 4 ) Pt [P (〇Bu) 3 ] 4 ) (where Me is a methyl group, and Bu is butyl Group, V i is a vinyl group, P h is a phenyl group, n and m are integers.), Dicarponyl dichloroplatinum, Karstedt's catalyst, and US patents of Ashby No. 3 1 5 9 6 0 1 and No. 3 1 5 9 6 6 2 The platinum-hydrocarbon complexes described in the specification, as well as the platinum alcohol catalysts described in Lamoreaux, US Pat. No. 3,220,972, are also included. Also useful in the present invention are the platinum chloride one-year-old refin complexes described in Modic US Patent No. 3,516,446. R h C l (PP h 3 ) 3 , R h C l 3 , R h / A i 20 3 < R u C l 3 , I r C l 3 , F e C l A 1 C 1 . 3, P d C l 2 '2 H 2 〇, 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.
触媒の添加量は特に限定されないが， ヒドロシリル基 1モルに対して、 1 0 -'〜 1 0 _8モルの範囲が好ましく、 より好ましくは、 1 0-2〜 1 0—6 モ ルの範囲である。 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.
上記の触媒と共に助触媒としてホスフィ ン系化合物及びホスフィ ン錯体 を使用することができる。 そのようなホスフィ ン系化合物としては、 トリ フエニルホスフィ ン、 PM e 3、 P E t 3、 P P r 3 (ここで、 P rはプロピ ル基を表す。 以下同様。）， P (n - B u) 3, P ( c y c 1 o - C6Hn) 3, P ( p - CGH4M e ) 3、 P ( o - CBH,M e ) 3等があるがこれらに限定さ れるものではない。 ホスフィ ン錯体としては、 例えば、 C r (C O) 5P P h3 、 C r (C〇） 4 (P P h3) 2 (シス及びトランス異性体）、 C r (C O) 3 ( P P h3) 3 ( f a c及び me r異性体）， これら C r化合物の Mo及び V 類縁体、 F e ( CO) 4P P h3, F e (C O) 3 ( P P h 3) 2、 ならびにこれ ら F e化合物の R u及び〇 s類縁体、 C o C （P P h3)、 R h C 1 (P P h 3) 3、 R h C l (C O) ( P P h3) 3、 I r C l (C O) ( P P h ) 2、 N i C l 2 (P P h) 2、 P d C 12 ( P P h ) P t C l 2 (P P h) 2、 及び C 1 A u ( P P h 3) がある。 さらに、 トリフエニルホスフィ ン以外のホス フィ ンを含有する上記の金属の錯体等のような金属錯体も有効な助触媒と なりうる。 さらに、 P (0 P h ) 3等のようなホスファイ ト、 A s P h3等 のようなアルシン及び S b P h3等のようなスチビンを含有する錯体も有効 な助触媒となりうる。 Phosphinic compounds and phosphine complexes as cocatalysts with the above catalysts Can be used. Such phosphine emission type compounds, tri Fueniruhosufi emissions, PM e 3, PE t 3 , PP r 3 ( where, P r represents a propyl Le group forth..), P (n - B u) 3, P (cyc 1 o - C 6 H n) 3, P (p - C G H 4 M e) 3, P - which (o C B H, M e ) there are 3 such is limited to is not. Examples of the phosphine complex include C r (CO) 5 PP h 3 , C r (C〇) 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. Furthermore, 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.
助触媒の添加量は特に限定されないが、 触媒 1モルに対して、 1 0 〜 The amount of the cocatalyst added is not particularly limited.
102 モルの範囲が好ましく， より好ましくは 1 0 -'〜 1 01 モルの範囲であ る。 Preferably 10 2 mols, more preferably Ru 1 0 -'～ 1 0 1 mols der.
ヒ ドロシリル化反応においては、 溶剤の使用は特に必要とされないが、 始発原料等が固体あるいは高粘度のものであって、 撹拌等の操作に困難を ともなう場合には適宜不活性有機溶剤を使用することは差し支えなく、 こ れにはベンゼン、 トルエン、 キシレン等の芳香族炭化水素系溶剤、 へキサ ン、 オクタン等の脂肪族炭化水素系溶剤、 ェチルエーテル、 プチルェ一テ ル、 テトラヒ ドロフラン等のエーテル系溶剤、 メチルェチルケトン等のケ トン系溶剤、 クロ口ホルム、 塩化メチレン、 トリクロロエチレン等のハロ ゲン化炭化水素系溶剤、 酢酸ェチル等のエステル系溶剤等が例示される。 用いる溶剤の量は， 特に限定されないが、 経済性の点から用いる反応剤の 総量 1 0 0重量部に対して 1 0 0重量部以下が好ましく用いられる。 In the hydrosilylation reaction, the use of 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. These 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. Solvent, methyl ethyl ketone, etc. Examples of the solvent 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.
本発明に使用される （ a)、 ( b ) 両成分及びヒドロシリル化触媒の添加 方法については， 3成分を一括して仕込む方法、 （b〉 成分に （ a) 成分と ヒ ドロシリル化触媒とを添加する方法、 （ a) 成分及びヒ ドロシリル化触媒 に （ b ) 成分を添加する方法、 （ a) 成分を （ b) 成分及び触媒へ添加する 方法、 各成分を同時に添加する方法等が考えられるが、 特に制限はない。  Regarding the method of adding both the components (a) and (b) and the hydrosilylation catalyst used in the present invention, 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.
しかし、 ヒ ドロシリル基が反応後も残存するように反応させるためには、 However, in order for the reaction so that the hydrosilyl group remains after the reaction,
( a ) 成分である多価ハイ ドロジェンシリコン化合物が （ b ) 成分に対し 常に過剰に存在することが望ましいと考えられるので、 （ b) 成分であるァ ルケ二ル基を含有する有機化合物とヒ ド口シリル化触媒を混合したものを、Since it is desirable that the polyvalent hydrogen silicon compound (a) is always present in excess with respect to the component (b), it is desirable to use an organic compound containing a alkenyl group as the component (b). The mixture of the hydrid silylation catalyst is
( a ) 成分である多価ハイ ドロジェンシリコン化合物に添加する方法が好 ましい。 (a) The method of adding to the polyvalent hydrogen silicon compound as the component is preferable.
( a) 成分と （b ) 成分との混合比は， ヒ ドロシリル基とアルケニル基 のモル比でヒ ド口シリル基が過剰になるように設定すればよい。 好ましく は得られる硬化剤の 1分子中に平均で 1 個を超える数のヒ ドロシリル基が 残存するように設定することが、 硬化剤として使用するときの硬化性の点 から好ましい。  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.
また、 本発明の硬化剤は、 （b ) 成分を過剰の （ a) 成分と反応させた後 に、 未反応の （ a ) 成分を蒸留、 吸着、 沈殿、 抽出等により除去する方法 によっても得ることができる。  Further, 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.
反応温度は 0〜 2 0 0 ：、 好ましくは 5 0〜 1 5 0でがよい。 反応温度 が 0でより低いと触媒活性が充分でなく、 そのため反応速度が遅くなる。 また、 1 5 0 より高くなると触媒が失活することが多い。 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.
本発明の硬化剤を （ a ) 成分と （ b ) 成分との反応で得た場合に、 硬化 剤中に未反応のヒ ドロシリル基と場合によっては遷移金属触媒が存在する ために、 保存期間中にヒ ドロシリル基同士あるいはヒ ドロシリル基と系中 の水が徐々に反応することにより粘度の増大やゲル化を起こす可能性があ る。  When 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. In addition, there is a possibility that 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.
これを避けるために、 ヒドロシリル化反応により硬化剤を合成した後に 触媒の失活を目的とした添加剤を添加してもよい。 用いられる添加剤の例 としては、 ジメチルマレート、 ベンゾチアゾール、 2 -ヒ ドロキシ- 2-メチ ル- 1 -ブチン等のアセチレンアルコール類等が挙げられる。 用いる添加剤 の量は特に限定されないが、 貯蔵安定性と硬化剤の硬化性を両立させる点 から反応に用いた触媒 1モルに対して 1〜 102モルの範囲が好ましく、 よ り好ましくは 1〜 3 0モルの範囲である。 To avoid this, an additive for deactivating the catalyst may be added after synthesizing the curing agent by a hydrosilylation reaction. Examples of additives used include acetylene alcohols such as dimethyl malate, benzothiazole, 2-hydroxy-2-methyl-1-butyne and the like. Without limitation 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.
あるいは、 上記の問題を避けるために硬化剤より ヒ ドロシリル化触媒を 除去してもよい。 除去方法としては、 反応溶液をシリカ， シリカゲル， ァ ルミナ、 イオン交換樹脂、 活性炭等と撹拌処理、 カラム処理する方法、 又 は中性ないし弱酸性の水溶液で水洗する方法等が例示される。  Alternatively, the hydrosilylation catalyst may be removed from the curing agent to avoid the above problems. Examples of 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.
第二の硬化剤は， 次の （ i ) 、 ( i i) 及び （ i i i ) 成分 ：  The second curing agent comprises the following components (i), (ii) and (iiii):
( i) 1分子中のゲイ素原子の数が 3〜 1 0個である， 鎖状及びノ又は 環状のオルガノハイ ドロジェンシロキサン  (i) Linear and / or cyclic organohydrogensiloxanes having from 3 to 10 gay atoms in one molecule
( ii) ( i ) 成分のヒ ドロシリル基と反応しうる官能基を 1分子中に 2 偭以上有する化合物、  (ii) a compound having at least 2% of a functional group in one molecule capable of reacting with the hydrosilyl group of the component (i);
( iii) ( i) 成分のヒ ドロシリル基と反応しうる官能基を 1分子中に 1 個含有する有機化合物  (iii) An organic compound containing one functional group per molecule that can react with the hydrosilyl group of the component (i)
を反応することによって得られ、 しかも U) 成分由来のヒ ドロシリル 基が実質上残存した化合物である。 And the hydrosilyl derived from the U) component This is a compound in which the group substantially remains.
上記 （ i) 成分である鎖状又は環状のオルガノハイ ドロジェンシロキ サンの具体的な例としては、 次の一般式 （ 1 6 ) 及び （ 1 7 )  Specific examples of the linear or cyclic organohydrogensiloxane as the component (i) include the following general formulas (16) and (17)
Figure imgf000026_0001
Figure imgf000026_0001
(式 （ 1 6 ) 中， j ≥2、 k≥ 0、 p≥ 1 . 3≤ (j+ k ) X p≤ 8であ り 、 R 2 6は， 水素原子及び炭素数が 1 〜 2 0の 1価の有機基よ り選ば れる基を表し、 1個以上の芳香族置換基を含有していてもよい。 それぞ れの R 2 6は、 同じであっても異なっていてもよい。 〉 (In Equation (16), j ≥ 2, k ≥ 0, p ≥ 1.3 ≤ (j + k) X p ≤ 8, and 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.
Figure imgf000026_0002
Figure imgf000026_0002
(式 （ 1 7 ) 中、 j ≥ 2、 k≥ 0、 q≥ 1 , 3≤ (j+ k ) X q ^ l Oで あり、 R 2 6は、 水素原子及び炭素数が 1 〜 2 0の 1価の有機基よ り選 ばれる基を表し、 1個以上の芳香族置換基を含有していてもよい。 それ ぞれの R 2 6は、 同じであっても異なっていてもよい。 ） (In the formula (17), j ≥ 2, k ≥ 0, q ≥ 1, 3 ≤ (j + k) X q ^ l O, and 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.)
で表されるものが挙げられる。 Are represented.
この鎖状及び環状シロキサン 1分子あたりのヒ ドロシリル基の数は、 2個以上 1 0個以下であることが好ましく、 より好ましく は 2個以上 6 個以下である。 1分子あたりのヒ ドロシリル基が 2個未満であると、 最 終的に得られる発泡体の物理的強度が低下し、 その結果収縮が抑制され にく くなり、 逆に 1 0個を越えると、 収縮のみならず発泡体に亀裂が生 じる場合がある。 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. .
上記 （ ϋ 成分のより具体的な例としては、 ポリ メチルハイ ドロジェ ンシロキサン、 ポリェチルハイ ドロジェンシロキサン， ポリ フエニルハ イ ドロジェンシロキサン等や、 1 , 3 , 5—ト リ メチルシクロ ト リ シ口 キサン、 1， 3 , 5 , 7—テ トラメチルシクロテ トラシロキサン、 1. 3 , 5 , 7 , 9—ペンタメチルシクロペン夕シロキサン、 及びこれらの 混合物等が挙げられる。  More specific examples of the above-mentioned (（component 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.
次に （ii) 成分である、 ) 成分のヒ ドロシリル基と反応しうる官 能基を分子中に 2個以上含有する化合物について述べる。  Next, the compound containing two or more functional groups capable of reacting with the hydrosilyl group of the component (ii) in the molecule will be described.
( i i) 成分の、 ヒ ドロシリル基と反応しうる官能基としては， ビニル 基、 ァリル基、 アク リル基、 メタク リル基等の炭素一炭素二重結合や、 〇H基、 カルボキシル基等を有する化合物が挙げられ、 これらの 2種以 上が 1分子内に存在してもよい。  (ii) 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 〇H group and a carboxyl group. Compounds may be mentioned, and two or more of these may be present in one molecule.
炭素一炭素二重結合は分子内のどこに存在してもよいが、 反応性の点 から側鎖又は末端に存在するのが好ましい。 1分子中におけるヒ ドロシ リル基と反応しうる官能基の数は、 2個以上 4個以下が好ましく 、 2個 以上 3個以下がより好ましい。 1分子中におけるヒ ドロシリル基と反応 しうる官能基の数が 4個を越えると、 ) 成分と （Π) 成分との反応 の際にゲル状になる場合があり好ましくない。  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.
(ii) 成分の骨格については特に制限がなく、 通常の有機単量体骨格 又は有機重合体骨格、 水等の無機化合物が挙げられる。  (ii) 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.
有機単量体骨格としては， 例えば炭化水素系、 芳香族炭化水素系、 フ エノ一ル系、 ビスフエノール系、 エポキシ樹脂モノマー、 イソシアナ一 ト又はこれらの混合物が挙げられる。 有機重合体では、 ポリエーテル系、 ポリエステル系、 ポリカーボネート系、 飽和炭化水素系、 ポリアク リル 酸エステル系、 ポリアミ ド系， ジァリルフタレー ト系、 フエノールーホ ルムアルデヒ ド系 （フエノール樹脂系） 、 ポリウレタン系、 ポリ ウレァ 系、 メラミ ン系重合体、 エポキシ樹脂等の骨格が挙げられる。 Examples of the organic monomer skeleton 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.
( i i) 成分の具体的な例としては、 1 , 9 ーデカジエン等の α， ω - アルカジエン、 ジビニルベンゼン、 ジァリルベンゼン、 1. 4 一ブタン ジオール及びァリルエーテル、 無水フ夕ル酸及びそのァリルエステル、 〇， Ο ' —ジァリリレビスフエノール A、 2 , 2 ' 一ジァリルビスフエノ ール A , エチレンダリ コールあるいはジエチレンダリ コール及びこれら のァリルエーテル、 ァリル末端ポリプロピレンォキシ ド及びポリェチレ ンォキシ ド、 無水フ夕ル酸一エチレンダリ コール重合体あるいは無水フ タル酸—ジエチレングリコール重合体のァリルエステル、 9 —デセン— 1 一オール、 エチレングリコールモノアリルエーテル等が挙げられる。  (ii) Specific examples of the component include α, ω-alkadiene such as 1,9-decadiene, divinylbenzene, diarylbenzene, 1.4-butanediol and aryl ether, furanic anhydride and its aryl ester, 〇, Ο '—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.
( i i) 成分の分子量は特に限定されないが、 1 0 0， 0 0 0程度以下 のものが適宜使用でき、 1 0 , 0 0 0以下のものが好ましい。  Although 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.
次に、 （iii) 成分である、 （i) 成分のヒ ドロシリル基と反応しうる 官能基を分子中に 1個含有する有機化合物について述べる。  Next, an organic compound containing one functional group in the molecule that can react with the hydrosilyl group of the component (i), which is the component (iii), will be described.
(i i i) 成分の、 ヒ ドロシリル基と反応しうる官能基としては、 ビニ ル基、 ァリル基、 アク リル基， メタク リル基等の炭素一炭素二重結合や、 〇 H基、 カルボキシル基等を有する化合物が挙げられる。  (iii) 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 〇H group and a carboxyl group. Compounds.
炭素一炭素二重結合は分子内のどこに存在してもよいが， 反応性の点 から側鎖又は末端に存在するのが好ましい。  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.
( ii i) 成分の骨格としては、 （i i) 成分の骨格と して挙げた有機単 量体及びノ又は有機重合体等が例示される。 ( i i i) 成分の具体的な例としては、 1 一へキセン、 1 ーォクテン、 1 ーデセン等の α—ォレフイ ンや、 1 —プロパノール、 1 一ォク夕ノー ル、 エチレングリコールモノェチルエーテル等のアルコール類、 2 —ェ チルへキサン酸等のカルボン酸類、 アク リル酸ブチル， メタク リル酸メ チル等の （メタ） アク リル類、 スチレン、 4ーメチルスチレン， 2 , 4 —ジメチルスチレン、 α—メチルスチレン、 4—プロモスチレン， 2 — ビニルナフタレン、 ァリルベンゼン、 ァリルァエソール、 ァリルフエ二 ルエーテル， ο—ァリルフエノール、 ρ —イソプロぺニルフエノール等 の芳香族系化合物、 片末端がァリル基， 〇Η基、 （メ夕） アク リル基、 カルボキシル基、 他の末端がヒ ドロシリル基と反応しない有機基で置換 されたポリオキシアルキレン， ポリエステル、 アク リル重合体等が挙げ られる。 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). (iii) Specific examples of the component include α-olefins such as 1-hexene, 1-octene and 1-decene, and 1-propanol, 1-octanol, ethylene glycol monoethyl ether and the like. Alcohols, carboxylic acids such as 2-ethylhexanoic acid, (meth) acrylics such as butyl acrylate, methyl methacrylate, styrene, 4-methylstyrene, 2,4-dimethylstyrene, α-methylstyrene , 4-bromostyrene, 2-vinyl naphthalene, arylbenzene, arylazole, arylphenyl ether, ο-arylphenol, ρ-isopropenylphenol, and other aromatic compounds, one end of which is an aryl group, 〇Η 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.
( i i i) 成分の分子量は特に限定されないが， 1 0 0 , 0 0 0程度以 下のものが適宜使用でき、 1 0 ， 0 0 0以下のものが好ましい。  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.
上記 （ i) 、 ( i i) > ( i ii) 各成分の混合比， すなわち （i) 成分の ヒ ドロシリル基のモル数を X , ( i i) 成分の （ i ) 成分と反応しう る官 能基のモル数を y、 ( i i i) 成分の （ i ) 成分と反応しうる官能基のモル 数を z とした場合の y X及び z / Xの値については特に制限はないが. 0 . 0 l ≤ y / x≤ 0 . 5 、 0 . 0 0 1 ≤ z / x≤ 0 . 8であることが 好ましく 、 0 . l ≤ y / x≤ 0 . 4、 0 . 0 1 ≤ z / ≤ 0 . 4である ことがよ り好ましい。  (I), (ii)> (iii) The mixing ratio of each component, that is, the number of moles of the hydrosilyl group of the component (i) is X, the function of reacting with the component (i) of the component (ii). There are no particular restrictions on the values of yX and z / X when the number of moles of the group is y and the number of moles of the functional group capable of reacting with the component (i) of the component (iii) is z. l ≤ y / x≤0.5, 0.01 ≤z / x≤0.8, preferably 0.l≤y / x≤0.4, 0.01 ≤z / ≤0 More preferably, it is 4.
ノ が 0. 0 1 より小さいと， 相溶性が十分でなく、 逆に 0 . 5 を 越えると U) 成分と （ii) 成分との反応時において高分子量化等に伴 う粘度上昇等が起こるため好ましくない。 また、 2 が 0 . 0 0 1 よ り小さいと系の相溶性が十分でなく、 その結果発泡体のセルが荒れる等 の傾向を示すようになり、 逆に 0. 8を越えると本発明の目的である収 縮を抑制する効果が少なくなる傾向が生じる。 If the ratio is less than 0.01, 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.
なお、 （i) 、 ( i i) , ( i i i) 成分をそれぞれ反応させるには、 上記 したヒ ドロシリル化触媒等を適宜用いることができる.  In order to react the components (i), (ii), and (iiii), respectively, the above-mentioned hydrosilylation catalyst or the like can be appropriately used.
上記 （ i) 成分、 （i i) 成分、 i i) 成分を反応させて得られる化合 物は、 （ i i) 成分が多官能であるため種々の構造を有するものの混合物 となる力 その一つの例としては、 次式で表される化合物を含む混合物 が挙げられる。 なお、 これらの混合物は精製せずにそのまま使用するこ とができる。  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.
Figure imgf000030_0001
Figure imgf000030_0001
(式中、 nは 1 以上 1 0 0以下、 好ましくは 4 0以下の整数を示す。 ） 上記第一及び第二の硬化剤は、 これを発泡性樹脂組成物に用いた場合に、 発泡終了後の収縮が特に少ないという効果が得られる。  (In the formula, n represents an integer of 1 or more and 100 or less, preferably 40 or less.) When the first and second curing agents are used in a foamable resin composition, foaming is completed. The effect that the subsequent shrinkage is particularly small is obtained.
次に第三の硬化剤であるポリォキシアルキレン鎖及び芳香族含有有機基 で変性されたポリオルガノハイ ドロジェンシロキサンについて述べる。 第三の硬化剤は、 次の式 （ 6 ) あるいは式 （ 7 ) で示される構造を有す る化合物である。
Figure imgf000031_0001
Next, a third curing agent, a polyorganohydrogensiloxane modified with a polyoxyalkylene chain and an aromatic-containing organic group, will be described. The third curing agent is a compound having a structure represented by the following formula (6) or (7).
Figure imgf000031_0001
(式 （ 6 ) 中、 m≥2 , n≥0 , 1 , k , q > l、 pは 0〜 5の整数、 1 0≤ (m+ n + l + k) X q≤8 0であり、 Rs , R7 は、 炭素数 0〜 6の 1価の置換基， R8 は、 分子量が 1 0 0〜 1 0， 0 0 0のポリオキシアル キレン鎖を示し、 R9 , Ria は、 水素又は炭素数 1〜 2 0の炭化水素基を 示す。 m個， n個， 1個， k個の R6 . n個， p個の R7 は、 それぞれ同 じものでも異なるものでもよい。 Xは、 構成元素として C, H, N. 〇， S , ハロゲンのみを含む炭素数 0〜 1 0の 2価の置換基を示す。） (In Equation (6), m≥2, n≥0, 1, k, q> l, p is an integer from 0 to 5, 10≤ (m + n + l + k) X q≤80, 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. m pieces, n pieces of a hydrocarbon group with carbon number 1-2 0, 1, k-number of R 6. 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.)
Figure imgf000031_0002
Figure imgf000031_0002
(式 （ 7 ) 中， m≥2、 n≥0 , 1 , k, q≥ l、 pは 0〜 5の整数、 3 ≤ (m+ n + l + k) X Q≤2 0であり、 R6. R7. R8. Xは、 式 （ 6 ) と 同じ。） (In the formula (7), m≥2, n≥0, 1, k, q≥ l, p is 0-5 integer, 3 ≤ (m + n + l + k) XQ≤2 is 0, R 6 R 7 .R 8 .X is the same as equation (6).)
上記式 （ 6〉 又は式 （ 7 ) で示されるポリオルガノハイ ドロジェンシロ キサンを得る方法としては、 末端に二重結合 （例えばァリル基） や〇H基 等のヒ ドロシリル基と反応しうる官能基を有するポリオキシアルキレン化 合物及び芳香環含有有機基と、 ポリオルガノハイ ドロジェンシロキサンと の反応による方法や、 予めポリォキシアルキレン鎖及び芳香環含有有機基 を有する珪素化合物を用いてボリオルガノ八イ ドロジェンシロキサンを合 成する方法や， あるいは上記珪素化合物とポリオルガノシロキサンとの再 分配反応等が利用できる。 As a method for obtaining the polyorganohydrogensiloxane represented by the above formula (6) or (7), a double bond (for example, an aryl group) or a 〇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.
具体的には、 例えば次の式 （ 1 8) 及び式 （ 1 9) ;  Specifically, for example, the following equations (18) and (19);
CI 8)
Figure imgf000032_0001
CI 8)
Figure imgf000032_0001
(式 （ 1 8 ) 中、 m≥2、 n≥ 0 , p≥ l 、 1 0≤ (m+ n) X p≤8 0で あり、 R6. R7 , R9 , R 1 0 は， 上記と同じ。）、 (In the formula (1 8), m≥2, n≥ 0, a p≥ l, 1 0≤ (m + n) X p≤8 0, R 6. R 7, R 9, R 1 0 is the Same as.),
Figure imgf000032_0002
Figure imgf000032_0002
(式 （ 1 9 ) 中、 m≥2 , n≥0、 q≥ 1. 3≤ (m+ n) X q^2 0であ り， R 6 , R7は， 上記と同じ。） (In the formula (1 9), m≥2, n≥0 , q≥ 1. 3≤ (m + n) X q ^ 2 0 der Ri, R 6, R 7 are the same. As above)
で表される鎖状、 環状のポリオルガノハイ ドロジェンシロキサンと， A linear or cyclic polyorganohydrogensiloxane represented by
H2 C = C H C H2 ― [( P O) n — （E〇） m ] 1 —〇H H2 C = CHCH2 - [(P〇） n 一 ( E O) m ] 1 一 OCH3 H2 C = CHCH2 — [( P O) n 一 ( E O) m ] 1 一〇 C2 Hs H: C = CHCH2 - [(P O) n - ( E O) m ] 1 —〇C3 H7 H, C = CHCH2 - [( P O) n 一 ( E O) m ] 1 - O C 4 H9 H2 C = CHCH2 - C(P O) n - (E O) m ] 1 - O P h H 2 C = CHCH 2 ― [(PO) n — (E〇) m] 1 —〇H H 2 C = CHCH 2 -[(P〇) n one (EO) m] 1 one OCH 3 H 2 C = CHCH 2 — [(PO) n one (EO) m] 1 one C 2 H s H: C = CHCH 2 -[(PO) n-(EO) m] 1 —〇C 3 H 7 H, C = CHCH 2 -[(PO) n one (EO) m] 1-OC 4 H 9 H 2 C = CHCH 2 -C (PO) n-(EO) m] 1-OP h
HO - C(P O) n - (E〇） in ] 1 — CH3 HO-C (PO) n-(E〇) in] 1 — CH 3
HO - [(P O) n 一 （E〇） m ] I - C, H5 HO-[(PO) n one (E〇) m] I-C, H 5
HO - C(P O) n 一 （E〇） m ] I - C3 H7 HO-C (PO) n one (E〇) m] I-C 3 H 7
HO- [( P O) n - (E〇） m ] 1 - C4 H9 HO- [(PO) n-(E〇) m] 1-C 4 H 9
HO- [( P O) n 一 （E〇） Di ] 1 一 P h  HO- [(P O) n one (E〇) Di] 1 one P h
(上記各式において、 1≤ (m+ n) x 1≤ 8 0 , m, n≥0 , 1≥ 1 ) 等のポリエーテル系化合物と、 スチレン， 4—メチルスチレン、 2 , 4— メチルスチレン、 α—メチルスチレン、 4ーブロモスチレン、 2—ビニル ナフタレン、 ァリルベンゼン、 ァリルァニソール、 ァリルフエニルエーテ ル、 ο—ァリルフエノール、 ρ—イソプロぺニルマエノ一ル、 フエノール、 〇—ク レゾール、 ベンジルアルコール、 フエネチルアルコール， 安息香酸、 4ーヒ ドロキシ安息香酸等の芳香環含有化合物との反応が挙げられる。 また、 上記式 （ 1 8 ) 及び式 （ 1 9 ) で表される鎖状、 環状のポリオル ガノハイ ドロジェンシロキサンと上記芳香環含有化合物との反応物と、  (In each of the above formulas, a polyether compound such as 1≤ (m + n) x1≤80, m, n≥0, 1≥1) and styrene, 4-methylstyrene, 2,4-methylstyrene, α-Methylstyrene, 4-bromostyrene, 2-vinylnaphthalene, arylbenzene, arylanisole, arylphenylether, ο-arylphenol, ρ-isopropenylmaenoyl, phenol, vinylcresol, benzyl alcohol, phenylethyl alcohol Benzoic acid, 4-hydroxybenzoic acid, and the like. Further, 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,
Rfc R 8 R 6 R fc R 8 R 6
Rs— Si— O--Si— O- -Si— R ,10 (20) R s — Si— O—Si— O- -Si— R, 10 (20)
R 6  R 6
R 6 6  R 6 6
Π R  Π R
(式 （ 2 0 ) 中、 5≤n≤8 0であり、 R6, 8 - R9， R 1。は、 上記と 同じ。） や、
Figure imgf000034_0001
(In the equation (2 0), 5≤n≤80, and R 6 , 8 -R 9 , R 1 are the same as above.)
Figure imgf000034_0001
(式 （ 2 1 ) 中、 3≤n≤ 2 0であり、 R6， R8は、 上記と同じ。） 等との再分配、 平衡化反応等が挙げられる。 (In the formula (21), 3≤n≤20, and R 6 and R 8 are the same as described above.), An equilibrium reaction, and the like.
式 （ 1 8 ) で表されるポリオルガノハイ ドロジェンシロキサンの具体的 な例としては、 ポリメチルハイ ドロジェンシロキサン， ポリェチルハイ ド ロジェンシロキサン、 ポリフエニルハイ ドロジェンシロキサン， メチルハ ィ ドロジェンシロキサン—ジメチルシロキサン共重合体、 メチルハイ ドロ ジェンシロキサン—ジェチルシロキサン共重合体、 メチルハイ ドロジェン シロキサン—メチルフエニルシロキサン共重合体， 及びェチルハイ ドロジ ェンシロキサン—ジメチルシロキサン共重合体等が挙げられる。  Specific examples of the 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.
また、 式 （ 1 9 ) で表されるシクロシロキサンにおけるシロキサン単位 の具体的な例としては、 メチルハイ ドロジェンシロキサン、 ェチルハイ ド ロジェンシロキサン、 フエニルハイ ドロジェンシロキサン、 ジメチルシロ キサン、 ジェチルシロキサン、 メチルフニニルシロキサン等が挙げられ、 これらが共重合して環状体を成したものが用いられる。  Further, specific examples of the 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.
ここで、 式 （ 6 ) 及び式 （ 7 ) に示したポリシロキサンにおいて、 全シ ロキサン単位に対するポリォキシアルキレン基及び芳香環含有有機基が結 合した珪素原子の割合、 すなわち式 （6 ) 及び式 （ 7 ) における  Here, in the polysiloxane represented by the formulas (6) and (7), the ratio of the silicon atom in which the polyoxyalkylene group and the aromatic ring-containing organic group are bonded to all the siloxane units, that is, the formulas (6) and (6) In equation (7)
{( I + k ) / (m+ n + l + k)} 1 0 0 (%) を変性率を呼ぶことにする。  {(I + k) / (m + n + l + k)} 100 (%) is called a denaturation rate.
十分な整泡性を得るためには、 他成分の組成や混合比にもよるが， 上記 変性率は、 一般的には 5〜 9 0 %がよく、 5〜 2 5 %が特に好ましい。 た だし、 変性率には分布が存在するので、 ここで挙げる数値は平均値とする。 変性率が 5 %より低いと炭素一炭素二重結合を有する有機化合物との相溶 性が悪くなり、 整泡性が低下し、 発泡体のセルが微細にならず、 場合によ つては発泡途中に破泡が生じ， 十分な発泡倍率が得られないことがある。 逆に変性率が 9 0 %より高いとヒ ドロシリル基当量が大きくなり、 この化 合物を硬化剤として単独で用いて発泡体を得るためには，多量を必要とし、 発泡倍率の低い発泡体しか得られないので好ましくない。 In order to obtain a sufficient foam controllability, 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. Was However, since the denaturation rate has a distribution, 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.
また、 上記変性率中に占める芳香環含有有機基が結合した割合、 すなわ ち k Z ( 1 + k ) は、 発泡体製造時の混合物の相溶性への悪影響を生じな い範囲で任意に調節することができる。  The ratio of the aromatic ring-containing organic groups bonded to the modification ratio, that is, kZ (1 + k), is arbitrarily set within a range that does not adversely affect the compatibility of the mixture during foam production. Can be adjusted.
ポリォキシアルキレン鎖の構造としては、 ォキシエチレン単位の割合が 多いほうが好ましく， 全ォキシアルキレン単位に対するォキシエチレン単 位の割合は、 数単位で 5 0〜 1 0 0 %のものが好ましい。 ォキシアルキレ ン単位の割合がこれより小さいと十分な整泡性が得られない。  As for the structure of the polyoxyalkylene chain, it is preferable that 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.
ォキシアルキレン鎖の分子量は、 特に限定されないが、 数平均分子量で 1 0 0〜 3 0 0 0が好ましく、 2 0 0〜 1 0 0 0が特に好ましい。 数平均 分子量が 1 0 0より小さいと十分な整泡性が得られず、 逆に 3 0 0 0より 大きいとヒ ドロシリル基の密度が低下するため、 発泡体を製造する上で十 分に硬化させるには多量を用いねばならず、 従って， 発泡倍率の低い発泡 体しか得られないので好ましくない。  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.
上記した第一〜第三の硬化剤は、 1種を単独で用いてもよく、 2種以上 を併用してもよい。  One of the above-mentioned first to third curing agents may be used alone, or two or more thereof may be used in combination.
なお、 本発明の硬化剤におけるヒドロシリル基の個数については、 少な く とも 1分子中に平均して 1個あればよい力 相溶性を損なわない限り多 いほうが好ましい。 本発明の硬化剤を用いてヒ ド口シリル化反応により炭 素一炭素二重結合を有する有機化合物を硬化させる場合、 該ヒ ドロシリル 基の個数が 2個未満であると、 硬化が遅く、 硬化不良を起こす場合が多い。 また、 本発明の硬化剤を発泡性樹脂組成物に適用する場合、 当該硬化剤と 〇H基含有化合物とが脱水素縮合して、 発泡に関与するのであるから、 該 ヒ ドロシリル基の個数は、 目的とする発泡倍率によって決まるが、 一般に 3個以上であることが好ましい。 一方、 当該個数の上限については、 化合 物の入手の容易性や発泡と硬化のバランス等から 8 0以下が好ましく、 5 0以下がより好ましい。 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. Using the curing agent of the present invention, 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. Further, when the curing agent of the present invention is applied to a foamable resin composition, the curing agent and the 〇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. On the other hand, 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.
2 . 硬化性組成物 2. Curable composition
第二の発明に係る硬化性組成物は、  Curable composition according to the second invention,
( A ) 分子内に少なくとも 1個のアルケニル基を含有する有機化合物、 (A) an organic compound containing at least one alkenyl group in the molecule,
( B ) 有機系硬化剤、 (B) an organic curing agent,
( C ) ヒ ドロシリル化触媒  (C) Hydrosilylation catalyst
を必須成分として含有してなるものである。 各成分について以下に述べる。 ( B ) 成分 As an essential component. Each component is described below. (B) component
本発明の （B ) 成分である有機系硬化剤としては、 第一の発明として述 ベた各種の硬化剤を用いることができ、 好ましい分子構造等についても第 一の発明のものが適用できる。  As the organic curing agent which is the component (B) of the present invention, 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.
また、 （B ) 成分である硬化剤としては、 （A ) 成分との相溶性に影響を 与えない範囲で， ヒ ドロシリル基を有する他の硬化剤を併用することもで さる。  Further, as the 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.
( A ) 成分  (A) component
本発明の （A ) 成分である分子中に少なく とも 1個の炭素—炭素二重結 合を含有する有機化合物は、 骨格にシロキサン結合を実質的にもたないも のであればその構造に特に制限はなく、 低分子化合物、 重合体等の各種分 子構造をもつものが用いられる。 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. There is no limitation, various components such as low molecular weight compounds and polymers Those having a child structure are used.
( A ) 成分において、 その分子構造を、 骨格部分と、 その骨格に共有結 合によつて結合している炭素-炭素二重結合を有するアルケニル基とに分 けて考えた場合、 炭素一炭素二重結合を有するアルケニル基は分子内のど こに存在してもよいが、 反応性の点から側鎖又は末端に存在するのが好ま しい。  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.
( A ) 成分を具体的に例示するならば、 低分子化合物としては， ジァリ ルフタレ一ト^のエステル系化合物、 エチレングリコールジァリルエーテ ル等のエーテル系化合物、 2 , 6 -ジァリルフエノール、 2 , 2 ' -ジァリルビ スフエノ一ル A等のフエノール系化合物等が挙げられる。  Specific examples of the component (A) 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.
重合体としては、 各種重合体の末端あるいは主鎖中にアルケニル基を導 入したものが挙げられ、 各種重合体の具体例としては、 ポリオキシェチレ ン、 ポリオキシプロピレン、 ポリオキシテ卜ラメチレン、 ポリオキシェチ レン一ポリオキシプロピレン共重合体等のポリエーテル系重合体、 アジピ ン酸等の 2塩基酸とグリコールとの縮合又はラク トン類の開環重合で得ら れるポリエステル系重合体、 エチレン—プロピレン系共重合体、 ポリイソ ブチレン、 イソブチレンとイソプレン等との共重合体、 ポリクロ口プレン、 ポリイソプレン、 イソプレンとブタジエン、 アクリ ロニトリル、 スチレン 等との共重合体、 ポリブタジエン、 ブタジエンとスチレン、 ァク リ ロニト リル等との共重合体、 ポリイソプレン、 ポリブタジエン、 イソプレンある いはブタジエンとアクリ ロニトリル、 スチレン等との共重合体を水素添加 して得られるポリオレフイ ン系重合体、 ェチルァクリ レート、 プチルァク リ レート等のモノマーをラジカル重合して得られるポリァクリル酸エステ ル、 ェチルァクリ レート， ブチルァク リ レート等のアク リル酸エステルと 酢酸ビニル、 アクリ ロニト リル、 メチルメタク リ レート、 スチレン等との アクリル酸エステル系共重合体， 前記有機重合体中でビニルモノマーを重 合して得られるグラフ ト重合体、 ポリサルファイ ド系重合体、 ε—ァミノ 力プロラクタムの開環重合によるナイロン 6、 へキサメチレンジァミンと アジピン酸の縮重合によるナイロン 6 6、 へキサメチレンジァミンとセバ シン酸の縮重合によるナイロン 6 1 0 、 ε —アミノウンデカン酸の縮重合 によるナイロン 1 1 、 ε —アミノラゥロラクタムの開環重合によるナイ口 ン 1 2、 上記のナイロ のうち 2成分以上の成分を有する共重合ナイロン 等のポリアミ ド系重合体、 例えばビスフエノール Αと塩化カルボニルより 縮重合して製造されたポリカーボネート系重合体、 ジァリルフタレート系 重合体、 ノボラック樹脂、 レゾール樹脂等のフエノール系重合体等が例示 される。 Examples of the polymer include those in which an alkenyl group is introduced into the terminal or main chain of various polymers. Specific examples of the 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 ε-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 ε-aminoundecanoic acid, ε-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.
上記分子構造をもつ化合物のうち、 （B ) 成分の， ヒ ドロシリル基含有有 機系硬化剤の極性の高い化合物との相溶性が良好であるという特長を活か すという点から、 エステル系化合物、 エーテル系化合物、 フエノール系化 合物、 ポリエステル系重合体、 アクリル酸エステル系重合体、 アクリル酸 エステル系共重合体、 ポリエーテル系重合体， ポリカーボネート系重合体， フエノール系重合体が好ましい。  Among the compounds having the above-mentioned molecular structure, 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.
更に、 分子内に少なく とも 1個のフエノール基を含有する化合物である 場合が特に好ましい。  Further, a compound containing at least one phenol group in the molecule is particularly preferred.
より具体的な好ましい搆造としては、 下記一般式 （ 8 ) 〜式 （ 1 0 )  More specifically, preferred constructions include the following general formulas (8) to (10).
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000038_0001
Figure imgf000039_0001
( 1 0 )
Figure imgf000039_0002
( Ten )
Figure imgf000039_0002
(式 （ 8 ) 〜式 （ 1 0 ) において、 R 1 1は、 H又は CH3を示し、 R 12, R 1 3 , R 1 6, R17, R18, R2 Zは、 炭素数 0 ~ 6の 2価の置換基を示し、 R 14, R 15, R 1 S, R 2 °, R 2 1, R23. R24は、 炭素数 0 ~ 6の 1価の置換基を示 し、 X1, X2 は， 炭素数 0〜 1 0の 2価の置換基を示す。 また、 式 （ 8 ) に おいて、 n. mは、 0〜 3 0 0の整数、 I は、 1〜 3 0 0の整数、 ： . qは、 0〜 3の整数を示し、 式 （ 9 ) において、 n, m, 1は、 0〜 3 0 0の整数、 s は， 1〜 3 0 0の整数、 p, q, r は、 0〜 3の整数を示し. 式 （ 1 0 ) に おいて、 n, mは、 0〜 4の整数を示す。） (In the formulas (8) to (10), R 11 represents H or CH 3 , and R 12 , R 13 , R 16 , R 17 , R 18 , and R 2 Z each have 0 carbon atoms. represents a divalent substituent of ~ 6, R 14, R 15 , R 1 S, R 2 °, R 2 1, R 23. 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, and in the formula (8), nm is an integer of 0 to 300, and I is 1 Q represents an integer of 0 to 3, and in the formula (9), n, m, 1 are integers of 0 to 300, and s is an integer of 1 to 300. Integers, p, q, and r represent integers of 0 to 3. In the formula (10), n and m represent integers of 0 to 4.)
のうちのいずれか 1種以上の構造を分子骨格として有するものが挙げられ る。 And those having at least one kind of structure as a molecular skeleton.
( A) 成分の分子内に少なく とも 1個のアルケニル基を含有する有機化 合物の製造方法としては， 種々提案されているものを用いることができる が、 例えば、 水酸基、 アルコキシド基、 カルボキシル基、 エポキシ基等の 官能基を有する前駆体化合物に、 上記官能基に対して反応性を示す活性基 及びアルケニル基を有する有機化合物を反応させることによりアルケニル 基を導入する方法がある。 上記官能基に対して反応性を示す活性基とアルケニル基との両方を有す る有機化合物の例としては、 アクリル酸， メタクリル酸、 ビニル酢酸、 ァ ク リル酸ク口ライ ド、 ァクリル酸プロマイ ド等の C 3 ~ C 20 の不飽和脂肪 酸、 酸ハライ ド、 酸無水物等やビニルアルコール， ァリルアルコール、 3— ブテン— 1一オール、 4一ペンテン— 1一オール、 5—へキセン— 1一オール、 6—ヘプテン一 1—オール、 7—ォクテン一 1—オール、 8—ノネン一 1ーォ一 ル、 9—デセン一 1—オール、 2— （ァリルォキシ） エタノール、 ネオペン チルダリコ一ルモノアリルエーテル、 グリセリ ンジァリルエーテル， トリ メチロールプロパンジァリルエーテル、 トリメチロールエタンジァリリレエ 一テル、 ペン夕エリスリ トールトリアリルエーテル、 1 , 2, 6—へキサント リ オールジァリルエーテル、 ソルビタンジァリルエーテル、 ビニルベンジル アルコール等の不飽和脂肪族アルコール， ァ リ ルク ロ ロホルメー トAs a method for producing 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. There is a method of introducing an alkenyl group by reacting a precursor compound having a functional group such as an epoxy group with an organic compound having an alkenyl group and an active group having reactivity with the functional 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. C3 to C20 unsaturated fatty acids, acid halides, acid anhydrides, etc., vinyl alcohol, aryl alcohol, 3-buten-1-ol, 4-penten-1-ol, 5-hexene — 1-ol, 6-heptene 1-ol, 7-octen 1-ol, 8-nonene 1-ol, 9-decene 1-1-ol, 2- (aryloxy) ethanol, neopentyl diol Allyl ether, glyceryl diaryl ether, trimethylol propane diaryl ether, trimethylol ethane diaryli ether, terpenyl erythritol triallyl ether, 1 , 2,6-hexanthyl diaryl ether, sorbitan diaryl ether, unsaturated aliphatic alcohols such as vinylbenzyl alcohol, aryl chloroformate
( CH2 = CHCH2OCOC l ) , ァリルブロモホルメート （CH2=CHCH20C0B r ) 等の C 3〜 C 20 の不飽和脂肪族アルコール置換炭酸ハライ ド、 ァリルクロライ ド、 ァ リルブロマイ ド、 ビニル （クロロメチル） ベンゼン、 ァリル （クロロメチ ル） ベンゼン、 ァリル （ブロモメチル） ベンゼン、 ァリリレ （クロロメチル） エーテル、 ァリリレ （クロロメ トキシ） ベンゼン、 1—ブテニル （クロロメチ ル） エーテル， 1—へキセニル （クロロメ トキシ） ベンゼン、 ァリルォキシ (CH 2 = CHCH 2 OCOC l ), § Lil bromo formate (CH 2 = CHCH 2 0C0B r ) such C. 3 to C 20 unsaturated aliphatic alcohol-substituted carbonic pay de of Arirukurorai de, § Riruburomai de, vinyl (Chloromethyl) benzene, aryl (chloromethyl) benzene, aryl (bromomethyl) benzene, arylyl (chloromethyl) ether, arylyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy) Benzene, aryloxy
(クロロメチル） ベンゼン， ァリルイソシァネート、 ァリリレグリシジルェ 一テル等が挙げられる。 (Chloromethyl) benzene, aryl isocyanate, aryl glycidyl ether and the like.
また、 重合中にアルケニル基を導入する方法もある。 例えばラジカル重 合法で （A ) 成分の有機重合体を製造する場合に， ァリルメタクリ レート、 ァリルァク リ レート等の分子中にラジカル反応性の低いアルケニル基を有 するビニルモノマー、 ァリルメルカプタン等のラジカル反応性の低いアル ケニル基を有するラジカル連鎖移動剤を用いることにより、 重合体の主鎖 又は末端にアルケニル基を導入することができる。 本発明の組成物を用い てゴム状硬化物を作製する場合には、 （A ) 成分のアルケニル基は分子末端 に存在する方が硬化物の有効網目鎖長が長くなるので好ましい。 There is also a method of introducing an alkenyl group during polymerization. For example, when an organic polymer of the component (A) is produced by a radical polymerization method, 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. By using a radical chain transfer agent having an alkenyl group with low reactivity, the main chain of the polymer can be improved. Alternatively, an alkenyl group can be introduced at the terminal. When a rubber-like cured product is produced using the composition of the present invention, it is preferable that 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.
他に、 エステル交換法を用いてアルケニル基を導入する方法がある。 こ の方法はポリエステル樹脂ゃァク リル樹脂のエステル部分のアルコール残 基をエステル交換触媒を用いてアルケニル基含有アルコール又はアルケニ ル基含有フエノ一ル誘導体とエステル交換する方法である。 アルコール残 基との交換に用いるアルケニル基含有アルコール及びアルケニル基含有フ エノ一ル誘導体は、 ァリルアルコールゃァリルグリコール、 ビスフエノー ル A等の少なく とも 1個のアルケニル基を有し、 少なく とも 1個の O H基 を有するアルコール又はフエノール誘導体であればよい。 触媒は使用して もしなくてもよいが、 使用する場合は、 酸、 チタン系、 アルミニウム系あ るいは錫系の触媒が好ましい。 具体的には， ビスフエノール A等のジァリ ルカ一ポネート、 ビス （メタ） アクリル酸エステル等が挙げられる。  Another method is to introduce an alkenyl group using a transesterification method. In this 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.
また、 本発明の （A ) 成分としては， 上記のように分子内に 1個以上の フエノ一ル性水酸基を含有する化合物が好ましいが、 この化合物を製造す る方法としては、 例えば、 フエノール、 ク レゾール、 キシレノール， レゾ ルシン、 カテコール、 ピロガロール等を用いたノボラック及び/又はレゾ —ル型フエノールや、 ビスフエノール A、 ビスフエノール F、 ビスフエノ —ル S、テトラブロモビスフエノール A等のビスフエノール系化合物類に、 フェノール性水酸基に対して反応性を示す活性基とアルケニル基の両方を 有する有機化合物を反応させることによりアルケニル基を導入する方法が 挙げられる。 具体的な反応としては、 〇， O '—ジァリルビスフエノール A、 2 , 2 '—ジァリルビスフエノール A等のフエノ一ル類と塩化ァリル、 臭化 ァリル等とを塩基触媒存在下で反応させる方法や、 ビスフエノール A等の フエノール類をァリルグリシジルェ一テルゃグリシジルメタクリ レー卜等 とエポキシ化触媒下で反応させる方法、 4, 4 'ーメチレンビス （フエニル イソシァネー卜） やトリ レン一 2， 6ージイソシァネート等のイソシァネー トとァリルアルコール又はァリルァミンとをウレタン化触媒存在下で反応 させる方法が例示される。 また、 必要に応じ、 末端、 主鎖あるいは側鎖に 〇H基、 アルコキシド基、 カルボキシル基、 エポキシ基等の官能基を有す る主鎖骨格を予め合成し、 前述の方法に例示される方法によりアルケニル 基を導入する方法もある。 The component (A) of the present invention is preferably a compound containing one or more phenolic hydroxyl groups in the molecule as described above. Examples of 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. As a specific reaction, phenols such as 〇, 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 A method in which phenols are reacted with allylic glycidyl ether glycidyl methacrylate in the presence of an epoxidation catalyst, and isocyanates such as 4,4′-methylenebis (phenyl isocyanate) and tolylene 1,2,6-diisocyanate. And a method of reacting the compound with aryl alcohol or arylamine in the presence of a urethanation catalyst. Further, if necessary, a main chain skeleton having a functional group such as a 〇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.
他に、 アルケニル基を有する化合物を一部又は全部に用いてフエノール 樹脂骨格を合成する方法がある。 これは， 二重結合を有する芳香族化合物 とフエノール類とを、 例えば、 ホルムアルデヒドゃジイソシアナ一トによ り反応させる方法であり、 具体的には、 ァリルフエノールと他のフエノー ル類とを酸又は塩基存在下， ホルムアルデヒ ド等により， 重縮合させる方 法である。 また、 ビス （メタ） アクリル酸エステルに対し、 ァリルアルコ ール、 ァリルグリコール等がマイケル付加して得られるァリルエーテル系 化合物等も用いることができる。  In addition, there is a method of synthesizing a phenol resin skeleton using a part or all of a compound having an alkenyl group. This 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.
以上のようなアルケニル基と有機化合物との結合様式には特に制限はな く， 炭素一炭素結合で直接結合している場合の他に、 エーテル、 エステル， カーボネー ト、 アミ ド、 ウレタン結合等を介して該アルケニル基が有機化 合物に結合しているもの等が例示される。  There is no particular limitation on the bonding mode between the alkenyl group and the organic compound as described above. In addition to the case where the carbon atom is directly bonded by a carbon-carbon bond, ether, ester, carbonate, amide, urethane bond, etc. And the like, in which the alkenyl group is bonded to the organic compound via the above.
( A) 成分の分子量については、 硬化物の特性及び （B) 成分との相溶 性等の点から i 0 0〜 5 0 0 0 0が好ましく， 1 0 0 ~ 2 0 0 0 0が特に 好ましい。  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.
( A) 成分の有機化合物の炭素—炭素二重結合の数は、 1分子当たりの 平均で 1 . 0個を越えることが好ましく、 特に 2個以上 5個以下であるこ とが好ましい。 （A ) 成分の 1分子内の炭素一炭素二重結合の数が 1個以下 の場合は、 （B ) 成分と反応してもグラフ 卜構造となるのみで架橘構造とな らないためである。 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.
上記 （B ) 成分と （A ) 成分の比率は、 ヒ ド□シリル基のアルケニル基 に対するモル比で 0 . 2〜 5 0が好ましく、 0 . 4 ~ 2 5がより好ましい。 モル比が 0 . 2より小さくなると， 本発明の組成物を硬化した場合に硬化 が不充分でベトツキのある強度の小さい硬化物しか得られず， またモル比 が 5 0より大きくなると硬化後も硬化物中に活性なヒ ドロシリル基が多量 に残存するので、 クラック、 ポイ ドが発生し、 均一で強度のある硬化物が 得られない傾向がある。  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. When the molar ratio is less than 0.2, 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.
( C ) 成分  (C) component
本発明の （C ) 成分であるヒ ドロシリル化触媒については、 特に制限な く任意のものが使用できる。  As the hydrosilylation catalyst as the component (C) of the present invention, any catalyst can be used without particular limitation.
具体的には、 第 1の発明であるヒ ドロシリル基含有有機系硬化剤につい て述べたのと同様の触媒を用いることができる。 これらの触媒は単独で使 用してもよく、 2種以上併用してもよい。 触媒活性の点から塩化白金酸、 白金一才レフイ ン錯体、 白金—ビニルシロキサン錯体等が好ましい。 触媒 量としては特に制限はないが、 （A ) 成分中のアルケニル基 1モルに対して 1 0 -1〜 1 0 _8モルの範囲で用いるのがよい。 好ましくは 1 0—3~ 1 0 _6モ ルの範囲で用いるのがよい。 Specifically, 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. From the viewpoint of catalytic activity, 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.
その他の成分 Other ingredients
硬化物を調製する際には， （A )、 ( B ) 及び （C ) の三成分の他に、 その 使用目的に応じて溶剤、 接着性改良剤、 物性調整剤、 保存安定性改良剤、 可塑剤、 充填剤、 老化防止剤、 紫外線吸収剤、 金属不活性化剤、 オゾン劣 化防止剤， 光安定剤、 アミン系ラジカル連鎖禁止剤、 リ ン系過酸化物分解 剤、 滑剤、 顔料、 発泡剤、 難燃剤等の各種添加剤を適宜添加できる。 When preparing a cured product, in addition to the three components (A), (B) and (C), a solvent, an adhesion improver, a physical property modifier, a storage stability improver, Plasticizers, fillers, antioxidants, UV absorbers, metal deactivators, ozone deteriorating agents, light stabilizers, amine radical chain inhibitors, phosphorus peroxide decomposition Various additives such as agents, lubricants, pigments, foaming agents, and flame retardants can be added as appropriate.
上記充填剤の具体例としては、 たとえば、 ガラス繊維、 炭素繊維、 マイ 力、 グラフアイ ト、 ケイソゥ土、 白土、 ヒュームシリカ、 沈降性シリカ、 無水ケィ酸、 アルミナ、 カーボンブラック、 炭酸カルシウム、 クレー、 夕 ルク、 酸化チタン、 炭酸マグネシウム、 硫酸バリウム， 石英、 アルミニゥ ム微粉末、 フリ ン ト粉末、 亜鉛末， 無機バルーン、 ゴムグラニュー、 木粉、 フエノール樹脂、 メラミ ン樹脂、 塩化ビニル樹脂等が挙げられ.る。  Specific examples of 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. .
上記老化防止剤としては、 一般に用いられている老化防止剤、 たとえば クェン酸やリン酸、 硫黄系老化防止剤等が用いられる。  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.
上記硫黄系老化防止剤としては、 メルカプ夕ン類、 メルカブタンの塩類. スルフィ ドカルボン酸エステル類や、 ヒンダードフエノール系スルフィ ド 類を含むスルフィ ド類、 ポリスルフィ ド類、 ジチォカルボン酸塩類， チォ ウレァ類、 チォホスフェイ ト類、 スルホニゥム化合物、 チオアルデヒ ド類、 チオケトン類、 メルカプタール類、 メルカプト一ル類、 モノチォ酸類， ポ リチォ酸類、 チォアミ ド類、 スルホキシド類等が挙げられる。  Examples of the sulfur-based antioxidants include mercaptans and salts of mercaptan. Sulfidocarboxylic acid esters, sulfides including hindered phenol-based sulfides, polysulfides, dithiocarboxylates, and thioureas. Thiophosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioic acids, polythioic acids, thioamides, sulfoxides and the like.
上記ラジカル禁止剤としては、 たとえば 2 , 2 ' -メチレン—ビス （4 -メチ ル- 6 - 1 -ブチルフエノール）、 テトラキス （メチレン- 3 ( 3, 5 -ジ - t -ブチル -4- ヒ ドロキシフエニル） プロピオネート） メタン等のフエノール系ラジカル 禁止剤や、 フエ二ルー 0—ナフチルァミン、 α —ナフチルァミン、 Ν', Ν ' -第 二ブチル -Ρ-フエ二レンジァミン， フエノチアジン、 Ν, N' -ジフエニル- Ρ-フ ェニレンジァミン等のアミン系ラジカル禁止剤等が挙げられる。  Examples of the radical inhibitor include 2,2'-methylene-bis (4-methyl-6-6-1-butylphenol) and tetrakis (methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl). ) Propionate) Phenyl radical inhibitors such as methane, phenyl, 0-naphthylamine, α-naphthylamine, Ν ', Ν'-secondary butyl- 第 -phenylenediamine, phenothiazine, Ν, N'-diphenyl-Ρ -Amine-based radical inhibitors such as phenylenediamine.
上記紫外線吸収剤としては、 例えば 2 ( 2 ' -ヒドロキシ -3' , 5 ' -ジ-卜プチ ルフエ二ル） ベンゾトリァゾ一ル、 ビス （2, 2, 6, 6-テトラメチル -4-ピペリ ジン） セバケート等が挙げられる。  Examples of the ultraviolet absorber include 2 (2'-hydroxy-3 ', 5'-dibutylphenyl) benzotriazole and bis (2,2,6,6-tetramethyl-4-piperidine). ) Sebacate and the like.
上記接着性改良剤としては、 一般に用いられている接着剤やアミノシラ ン化合物、 エポキシシラン化合物等のシランカップリ ング剤、 その他の化 合物を用いることができる。 このような接着性改良剤の具体例としては、 フエノール樹脂、 エポキシ樹脂、 ァ一ァミノプロビルトリメ トキシシラン、 N- ( /3—アミノエチル） ァミノプロピルメチルジメ トキシシラン、 クマ口 ンーインデン樹脂、 ロジンエステル樹脂， テルペン—フエノール樹脂、 α ーメチルスチレン一ビニルトルエン共重合体、ポリェチルメチルスチレン、 アルキルチタネート類、 芳香族ポリイソシァネート等を挙げることができ る。 Examples of the adhesion improver 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, α-methylstyrene-vinyltoluene copolymers, polymethylmethylstyrene, alkyl titanates, and aromatic polyisocyanates.
上記難燃剤としては、 テトラブロモビスフエノール Α、 テトラブロモビ スフエノ一ル Αエポキシ、 デカブロモジフエ二ルォキサイ ド等のハロゲン 系剤、 トリェチルホスフェート、 トリクレジルホスフェート、 卜リス （ク ロロェチル） ホスフエ一卜， ト リス （クロ口プロピル） ホスフェート、 卜 リス （ジクロ口プロピル） ホスフェート、 ポリ燐酸アンモニゥム、 赤燐等 の燐系難燃剤、 水酸化アルミニウム、 水酸化マグネシウム、 三酸化アンチ モン、 五酸化アンチモン等の無機系難燃剤等があげられる。 これら難燃剤 は、 1種を単独で使用しても， 2種以上を併用してもよい。  Examples of 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.
硬化物の製造 Production of cured product
上記 （A ) 及び （B ) 成分， 好ましくはさらに （C ) 成分、 必要に応じ てさらにその他の添加成分を混合し、 硬化させれば発泡等の現象を伴うこ となく、 深部硬化性に優れた均一な硬化物が得られる。  The above-mentioned components (A) and (B), preferably further the component (C), and if necessary, other additive components are mixed and cured. A uniform cured product is obtained.
硬化物の性状は、 用いる （A ) 及び （B ) 成分の重合体の主鎖骨格や分 子量等に依存するが、 ゴム状のものから樹脂状のものまで製造することが 可能である。  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.
硬化条件については特に制限はない力 一般に 0〜 2 0 0 t:で 1 0秒〜 4時間、 好ましくは 3 0〜 1 5 0 で 1 0秒〜 4時間硬化するのがよい。 特に 8 0〜 1 5 0 t:での高温では 1 0秒〜 1時間程度の短時間で硬化する ものも得られる。 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.
組成物の配合方法については特に限定はないが、 作業性の面から硬化性 組成物の （A )、 ( B ) 成分それぞれを実質的な成分とする 2種以上の組成 物を調製した後、 それらを混合することにより、 硬化させることが望まし い。 触媒である （C ) 成分の添加方法にも特に制限はなく、 作業上容易な 方法を選択すればよく、 （A ) 成分と （B ) 成分のどちらかに混合して用い ても、 また、 （A ) 成分， （B ) 成分の混合と同時に、 又は、 混合終了後に 添加しても良い。  Although there is no particular limitation on 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.
硬化物製造の具体的な方法としては、 本発明の硬化性組成物と触媒、 さ らに必要に応じて添加剤を適当な組み合わせで事前に混合した 2液又はそ れ以上の数の別々の混合物を使用直前に混合し、 押出、 又は注入させる方 法が望ましい。 混合方法としては、 特に限定されないが、 ハンドミキシン グ、 電動ミキサー、 スタティ ックミキサー、 衝突混合等の通常、 ウレタン 樹脂、 エポキシ樹脂、 フエノール樹脂で使用されている方法を用いること ができる。  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.
3 . 発泡性樹脂組成物  3. Foamable resin composition
第三の発明に係る発泡性樹脂組成物は、 第二の発明の硬化性組成物に、 ( D ) 発泡剤及び 又は〇H基を有する化合物をさらに必須成分として含 有してなるものである。  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 〇H group as essential components. .
本発明の発泡性樹脂組成物においては、 （A ) 成分と （B ) 成分とが耐候 性に優れた S i一 C結合を生成するヒ ドロシリル化反応によって付加型の 架橋反応を行うことにより硬化し、 これと同時に前記 （A ) 成分と （B ) 成分との反応熱により発泡剤が気化又は分解し， あるいは （B ) 成分と （D ) 成分とが反応して水素ガスを発生することにより発泡し、 発泡体が形成さ れる。 In the foamable resin composition of the present invention, 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. At the same time, 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.
すなわち、 本発明の発泡性樹脂組成物では、 （A ) 成分として分子骨格中 にシロキサン単位を含まない有機化合物を用いることにより、 前記先行技 術に開示されたごときシリコーンフォームに比べ、 圧縮強度、 塗装性、 接 着性、 汚染性、 埃付着性等が向上したものが得られる。  That is, in the foamable 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.
また、 （B ) 成分を種々に変化させることにより、 硬質から半硬質及び軟 質といった幅広い物性を有するものが得られる。  In addition, 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.
特に， （B ) 成分として特定の構造を有する化合物を用いることにより、 発泡倍率が高く， かつ独立気泡率の高い発泡体を得ることができる。  In particular, by using a compound having a specific structure as the component (B), a foam having a high expansion ratio and a high closed cell rate can be obtained.
本発明の （B ) 成分である有機系硬化剤としては， 第一の発明で説明し た各種の硬化剤を用いることができ、 好ましい分子構造、 他の硬化剤との 併用等についても第一及び第二の発明で述べたものが適用できる。  As the organic curing agent which is the component (B) of the present invention, 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.
本発明の （A ) 成分である分子中に少なく とも 1個の炭素一炭素二重結 合を含有する有機化合物としては特に制限はなく、 第二の発明で説明した とおりの低分子化合物、 重合体等の各種分子構造をもつものを使用するこ とができる。  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.
( A ) 成分の骨格は， （B ) 成分との相溶性が良好であるという特長を活 かすものであることが好ましく， ポリシロキサン一有機ブロックコポリマ —やポリシロキサン—有機グラフ トコポリマーのようなシロキサン単位（ S i - O - S i ) は含まず、 構成元素として炭素、 酸素、 水素、 窒素、 ィォ ゥ、 ハロゲンのうちのいずれか 1種以上のみを含む骨格であるものが好ま しい。 例えば、 ポリエーテル系、 ポリエステル系、 ポリカーボネート系、 飽和炭化水素系、 ポリアクリル酸エステル系， ポリアミ ド系、 フエノール 一ホルムアルデヒ ド系 （フエノール榭脂系） 等の骨格である。 また単量体 骨格としては、 例えばフエノール系、 ビスフエノ一ル系、 又はこれらの混 合物が挙げられる。 It is preferable that 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. Preference is given to those having no siloxane unit (Si-O-Si) and a skeleton containing only one or more of carbon, oxygen, hydrogen, nitrogen, thio, and halogen as constituent elements. For example, a skeleton of a polyether type, a polyester type, a polycarbonate type, a saturated hydrocarbon type, a polyacrylate type, a polyamide type, a phenol monoformaldehyde type (phenol-fat type) and the like. The monomer skeleton may be, for example, a phenol-based, bisphenol-based, or a mixture thereof. Compounds.
これらのうち、 ポリエーテル系重合体骨格は， 軟質の発泡体を得るため に好適に使用される。 その例としては、 ポリオキシエチレン、 ポリオキシ プロピレン， ポリオキシテ トラメチレン、 ポリオキシエチレン一ポリオキ シプロピレン共重合体等が挙げられる  Among these, the polyether-based polymer skeleton is suitably used for obtaining a soft foam. Examples thereof include polyoxyethylene, polyoxypropylene, polyoxytetramethylene, and polyoxyethylene-polyoxypropylene copolymer.
—方、 ポリシロキサン骨格に比べて T gが高い、 その他の重合体骨格も 発泡体を得るために好適に使用される。  On the other hand, other polymer skeletons having a higher Tg than the polysiloxane skeleton are also suitably used for obtaining a foam.
また、 （A) 成分の有機化合物は、 他の成分との均一な混合が可能で、 ス プレー、 注入等により発泡体が得られるように， 1 0 0 以下の温度にお いて流動性があることが好ましい。 その構造は線状でも枝分かれ状でもよ く， 分子量は特に限定されないが， 1 0 0 ~ 1 0 0, 0 0 0程度の任意のも のが好適に使用でき、 有機重合体であれば， 5 0 0〜 2 0 , 0 0 0のものが 特に好ましい。 分子量が 5 0 0未満では可とう性の付与等の有機重合体の 利用による特徴が発現し難く、 分子量が 1 0 0, 00 0を越えるとァルケ二 ル基とヒ ドロシリル基との反応による架橋の効果が発現し難い傾向がある。  In addition, 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. Is preferred. 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.
(D) 成分  (D) Ingredient
次に （D) 成分の発泡剤及び 0 H基を有する化合物について述べる。 発 泡剤と〇H基を有する化合物については、 それぞれ単独で用いても併用し ても良い。  Next, 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 〇H group may be used alone or in combination.
発泡剤の種類に特に制限はなく、 例えば、 通常、 ポリウレタン， フエノ —ル、 ポリスチレン、 ポリオレフイ ン等の有機発泡体に用いられるものか ら選択して用いることが可能である。 安定した発泡体を製造するには、 揮 発性化合物を発泡剤として予め組成物に添加し、 発熱や減圧により発泡さ せる方法が好ましい。  The type of the foaming agent is not particularly limited. For example, it can be used by selecting from those usually used for organic foams such as polyurethane, phenol, polystyrene, and polyolefin. In order to produce a stable foam, 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.
発泡剤が揮発性化合物の場合には、その沸点は 1 0 0で以下が好ましく、 8 0 °C以下がより好ましく、 5 0 以下が特に好ましい。 使用する装置や 取り扱いの容易さ等を考えると、 沸点が— 3 0 から 3 5 程度のものが 好ましい。 When the 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.
また、 発泡剤の （A ) 成分に対する溶解度は、 2 3 X:において （A ) 成分 1 0 0重量部に対し 5重量部以上が好ましく 、 1 0重量部以上がよ り好ましく 、 1 5重量部以上がさらに好ましい。 溶解度が 5重量部より 少ないと、 発泡体のセルが荒れるので好ましくなく、 また、 所望の髙倍 率の発泡体が得られにく い。  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.
発泡剤の （A ) 成分に対する溶解度は、 例えば次の方法によ り求めら れる。 すなわち発泡剤の沸点が 2 3で以上であれば、 （ A ) 成分の重量 と、 発泡剤を溶解させた後の重量を測定し、 その差を求めればよく 、 ま た、 発泡剤の沸点が 2 3。C未満である等の垤由で上記方法により測定が 困難な場合には、 体積既知の耐圧容器に （A ) 成分と発泡剤を秤量した のち、 耐圧容器の空隙部の体積と圧力から、 溶解していない発泡剤の量 を求め、 これに基づいて溶解度を求めることができる。  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.
発泡剤の種類は特に限定されないが、 作業性と安全性との面から、 炭化 水素、 ケ トン系化合物、 フロン、 エーテル等の有機化合物、 二酸化炭素、 窒素、 空気等から選ばれる化合物を単独あるいは 2種以上併用して用いる ことが好ましい。  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.
炭化水素としては、 メタン、 ェタン、 プロパン、 n —ブタン， イソブタ ン、 n —ペンタン、 イソペンタン、 ネオペンタン、 n —へキサン、 2 —メ チルペンタン、 3 —メチルペンタン、 2 , 2—ジメチルブタン、 2 , 3 —ジ メチルブタン、 シクロペンタン、 シクロブタン、 シクロペンタン、 シクロ へキサン等が挙げられる。 これらのうち、 取り扱いの容易さ等からプロパ ン、 n —ブタン、 イソブタン、 n —ペンタン、 シクロペンタンが好ましい。 ケ トン系化合物の例としては、 アセ トン， メチルェチルケ トン、 メチ ルイソプロピルケトン等が挙げられる。 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. Of these, 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.
フロン類としては、 トリクロ口フルォロメタン （R 1 1 )、 ジクロロジフ ルォロメタン （R 1 2 ), クロ口 トリフルォロメタン （R 1 3 ), ブロモト リフルォロメタン （R 1 3 B 1 ), テトラフルォロメ夕ン （R 1 4), ジク ロロフルォロメタン （R 2 1 )、 クロロジフルォロメ夕ン （R 2 2 )、 トリ フルォロメタン （R 2 3 )、 ジフルォロメタン （R 3 2 )、 フルォロメタン ( R 4 1 ) , テトラクロロジフルォロェ夕ン （R 1 1 2 )、 トリクロ口 トリ フルォロェ夕ン （R l 1 3 )、 ジクロロテトラフルォロェタン （R 1 1 4)、 ジブロモテトラフルォロェタン （R 1 1 4 B 2 ), クロ口ベン夕フルォロェ タン （R 1 1 5 ), へキサフルォロェタン （R 1 1 6 )、 クロ口 トリフルォ ロェタン （R 1 2 3 ), テトラフルォロェタン （R 1 3 4 a)、 ジクロロフ ルォロェタン （R 1 4 1 b)、 クロロジフルォロェタン （R 1 4 2 b) ジフ ルォロェタン （R 1 5 2 a)、 ォク夕フルォロプロパン （R 2 1 8 )、 ジク ロロペン夕フルォロプロパン （R 2 2 5 )、 へキサフルォロプロパン （R 2 3 6 e a)、 ペン夕フルォロプロパン （R 2 4 5 f a；)、 ォク夕フルォロシ クロブタン （R C 3 1 8〉、 へキサフルォロブタン （R 3 5 6 m f f m)、 ペン夕フルォロブタン （R 3 6 5m i c ), デカフルォロペンタン （R 4 3 1 0 m e e ) 等が挙げられる。  Examples of chlorofluorocarbons include trifluoromethane (R11), dichlorodifluoromethane (R12), trifluoromethane (R13), bromotrifluoromethane (R13B1), and tetrafluoromethane (R14). ), Dichloromethane (R 21), chlorodifluoromethane (R 22), trifluoromethane (R 23), difluoromethane (R 32), fluoromethane (R 41), tetrachlorodifluor Ororoe (R1 12), Triclo mouth Trifluore (Rl 13), Dichlorotetrafluoroe (R114), Dibromotetrafluore (R114B2) ), Black-mouthed benzofuroroethane (R1 15), hexafluorene (R1 16), black-mouthed trifluorene (R123), tetrafluorene (R134a) ), Dichlorofluoroethane (R141b), chlorodiflu Orolotan (R14 2b) Gifololotan (R152a), Okurofluoropropane (R218), Dichloropenafluoropropane (R225), Hexafluoropropane (R23) 6 ea), Penyu Fluoropropane (R2 45 fa;), Okyu Fluorosiclobutane (RC 3 18>), Hexafluorobutane (R 356 mffm), Penyu Fluorobutane (R 365 5m) ic), decafluoropentane (R 4 310 mee) and the like.
環境問題等を考慮すると、 クロ口フルォロカ一ボン （C F C) よりは、 ハイ ド口クロ口フルォロカーボン （HC F C)、 いわゆる代替フロンが好ま しく、 更にハイ ド口フルォロカーボン （HF C) を使用するのが特に好ま しい。 すなわち、 テトラフルォロェタン、 ジフルォロェタン、 ォク夕フル ォロプロパン、 へキサフルォロプロパン、 ペン夕フルォロプロパン、 ォク 夕フルォロシクロブタン、 へキサフルォロブタン、 ペン夕フルォロブタン が特に優れている。 Considering environmental issues, it is preferable to use chlorofluorocarbon (HCFC), a so-called alternative fluorocarbon, rather than chlorofluorocarbon (CFC), and to use fluorocarbon (HFC). Especially preferred. That is, tetrafluoroethane, difluoroethane, okofuropropane, hexafluoropropane, pentafluoropropane, okofurocyclobutane, hexafluorobutane, pentafluorobutane Is particularly excellent.
エーテル類としては、 ジメチルエーテル、 ジェチルエーテル、 ェチルメ チルエーテル、 ジプロピルエーテル， ジイソプロピルエーテル、 プチルメ チルエーテル、 ブチルェチルエーテル、 t e r t—ブチルメチルエーテル， t e r t ーブチルェチルェ一テル、 1. 1ージメチルプロピルメチルエーテ ル、 メチルペン夕フルォロェチルエーテル、 2, 2, 2— トリフルォロェチ ルエーテル、 メチル （トリフルォロメチル） テトラフルォロェチルエーテ ル等が挙げられる。  Examples of 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.
上記の中でも好適に用いられる発泡剤としては、 （A) 成分の構造等 にもよる力^ 炭化水素類やフロン類等が挙げられ、 これらの中でも （ A ) 成分 1 0 0重量部に対する 2 3 °Cにおける溶解度が 5重量部以上である 炭素数 2又は 3のハイ ド口フルォロカーボン （H F C) 、 炭素数 1から 3のハイ ド口クロ口フルォロカーボン （HC F C) 、 炭素数 3〜 6の炭 化水素、 炭素数 3 ~ 5のケトン系化合物、 及び炭素数 2〜 6のエーテル 類のうちから選ばれるいずれか 1種以上が特に好適に用いられる。 環境 問題等の点からは、 炭化水素、 ハイ ド口クロ口フルォロカ一ボン （H C F C ) 、 ハイ ド口フルォロカーボン （H F C) が好ましい。  Among the above, 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. Soluble at 5 ° C of 5 parts by weight or more Fluorocarbon (HFC) with 2 or 3 carbon atoms, Fluorocarbon with 1 to 3 carbon atoms (HCFC), 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. From the viewpoint of environmental problems, hydrocarbons, fluorinated carbon fluoride (HFCFC) and fluorinated carbon (HFC) are preferred.
また、 他の発泡方法として、 例えば N a HC〇3, (NH4 ) 2C〇3、 NH4 H C〇3、 NH2N〇2、 C a (N3 ) 2、 N a B H4等の無機系発泡剤、 ァゾジ カルボンアミ ド、 ァゾビスイソプチロニトリル、 バリウムァゾジカルボキ シレー ト、 ジニトロソペンタメチレンテトラミン， パラ トルエンスルホニ ルヒ ドラジッ ド等の有機系発泡剤、 ィソシァネートと活性水素基含有化合 物との反応による二酸化炭素の発生、 機械的な攪拌等等を併用することも 可能である。 Further, as other blowing method, for example, N a HC_〇 3, (NH 4) 2 C_〇 3, NH 4 HC_〇 3, NH 2 N_〇 2, C a (N 3) 2, N a BH 4 , etc. 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.
次に、 OH基を有する化合物について述べる。 本発明で用いる〇 H基を有する化合物の種類は特に限定されないが、 従 来のシリ コーンフォームで多く用いられている O H基含有 （ポリ） シロキ サンではなく、 他の成分との相溶性が良好であり、 シロキサン結合を分子 骨格中に含まないものが好ましい。 具体的には、 〇H基が炭素原子と直接 結合している有機化合物及び水のいずれか一方又は両方を用いるのが好ま しく、 これにより炭素一炭素二重結合を有する有機化合物を使用する効果 がより顕著になる。 〇H基が炭素原子と直接結合している化合物とは、 ァ ルコール類、 カルボン酸類等である。 Next, compounds having an OH group will be described. 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 〇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.
アルコール類としては、 メタノール， エタノール、 n—プロパノール、 i s o—プロパノール， n—ブ夕ノール. i s o—ブ夕ノール、 t e r t —ブ夕ノール、 エチレングリコールモノメチルエーテル、 エチレングリコ —ルモノェチルエーテル， エチレングリコールモノプロピルエーテル， ェ チレングリコールモノブチルエーテル、 ジエチレングリコールモノメチル エーテル、 エチレングリコールモノフエニルエーテル， エチレングリコー ルモノアリルエーテル、 グリセリンジァリルエーテル等の 1価のアルコ一 ル、 エチレングリコール、 プロピレングリコール、 1 , 4ーブチレングリコ ール、 1 , 3—ブチレングリコ一ル、 2 , 3 —ブチレングリコール， ジェチ レングリコール、 トリエチレングリコール、 ネオペンチルグリコール、 1 . 6—へキサメチレングリコール， 1 , 9—ノナメチレングリコ一ル、 グリセ リ ン、 トリ メチロールプロパン、 ペンタエリスリ トール、 ソルビトール' スクロース、 グリセリンモノアリルエーテル等の多価アルコール、 ポリブ ロピレングリコール， ボリエチレングリコ一ル及びこれらの共重合体、 ポ リテ卜ラメチレングリコール等のポリエーテルポリオール（ソルビトール、 スクロース、 テトラエチレンジァミン、 エチレンジァミン等を開始剤とし た一分子内に〇H基を 3個以上含むものも含む）、アジペート系ポリオール、 ポリ力プロラク トン系ポリオール、 ポリカーボネート系ポリオール等のポ リエステルポリオール、 エポキシ変性ポリオール， ポリエーテルエステル ポリオール、 ベンジリ ックエーテル型フエノールポリオ一ル等のフエノー ル系ポリオール， ルミフロン （旭硝子社製） 等のフッ素ポリオール、 ポリ ブタジエンポリオール， 水添ポリブタジエンポリオ一ル、 ひまし油系ポリ オール、 ハロゲン含有難燃性ポリオ一ル， リン含有難燃性ポリオール、 フ ェノール、 クレゾール、 キシレノール、 レゾルシン、 カテコール、 ピロガ ロール， ビスフエノール A、 ビスフエノール B、 ビスフエノール S、 フエ ノール樹脂等のフェノール性水酸基を有する化合物， 2 —ヒ ドロキシェチ ル （メタ） ァク リ レート、 2—ヒ ドロキシプロピル （メタ） ァク リ レート、 2—ヒ ドロキシェチルビニルエーテル、 N—メチロール （メタ） アク リル アミ ド、 東亜合成化学工業 （株） 製のァロニクス 5 7 0 0 、 4ーヒ ドロキ シスチレン、 日本触媒化学工業 （株） 製の H E— 1 0 、 H E— 2 0 、 H P 一 1 0及び H P — 2 0 (いずれも末端に〇H基を有するァクリル酸エステ ルオリゴマー）、 日本油脂 （株） 製のブレンマ一 P Pシリーズ （ポリプロピ レングリコールメタクリ レート）、 ブレンマー P Eシリーズ （ポリエチレン グリコールモノメタクリ レート）、 ブレンマ一 P E Pシリーズ （ポリエチレ ングリコールポリプロピレンダリコールメ夕クリ レート）、 ブレンマー A PAlcohols 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, sorbitol 'sucrose, glycerin monoallyl ether, polypropylene glycol, polyethylene glycol and the like. Polyether polyols such as copolymers and polytetramethylene glycol (including those containing three or more 〇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.). Polybutadiene polyol, hydrogenated polybutadiene polyol, castor oil-based polyol, halogen-containing flame-retardant polyol, phosphorus-containing flame-retardant polyol, phenol, cresol, xylenol, resorcin, catechol, pyrogallol, bisphenol A, Compounds having a phenolic hydroxyl group, such as bisphenol B, bisphenol S, and phenol resin, 2-hydroxyhydroxy (meth) acrylate, 2-hydroxypropyl ( A) Acrylate, 2-hydroxyhexyl vinyl ether, N-methylol (meth) acrylyl amide, Aronix 570, 4-hydroxystyrene, manufactured by Toa Gosei Chemical Industry Co., Ltd. HE-10, HE-20, HP110 and HP-20 (all acrylate acrylate oligomers having terminal 〇H groups) manufactured by Kogyo Co., Ltd., Bremen manufactured by NOF Corporation PP series (polypropylene glycol methacrylate), Blemmer PE series (polyethylene glycol monomethacrylate), Blemmer PEP series (polyethylene glycol polypropylene acrylate copolymer), Blemmer AP
- 4 0 0 (ポリプロピレングリコールモノアクリ レー卜）、 ブレンマー A E-400 (polypropylene glycol monoacrylate), Blemmer A E
- 3 5 0 (ポリエチレングリコールモノアクリレート〉、 ブレンマ一 NKH - 5 0 5 0 (ポリプロピレングリコールポリ トリメチレンモノアクリ レー ト） 及びブレンマー G LM (グリセロールモノメタクリレート）、 OH基含 有ビニル系化合物と ε —カブロラク トンとの反応により得られる ε —カブ 口ラク トン変性ヒ ドロキシアルキルビニル系モノマー等の〇Η基含有ビニ ル系モノマー （これらは （Α) 成分と （D) 成分の兼用物質としても利用 できる）、 前記〇H基含有ビニル系モノマーとアクリル酸、 メ夕クリル酸、 それらの誘導体等との共重合により得ることができる〇H基を有するァク リル樹脂、 その他アルキド樹脂、 エポキシ樹脂等の O H基を有する樹脂が 挙げられる。 -350 (polyethylene glycol monoacrylate), Blemmer-NKH-550 (polypropylene glycol polytrimethylene monoacrylate) and Blemmer GLM (glycerol monomethacrylate), OH-containing vinyl compounds and ε 〇Η-containing vinyl-based monomers such as ε-cubic lactone-modified hydroxyalkylvinyl monomers obtained by reaction with cabrolactone (these are also used as a dual-purpose substance of component (Α) and component (D)) ), An acrylic resin having a 〇H group, other alkyd resin, epoxy resin, etc., which can be obtained by copolymerization of the 〇H group-containing vinyl monomer with acrylic acid, methacrylic acid, a derivative thereof and the like. And a resin having the following OH group.
これらの O H基含有化合物の中でも、 硬化反応時の発熱による蒸発 · 気 化等によって気泡の合一、 肥大化、 破泡等の悪影響を及ばさないことから、 炭素数 3以上のアルコールが望ましく、 具体的には、 n—プロパノール、 i s o —プロパノーリレ， n —ブタノール、 i s o —ブ夕ノール、 t e r t ーブ夕ノール、 エチレングリコールモノメチルエーテル、 エチレングリコ ールモノェチルエーテル、 エチレングリコールモノプロピルエーテル、 ェ チレンダリ コールモノブチルエーテル、 ジエチレングリコールモノメチル エーテル等が好ましい。 さらにヒドロシリル基との反応の容易さや脱水素 縮合が進行しても架橋が起こらないこと，及び取扱いの際の臭気の面から， n —プロパノール、 n —ブ夕ノール、 エチレングリコールモノメチルエー テル、 ジエチレングリコールモノメチルエーテル、 エチレングリコールモ ノフエニルエーテル等の 1級アルコールが特に好ましい。  Among these OH group-containing compounds, 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. Specifically, n-propanol, iso-propanolyl, n-butanol, iso-butanol, tert-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol Preferred are coal monobutyl ether, diethylene glycol monomethyl ether and the like. Furthermore, 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.
—方、 カルボン酸類としては、 酢酸、 プロピオン酸、 n —酪酸、 イソ酪 酸、 n—吉草酸、 へキサン酸、 2—ェチルへキサン酸、 マロン酸、 こはく 酸、 アジピン酸、 m e s o— 1 , 2 , 3 , 4 —テトラカルボン酸、 安息香酸、 フ夕ル酸、 イソフタル酸、 テレフタル酸等が挙げられる。 この中でも、 ヒ ド口シリル基との反応の容易さや脱水素縮合が進行しても架橋が起こらな いことから 1価のカルボン酸が好ましく、 さらに取扱時の臭気の面から 2 ーェチルへキサン酸が特に好ましい。  —On the other hand, 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. Of these, 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.
水酸基当量が大きくなると添加する O H基含有化合物の体積が大きくな り、 発泡倍率が上がらなくなるため、 水酸基当量が 1 〜 3 3 m m o 1 / の化合物が好ましく、 反応性の点から 2. 5 ~ 2 5 mm o 】 Zgのものが より好ましい。 When 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.
また発泡速度の調整のために 2種類以上の〇H化合物を併用することも 可能である。 併用する例としては、 n—プロパノール等の 1級アルコール と i s o—プロパノール等の 2級アルコール、 カルボン酸と 1級アルコ一 ル、 あるいはカルボン酸と水との組み合わせが好ましい。 さらに硬化時間 の調整のためにエチレングリコール、 プロピレングリコール、 1 , 4ーブ夕 ンジオール、 グリセリン等の 2価以上の多価〇H化合物やエチレングリコ ールモノアリルエーテル， グリセリ ンモノアリルエーテル、 グリセリ ンジ ァリルエーテル、 ペン夕エリスリ トールジァリルエーテル、 ペン夕エリス リ トールトリァリルェ一テル、 ゥンデシレン酸等の分子内にヒ ドロシリル 化可能な炭素一炭素二重結合と〇H基との両方を合わせ持つ化合物を使用 することもできる。  It is also possible to use two or more ΔH 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. In addition, to adjust the curing time, divalent or higher polyvalent 〇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 〇H group in the molecule of phenyl ether, erythritol diaryl ether, erythritol triaryl ether, pendecylenic acid, etc. Compounds can also be used.
なお、 1分子内に 2個以上の〇H基を有する （D) 成分を用いた場合は. (B) 成分と （D) 成分との反応で水素ガスを発生するとともに架橋構造 を作るため、 硬化時間の調整のために少量を補助的に使用することは可能 である力 多量に用いるのは十分な発泡を行う前に硬化してしまうために 望ましくない。 また、 1分子内に炭素一炭素二重結合と OH基とを有する 化合物を （A) 成分と （D) 成分の兼用物質として用いることもできる。 上記 （A)、 （B)、 (D) の 3成分の配合割合は、 各成分の構造、 目的と する発泡倍率、 目的とする物性により適宜選択されるものであって特に限 定はされないが、 （B) 成分のヒドロシリル基のモル数 Xと、 （A) 成分の 炭素一炭素二重結合のモル数 y及び （D) 成分の〇H基のモル数 zの和と の比率が、 x : y + z = 3 0 ： 1〜 1 ： 3 0であることが好ましい。 さら に好ましくは、 X ： y + z = 1 0 ： 1〜 1 ： 1 0である。 ヒ ドロシリル基 のモル比が x ： y + z = 3 0 ： 1 を越えると架橋密度が低くなり、 十分な 機械的強度が得られず、 X ： y + z = 1 ： 3 0未満であると十分な発泡、 硬化が起こらない。 When component (D), which has two or more ΔH groups in one molecule, is used. 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. The ratio of the number of moles X of the hydrosilyl group of the component (B) to the sum of the number of moles y of the carbon-carbon double bond of the component (A) and the number of moles z of the 〇H group of the component (D) is x : y + z = 30: 1 to 1: 30 is preferable. More preferably, X: y + z = 1: 0: 1 to 1:10. Hydrosilyl group When the molar ratio of x: y + z = 30: 1 exceeds, the crosslinking density becomes low and sufficient mechanical strength cannot be obtained. When X: y + z = 1: 30 or less, sufficient foaming occurs. No curing occurs.
また、 （A ) 成分の炭素一炭素二重結合のモル数 yと （D ) 成分の〇H基 のモル数 z との比率には特に限定はなく， 目的とする発泡倍率、 目的とす る物性、 （ B ) 成分の骨格、 （D ) 成分の種類等により， 適宜選定すること ができるが、 一般的には y : z = 1 0 0 ： ：!〜 1 ： 1 0 0が好ましく、 y ： z = 1 0 ： 1 〜 1 ： 2 0がより好ましい。  The ratio of the number of moles y of the carbon-carbon double bond of the component (A) to the number of moles z of the 〇H group of the component (D) is not particularly limited. It can be appropriately selected according to the physical properties, the skeleton of the component (B), the type of the component (D), and the like. Generally, y: z = 1100::! To 1: 100 is preferable, and y: z : Z = 1 0: 1 to 1: 20 is more preferable.
なお、 本発明では、 前記 （B ) 成分と （D ) 成分との脱水素縮合、 及び ( A ) 成分と （B ) 成分との付加反応 （ヒ ドロシリル化反応） のための触 媒を適宜用いることができる。  In the present invention, 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.
ヒ ドロシリル化触媒及び助触媒の種類， 使用量等は、 第一及び第二の発 明に関し述べたものが本発明にも適用できる。  The types and amounts of the hydrosilylation catalyst and cocatalyst described in the first and second inventions can be applied to the present invention.
その他の成分 Other ingredients
本発明の発泡性樹脂組成物には、 さらに充填剤、 老化防止剤、 ラジカル 禁止剤、 紫外線吸収剤、 接着性改良剤、 難燃剤、 ボリジメチルシロキサン ーポリアルキレンォキシド系界面活性剤あるいは有機界面活性剤 （ポリェ チレングリコールアルキルフエニルエーテル等） 等の整泡剤、 酸あるいは 塩基性化合物 （ヒ ドロシリル基と〇H基との反応調整のための添加剤であ り、 酸で縮合反応を抑制し、 塩基で加速する。）、 保存安定改良剤、 オゾン 劣化防止剤、 光安定剤、 増粘剤、 可塑剤、 カップリ ング剤、 酸化防止剤、 熱安定剤、 導電性付与剤、 帯電防止剤、 放射線遮断剤、 核剤、 リン系過酸 化物分解剤、 滑剤、 顔料、 金属不活性化剤、 物性調整剤等を本発明の目的 及び効果を損なわない範囲において添加することができる。  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 〇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.
上記充填剤、 老化防止剤、 ラジカル禁止剤、 紫外線吸収剤、 接着性改良 剤、 難燃剤の例は、 第二の発明で説明したとおりである。 The above fillers, anti-aging agents, radical inhibitors, UV absorbers, improved adhesion Examples of the agent and the flame retardant are as described in the second invention.
発泡体の製造 Manufacture of foam
上記した本発明の発泡性樹脂組成物に、 必要に応じて触媒その他の添加 剤を混合し、 発泡硬化させることにより発泡体が製造される。  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.
発泡硬化させる温度は、 1 0 0 t:以下が好ましく、 現場発泡への適用を 考えると常温に近いのがより好ましい。 1 0 0 t:を越える高温では， （A ) 成分と （B ) 成分との付加型の架橋（硬化）反応速度が大きくなりすぎ、 （B ) 成分と （D ) 成分との反応で発生する水素ガスによる発泡とのバランスが とり難い。  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. At 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.
また、 本発明に係る発泡体の製造は、 本発明の発泡性樹脂組成物と触媒、 さらに必要に応じて添加剤を適当に組み合わせて事前に混合した 2液又は それ以上の数の別々の混合物を使用直前に混合し，基材表面に直接塗布し、 現場発泡させる方法や， 同様の混合物を使用直前に混合し、 注入発泡させ る方法により行うことができる。 混合方法としてはハンドミキシング、 電 動ミキサー、 スタティ ックミキサー、 衝突混合等の方法を用いることがで きる。 特に現場発泡させる場合にはスタティ ックミキサー又は衝突混合を 用いることが好ましい。  Further, 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. As a mixing method, a method such as hand mixing, an electric mixer, a static mixer, or collision mixing can be used. In particular, in the case of foaming in situ, it is preferable to use a static mixer or collision mixing.
本発明の発泡性樹脂組成物と触媒とを、 さらに必要に応じて添加剤を事 前に混合した 2液又はそれ以上の数の別々の混合物とする場合の組み合わ せ方としては次のようなものが挙げられるが、 すべての成分を混合する前 に水素の発生や硬化が進行しない組み合わせであればよく、 これらには限 定されない。 すなわち、  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. However, 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,
( 1 ) ( B ) 成分の一部及び （A ) 成分の混合物と、 （B ) 成分の一部， （D ) 成分及び （C ) 成分との混合物との 2液とする、  (1) a mixture of a part of the component (B) and the component (A) and a mixture of a part of the component (B), the component (D) and the component (C);
( 2 ) ( A ) 成分、 （D ) 成分及び （C〉 成分の混合物と、 （B ) 成分のみと の 2液とする、 あるいは、 (2) A mixture of component (A), component (D) and component (C), and only component (B) Or two liquids, or
( 3 ) ( A ) 成分、 （D ) 成分及び（C ) 成分の混合物と、 （B ) 成分及び（D ) 成分の混合物との 2液とする、 等である。  (3) Two liquids of a mixture of the component (A), the component (D) and the component (C), and a mixture of the component (B) and the component (D).
発泡体の成形方法も特に制限されず， 押出し発泡法、 連続発泡方法、 注 型成形方法， 不連続成形方法、 又は現場発泡施工方法等、 ポリウレタンフ オーム、 フエノールフォーム、 シリコーンフォーム等の製造に使用される 各種発泡成形方法が適宜利用できる。  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. Various foam molding methods can be used as appropriate.
上記連続発泡方法としては、 ベルトコンベア上に連続的に繰り出される 紙又はプラスチックフィルムの上で自由に発泡させるスラブ発泡法や、紙、 ベニヤ板、 金属板等の面材とともに成形し、 ラミネートするダブルコンペ ァ法等が用いられる。 注型成形方法は、 所望形状の型内に吐出発泡させ、 キュア硬化させて型の内面形状に添った成形品を作り上げる方法である。 不連続成形方法は、 サンドィツチパネル等の成形に用いられる。  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.
現場施工方法としては、 一液型簡易スプレー法、 二液型スプレー法、 二 液型注入法、 二液型塗布法等があり、 主に建築断熱用途に用いられる。 本発明における発泡体は、 （発泡体の体積） ノ （発泡体の体積一発泡体中 の空隙の体積） として表した、 単位体積当たりの発泡倍率において特に制 限はないが， 発泡体であることによる有用な特徴が顕著となる 2倍以上、 特に 4倍以上の発泡倍率を有するのが好ましい。  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.
上記したように、 本発明の発泡性樹脂組成物は、 常温あるいは比較的低 温の加熱下において発泡するので現場発泡が可能であり、 またイソシァネ 一トを含まず低毒性で、 かつ発泡倍率を上げることにより単位体積当たり の価格を下げることが可能であるという効果を有する。  As described above, since 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.
また、 この発泡性樹脂組成物を用いることを特徴とする本発明の製造方 法によれば， 耐候性、 塗装性、 接着性が良好であり、 燃焼時に有害なガス の発生がないという優れた特徵を有する発泡体が得られる。 Further, according to 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. Thus, a foam having an excellent characteristic of no generation of a foam is obtained.
しかも、 （A) 成分の組成 （骨格と架橋点間分子量） や各成分の配合比率 等の選択により、 硬質発泡体から軟質発泡体まで製造可能で、 発泡倍率も 低倍率から高倍率まで設定できる。 さらに、 化学発泡と架橋の反応速度を コントロールが可能であることや、 （B) 成分に特定の構造を持つ化合物を 用いることにより、 セル構造が微細で均一な発泡体を製造することが可能 となる。  In addition, by selecting the composition of the component (A) (molecular weight between the skeleton and the cross-linking point) and 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. . Furthermore, it is possible to control the reaction rate of chemical foaming and crosslinking, and to use a compound having a specific structure as the component (B) to produce a foam with a fine and uniform cell structure. Become.
[実施例] [Example]
次に、 本発明を実施例によってさらに具体的に説明する。 ただし、 本発 明は以下の実施例に限定されるものではない。  Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following embodiments.
合成例 1 Synthesis example 1
温度計、 攪拌装置子， 滴下漏斗、 コンデンサーを備えた 3 Lの四首丸底 フラスコに、 窒素雰囲気下、 1 , 3， 5 , 7—テトラメチルシクロテトラ シロキサン （信越化学 （株） 製 KF 9 9 0 2 ) 1 5 04 g及びトルェン 5 0 0 m l を入れた。 室温にて攪拌下、 白金一ビニルシロキサン錯体のキ シレン溶液 4 7. 2 IX 1 (白金原子にして 6. 2 1 0 " 6 m o 1 ) を トル ェン 2 0 m 1 に溶解させ添加した。 7 0 に加温して攪拌下、 2 , 2 ' -ジ ァリリレビスフエノール A 1 9 2 gをトルェン 2 0 0 m l に溶解させたもの を 3 0分かけて滴下漏斗から添加した。 添加終了後、 滴下漏斗をトルエン 3 0 m lで洗浄した。 得られた溶液を 7 0 tで 2 時間攪拌した後、 ベンゾ チアゾ一ル 1 6. 7 mgを添加した。 減圧下にトルエン及び未反応のテト ラメチルシクロテトラシロキサンを留去して、 47 0 gの茶色の粘稠な液 体を得た。 このものの核磁気共鳴、 質量分析、 赤外分光分析等の分析によ り、 式 ；
Figure imgf000060_0001
Under a nitrogen atmosphere, 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. After heating to 70 and stirring, a solution prepared by dissolving 19,2 g of 2,2'-diarylebisphenol A in 200 ml of toluene was added from a dropping funnel over 30 minutes. After that, the dropping funnel was washed with 30 ml of toluene, and the resulting solution was stirred at 70 t for 2 hours, and then 16.7 mg of benzothiazole was added. The lamethylcyclotetrasiloxane was distilled off to obtain 470 g of a brown viscous liquid, which was analyzed by nuclear magnetic resonance, mass spectrometry, infrared spectroscopy and the like to obtain the following formula:
Figure imgf000060_0001
で表される化合物と同定された。 It was identified as the compound represented by.
合成例 2 Synthesis example 2
温度計、 攪拌装置子、 滴下漏斗、 コンデンサーを備えた 2 Lの四首丸底 フラスコに、 窒素雰囲気下、 1 , 3， 5 , 7—テトラメチルシクロテトラ シロキサン 5 0 0 g及びトルエン 1 5 0 m 1 を入れた。 室温にて攪拌下， 白金—ビニルシロキサン錯体のキシレン溶液 1 5. 6 1 を トルエン 2 0 m l に溶解させ添加した。 7 0 °Cに加温して攪拌下、 ビスフエノール Aジ ァリルエーテル 64. 1 g をトルエン 6 0 m 1 に溶解させたものを 3 0分 かけて滴下漏斗から添加した。 添加終了後、 滴下漏斗をトルエン 2 0 m 1 で洗浄した。 得られた溶液を 7 0 てで 2時間攪拌した後， ベン チアゾー ル 4. 7 m gを添加した。 減圧下にトルエン及び未反応のテトラメチルシ クロテ トラシロキサンを留去して、 I 6 5 gの薄黄色のやや粘稠な液体を 得た。 このもの核磁気共鳴、 質量分析、 赤外分光分析等の分析により， 式；  Under a nitrogen atmosphere, 500 g of 1,3,5,7-tetramethylcyclotetrasiloxane and toluene 150 g were placed in a 2 L four-neck round bottom flask equipped with a thermometer, stirrer element, dropping funnel, and condenser. m 1 was inserted. While stirring at room temperature, 15.61 of a xylene solution of a platinum-vinylsiloxane complex was dissolved in 20 ml of toluene and added. A solution obtained by dissolving 64.1 g of bisphenol A diaryl ether in 60 ml of toluene was added from a dropping funnel over 30 minutes while heating to 70 ° C and stirring. After the addition was completed, the dropping funnel was washed with 20 ml of toluene. After the resulting solution was stirred at 70 ° C for 2 hours, 4.7 mg of benzothiazole was added. The toluene and unreacted tetramethylcyclotetrasiloxane were distilled off under reduced pressure to obtain I65 g of a pale yellow, slightly viscous liquid. The product was analyzed by nuclear magnetic resonance, mass spectrometry, infrared spectroscopy, etc.
Figure imgf000060_0002
で表される化合物と同定された。 合成例 3
Figure imgf000060_0002
It was identified as the compound represented by. Synthesis example 3
1 リ ッ トルの四つ口フラスコに， 撹拌棒、 滴下ロー ト、 上部に 3方コッ クを付けた冷却管、 温度計をセッ トした。 このフラスコに 1、 3、 5、 7 ーテトラメチルシクロテ卜ラシロキサン 1 2 0 g、 白金ービニルシロキサ ン錯体のキシレン溶液 2 4 1 ^ 1 ), トルエン 1 2 0 m l を入れた。 混合液 を 8 0 "Cに加熱し、 滴下ロー卜から〇ーァリルフエノール 6 7. 0 g ( 0. 5 0 mo 1 ) を 2 0分かけて滴下した。 8 0 でそのまま 2時間撹拌した。 反応混合物を核磁気共鳴の測定により、 ビニル基のピークが消失したこ とを確認し、 冷却した後、 活性炭 1 0 gを加え， 室温で 1時間撹拌した。 混合物を濾過し、 濾液を濃縮することにより、 3— ( 2—ヒ ドロキシフエ ニル） プロピル基で変性したメチルハイ ドロジェンシクロシ□キサンをや や粘稠液体として得た。 このポリシロキサンの S i H価を測定したところ、 8. I mmo I Zgであった。  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. Nuclear magnetic resonance measurement of the reaction mixture confirmed that the vinyl group peak had disappeared, and after 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. As a result, methylhydrogencyclosiloxane modified with a 3- (2-hydroxyphenyl) propyl group was obtained as a slightly viscous liquid. I mmo I Zg.
合成例 4 Synthesis example 4
滴下ロー ト、 上部に 3方コックを接続した冷却管、 温度計、 メカ二力 ルス夕一ラーを接続した 4ッロフラスコ内に、 1 , 3 , 5 , 7 —テ トラ メチルシクロテ トラシロキサン 6 0. l gを入れ、 3方コックより酸素 ノ窒素混合ガス （酸素含有量 1 % ) を流しながら 4 0 t:に加熱した。 P t —ビニルシロキサン （ 3 %キシレン溶液） 6. 5 mgを入れ、 滴下口 一卜より 〇， O ' —ジァリルビスフエノール A 3 0. 8 gを滴下し、 そ の後末端がァリル基およびメチル基で置換されたポリエチレンォキシ ド 重合体 （数平均分子量 4 0 0 ) 8. l gを滴下した。 そのまま 4 0度で 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 〇, O '— diarylbisphenol A3 0.8 g was added dropwise from a dropping port. And 8. lg of a polyethylene oxide polymer substituted with a methyl group (number average molecular weight: 400). At 40 degrees
1時間撹拌し、 反応を完結させたのち、 安定剤としてべンゾチアゾ一ル を添加した。 反応混合物を減圧下で加熱し揮発分を留去することにより やや粘調な透明液体を得た。 合成例 5 After stirring for 1 hour to complete the reaction, benzothiazole was added as a stabilizer. The reaction mixture was heated under reduced pressure to remove volatile components, thereby obtaining a slightly viscous transparent liquid. Synthesis example 5
1 リ ッ トルの四つ口フラスコに、 撹拌棒、 滴下ロート、 上部に三方コッ クを付けた冷却管、 温度計をセッ トした。 このフラスコに 1 , 3 , 5 , 7 —テ卜ラメチルシクロテトラシロキサン 1 2 0 g、 白金ービニルシロキサ ン錯体のキシレン溶液 2 4 1 l を入れた。 混合液を 4 0でに加熱し、 滴 下ロートから α—メチルスチレン 1 1. 8 g ( 0. 1 0 m o 1 ) を 5分か けて滴下した。 3 0分撹拌後、 反応混合物を 1 H— NMRによりビニル基 のピークが消失したことを確認し、 次に片末端がメチル基、 もう一方の末 端がァリル基でそれぞれ変性されたエチレンォキシド重合体 （数平均分子 量 3 5 0 ) 7 0 g (ァリル基◦ . 2 0 mo l ) を 1 0分かけて滴下し、 終 了後 8 O :でそのまま 2時間撹拌した。 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 α-methylstyrene was added dropwise from the dropping funnel over 5 minutes. After stirring for 30 minutes, the reaction mixture was confirmed by 1 H-NMR to have disappeared the peak of the vinyl group, and then ethylene oxide was modified with a methyl group at one end and an aryl group at the other end. 70 g of polymer (number average molecular weight: 350) (aryl group: 20 mol) was added dropwise over 10 minutes, and after completion, the mixture was stirred with 8 O: for 2 hours.
反応混合物を 1 H— NMRにより、 ピニル基のピークが消失したことを 確認し、 冷却した後、 活性炭 1 0 gを加え、 室温で 1時間撹拌した。 混合 物を濾過し， フエネチル基およびポリオキシアルキレン基で変性したシク ロテトラシロキサンを粘稠液体として得た。 このポリ シロキサンの S i H 価を測定したところ、 8. 3mmo l / であった。 The reaction mixture was confirmed by 1 H-NMR to confirm that the peak of the pinyl group had disappeared. After cooling, 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.
合成例 6 Synthesis Example 6
合成例 4に準じて、 1 , 3 , 5 , 7—テトラメチルシクロテトラシロキ サンの代わりに、 ポリオルガノハイ ドロジェンシロキサン （信越化学 （株） 製 K F— 9 9) 1 2 0 g , トルエン 1 2 0mし 白金—ビニルシロキサ ン錯体のキシレン溶液 2 4 1 1 を入れた。 混合液を 8 0 に加熱し、 合 成例 5 と同様に、 滴下ロートから α—メチルスチレン 1 1. 8 g、 ェチレ ンォキシド重合体 7 0 gを 1 0分かけて滴下し、 終了後 8 0 でそのまま 2時間撹拌した。  According to 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 α-methylstyrene and 70 g of ethylenoxide polymer were added dropwise from the dropping funnel over 10 minutes. And stirred for 2 hours.
反応混合物を 1 H— NMRにより、 ビニル基のピークが消失したことを 確認し、 冷却した後、 活性炭 1 0 gを加え、 室温で 1時間撹拌した。 混合 物を濾過し、 濾液を濃縮することにより、 フエネチル基およびポリオキシ アルキレン基で変性したメチルハイ ドロジエンポリシロキサンを粘稠液体 として得た。 このポリシロキサンの S i H価を測定したところ、 8. 3 m mo 1 /gであった。 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.
合成例 7 Synthesis Example 7
合成例 6に準じて、 α—メチルスチレンを用いずにポリオキシエチレン 重合体 7 0 gのみを用いて反応させたほかは同様の操作を行い、 ポリオキ シエチレン基で変性したメチルハイ ドロジェンポリシロキサンを粘稠液体 として得た。 このポリシロキサンの S i H価を測定したところ、 9. 3 m mo 1ノ gであった。  Following the same procedure as in Synthesis Example 6 except that the reaction was carried out using only 70 g of the polyoxyethylene polymer without using α-methylstyrene, a methylhydrogenpolysiloxane modified with a polyoxyethylene group was obtained. Obtained as a viscous liquid. When the SiH value of this polysiloxane was measured, it was 9.3 mmol per gram.
合成例 8 Synthesis Example 8
合成例 6に準じて、 ポリオキシエチレン重合体を用いずに、 α;—メチル スチレン 4 7. 2 gのみを用いて反応させたほかは同様の操作を行い、 変 性したメチルハイ ドロジェンシロキサンを粘調液体として得た。 S i H価 は 9. 6 mmo 1 /gであった。  Following the same procedure as in Synthesis Example 6 except that the reaction was carried out using only α-methylstyrene 47.2 g without using a polyoxyethylene polymer, the modified methylhydrogensiloxane was converted to a modified methylhydrogensiloxane. Obtained as a viscous liquid. The S i H value was 9.6 mmo 1 / g.
合成例 9 Synthesis Example 9
温度計， 還流冷却器、 滴下ロート， 攪拌モ一夕を備えた四つ口フラスコ に、 ノボラック型フエノール樹脂 （P S M4 2 6 1 , 群栄化学 （株） 製， 〇H含量 9. 7 1 mm o 1 / g ) 3 6. 9 g及びアセトン 1 6 0m l を入 れ、 攪拌しながら炭酸力リウム 5 0 gを添加した。 ァリルブロマイ ド 5 2 gを少量づっ滴下したのち、 5 5 で 6時間反応させた。 これをろ過し、 溏縮して， アルカリ、 酸の順で洗浄し、 珪酸アルミニウム 7. 4 gを添加 して攪拌した後、 さらにろ過、 濃縮して、 ヨウ素価により測定した不飽和 基含量が 7. 31111110 1 // 8の生成物4 0 8を得た。 この生成物は、 核磁 気共鳴の測定により水酸基がァリル化された〇ーァリル化ノボラック型フ ェノール樹脂であることが確認された。 In a four-necked flask equipped with a thermometer, a reflux condenser, a dropping funnel, and a stirring motor, a novolak-type phenol resin (PS M4261, manufactured by Gunei Chemical Co., Ltd., 〇H content: 9.71 mm o 1 / g) 36.9 g and acetone 160 ml were added, and 50 g of lithium carbonate was added with stirring. After dropping 52 g of aryl bromide in small amounts, the mixture was reacted with 55 for 6 hours. This was filtered, filtered, washed with an alkali and an acid in that order, added with 7.4 g of aluminum silicate, stirred, further filtered and concentrated, and the content of unsaturated groups as measured by iodine value was reduced. 7. give the product 4 0 8 31111110 1 / / 8. This product is Gas resonance measurements confirmed that it was a polyarylated novolak phenolic resin with hydroxyl groups arylated.
合成例 1 0 Synthesis example 10
合成例 3で得られた〇一ァリル化ノボラック型フエノール樹脂 4 0 gを 窒素雰囲気下で攪拌しながら 1 8 0でで 3時間加熱して、 ョゥ素価により 測定した不飽和基含量が 7 . 3 mm o 1 の転位生成物 4 0 gを得た。 この生成物は、 核磁気共鳴の測定によりァリル基が C 1 a i s e n転位し た Cーァリル化ノポラック型フエノール樹脂であることが確認された。 実施例 1  40 g of the mono-modified novolak-type phenol resin obtained in Synthesis Example 3 was heated at 180 ° C. for 3 hours while stirring under a nitrogen atmosphere, and the unsaturated group content measured by the iodine value was 7%. 40 g of rearranged product of 3 mm o 1 were obtained. The product was confirmed by nuclear magnetic resonance measurement to be a C-arylated nopolak type phenol resin in which an aryl group was C 1 aisen rearranged. Example 1
合成例 1で合成した化合物 7 . 9 g及び、 2 , 2 ' —ジァリルビスフエ ノール A 9 . 2 gを混合し， 白金—ビニルシロキサン錯体のキシレン溶液 0. 4 7 \ (白金原子にして 6 . 0 X 1 0 — 8m o l ) を加えてさらに混 合した。 この混合物はほぼ透明であり、 両者の相溶性が良好なことが示さ れた。 この混合物は、 厚さ 3 mmになるように型枠に流し込み、 5 0 で 3 時間静置して脱泡した後、 1 5 0 * で 1 時間加熱することにより硬化し て均一透明な成形体を与えた。 A mixture of 7.9 g of the compound synthesized in Synthesis Example 1 and 9.2 g of 2,2′-diallylbisphenol A was mixed with a platinum-vinylsiloxane complex in xylene solution 0.47 \ (6.0 in platinum atom). X 10 — 8 mol) was added and further mixed. This mixture was almost transparent, indicating good compatibility between the two. This mixture is poured into a mold so as to have a thickness of 3 mm, left at 50 for 3 hours to degas, and then cured by heating at 150 * for 1 hour to obtain a uniform and transparent molded product. Gave.
実施例 2 Example 2
2 , 2 ' —ジァリルビスフエノール A 9 . 2 gのかわりに、 2 , 2 ' ― ジァリルビスフエノール A 7 . 4 gおよびビスフエノール Aジァリルェ一 テル 1 . 8 gの混合物を用いた以外は実施例 1 と同様の操作を行った。 そ の結果混合物は完全に透明であり、 硬化して均一透明な成形体を与えた。 比較例 1  Instead of 9.2 g of 2,2'-diarylbisphenol A, a mixture of 7.4 g of 2,2'-diarylbisphenol A and 1.8 g of bisphenol A diarylether was used. Except for the above, the same operation as in Example 1 was performed. As a result, the mixture was completely transparent and cured to give a uniformly transparent molding. Comparative Example 1
合成例 1 で合成した化合物 7. 9 g のかわりに合成例 2で合成した化合 物 7. 9 g を用いた以外は実施例 1 と同様の操作を行った。 その結果混合 物は白濁し相溶しなかった。 また、 加熱しても得られたものは不均一であ り良好な硬化物を与えなかった。 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.
比較例 2 Comparative Example 2
合成例 1で合成した化合物 7 . 9 gのかわりに合成例 2で合成した化合物 7 . 9 g を用いた以外は実施例 2 と同様の操作を行った。 その結果混合物 は白濁し相溶しなかった。 また， 加熱しても得られたものは不均一であり 良好な硬化物を与えなかった。  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.
実施例 3 Example 3
合成例 1で合成した化合物 7 . 9 g、 及び合成例 9で合成した化合物 9 . 2 gを用い， 実施例 1 と同様の操作を行った。 混合物の相溶性は良好であ り、 加熱により均一透明な硬化物が得られた。  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.
実施例 4 Example 4
実施例 3に準じて、 合成例 9で合成した化合物の代わりに， 合成例 1 0 で合成した化合物 9 . 2 gを利用したほかは実施例 3 と同様の操作を行つ た。 混合物の相溶性は良好であり、 加熱により均一透明な硬化物が得られ た。  According to 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.
実施例 5 Example 5
実施例 1 に準じて、 合成例 1 で合成した化合物のかわりに、 合成例 3で 合成した化合物 7 . 7 gを用いて同様の操作を行った。 混合物の相溶性は 良好であり、 加熱により均一透明な硬化物が得られた。  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.
実施例 6 Example 6
実施例 1 に準じて、 合成例 1で合成した化合物のかわりに、 合成例 4で 合成した化合物 7 . 9 gを用いて同様の操作を行った。 混合物の相溶性は 良好であり、 加熱により均一透明な硬化物が得られた。  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.
実施例 7 Example 7
実施例 1 に準じて、 合成例 1で合成した化合物のかわりに、 合成例 5で 合成した化合物 7. 2 gを用いて同様の操作を行った。 混合物の相溶性は 良好であり、 加熱により均一透明な硬化物が得られた。 According to 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.
実施例 8 Example 8
実施例 1に準じて， 合成例 1で合成した化合物のかわりに、 合成例 6で 合成した化合物 7. 2 gを用いて同様の操作を行った。 混合物の相溶性は 良好であり、 加熱により均一透明な硬化物が得られた。  According to 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.
比較例 3 Comparative Example 3
実施例 1 に準じて、 合成例 1で合成した化合物のかわりに、 合成例 7で 合成した化合物 6. 6 g を用いて同様の操作を行った。 その結果混合物は 白濁し相溶しなかった。 また、 加熱しても得られたものは不均一であり良 好な硬化物を与えなかった。  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.
比較例 4 Comparative Example 4
実施例 1 に準じて、 合成例 1で合成した化合物のかわりに、 合成例 7で 合成した化合物 6. 3 g を用いて同様の操作を行った。 その結果混合物は 白濁し相溶しなかった。 また， 加熱しても得られたものは不均一であり良 好な硬化物を与えなかった。  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.
比較例 5 Comparative Example 5
実施例 1 に準じて、 合成例 1で合成した化合物のかわりに、 ポリメチル ハイ ドロジェンシロキサン （KF— 9 9 ) 3. 9g を用いて同様の操作を 行った。 その結果混合物は白濁し相溶しなかった。 また， 加熱しても得ら れたものは不均一であり良好な硬化物を与えなかった。  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.
比較例 6 Comparative Example 6
実施例 1に準じて、 合成例 1で合成した化合物のかわりに、 1 , 3 , 5 , 7—テトラメチルシクロテトラシロキサン （KF— 9 9 0 2 ) 3. 9 g を 用いて同様の操作を行った。 その結果混合物は白濁し相溶しなかった。 ま た、 加熱しても得られたものは不均一であり良好な硬化物を与えなかった。 実施例 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. Example 9
実施例 1 に準じて、 合成例 1で合成した化合物 7. 9 g、 末端ァリルェ 一テル化ポリプロピレンォキシド （数平均分子量約 8 0 0 0 ) 2 40 gを 用いて同様の操作を行った。 混合物の相溶性は良好であり、 加熱により均 一透明な硬化物が得られた。  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.
実施例 1 0 Example 10
実施例 1に準じて、 合成例 1で合成した化合物 7. 9 g、 末端ァリルェ ステル化フタル酸 ジエチレングリコール共重合体 （数平均分子量約 1 0 0 0) 3 0 gを用いて同様の操作を行った。 混合物の相溶性は良好であり、 加熱により均一透明な硬化物が得られた。  A similar operation was carried out using 7.9 g of the compound synthesized in Synthesis Example 1 and 30 g of a terminally arylesterified phthalic acid diethylene glycol copolymer (number-average molecular weight: about 100,000) according to Example 1. Was. The compatibility of the mixture was good, and a uniform and transparent cured product was obtained by heating.
実施例 1 1 Example 1 1
2 , 2 ' —ジァリルビスフエノール A 1 0. 8 g (ビニル基 0. 0 7 0 mo 1 )、 合成例 1で製造したヒ ドロシリル基を含有する化合物 9 · 2 0 g (S i H基 0. 0 7 0 mo l )、 および n—ブタン 1. 5 gを混合し均一液 とした。 ここに、 白金一ビニルシロキサンのキシレン溶液 （白金原子で 3. 0重量％ ) 4 3 m gを加えて 1 0秒間激しく撹拌混合したところ発熱しな がら発泡し、 硬質の発泡体が得られた。 発泡体を 2 3でで 2 4時間静置し、 発泡終了直後に対する寸法変化を百分率で表す （以下収縮率と称する） と 5 %以下であった。 得られた発泡体から立方体を切り出し、 重量を測定し 密度を求めたところ、 2 7. 5 k g Zm3であった。 A S TM— D 2 8 5 6に準じて独立気泡率を測定したところ、 8 5 %であった。 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. To this, 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. 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%.
実施例 1 2 Example 1 2
2 , 2 ' —ジァリルビスフエノール A 1 0. 8 gのかわりに、 2， 2 ' —ジァリルビスフエノール A 5. 3 9 g (ビニル基 0. 0 3 5 mo l ) と ビスフエノール Aジァリルエーテル 5. 3 9 g (ビエル基 0. 0 3 5 mo 1 ) の混合物を用いた以外は実施例 1 1 と同様の操作を行った。 得られた 発泡体の収縮率は 5 %以下， 密度は 2 2. 8 k g /m3 , 独立気泡率は 8 2 %であった。 Instead of 2,2'-diarylbisphenol A10.8 g, 2,2'-diarylbisphenol A 5.39 g (vinyl group 0.035 mol) The same operation as in Example 11 was performed, except that 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%.
実施例 1 3 Example 13
合成例 1で製造したヒ ドロシリル基を含有する化合物 9. 2 0 gのかわ りに、 合成例 3で製造したヒ ドロシリル基を含有する化合物 8. 6 4 gを 用いた以外は実施例 1 1 と同様の操作を行った。 得られた発泡体の密度は 2 7. 8 k gZm3、 独立気泡率は 7 0 %であった。 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%.
実施例 1 4 Example 14
2 , 2 ' —ジァリルビスフエノール A 1 0 · 8 gのかわりに、 合成例 9 で製造した〇—ァリル化ノボラック型フエノール樹脂 4. 8 g (ビニル基 0. 0 3 5 m o 1 ) と合成例 1 0で製造した Cーァリル化ノポラック型フ ェノール樹脂 4. 8 g (ビニル基 0. 0 3 5 mo l ) の混合物を用いた以 外は実施例 1 1 と同様の操作を行った。 得られた発泡体の収縮率は 5 %以 下、 密度は 3 8. 5 k g/m3、 独立気泡率は 6 0 %であった。 Instead of 2,8'-diallylbisphenol A 108 g, 〇-allylated novolak-type phenolic resin 4.8 g (vinyl group 0.035 mo 1) prepared in Synthesis Example 9 was used. The same operation as in Example 11 was performed except that a mixture of 4.8 g (0.035 mol of vinyl group) of the C-arylated nopolak phenol resin produced in Synthesis Example 10 was used. The resulting foam had a shrinkage of 5% or less, a density of 38.5 kg / m 3 and a closed cell ratio of 60%.
実施例 1 5 Example 15
n—ブタン 1. 5 gのかわりに 2—ェチルへキサン酸 3. 6 g ( 0. 0 2 5 m o 1 ) を用いた以外は実施例 1 1 と同様の操作を行った。 発泡体の 密度は 4 5. 9 k gZm3、 独立気泡率は 6 1 %であった。 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%.
実施例 1 6 Example 16
合成例 1で製造したヒ ドロシリル基を含有する化合物 9. 2 0 のかわ りに、 合成例 1で製造したヒドロシリル基を含有する化合物 4. 6 0 g ( S i H基 0. 0 3 5 mo l ) と合成例 6で製造した変性メチルハイ ドロジェ ンポリ シロキサン 5. 2 1 (S i H基 0. 0 3 5 mo l ) との混合物を 用いた以外は実施例 1 1 と同様の操作を行った。 得られた発泡体の密度は 2 4. 3 gZm3、 独立気泡率は 7 2 %であった。 Instead of the hydrosilyl group-containing compound 9.20 produced in Synthesis Example 1, the hydrosilyl group-containing compound 4.60 g (SiH group 0.035 mo) produced in Synthesis Example 1 was used. l) and the modified methylhydrogenpolysiloxane 5.21 (SiH group 0.035 mol) produced in Synthesis Example 6. The same operation as in Example 11 was performed except for using. The density of the obtained foam was 24.3 gZm 3 , and the closed cell ratio was 72%.
実施例 1 7 Example 17
2 , 2 ' —ジァリルビスフエノール A 1 0. 8 g (ビニル基 0. 0 7 0 mo 1 ), 合成例 4で製造したヒ ドロシリル基を含有する化合物 9. 2 0 g ( S i H基 0. 0 7 0 m o 1 )、 および H F C 2 4 5 ί a 3. 0 gを混合し 均一液とした。 実施例 1 1 と同様に白金—ビニルシロキサン溶液を加えて 1 0秒間激しく撹拌混合したところ発熱しながら発泡し、 硬質の発泡体が 得られた。 得られた発泡体の収縮率は 5〜 1 0 %, 密度は 3 0. 5 k g/ m3、 独立気泡率は 8 5 %であった。 2,2'-Diarylbisphenol A 10.8 g (vinyl group 7.00 mo 1), the compound containing a hydrosilyl group produced in Synthesis Example 4 9.20 g (SiH 0.070 mo 1) and 3.0 g of HFC245-a were mixed to obtain a homogeneous liquid. In the same manner as in Example 11, 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 rigid foam was obtained. The shrinkage ratio of the obtained foam was 5 to 10%, the density was 30.5 kg / m 3 , and the closed cell ratio was 85%.
実施例 1 8 Example 18
合成例 4で製造したヒドロシリル基を含有する化合物のかわりに、 合成 例 5で製造した変性シロキサン 8. 4 3 gを用いた以外は実施例 1 1 と同 様の操作を行った。 得られた発泡体の収縮率は 3 0 %であったが、 密度は 5 0 k /m 独立気泡率は 6 0 %であった。  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%.
実施例 1 9 Example 19
合成例 4で製造したヒ ドロシリル基を含有する化合物のかわりに、 合成 例 6で製造した変性シロキサン 9. 2 gを用いた以外は実施例 1 1 と同様 の操作を行った。 得られた発泡体の収縮率は 3 0 %であったが、 密度は 5 0 k g /m3 , 独立気泡率は 6 0 %であった。 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%.
実施例 1 9 Example 19
実施例 9で用いたポリプロピレンォキシド 2 8 0 g、 合成例 4で製造し たヒ ドロシリル基を含有する化合物 9. 2 0 g > および H F C 2 4 5 f a 1 0. O gを混合し均一液とした。 実施例 1 1 と同様に白金ービニルシロ キサン溶液を加えて 1 0秒間激しく撹拌混合したところ発熱しながら発泡 し、 軟質の発泡体が得られた。 得られた発泡体の密度は 2 0 0 k g Zm3 であった。 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 .
実施例 2 0 Example 20
実施例 1 0で用いた末端ァリルエステル化フ夕ル酸ノジエチレングリ コ ール共重合体 3 5 g、 合成例 4で製造したヒ ド□シリル基を含有する化合 物 9. 2 0 g , および H F C 24 5 f a 8. 0 gを混合し均一液とした。 実施例 1 1 と同様に白金一ビニルシロキサン溶液を加えて 1 0秒間激しく 撹拌混合したところ発熱しながら発泡し、 軟質の発泡体が得られた。 得ら れた発泡体の密度は 7 0 k g Zm3であった。 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. In the same manner as in Example 11, 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 .
比較例 7 Comparative Example 7
合成例 1で製造したヒ ド ΠΙシリル基を含有する化合物のかわりに、 1 , 3 , 5 , 7—テトラメチルシクロテトラシロキサン 4. 2 0 gを用いた以 外は実施例 1 1 と同様の操作を行った。 その結果ァリル化合物と S i H化 合物は相溶せず、 発泡体を形成しなかった。  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.
比較例 8 Comparative Example 8
合成例 1で製造したヒ ドロシリル基を含有する化合物のかわりに、 合成 例 7で製造した変性ポリ メチルハイ ドロジェンシロキサン 7. 2 9 gを用 いた以外は実施例 1 1 と同様の操作を行つた。 得られた発泡体は 8 0 k g ノ m3、 独立気泡率は 3 0 %であった。 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%.
比較例 9 Comparative Example 9
合成例 1で製造したヒ ドロシリル基を含有する化合物のかわりに、 合成 例 8で製造した変性ポリメチルハイ ドロジェンシロキサン 7. 5 3 gを用 いた以外は実施例 1 1 と同様の操作を行った。 得られた発泡体の密度を求 めたところ、 3 3 k gZm3であった。 独立気泡率を測定したところ、 1 0 %であった。 産業上の利用可能性 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. When the density of the obtained foam was determined, it was 33 kgZm 3 . When the closed cell rate was measured, it was 10%. Industrial applicability
本発明によれば、 極性の高い炭素 -炭素二重結合含有有機系化合物とも 十分な相溶性を有する硬化剤及び該硬化剤を用いた硬化性組成物及び発泡 性樹脂組成物を提供することができる。  According to the present invention, it is possible to provide 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.
本発明の硬化剤を用いた硬化性組成物は、 機械的強度に優れ、 透明性等 の外観にも優れるため、 その用途は特に限定されず， 一般の広い用途に使 用することができる。  Since 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.
その例としては， 例えば、 電機 · 電子部品等の封止材料、 自動車用アン ダーボディ一コート ' 建築用防水コーティ ング等のコーティ ング剤、 ガス ケッ ト材料、 シーリ ング材、 ゴム · 樹脂等の各種成形材料、 液状 ' 粉体状 等の各種塗料、 接着剤、 あるいは物性改良剤 ' 相溶化剤等の樹脂改質剤等 が挙げられる。  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.
また、 本発明の発泡性樹脂組成物によれば、 常温あるいは比較的低温の 加熱下において発泡硬化させることができ、 かつ発泡倍率が高く、 しかも 独立気泡率が高い発泡体が得られる。 従って. 高い発泡倍率により単位体 積当たりの価格を下げることができるとともに、 高い独立気泡率により断 熱性能が良い発泡体を得ることができるので、 防音、 断熱、 止水、 気密、 制振， 保護， クッション， 装飾等の種々の用途に広く適用することができ る。  Further, according to the foamable resin composition of the present invention, 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.
その具体例としては、 特に限定されるわけではないが、 例えば、 車両用 のクッション材、 天井材、 ドアトリム中材、 フロアクッション制振吸音材、 力一クーラー断熱材、 ダンパー用ェアーシ一ル材、 防水材、 ガスケッ ト， エアフィルタ一、 センタービラ一ガ一ニッシュ， ヘッ ドライナー、 クオ一 タート リム、 ダス トカバ一、 燃料タンク内セーフティーフォーム、 オイル フィルター、 フレキシブルコンテナー、 クラッシュパッ ド、 サンバイザー、 ヘッ ドレス 卜， インシュレーター、 ダッシュボード、 ドアパネル、 ピラー、 コンソールボックス、 エネルギー吸収バンパー、 冷凍車 ' 保冷車 ' タンク ローリ—車 . 冷凍コンテナ一車等の断熱材、 ガード防音材等， 船舶用の断 熱材、 浮力材、 F R Pボード芯材、 ブイ等、 寝装品用のクッショ ン材等、 家具等のクッション材、 パッキング材等、 電気，電子機器用のフィルター、 吸音断熱材、 プリンター吸音材、 ヘッ ドホーンィヤーパッ ト等、 包装用の 緩衝材、 建築用では屋根 ' 天井 · 壁 · 床の断熱材、 水道配管等のカバー、 ドアパネル、 サイジングパネル、 金属 ' サイジングパネル等の芯材， 間仕 切りパネルの芯材、 畳 .ふすま芯材、 バスタブ等の断熱保温芯材、 目地材、 シーリ ング材、 接着剤、 システム天井断熱パネル、 屋上断熱防水材、 冷凍 倉庫 · 気密倉庫等の気密断熱材， ブラン 卜のタンク · 配管の保温 · 保冷材 等、 家電用では冷蔵庫 . 冷凍庫 ' 電子ジャー等の断熱材、 ルームクーラ一 の結露防止材、 また、 スポーツ用品や医療品及び化粧用パフ、 Wパッ ト、 スリ ッパ、 サンダル、 剣山、 玩具等の生活用品用途が挙げられる。 Specific examples thereof 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. Materials, guard sound insulation materials, heat insulation materials for ships, buoyancy materials, FRP board core materials, buoys, cushion materials for bedding, cushion materials for furniture, packing materials, etc., filters for electric and electronic equipment , Sound-absorbing heat-insulating materials, printer sound-absorbing materials, headphone-yapats, etc., cushioning materials for packaging, roofing for construction, heat-insulating materials for ceilings, walls, floors, covers for water pipes, door panels, sizing panels, metal '' Core material such as sizing panel, partition panel core material, tatami mat bran material, bathtub Insulation core materials, jointing materials, sealing materials, adhesives, system ceiling insulation panels, roof insulation waterproofing materials, air-tight insulation materials for freezing warehouses, air-tight warehouses, etc., tanks for pipes, pipe insulation, heat insulation materials, etc. 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.
また、 本発明の発泡性樹脂組成物、 これを用いた発泡体及びその製造方 法は、 注型法における物品形状の型取りや、 型からのモデルサンプル作製 や装飾品作製などにも利用できるものである。  In addition, 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.

Claims

請求の範囲 The scope of the claims
1. 分子中に少なく とも 1個の炭素一炭素二重結合を含有する有機化合物 を硬化させる硬化剤であって、 1. a curing agent that cures an organic compound containing at least one carbon-carbon double bond in the molecule,
前記炭素一炭素二重結合を含有する有機化合物との相溶性が良好である ことを特徵とする有機系硬化剤。  An organic curing agent characterized by having good compatibility with the organic compound having a carbon-carbon double bond.
2. ( a) 下記一般式 （ 1 )  2. (a) The following general formula (1)
Figure imgf000073_0001
Figure imgf000073_0001
(式 （ 1 ) 中、 R1 は、 水素原子及び炭素数が 1 ~ 2 0の一価の有機基より 選ばれる基を表し、 それぞれの R' は同じであっても異なっていてもよい。 i ≥2、 j は 0又は正の数、 p≥ lであり、 かつ し 】 及び Pは， 3≤ ( i + j ) X p 5 0を満足する数である。） (In the formula (1), 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 is 0 or a positive number, p≥l, and] and P are numbers satisfying 3≤ (i + j) Xp50.)
で表される環状オリゴシロキサン及びノ又は下記一般式 （ 2 ) And a cyclic oligosiloxane represented by the general formula (2):
Figure imgf000073_0002
(式 （ 2) 中， R1は上記に同じ、 R2は、 水素原子， — S i (CH3) 3、 一 S i ( C H3) 2H及び炭素数が 1 ~ 2 0の一価の有機基より選ばれる基を 表し、 それぞれの R2は同じであっても異なっていてもよい。 k≥2 , 1 は 0又は正の数、 Q≥ 1であり、 かつ k , 1及び qは、 2≤ ( k + 1 ) X q≤ 5 0を満足する数である。）
Figure imgf000073_0002
(In the formula (2), R 1 is the same as above, R 2 is a hydrogen atom, — S i (CH 3 ) 3 , one S i (CH 3 ) 2 H and a monovalent having 1 to 20 carbon atoms. And each R 2 may be the same or different, k≥2, 1 is 0 or a positive number, Q≥1, and k, 1 and q Is a number that satisfies 2≤ (k + 1) Xq≤50.)
で表される鎖状ポリシロキサンと、 A linear polysiloxane represented by
(b) 下記一般式 （ 3)  (b) The following general formula (3)
Figure imgf000074_0001
Figure imgf000074_0001
(式 （ 3 ) 中、 m及び nはそれぞれ独立に 1〜 3の数を表し、 pは 0〜 2 の数を表す。 R3は、 1個以上の炭素一炭素二重結合を含有する炭素数 1〜(In the formula (3), m and n each independently represent a number of 1 to 3, p represents a number of 0 to 2. R 3 represents a carbon atom having at least one carbon-carbon double bond. Number 1 ~
2 5の一価の有機基を表し， mが 2以上の場合、 それぞれの R3は同じであ つても異なっていてもよい。 R*は， ハロゲン原子， 炭素数 1 ~ 6のアルコ キシ基、 炭素数 1 ~ 2 5の一価の有機基より選ばれる一価の基を表し、 P が 2の場合、 それぞれの R4は同じであっても異なっていてもよい。） で表される分子内に 1個以上の炭素一炭素二重結合及び 1個以上のフエノ ール性水酸基を有する化合物 25 represents a monovalent organic group, and when m is 2 or more, each R 3 may be the same or different. R * 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. When P is 2, each R 4 is They may be the same or different. ) A compound having at least one carbon-carbon double bond and at least one phenolic hydroxyl group in the molecule represented by
とを反応させて得られる請求の範囲第 1項記載の硬化剤。 2. The curing agent according to claim 1, obtained by reacting
3. 前記 j 及び Z又は 1が 0である請求の範囲第 2項記載の硬化剤。  3. The curing agent according to claim 2, wherein said j, Z or 1 is 0.
4. 前記 i力 3≤ i≤ 7を満足する数であり、 及び/又は前記 k力 2 ≤ k≤ 1 0を満足する数である請求の範囲第 3項記載の硬化剤。  4. The curing agent according to claim 3, wherein the curing agent has a number that satisfies the i force 3 ≦ i ≦ 7 and / or a number that satisfies the k force 2 ≤k ≦ 10.
5. 前記 （b) 成分として， 下記一般式 （4) 又は （ 5 )
Figure imgf000075_0001
5. As the component (b), the following general formula (4) or (5)
Figure imgf000075_0001
(式 （ 4) 及び式 （ 5) 中、 R5は、 水素原子あるいは 1個以上の炭素一炭 素二重結合を含有する炭素数 1〜 1 0の一価の有機基を表し、 それぞれの R5は同じであっても異なっていてもよい。 式 （ 5) 中、 は、 一 CH2—、 - C ( C H3) 2— > - CH (CH3) 一、 - C ( C F3) ！ー、 一 C O -、 — S 〇2—、 一〇一、 あるいは式：
Figure imgf000075_0002
で表される基より選ばれる二価の置換基を示す。） (In the formulas (4) and (5), R 5 represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms and containing at least one carbon-carbon double bond. R 5 may be the same or different: In the formula (5), is one CH 2 —, -C (CH 3 ) 2 —> -CH (CH 3 ) one, -C (CF 3 )ー ー, one CO-, — S 〇 2 —, one hundred one, or formula:
Figure imgf000075_0002
And a divalent substituent selected from the groups represented by )
で表される分子内に 1個以上の炭素一炭素二重結合及び 1個以上のフエノ ール性水酸基を有する化合物を含有することを特徵とする、 請求の範囲第Wherein the compound represented by the formula (1) contains a compound having at least one carbon-carbon double bond and at least one phenolic hydroxyl group.
2〜 4項のいずれか 1項に記載の硬化剤。 The curing agent according to any one of items 2 to 4.
6. (i) 1分子中のケィ素原子の数が 3〜 1 0個である、 鎖状及び Z 又は環状のオルガノハイ ドロジェンシロキサン，  6. (i) a chain and Z or cyclic organohydrogensiloxane having 3 to 10 silicon atoms per molecule;
(ii) 前記 （i) 成分のヒ ドロシリル基と反応しう る官能基を 1分子中 に 2個以上有する化合物、 及び (ii) a functional group capable of reacting with the hydrosilyl group of the component (i) in one molecule; A compound having at least two of
(iii) .前記 （i) 成分のヒ ドロシリル基と反応しうる官能基を 1分子中 に 1個含有する有機化合物  (iii) An organic compound containing, in one molecule, one functional group capable of reacting with the hydrosilyl group of the component (i).
を反応させて得られ、 かつ Π) 成分由来のヒ ドロシリル基が実質上残 存した化合物であることを特徵とする、 請求の範囲第 1項に記載の硬 化剤。 2. The hardener according to claim 1, wherein the hardener is a compound obtained by reacting the compound and (ii) a compound in which a hydrosilyl group derived from the component is substantially left.
7. 次の式 （ 6〉 又は式 （ 7〉 で示される構造を有することを特徵とする、  7. It has a structure represented by the following formula (6) or formula (7),
(6
Figure imgf000076_0001
(6
Figure imgf000076_0001
(式 （ 6 ) 中， m≥2 , n≥0、 1 . k . Q≥ 1 , pは 0〜 5の整数、 I 0≤ (m+ n + l + k) x q ^8 0であり、 Rs . R7 は、 炭素数 0〜 6 の 1価の置換基、 R8 は、 分子量が 1 0 0〜 1 0 , 0 0 0のポリオキシァ ルキレン鎖を示し、 R9 , R '。 は， 水素又は炭素数 1〜 2 0の炭化水素基 を示す。 m個， n個， 1個， k個の Rs , n個， p個の R' は、 それぞれ 同じものでも異なるものでもよい。 Xは， 構成元素として C, H. N, 〇， S , ハロゲンのみを含む炭素数 0〜 1 0の 2価の置換基を示す。） (In Equation (6), m≥2, n≥0, 1.k.Q≥1, p is an integer from 0 to 5, I0≤ (m + n + l + k) xq ^ 80, and R s. R 7 represents a monovalent substituent, R 8 of 0-6 carbon atoms, the molecular weight represents 1 0 0-1 0 0 0 0 Poriokishia alkylene chain, R 9, R '., the hydrogen Or a hydrocarbon group having 1 to 20 carbon atoms, m, n, 1, k, R s , n, and p R ′ may be the same or different. , And a divalent substituent having 0 to 10 carbon atoms containing only C, H. N, 〇, S, and halogen as constituent elements.)
Figure imgf000076_0002
(式 （ 7 ) 中、 m 2、 n≥ 0、 1 , k, d≥ 1. pは 0〜 5の整数、 3 ≤ (m+ n + I + k) X q≤2 0であり， R6 ， R7 , R8, Xは、 式 （ 6 ) と 同じ。）
Figure imgf000076_0002
(Where m 2, n ≥ 0, 1, k, d ≥ 1. p is an integer from 0 to 5, 3 ≤ (m + n + I + k) X q ≤ 20 and R 6 , R 7 , R 8 , and X are the same as in equation (6).)
8 - ( A) 分子中に少なく とも 1個の炭素一炭素二重結合を含有する有機化 合物、 及び  8-(A) an organic compound containing at least one carbon-carbon double bond in the molecule, and
(B) ヒドロシリル基を有する有機系硬化剤  (B) Organic curing agent having a hydrosilyl group
を必須成分とし、 前記 （B) 成分が請求の範囲第 1項〜第 7項のいずれか 1項に記載の硬化剤である硬化性組成物。 A curable composition wherein the component (B) is the curing agent according to any one of claims 1 to 7.
9. ( C) ヒドロシリル化触媒  9. (C) Hydrosilylation catalyst
をさらに含有することを特徵とする、 請求の範囲第 8項に記載の硬化性組 成物。 9. The curable composition according to claim 8, further comprising:
1 0. (A) 分子中に少なく とも 1個の炭素—炭素二重結合を含有する有機 化合物、 及び  10. (A) an organic compound containing at least one carbon-carbon double bond in the molecule, and
(B) ヒ ドロシリル基を有する有機系硬化剤  (B) Organic curing agent having a hydrosilyl group
(D) 発泡剤及び/又は OH基を有する化合物、  (D) a blowing agent and / or a compound having an OH group,
を必須成分とし、 前記 （B) 成分が請求の範囲第 1項〜第 7項のいずれか 1項に記載の有機系硬化剤である発泡性樹脂組成物。 A foamable resin composition comprising the essential component, and the component (B) being the organic curing agent according to any one of claims 1 to 7.
1 1. (C) ヒドロシリル化触媒  1 1. (C) Hydrosilylation catalyst
をさらに含有することを特徵とする、 請求の範囲第 1 0項に記載の硬化性 組成物。 10. The curable composition according to claim 10, further comprising:
1 2. 前記 （A) 成分の有機化合物の分子骨格が、 炭素、 酸素、 水素、 窆 素、 ィォゥ、 ハロゲンのうちのいずれか 1種以上の元素のみからなる、 請 求の範囲第 1 0項又は第 1 1項記載の発泡性樹脂組成物。  1 2. The scope of claim 10, wherein the molecular skeleton of the organic compound as the component (A) comprises only one or more of carbon, oxygen, hydrogen, hydrogen, hydrogen, halogen, and halogen. Or the foamable resin composition according to item 11;
1 3. 前記 （A) 成分の有機化合物が、 下記一般式 （ 8 ) 〜式 （ 1 0 ) ;
Figure imgf000078_0001
1 3. The organic compound as the component (A) is represented by the following general formulas (8) to (10);
Figure imgf000078_0001
(式 （ 8 ) 〜式 （ 1 0) において、 R 1 1は、 H又は CH3 を示し、 R 12、 R 13、 R 16、 R'7、 R'8、 R22は、 炭素数 0 ~ 6の 2価の置換基を示し、 R 14、 R 1 S、 R 1 9、 R 20 , R 2 1 、 R 23、 R24は、 炭素数 0〜 6の 1価 の置換基を示し、 X2 は、 炭素数 0〜 1 0の 2価の置換基を示す。 ま た、 式 （ 8〉 において、 n,mは、 0〜 3 0 0の整数， 1は、 1〜 3 0 0の 整数、 p . Qは、 0〜 3の整数を示し、 式 （ 9 ) において、 n. m. 1 は、 0 〜 3 0 0の整数、 s は、 〜 3 0 0の整数、 p. Q. rは、 0〜 3の整数を示 し、 式 （ 1 0 ) において、 n， mは、 0〜 4の整数を示す。） (In the formulas (8) to (10), R 11 represents H or CH 3 , and R 12 , R 13 , R 16 , R ′ 7 , R ′ 8 , and R 22 each have 0 to 0 carbon atoms. It indicates 6 divalent substituents, R 14, R 1 S, R 1 9, R 20, R 2 1, R 23, R 24 is a monovalent substituent 0-6 carbon atoms, X 2 represents a divalent substituent having 0 to 10 carbon atoms, and in the formula (8), n and m are integers of 0 to 300, and 1 is an integer of 1 to 300. , P.Q represents an integer of 0 to 3, and in the formula (9), nm 1 is an integer of 0 to 300, s is an integer of 3300, and p.Q.r is 0. Represents an integer of 3 to 3, and in the formula (10), n and m represent integers of 0 to 4.)
のうちのいずれか 1種以上の構造を分子骨格として有する、 請求の範囲第 1 0項又は第 1 1項記載の発泡性樹脂組成物。 12. The foamable resin composition according to claim 10, wherein the foamable resin composition has at least one of the following structures as a molecular skeleton.
1 4. 前記 （A) 成分の有機化合物の炭素一炭素二重結合の数が、 1分子 あたり平均 2個以上であることを特徵とする、 請求の範囲第 1 0 ~ 1 3項 のいずれか 1項に記載の発泡性樹脂組成物。 14. The organic compound as the component (A), wherein the number of carbon-carbon double bonds of the organic compound is 2 or more on average per molecule. The foamable resin composition according to any one of the above.
1 5. 前記 （D) 成分の発泡剤が、 炭化水素、 ハイ ド口クロ口フルォロカ 一ボン、 又はハイ ド口フルォロカーボンから選ばれる化合物、 あるいはそ れらの混合物である、 請求の範囲第 1 0 ~ 1 4項のいずれか 1項に記載の 発泡性樹脂組成物。  15. The foaming agent as the component (D) is a compound selected from hydrocarbons, fluoridated fluorocarbons, and fluoridated carbons, or a mixture thereof. 15. The foamable resin composition according to any one of items 14 to 14.
1 6. 前記 （D) 成分の〇H基を有する化合物が、 アルコール、 カルボン 酸、 及び水のうちの 1種以上からなることを特徵とする、 請求の範囲第 1 0〜 1 5項のいずれか 1項に記載の発泡性樹脂組成物。  1 6. The compound according to any one of claims 10 to 15, wherein the compound having a 〇H group of the component (D) comprises at least one of an alcohol, a carboxylic acid, and water. Or the foamable resin composition according to item 1.
1 7. 請求の範囲第 1 0 ~ 1 6項のいずれか 1項に記載の発泡性樹脂組成 物を反応させて得られる発泡体。  1 7. A foam obtained by reacting the foamable resin composition according to any one of claims 10 to 16.
1 8. 請求の範囲第 1 0〜 1 6項のいずれか 1項に記載の発泡性樹脂組成 物を常温あるいは比較的低温の加熱下において反応させ、 発泡硬化させる ことを特徵とする発泡体の製造方法。  1 8. A foamed material characterized in that the foamable resin composition according to any one of claims 10 to 16 is reacted under normal temperature or relatively low temperature heating, and foamed and hardened. Production method.
PCT/JP1998/004988 1997-11-06 1998-11-05 Hardener, curable composition and foamable resin composition both containing the hardener, and foam made from the foamable resin composition and process for producing the same WO1999024509A1 (en)

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