JP2009084353A - Manufacturing method of curable composition, curable composition, and its cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a curable composition which contains a vinyl polymer giving a cured product showing generally satisfactory mechanical characteristics, oil resistance, heat resistance and the like and can be cured by a hydrosilylation reaction and from which the cured product having a small compression set can be obtained, and to provide the cured product. <P>SOLUTION: The manufacturing method of the curable composition containing (A) a polyoxyalkylene polymer having at least one alkenyl group in which hydrosilylation reaction is possible in its molecule and/or the vinyl polymer, (B) a compound (II) containing a hydrosilyl group, (C) a hydrosilylation catalyst and (D) a filler, includes a step for mixing the component (A) and the component (D) under condition of reduced pressure while heating the components at 90°C or above. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a liquid curable composition, a curable composition obtained by the production method, and a cured product thereof. More specifically, the curing can provide a cured product having a small compression set, comprising an alkenyl group-containing polyoxyalkylene polymer and / or vinyl polymer, a hydrosilyl group-containing compound, a hydrosilylation catalyst, and a filler. The present invention relates to a method for producing an adhesive composition, a curable composition obtained by the production method, and a cured product thereof.

  A molded product containing a polyoxyalkylene polymer or a vinyl polymer as a main component can be obtained by kneading a high molecular weight polymer together with various additives in a heated state using a roll, a mill, or the like, followed by molding. For example, a molded product of acrylic rubber containing a (meth) acrylic polymer as a main component is heat vulcanized after kneading a compound such as a filler and a vulcanizing agent with unvulcanized rubber (acrylic rubber). Is obtained. However, it is inferior in workability, such as sticking to a roll during kneading and being difficult to smooth during sheeting, and it has poor workability such as non-fluidity during molding and a low vulcanization rate, and is easy to scorch. There is a problem such as poor curability (Non-Patent Document 1).

  Therefore, as a method for solving these problems, the present inventors developed a (meth) acrylic polymer having a narrow molecular weight distribution having an alkenyl group at the terminal (Patent Document 1), and containing an alkenyl group at the terminal. The molded object (patent document 2) and the on-site molded gasket (patent document 3, patent document 4) which harden | cure the curable composition containing the vinyl polymer and hydrosilyl group containing compound to be proposed are proposed. When a (meth) acrylic polymer having a reactive functional group at the molecular end is used, the molecular weight between the crosslinking points can be effectively obtained, and the molecular weight of the main chain itself can be reduced. As a result, it is expected that processability will be improved. Also, the hydrosilylation reaction used for curing a curable composition containing a vinyl polymer containing an alkenyl group at the terminal and a hydrosilyl group-containing compound is very slow or substantially progresses at low temperatures. Without heating, it has a feature of excellent thermal potential that the reaction is completed quickly by heating. Therefore, this curable composition has an advantage that a cured product can be obtained quickly without scorching during molding. Therefore, a curable composition containing a vinyl polymer containing an alkenyl group at the terminal and a hydrosilyl group-containing compound is excellent in moldability, and can give a molded article having excellent oil resistance and heat resistance after molding. . However, there are cases where these molded articles have insufficient strength and hardness, and generally a filler is added to compensate for this defect. However, this type of molded rubber to which a filler is added has low resistance to compression under heating as it is, and compression set, which is one index indicating resistance to compression, is insufficient. Therefore, it is necessary to improve the compression set to be used as a molded product that undergoes compression deformation for a long time, for example, as a sealant. In order to obtain a compression set sufficient for practical use, a molded product obtained by injection molding, transfer molding, press molding or the like is further subjected to heat treatment (secondary vulcanization) for a long time at a high temperature of 150 to 200 ° C. Is called. However, this method requires a process in which molded rubber once molded is placed in a high-temperature oven and heated for a long time, and there is a problem that work efficiency is low and productivity is poor.

  Conventionally, various sealing materials such as O-rings, oil seals, packings, and gaskets that require heat resistance, compression set, and oil resistance, and excellent cross-linking properties such as halogen groups, epoxy groups, and carboxyl groups. In recent years, further improvement in heat resistance and realization of low compression set have been demanded. It has long been known that acrylic rubbers having a halogen group or an active halogen group as a crosslinking point can give a vulcanizate having a smaller compression set than an acrylic rubber having an epoxy group as a crosslinking point (patent) Document 5) has the drawback that this vulcanizate having a halogen group as a crosslinking point is not necessarily sufficiently resistant to metal corrosion and lacks storage stability before vulcanization. On the other hand, acrylic rubber having a carboxyl group as a crosslinking point has been actively studied in recent years because it is superior in heat resistance and compression set than conventional acrylic rubber using an epoxy group, a halogen group or the like. It has been proposed to vulcanize an acrylic rubber copolymerized with a fumaric acid mono-lower alkyl ester using an aromatic diamine vulcanizing agent and a guanidine vulcanizing aid (Patent Document 6). Scorch may occur. Furthermore, a method using a strong base vulcanizing agent as a cross-linking agent has been proposed (Patent Document 7). However, a strong base compound is highly toxic, and it is difficult to knead and handle the rubber composition after kneading. In addition, when these strong base vulcanizing agents are used, scorching may occur during vulcanization. It has been proposed to contain a carboxyl group-containing acrylic rubber and silica obtained by firing wet process silica (Patent Document 8), but has the problem that scorch is early and inferior in storage stability, and the fired silica is expensive, Moreover, there exists a difficulty that the filler which can be used is limited to a baking silica. Further, a method for improving heat resistance and compression set by containing a chlorine group-containing silane coupling agent and silica in a carboxyl group-containing acrylic rubber has been proposed (Patent Document 9). Due to the chlorine group contained in the ring agent, the metal corrosiveness is inferior. As described above, conventionally known methods for improving the compression set of acrylic rubber having a crosslinking point such as a halogen group, an epoxy group, and a carboxyl group include a compounding agent such as a filler, a crosslinking agent, and a crosslinking aid. Mainly from the point of view of ingenuity. However, once the crosslinking type is different, depending on the type, amount and combination of the compounding agents, the properties of the curable composition, storage stability, vulcanization speed, mechanical properties of the resulting cured product, heat resistance, compression set It is clear that various properties such as oil resistance are greatly changed, and it is difficult to apply the conventional acrylic rubber technology to a curable composition of a hydrosilylation curable type having a different crosslinking type. No applicable technology has been found.

  On the other hand, although the main chain is completely different, there is a similar problem in the silicone rubber region using the same curing type as that of the present invention, and various studies have been made to solve the conventional problems. For example, a method of heating and mixing organopolysiloxane containing alkenyl groups, reinforcing silica, and organohydrogenpolysiloxane at 100 ° C. or higher is disclosed (Patent Document 10), which is compatible with vinyl polymers. When organohydrogenpolysiloxane is used, when heated and mixed at 100 ° C. or higher, there is a problem that gelation occurs during the production of the curable composition. In addition, a method of heating and mixing wet silica at a temperature of 80 ° C. or lower when mixing an organopolysiloxane containing an alkenyl group, an organohydrogenpolysiloxane, a platinum-based catalyst, and wet silica is disclosed (Patent Document 11). However, in this method, the moisture contained in the wet silica is not removed, and bubbles are generated in the cured product due to the influence of moisture remaining when the cured product is produced, which causes a problem in appearance. Moreover, after mixing an organopolysiloxane containing an alkenyl group and reinforcing silica, heat treating, adding aminosilane and further removing aminosilane has been proposed (Patent Document 12). In this method, aminosilane is proposed. The process of addition and removal is necessary, and there is a problem that the operation is complicated.

Further, it is disclosed that a composition containing an alkenyl group-containing polyfluoro compound and hydrophobic silica powder, which uses the same curing mode as that of the present invention, is kneaded under a heating / depressurization condition with a planetary mixer. (Patent Document 13). However, its purpose is to make the polyfluoro compound easy to wet the silica powder surface in order to prevent isocyanurate, organosiloxane, etc. for imparting self-adhesion from adsorbing to the silica surface. Although it has been disclosed that the effect of reducing the viscosity of the adhesive component and improving the adhesive properties is disclosed, no study has been conducted for the purpose of improving mechanical properties such as compression set.
JP-A-9-272714 JP 2000-154255 A JP 2000-154370 A JP 2003-113288 A JP 2004-59821 A JP 11-92614 A Japanese Patent Laid-Open No. 11-80488 JP 2004-168885 A JP 2006-249237 A JP-A-10-120905 JP-A-10-130507 Japanese Patent Laid-Open No. 7-278437 Japanese Patent Laying-Open No. 2005-2142 Journal of the Japan Rubber Association, Vol. 73, No. 10, 555 (2000)

  The objective of this invention is providing the manufacturing method of the curable composition which can obtain hardened | cured material with a small compression set in the curable composition which can be hardened | cured by hydrosilylation reaction, and its hardened | cured material.

  As a result of intensive studies in view of the above-mentioned present situation, the present inventors have found that the above-mentioned problems can be improved by bringing the vinyl polymer and the filler into a reduced pressure state in addition to heating. The headline and the present invention were completed.

  That is, the present invention relates to (A) a polyoxyalkylene polymer and / or a vinyl polymer (hereinafter referred to as “alkenyl group capable of hydrosilylation reaction”) containing at least one alkenyl group capable of hydrosilylation reaction in the molecule. In the molecule thereof, the “polyoxyalkylene polymer and / or vinyl polymer” may be simply referred to as “organic polymer (I)”), (B) hydrosilyl group-containing compound ( II), a method for producing a curable composition containing (C) a hydrosilylation catalyst and (D) a filler, wherein the component (A) and the component (D) are at 90 ° C. or higher under reduced pressure. It is related with the manufacturing method of a curable composition including the process mixed while heating.

  In the manufacturing method of the said curable composition, it is preferable that the said heating is 180 degreeC or more.

  The vinyl polymer containing at least one alkenyl group capable of hydrosilylation in the molecule is preferably a hydrocarbon polymer and / or a (meth) acrylic polymer.

  The vinyl polymer containing at least one alkenyl group capable of hydrosilylation reaction in the molecule preferably has a molecular weight distribution of less than 1.8.

  The vinyl polymer containing at least one alkenyl group capable of hydrosilylation in the molecule includes a (meth) acrylic monomer, an acrylonitrile monomer, an aromatic vinyl monomer, a fluorine-containing vinyl monomer, and a silicon-containing vinyl polymer. Those produced by mainly polymerizing at least one selected from the group consisting of monomers are preferred, (meth) acrylic polymers are more preferred, acrylic polymers are more preferred, and acrylate ester polymers are particularly preferred. .

  The vinyl polymer containing at least one alkenyl group capable of hydrosilylation in the molecule is ethyl acrylate, butyl acrylate, 2-methoxyethyl acrylate, 2-methoxybutyl acrylate, acrylic acid 2 -It may be produced mainly by polymerizing at least one selected from the group consisting of ethylhexyl and stearyl acrylate.

  The main chain of the vinyl polymer containing at least one alkenyl group capable of hydrosilylation reaction in the molecule may be one produced by a living radical polymerization method. As the living radical polymerization, Atom transfer radical polymerization is preferred.

The vinyl polymer containing at least one alkenyl group capable of hydrosilylation reaction in the molecule includes the following steps:
(1a) By polymerizing a vinyl monomer by an atom transfer radical polymerization method, the general formula (1)
-C (R ¹ ) (R ² ) (X) (1)
(In the formula, R ¹ and R ² represent a group bonded to an ethylenically unsaturated group of a vinyl monomer. X represents chlorine, bromine or iodine.)
A vinyl polymer having a terminal structure represented by
(2a) converting the terminal halogen of the polymer into a substituent having an alkenyl group capable of hydrosilylation reaction;
Or obtained by:
(1b) A vinyl polymer is produced by polymerizing a vinyl monomer by a living radical polymerization method,
(2b) reacting the polymer with a compound having at least two alkenyl groups having low polymerizability;
May be obtained.

  The organic polymer (I) preferably has an alkenyl group capable of hydrosilylation reaction at the end of the molecular chain.

  In the method for producing the curable composition, the (B) hydrosilyl group-containing compound (II) is preferably an organohydrogenpolysiloxane.

  In the method for producing the curable composition, the filler (D) is preferably silica, and more preferably surface-untreated silica.

  This invention relates to the curable composition obtained by the manufacturing method of the said curable composition, and the hardened | cured material formed by hardening | curing the said curable composition.

  ADVANTAGE OF THE INVENTION According to this invention, the curable composition which can obtain hardened | cured material with a small compression set can be manufactured in the curable composition which can be hardened | cured by hydrosilylation reaction.

  Below, the manufacturing method of the curable composition of this invention and its hardened | cured material are explained in full detail.

  First, the component (A) contained in the curable composition of the present invention is a polyoxyalkylene polymer and / or a vinyl polymer containing at least one alkenyl group capable of hydrosilylation reaction in the molecule, (B The hydrosilyl group-containing compound (II), (C) hydrosilylation catalyst, and (D) filler will be described.

<< (A) Organic polymer (I) >>
The main chain of the organic polymer (A) containing at least one alkenyl group capable of hydrosilylation reaction in the molecule of the present invention is a polyoxyalkylene polymer or vinyl polymer. As the vinyl polymer, Hydrocarbon polymers and (meth) acrylic polymers are preferred.
Specifically, polyoxyalkylene heavy polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Copolymer; ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or copolymer of butadiene and acrylonitrile and / or styrene, polybutadiene, isoprene or butadiene Copolymer of acrylonitrile and styrene, hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers, ethyl (meth) acrylate, butyl ( (A) (meth) acrylic polymer obtained by radical polymerization of monomers such as acrylate, (meth) acrylic acid monomer, vinyl polymer obtained by radical polymerization of monomers such as vinyl acetate, acrylonitrile, styrene, Examples thereof include a vinyl polymer such as a graft polymer obtained by polymerizing a vinyl monomer in the polyoxyalkylene polymer. Of the organic polymers having the main chain skeleton, a (meth) acrylic polymer is preferable from the viewpoint of excellent heat resistance, oil resistance, cold resistance, etc. of the obtained cured product, and a (meth) acrylic acid ester type is preferable. A polymer is more preferable, and an acrylic ester polymer is most preferable.
From the viewpoint that the glass transition temperature is relatively low and the obtained cured product is excellent in cold resistance, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, polyoxyalkylene polymers, A (meth) acrylic polymer is preferred. These organic polymers (I) may be a single type of organic polymer or a mixture of a plurality of types of organic polymers. When mixing and using multiple types, it is preferable that these organic polymers are compatible.

  In the present invention, an organic polymer having a main chain skeleton other than the above and containing at least one alkenyl group capable of hydrosilylation in the molecule can be used in combination as long as the effects of the present invention are not impaired. The main chain skeleton is not particularly limited. For example, a polyester polymer obtained by condensation of a dibasic acid such as adipic acid with glycol or ring-opening polymerization of lactones; a polysulfide polymer; Nylon 6 by ring-opening polymerization of ε-caprolactam, nylon 6.6 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 6.10 by condensation polymerization of hexamethylenediamine and sebacic acid, by condensation polymerization of ε-aminoundecanoic acid Nylon 11, nylon 12 by ring-opening polymerization of ε-aminolaurolactam, polyamide polymer such as copolymer nylon having two or more components among the above nylons; for example, produced by condensation polymerization from bisphenol A and carbonyl chloride Polycarbonate polymer, diallyl phthalate polymer, etc. And the like. When mixing and using these, it is preferable that the organic polymer (I) and these organic polymers are compatible.

<Main chain>
The polyoxyalkylene polymer containing at least one alkenyl group capable of hydrosilylation in the present invention (hereinafter sometimes simply referred to as “polyoxyalkylene polymer”) is specifically mentioned. The polymer has a main chain having a repeating unit represented by the general formula (3). General formula (3):
—R ⁴ —O— (3)
(Wherein R ⁴ is a divalent alkylene group)
R ⁴ in the general formula (3) is preferably a linear or branched alkylene group having 1 to 14, more preferably 2 to 4 carbon atoms. Specific examples of the repeating unit represented by the general formula (3) include —CH ₂ O—, —CH ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) O—, —CH ₂ CH (C ₂ H _{5 ) O -, - CH 2 C} (CH 3) 2 O -, - CH 2 CH 2 CH 2 CH 2 O- and the like. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, a polymer having —CH ₂ CH (CH ₃ ) O— as the main repeating unit is preferable from the viewpoint of availability and workability. The main chain of the polymer may contain a repeating unit other than the oxyalkylene group. In this case, the total of oxyalkylene units in the polymer is preferably 80% by weight or more, particularly 90% by weight or more.

  The vinyl polymer containing at least one alkenyl group capable of hydrosilylation reaction in the present invention (hereinafter sometimes simply referred to as “vinyl polymer”) is a vinyl polymer constituting the main chain. It does not specifically limit as a monomer, A various thing can be used. Specifically, (meth) acrylic acid monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, silicon-containing vinyl monomers, maleimides such as various monomers described in JP-A-2005-232419, paragraph [0018] Examples thereof include vinyl monomers, nitrile group-containing vinyl monomers, amide group-containing vinyl monomers, vinyl esters, alkenes, conjugated dienes, vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. These may be used alone or a plurality of these may be copolymerized. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  Among these, it is produced mainly by polymerizing at least one monomer selected from the group consisting of (meth) acrylic acid monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. It is preferable that Here, “mainly” means that 50 mol% or more of the monomer units constituting the vinyl polymer is the above monomer, and preferably 70 mol% or more.

  In particular, from the physical properties of the product, aromatic vinyl monomers and / or (meth) acrylic acid monomers are preferable, acrylic ester monomers and / or methacrylic ester monomers are more preferable, and acrylic ester monomers are more preferable. Particularly preferred acrylic ester monomers include alkyl acrylate monomers, specifically ethyl acrylate, 2-methoxyethyl acrylate, stearyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic acid. 2-methoxybutyl.

  In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in this case, these preferred monomers may be contained in a weight ratio of 40% by weight or more. preferable.

  Examples of the vinyl polymer in the present invention include (1) polymerizing an olefin compound having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene and isobutylene as a main monomer, and (2) butadiene, isoprene and the like. A hydrocarbon polymer which can be obtained by a method such as homopolymerizing a diene compound such as the above, or hydrogenating it after copolymerizing with the olefin compound is also usable. The isobutylene polymer and the hydrogenated polybutadiene polymer are preferable because it is easy to introduce a functional group at a terminal, easily control the molecular weight, and can increase the number of terminal functional groups, and an isobutylene polymer is preferable. .

  In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, or may be a copolymer with other monomers, but the repeating unit derived from isobutylene is 50 from the viewpoint of rubber properties. What contains more than weight% is preferable, What contains 80 weight% or more is more preferable, What contains 90 to 99 weight% is especially preferable.

  Said hydrocarbon polymer may be used independently and may be used together 2 or more types.

  The molecular weight distribution of the organic polymer (I) in the present invention, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is particularly limited. However, in the case of a vinyl polymer, it is preferably less than 1.8, more preferably 1.7 or less, still more preferably 1.6 or less, and even more preferably 1.5 or less. Particularly preferably, it is 1.4 or less, and most preferably 1.3 or less. If the molecular weight distribution is too large, the viscosity at the molecular weight between the same cross-linking points increases and the handling tends to be difficult. In the GPC measurement in the present invention, chloroform is used as the mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

  The number average molecular weight of the organic polymer (I) in the present invention is not particularly limited, but when measured by GPC, a range of 500 to 1,000,000 is preferable, and 1,000 to 100,000 is more preferable. 5,000 to 80,000 are more preferred, and 8,000 to 50,000 are even more preferred. If the molecular weight is too low, the original characteristics of the organic polymer (I) tend to be hardly expressed, while if it is too high, handling tends to be difficult.

  The structure of the organic polymer (I) of the present invention may be a linear polymer, a branched polymer, or a mixture thereof.

<Synthesis method>
The method for polymerizing the polyoxyalkylene polymer of the present invention is the usual polymerization method of oxyalkylene (anionic polymerization method using caustic alkali) disclosed in JP-A-50-13396, etc., JP-A-50-149797. A polymerization method using a chain extension reaction method using this polymer as a starting material, a polymerization method using a cesium metal catalyst disclosed in Japanese Patent Application Laid-Open No. 7-179597, Japanese Patent Application Laid-Open No. 61-197631, Polymerization method using porphyrin / aluminum complex catalyst disclosed in JP-A-61-215622, JP-A-61-215623, JP-A-61-218632, disclosed in JP-B-46-27250 and JP-B-59-15336 A polymerization method using a composite metal cyanide complex catalyst, a catalyst comprising a polyphosphazene salt disclosed in JP-A-10-273512, etc. It can be obtained by a polymerization method or the like are.

  Practically, a method using a double metal cyanide complex catalyst is preferable from the viewpoint of catalyst availability and polymerization stability. A known method can be used as a method for producing the double metal cyanide complex catalyst. For example, U.S. Pat. Nos. 3,278,457, 3,278,459, 5,891,818, 5,767,323, 5,767,323, 5,536,883 No. 5,482,908, No. 5,158,922, No. 4,472,560, No. 6,063,897, No. 5,891,818, No. 5,627,122, The methods described in JP-A-5,482,908, JP-A-5,470,813, JP-A-5,158,922 and the like are preferable.

  In addition, in the case of a hydrocarbon polymer, particularly an isobutylene polymer, which is one of the preferred embodiments of the vinyl polymer of the present invention, an inifer polymerization (JP Kennedy et al., Found by Kennedy et al. J. Polymer Sci., Polymer Chem. Ed. 1997, 15, 2843). According to this polymerization method, it is known that a molecular weight of about 500 to 100,000 can be polymerized with a molecular weight distribution of 1.5 or less, and various functional groups can be introduced into molecular terminals.

  In addition to the hydrocarbon polymer polymerization method, the vinyl polymer of the present invention can be obtained by various polymerization methods and is not particularly limited. However, the radical polymer is not limited in terms of the versatility of the monomer and ease of control. A polymerization method is preferred, and among the radical polymerizations, controlled radical polymerization is more preferred. This controlled radical polymerization method can be classified into a “chain transfer agent method” and a “living radical polymerization method”. Living radical polymerization, in which the molecular weight and molecular weight distribution of the resulting vinyl polymer can be easily controlled, is further preferred, and atom transfer radical polymerization is particularly preferred from the viewpoint of availability of raw materials and ease of introduction of a functional group at the polymer terminal. The above radical polymerization, controlled radical polymerization, chain transfer agent method, living radical polymerization method, and atom transfer radical polymerization are known polymerization methods. For example, JP-A-2005-232419 and Reference can be made to the description in Japanese Unexamined Patent Application Publication No. 2006-291073.

  The atom transfer radical polymerization, which is one of preferred methods for synthesizing the vinyl polymer in the present invention, will be briefly described below.

  In atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl-position), or a sulfonyl halide. A compound or the like is preferably used as an initiator. Specific examples include compounds described in paragraphs [0040] to [0064] of JP-A-2005-232419.

  In order to obtain a vinyl polymer having two or more alkenyl groups capable of hydrosilylation in one molecule, an organic halide having two or more starting points or a sulfonyl halide compound is used as an initiator. preferable. For example,

等が挙げられる。

Etc.

  There is no restriction | limiting in particular as a vinyl-type monomer used in atom transfer radical polymerization, All the illustrated vinyl-type monomers mentioned above can be used suitably.

  Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses a periodic table group 7, group 8, group 9, group 10, or group 11 element as a central metal, More preferably, it is zero valence. Of copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel as a central metal, particularly preferably a copper complex. Specific examples of the monovalent copper compound used to form the copper complex include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, and oxidized oxide. Cuprous, cuprous perchlorate, and the like. In the case of using a copper compound, 2,2′-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity These polyamines are added as ligands.

The polymerization reaction can be carried out without solvent, but can also be carried out in various solvents. It does not specifically limit as a kind of solvent, The solvent of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0067]] is mentioned. These may be used alone or in combination of two or more. Polymerization can also be performed in an emulsion system or a system using supercritical fluid CO ₂ as a medium.

  Although superposition | polymerization temperature is not limited, It can carry out in the range of 0-200 degreeC, Preferably, it is the range of room temperature-150 degreeC.

<Alkenyl group capable of hydrosilylation reaction>
The alkenyl group capable of hydrosilylation reaction contained in the organic polymer (I) used in the present invention is not limited, but is preferably represented by the general formula (2).
H ₂ C═C (R ³ ) − (2)
(In the formula, R ³ represents hydrogen or an organic group having 1 to 20 carbon atoms.)
Although it does not specifically limit as said C3-C20 organic group of said R < ³ >, A C1-C20 alkyl group, a C6-C20 aryl group, and a C7-C20 aralkyl group are mentioned preferably. Specifically, the following groups are exemplified.
_{- (CH 2) n -CH 3} , -CH (CH 3) - (CH 2) n -CH 3, -CH (CH 2 CH 3) - (CH 2) n -CH 3, -CH (CH 2 CH _{3) 2, -C (CH 3} ) 2 - (CH 2) n -CH 3, -C (CH 3) (CH 2 CH 3) - (CH 2) n -CH 3, -C 6 H 5, - _{C 6 H 4 (CH 3)} , - C 6 H 3 (CH 3) 2, - (CH 2) n -C 6 H 5, - (CH 2) n -C 6 H 4 (CH 3), - ( _{CH 2) n -C 6 H 3} (CH 3) 2
(N is an integer of 0 or more, and the total carbon number of each group is 20 or less)
From the viewpoint of the activity of the hydrosilylation reaction, R ³ is more preferably hydrogen or a methyl group.

  The alkenyl group capable of undergoing hydrosilylation reaction in the organic polymer (I) is not particularly limited, but is preferably not activated by a carbonyl group, alkenyl group or aromatic ring conjugated with the carbon-carbon double bond. .

  The form of bonding between the alkenyl group capable of hydrosilylation reaction and the main chain of the organic polymer (I) is not particularly limited, but via a carbon-carbon bond, ester bond, ether bond, carbonate bond, amide bond, urethane bond, etc. Are preferably combined.

The organic polymer (I) has at least one alkenyl group capable of hydrosilylation reaction in the molecule, and an average of 1.2 to 1 molecule per molecule of the organic polymer from the viewpoint of the mechanical properties of the cured product. Those having 3.0 are preferred. Although not specifically limited, specifically, the average value obtained by ¹ H-NMR analysis of the number of alkenyl groups capable of hydrosilylation introduced per molecule of the organic polymer is 1.2 to 3 The number is preferably 0.0, and more preferably 1.5 to 2.5.

  When rubber properties are particularly required for the cured product obtained from the curable composition of the present invention, the molecular weight between crosslinking points that greatly affects rubber elasticity can be increased. At least one is preferably at the end of the molecular chain (main chain). More preferably, all alkenyl groups capable of hydrosilylation reaction are present at the molecular chain ends.

  Various methods can be used for introducing an alkenyl group into the polyoxyalkylene polymer. For example, it can be introduced by copolymerization of a monomer having an alkenyl group such as allyl glycidyl ether and an oxyalkylene monomer. In addition, by reacting an oxyalkylene polymer having a functional group such as a hydroxyl group or an alkoxide group on the main chain or side chain with an organic compound having a functional group and an alkenyl group reactive to these functional groups, Alkenyl groups can be introduced into the main chain or side chain. In particular, when an alkenyl group is present at the end of the main chain of the polymer, the effective network chain length in the cured product is increased, and thus a cured product having excellent mechanical properties can be obtained.

  Examples of the organic compound having a functional group and an alkenyl group having reactivity with the above functional group include those having 3 to 20 carbon atoms such as acrylic acid, methacrylic acid, vinyl acetate, acrylic acid chloride or acrylic acid bromide. Saturated fatty acid acid halide, acid anhydride, allyl chloroformate, allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) ether, allyl ( Chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy) benzene, allyloxy (chloromethyl) benzene and the like.

  Examples of the method for producing a vinyl polymer containing at least one alkenyl group capable of hydrosilylation reaction in the present invention, particularly a hydrocarbon polymer having a main chain skeleton, include Japanese Patent Publication No. 4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, JP-A-1-197509, JP-A-2539445, JP-A-2873395, JP-A-7-53882 Although it is described in the book etc., it is not specifically limited to these.

  The vinyl polymer having at least one alkenyl group capable of hydrosilylation reaction at the molecular end of the present invention, in particular, the (meth) acrylic polymer having a main chain skeleton is disclosed in JP-B-3-14068 and JP-B-4-55444. No. 6, JP-A-6-221922 and the like. However, since these methods are free radical polymerization methods using the above-mentioned “chain transfer agent method”, the resulting polymer has a relatively high proportion of alkenyl groups capable of hydrosilylation reaction at the molecular chain ends. The molecular weight distribution (Mw / Mn) is generally as large as 2 or more, and the viscosity is increased. Therefore, in order to obtain a vinyl polymer having a narrow molecular weight distribution and a low viscosity and having an alkenyl group capable of hydrosilylation reaction at the molecular chain terminal at a high ratio, the above-mentioned “living radical polymerization method” is used. Is preferably used.

  As a method for introducing an alkenyl group capable of hydrosilylation reaction into the obtained vinyl polymer, a known method can be used. For example, the method of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0074]-[0099] is mentioned. Among these methods, the diene compound addition method is preferable because it is easier to control. In the case of obtaining from a vinyl polymer containing at least one hydroxyl group in the molecule, a method of reacting alkenyl alcohol at the end of the polymerization from the viewpoint of easier control, and reacting a stabilized carbanion at the reaction terminal of the polymer It is preferable to use a vinyl polymer containing at least one hydroxyl group in the molecule obtained by the method.

  Here, a diene compound addition method, which is one of preferable introduction methods, will be briefly described below. In the diene compound addition method, a vinyl polymer obtained by living radical polymerization of a vinyl monomer is reacted with a compound having at least two alkenyl groups having low polymerizability (hereinafter referred to as “diene compound”).

Examples of the alkenyl group of the diene compound include a terminal alkenyl group [CH ₂ ═C (R) —R ′; R is hydrogen or an organic group having 1 to 20 carbon atoms, and R ′ is a monovalent or divalent one having 1 to 20 carbon atoms. R and R ′ may be bonded to each other to have a cyclic structure. ] Or an internal alkenyl group [R′—C (R) ═C (R) —R ′; R is hydrogen or an organic group having 1 to 20 carbon atoms, R ′ is a monovalent or divalent group having 1 to 20 carbon atoms It is an organic group, and two R or two R ′ may be the same or different from each other. Any two of two R and two R ′ may be bonded to each other to have a cyclic structure. ], But a terminal alkenyl group is more preferable. R is hydrogen or an organic group having 1 to 20 carbon atoms. Examples of the organic group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms. The aralkyl group is preferably. Among these, as R, hydrogen or a methyl group is particularly preferable. Examples of the monovalent or divalent organic group having 1 to 20 carbon atoms of R ′ include a monovalent or divalent alkyl group having 1 to 20 carbon atoms, a monovalent or divalent aryl group having 6 to 20 carbon atoms, A monovalent or divalent aralkyl group having 7 to 20 carbon atoms is preferred. Among these, R ′ is particularly preferably a methylene group, an ethylene group, or an isopropylene group. At least two alkenyl groups of the diene compound may be the same or different from each other, and at least two alkenyl groups of the diene compound may be conjugated.

  Specific examples of the diene compound include isoprene, piperylene, butadiene, myrcene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene, etc. 5-hexadiene, 1,7-octadiene and 1,9-decadiene are preferred.

  A vinyl radical having an alkenyl group at the target terminal is obtained by conducting a living radical polymerization of a vinyl monomer and isolating the resulting polymer from the polymerization system and then subjecting the isolated polymer and the diene compound to a radical reaction. Although it is possible to obtain a polymer, a method of adding a diene compound to the polymerization reaction system at the end of the polymerization reaction or after completion of the reaction of the predetermined vinyl monomer is more preferable because it is simple.

  The addition amount of the diene compound may be an equivalent amount or a small excess amount with respect to the polymer growth terminal when the diene compound having a large difference in reactivity between the two alkenyl groups is used. When using a diene compound having the same or little difference in properties, it is preferably an excess amount relative to the polymer growth terminal, specifically preferably 1.5 times or more, more preferably 3 times or more, particularly Preferably it is 5 times or more.

  Of the above-described production methods, those obtained by the following method are particularly preferred as the vinyl polymer containing at least one alkenyl group capable of hydrosilylation reaction in the curable composition of the present invention. It is.

As the first method,
(1a) By polymerizing a vinyl monomer by an atom transfer radical polymerization method, the following general formula (1)
-C (R ¹ ) (R ² ) (X) (1)
(In the formula, R ¹ and R ² represent a group bonded to an ethylenically unsaturated group of a vinyl monomer. X represents chlorine, bromine or iodine.)
A vinyl polymer having a terminal structure represented by
(2a) converting the terminal halogen of the polymer into a substituent having an alkenyl group capable of hydrosilylation reaction;
A method is mentioned.

As a second method,
(1b) A vinyl polymer is produced by polymerizing a vinyl monomer by a living radical polymerization method,
(2b) reacting the polymer with a compound having at least two low-polymerizable alkenyl groups;
A method is mentioned.

<< (B) Hydrosilyl group-containing compound (II) >>
As the component (B) hydrosilyl group-containing compound (II), a polyoxyalkylene polymer and / or a vinyl polymer containing at least one alkenyl group of component (A) capable of hydrosilylation reaction in the molecule. As long as it is a hydrosilyl group-containing compound that can be cured by crosslinking, various compounds can be used, and organohydrogenpolysiloxane is preferred.

  As the organohydrogenpolysiloxane, a known linear or cyclic organohydrogenpolysiloxane can be used. When the (meth) acrylic polymer is used as the component (A), the (meth) acrylic polymer is used. Aromatic ring-containing chain-like or cyclic organohydrogensiloxane is preferable from the viewpoint of compatibility. Specific examples thereof include hydrosilyl group-containing compounds described in paragraphs [0088] to [0093] of JP-A-2006-291073.

  A linear or cyclic organohydrogenpolysiloxane in which a part of the hydrosilyl group is substituted with a low molecular weight compound having two or more alkenyl groups in the molecule can also be used. Specifically, a modified hydrosilyl group obtained by slowly dropping a low molecular compound having two or more alkenyl groups in the molecule in the presence of a hydrosilylation catalyst described later with respect to an excessive amount of the above hydrosilyl group-containing compound. The containing compound can be used as the hydrosilyl group-containing compound (II). Examples of the low molecular compound having two or more alkenyl groups in the molecule include aliphatic hydrocarbon compounds, ether compounds, ester compounds, carbonate compounds, isocyanurate compounds and aromatic hydrocarbon compounds. Specifically, compounds described in paragraph [0094] of JP-A-2006-291073 can be used. Of such modified hydrosilyl group-containing compounds, the availability of raw materials, the ease of removal of excessively used hydrosilyl group-containing compounds, and the use of (meth) acrylic polymers as component (A) In consideration of compatibility with the (meth) acrylic polymer, the following may be preferably mentioned.

本発明の硬化性組成物における（Ｂ）成分の配合量としては特に限定されないが、硬化性の面から、（Ａ）成分中のヒドロシリル化反応可能なアルケニル基と（Ｂ）成分中のＳｉＨ（ヒドロシリル）基のモル比（（Ｂ）／（Ａ））が５〜０．２の範囲にあることが好ましく、２．５〜０．４であることが特に好ましい。モル比が５より大きいと、硬化後も硬化物中に活性なヒドロシリル基が多く残るので、クラック、ボイドが発生し、均一で強度のある硬化物が得られにくくなる傾向があり、０．２より小さいと、硬化が不十分で強度の小さい硬化物が得られ易くなる傾向がある。

Although it does not specifically limit as a compounding quantity of (B) component in the curable composition of this invention, From the sclerosing | hardenable surface, the alkenyl group which can be hydrosilylated in (A) component, and SiH (B) in component (B) The hydrosilyl) group molar ratio ((B) / (A)) is preferably in the range of 5 to 0.2, particularly preferably 2.5 to 0.4. If the molar ratio is larger than 5, a large number of active hydrosilyl groups remain in the cured product even after curing, so that cracks and voids are generated, and it is difficult to obtain a uniform and strong cured product. If it is smaller, a cured product with insufficient strength and low strength tends to be obtained.

  In the curable composition of the present invention, the hydrosilyl group-containing compound (II) may be used alone or in combination of two or more.

<< (C) Hydrosilylation Catalyst >>
There is no restriction | limiting in particular about the hydrosilylation catalyst which is (C) component in this invention, The well-known hydrosilylation catalyst normally used for hydrosilylation reaction can be used arbitrarily. Specific examples include platinum catalysts and hydrosilylation catalysts described in paragraph [0137] of JP-A-2005-232419. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac) _{2 and the} like are preferable.

Although there is no restriction | limiting in particular as the usage-amount of the (C) hydrosilylation catalyst in the curable composition of this invention, 10 ^{< -1} > ^-10 <^-8> mol with respect to ¹ mol of alkenyl groups which can be hydrosilylated in (A) component. It is preferable to use in the range. More preferably, it is the range of 10 ^<-2 > ^{-10 < -6>} mol. In addition, the hydrosilylation catalyst is generally expensive and corrosive, and may generate a large amount of hydrogen gas to foam the cured product, so it is better not to use more than 10 ⁻¹ mol.

<< (D) Filler >>
There is no restriction | limiting in particular about the filler which is (D) component in this invention, Arbitrary things can be used. Specific examples include various fillers described in paragraph [0134] of JP-A-2006-291073.

In the case where the reinforcing property is added particularly for the purpose, fine powder silica such as fumed silica and wet method silica is preferable. Among these, particles having a particle diameter of 50 μm or less and a specific surface area (by BET method (low-temperature low-humidity physical adsorption of inert gas)) of 80 m ² / g or more are preferable from the effect of reinforcing properties. More specific examples of the reinforcing silica include, but are not limited to, fumed silica Japan Aerosil and Degussa Aerosil, Tokuyama Leolosil, Excelica, Cabot Cab-O-Sil, Francil from Francor, Arc Silica from PPG, Nipsil Nipgel from Tosoh Silica, which is a wet process silica, Toksil from Tokuyama, Fine Seal, Carplex from Degussa, Ultrasil, Sipernat, Silicia from Fuji Silysia , Silo Hovic, Mizusukasil of Mizusawa Chemical Co., Syloid of WR Grace, Silcron of SCM, Gasil of Crossfield, etc.

  The surface of the reinforcing silica can be surface-treated with organosilane, organosilazane, diorganocyclopolysiloxane, etc., but when the surface-treated silica is used, the fluidity of the resulting curable composition However, when the curable composition is produced, it is easy to entrain the foam, and it is difficult to remove the entrained foam. There is. Further, since surface-treated silica is generally more expensive than untreated silica (surface-untreated silica), the surface treatment rate of the silica used is preferably low, preferably 70% or less, more preferably 30%. Hereinafter, silica (surface-untreated silica) not particularly subjected to surface treatment is particularly preferable. When the surface-untreated silica is used, there is an advantage that the resulting curable composition has good fluidity, little foam is involved in the production, and removal of the involved foam is easy.

  Although there is no restriction | limiting in particular as addition amount of this reinforcing silica, Preferably it is 0.1-100 weight part with respect to 100 weight part of (A) component, More preferably, it is 0.5-80 weight part, More preferably 1 to 50 parts by weight. When the blending amount is less than 0.1 parts by weight, the effect of improving the reinforcing property may not be sufficient, and when it exceeds 100 parts by weight, the workability of the curable composition may be deteriorated. Moreover, the said reinforcing silica may be used independently and may be used together 2 or more types. Moreover, you may mix and use surface-treated silica and surface untreated silica in arbitrary ratios.

  In the case where the reinforcing property is not so important, a filler described in paragraph [0136] of Japanese Patent Application Laid-Open No. 2006-291073 is mentioned, although not particularly limited. Among these fillers, crystalline silica, fused silica, dolomite, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable because they are easily available.

  In particular, when it is desired to obtain a cured product having high hardness with these fillers, mainly crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, carbon black, colloidal calcium carbonate, light calcium carbonate, calcined clay, clay In addition, a filler selected from active zinc white and the like can be added.

  Further, calcium carbonate that has been surface treated with a surface treating agent can be used. When surface-treated calcium carbonate is used, the fluidity at the time of molding of the composition of the present invention is improved as compared with the case where calcium carbonate that has not been surface-treated is used.

  Examples of the surface treatment agent include surface treatment agents described in paragraph [0161] of JP-A-2005-232419.

  The treatment amount of the surface treatment agent is preferably in the range of 0.1 to 20% by weight and more preferably in the range of 1 to 5% by weight with respect to calcium carbonate. When the treatment amount is less than 0.1% by weight, the workability improvement effect may not be sufficient, and when it exceeds 20% by weight, the storage stability of the curable composition may be lowered.

  On the other hand, heavy calcium carbonate may be added for the purpose of reducing the viscosity, increasing the amount of the compound, reducing the cost, etc., but when using this heavy calcium carbonate, the description in paragraph [0163] of JP-A-2005-232419 Things can be used.

  The fillers other than the reinforcing silica may be used alone or in combination of two or more according to the purpose and necessity. Moreover, you may use together with a reinforcing silica. In the case of using a filler other than the reinforcing silica, it is preferable to use the filler in the range of 5 to 1000 parts by weight with respect to 100 parts by weight of the component (A), and in the range of 20 to 500 parts by weight. It is more preferable to use in the range of 40 to 300 parts by weight. When the blending amount is less than 5 parts by weight, the effect of improving the breaking strength, breaking elongation and hardness of the cured product may not be sufficient, and when it exceeds 1000 parts by weight, the fluidity of the curable composition and the production Workability may be reduced.

<< Other additives >>
The curable composition of the present invention contains the above components (A), (B), (C), and (D). In order to adjust the physical properties, various additives such as, for example, , Cure modifier, metal soap, fine hollow particles, plasticizer, adhesion-imparting agent, solvent, flame retardant, antioxidant, light stabilizer, UV absorber, physical property modifier, radical inhibitor, metal deactivator In addition, an ozone degradation inhibitor, a phosphorus peroxide decomposer, a lubricant, a pigment, a foaming agent, a photocurable resin, and the like may be appropriately blended as necessary. These various additives may be used alone or in combination of two or more.

<Curing modifier>
The curable composition of the present invention may further contain a curing regulator as necessary in order to achieve both a balance between storage stability and curability.
There is no restriction | limiting in particular as a hardening regulator, Although arbitrary things can be used, It is preferable that it is a compound containing an aliphatic unsaturated bond.

  As a compound containing an aliphatic unsaturated bond, for example,

（式中、Ｒ^ａ、Ｒ^ｂは、同一又は異なって、水素原子、炭素数１〜１０のアルキル基、又は、炭素数６〜１０のアリール基を表し、両者は相互に連結していてもよい。）で示されるアセチレンアルコール類が例示される。特に、これらアセチレンアルコール類においては、Ｒ^ａあるいはＲ^ｂのかさ高さが貯蔵安定性に大きく関与しており、Ｒ^ａあるいはＲ^ｂがかさ高いものが高温での貯蔵安定性に優れることから好ましい。しかし、かさ高いものになりすぎると、貯蔵安定性には優れるものの、硬化性が悪くなるという欠点があり、貯蔵安定性と硬化性のバランスのとれたアセチレンアルコールを選ぶことが重要である。

(In formula, R ^<a> , R ^<b> is the same or different, represents a hydrogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group, and even if both are connected mutually. Acetylene alcohols represented by the following formula: In particular, in these acetylene alcohols, the bulkiness of R ^a or R ^b is greatly involved in storage stability, and those having a high R ^a or R ^b are preferred because they are excellent in storage stability at high temperatures. . However, if it becomes too bulky, the storage stability is excellent, but there is a drawback that the curability is deteriorated, and it is important to select an acetylene alcohol having a balance between the storage stability and the curability.

  Examples of acetylene alcohols having a good balance between storage stability and curability include acetylene alcohols described in paragraph [0143] of JP-A-2005-232419. Among these, 1-ethynyl-1-cyclohexanol and 3,5-dimethyl-1-hexyn-3-ol are more preferable from the viewpoint of availability.

  Examples of the compound containing an aliphatic unsaturated bond that improves storage stability at high temperatures other than acetylene alcohols include the compounds described in JP-A-2005-232419, paragraphs [0144] to [0152].

The amount of the curing modifier used can be selected almost arbitrarily as long as it is uniformly dispersed in the component (A) and the component (B), but is 2 to 10,000 moles relative to the (C) hydrosilylation catalyst. It is preferable to use in the range of equivalents. More preferably, it is the range of 5-1000 molar equivalent. When it is less than 2 molar equivalents, the storage stability may be insufficient, and when it exceeds 10,000 molar equivalents, curing tends to be slow.
Moreover, a hardening regulator may be used independently and may use 2 or more types together.

<Metal soap>
The curable composition of the present invention may further contain a metal soap as necessary in order to enhance mold releasability.

  There is no restriction | limiting in particular about metal soap, Arbitrary things can be used. Metal soap is generally a combination of long-chain fatty acids and metal ions, and has a nonpolar or low polarity part based on fatty acids and a polar part based on the part bound to metal in one molecule. Can be used.

  Examples of the long chain fatty acid include saturated fatty acids having 1 to 18 carbon atoms, unsaturated fatty acids having 3 to 18 carbon atoms, and aliphatic dicarboxylic acids. Among these, a saturated fatty acid having 1 to 18 carbon atoms is preferable from the viewpoint of availability, and a saturated fatty acid having 6 to 18 carbon atoms is particularly preferable from the viewpoint of the releasability effect.

  Examples of the metal ions include alkali metals (lithium, sodium, potassium), alkaline earth metals (magnesium, calcium, barium), zinc, lead, cobalt, aluminum, manganese, strontium, and the like.

  If a metal soap is illustrated more concretely, the metal soap of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0155] will be mentioned.

  Among these metal soaps, metal stearates are preferable from the viewpoint of availability and safety, and particularly from the viewpoint of economy, one or more selected from the group consisting of calcium stearate, magnesium stearate, and zinc stearate. Is most preferred.

  Although there is no restriction | limiting in particular as addition amount of this metal soap, It is preferable to use normally in the range of 0.025-5 weight part with respect to 100 weight part of (A) component, and 0.05-4 weight part is used. Is more preferable. If the blending amount is more than 5 parts by weight, the physical properties of the cured product tend to decrease, and if it is less than 0.025 part by weight, mold releasability tends to be difficult to obtain.

<Micro hollow particles>
For the purpose of reducing the weight and cost without causing a significant decrease in physical properties, fine hollow particles can be added in combination with the above reinforcing filler.

Such fine hollow particles (hereinafter sometimes referred to as “balloons”) are not particularly limited, but have a diameter as described in “Latest Technology for Functional Fillers” (CMC). Examples thereof include hollow bodies (inorganic balloons and organic balloons) made of inorganic or organic materials of 1 mm or less, preferably 500 μm or less, more preferably 200 μm or less. In particular, it is preferable to use a micro hollow body having a true specific gravity of 1.0 g / cm ³ or less, and more preferably to use a micro hollow body having a specific gravity of 0.5 g / cm ³ or less.

  As the inorganic balloon and the organic balloon, balloons described in paragraphs [0168] to [0170] of JP-A-2005-232419 can be used.

  The balloons may be used alone or in combination of two or more. Furthermore, the surface of these balloons is made of fatty acid, fatty acid ester, rosin, rosin acid lignin, silane coupling agent, titanium coupling agent, aluminum coupling agent, polypropylene glycol, etc. to improve dispersibility and workability of the compound. Those processed in the above can also be used. These balloons are used for weight reduction and cost reduction without impairing flexibility and elongation / strength among physical properties when the compound is cured.

  Although the addition amount of a balloon is not specifically limited, Preferably it is 0.1-50 weight part with respect to 100 weight part of (A) component, More preferably, it can be used in 0.1-30 weight part. If the amount is less than 0.1 parts by weight, the effect of reducing the weight is small. If the amount is more than 50 parts by weight, a decrease in tensile strength may be observed among the mechanical properties when the compound is cured. Moreover, when the specific gravity of a balloon is 0.1 or more, the addition amount is preferably 3 to 50 parts by weight, more preferably 5 to 30 parts by weight.

<Plasticizer>
A plasticizer can be mix | blended with the curable composition used by this invention as needed.

  Although it does not specifically limit as a plasticizer, For example, the plasticizer of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0173] is mentioned by the objectives, such as adjustment of a physical property and adjustment of a property.

  Among these, polyester plasticizers and vinyl polymers are preferable because the effect of reducing the viscosity is remarkable and the volatilization rate during the heat resistance test is low. Among them, a polymer plasticizer which is a polymer having a number average molecular weight of 500 to 15000 is added, so that the viscosity of the curable composition and the tensile strength and elongation of the cured product obtained by curing the composition are increased. Compared with the case where a low molecular plasticizer which is a plasticizer which does not contain a polymer component in the molecule can be adjusted, the initial physical properties can be maintained over a long period of time. Although not limited, the polymer plasticizer may or may not have a functional group.

  Although the number average molecular weight of the said polymeric plasticizer was described as 500-15000, More preferably, it is 800-10000, More preferably, it is 1000-8000. If the molecular weight is too low, the plasticizer may flow out over time when exposed to heat or in contact with a liquid, and the initial physical properties may not be maintained over a long period of time. Moreover, when molecular weight is too high, a viscosity will become high and there exists a tendency for workability | operativity to fall.

  Among these polymer plasticizers, those compatible with the component (A) are preferable. When a vinyl polymer is used as the component (A), a vinyl polymer is preferable from the viewpoints of compatibility, weather resistance, and heat aging resistance. Among the vinyl polymers, a (meth) acrylic polymer is more preferable, and an acrylic polymer is more preferable. Examples of the method for synthesizing the acrylic polymer include those obtained by conventional solution polymerization and solvent-free acrylic polymers. The latter acrylic plasticizer does not use a solvent or a chain transfer agent, and is a high-temperature continuous polymerization method (USP 4414370, JP 59-6207, JP-B-5-58005, JP 1-331522, USP 5010166). It is more preferable for the purpose of the present invention. Examples thereof include, but are not limited to, Toagosei UP series and the like (see the Industrial Materials October 1999 issue). Of course, the living radical polymerization method can also be mentioned as another synthesis method. According to this method, the molecular weight distribution of the polymer is narrow and the viscosity can be lowered, and the atom transfer radical polymerization method is more preferable, but it is not limited thereto.

  The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and is preferably less than 1.8. 1.7 or less is more preferable, 1.6 or less is still more preferable, 1.5 or less is more preferable, 1.4 or less is especially preferable, and 1.3 or less is the most preferable.

  The plasticizer containing the above-mentioned polymer plasticizer may be used alone or in combination of two or more, but is not necessarily required. Further, if necessary, a high molecular plasticizer may be used, and a low molecular plasticizer may be further used in a range that does not adversely affect the physical properties.

  These plasticizers can also be blended at the time of polymer production.

  Although the usage-amount in the case of using a plasticizer is not limited, Preferably it is 1-200 weight part with respect to 100 weight part of (A) component, More preferably, it is 5-100 weight part. If the amount is less than 1 part by weight, the effect as a plasticizer tends to be hardly exhibited, and if it exceeds 200 parts by weight, the mechanical strength of the cured product tends to be insufficient.

  In addition to the plasticizer, a reactive diluent described below may be used in the present invention.

  Examples of the reactive diluent include organic compounds having at least one alkenyl group or alkynyl group capable of undergoing hydrosilylation reaction in the molecule. This organic compound lowers the viscosity of the composition before curing, and bonds with the SiH group of the hydrosilyl group-containing compound (II) by a hydrosilylation reaction during the curing reaction, and is eventually taken into the network structure.

  Therefore, in the present invention, there is no particular limitation as long as it is an organic compound having at least one alkenyl group or alkynyl group capable of undergoing hydrosilylation reaction in the molecule, but a vinyl polymer is used as the component (A) of the present invention. When used, a compound having a polar group such as an ester group is preferred from the viewpoint of good compatibility with the vinyl polymer. Further, the lower the molecular weight, the easier it is to be compatible with each other, but this is preferable. In addition, from the viewpoint of heat aging resistance, weather resistance, etc., which are characteristics of the cured product obtained from the curable composition of the present invention, this reactive diluent has a carbon-carbon unsaturated bond having low activity against hydrosilylation. More preferably, it is not present.

In addition, when using a low-boiling compound that can volatilize during curing and curing as a reactive diluent, it may cause a shape change before and after curing, or may adversely affect the environment due to volatiles. An organic compound having a boiling point at room temperature of 100 ° C. or higher is particularly preferable.
Specific examples of the reactive diluent include 1-octene, 4-vinylcyclohexene, allyl acetate, 1,1-diacetoxy-2-propene, methyl 1-undecenoate, 8-acetoxy-1,6-octadiene and the like. However, it is not limited to these.

  The addition amount of the reactive diluent is not particularly limited as long as it does not hinder the formation of a three-dimensional crosslinked structure by the hydrosilylation reaction between the organic polymer (I) and the hydrosilyl group-containing compound (II). When the addition amount of the reactive diluent becomes excessive, the SiH group of the hydrosilyl group-containing compound (II) is consumed by the hydrosilylation reaction with the unsaturated group of the reactive diluent, and the organic polymer (I) The formation of a three-dimensional cross-linked structure due to may be insufficient. Although not particularly limited, specifically, the amount of the reactive diluent added is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the component (A). 70 parts by weight, more preferably 1 to 50 parts by weight.

<Solvent>
A solvent can be mix | blended with the curable composition of this invention as needed.
Solvents that can be blended include, for example, aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone A solvent etc. are mentioned. These solvents may be used during production of the polymer.

<Adhesive agent>
When the curable composition of the present invention is used alone as a molding rubber, it is not particularly necessary to add an adhesion-imparting agent. However, when it is used for two-color molding with a different substrate, an organic polymer is used. It is possible to add an adhesion-imparting agent to such an extent that the crosslinking reaction between (I) and the hydrosilyl group-containing compound (II) is not significantly inhibited and the physical properties of the resulting cured product are not significantly affected.

  The adhesiveness imparting agent that can be blended is not particularly limited as long as it imparts adhesiveness to the curable composition, but is preferably a crosslinkable silyl group-containing compound, and more preferably a silane coupling agent. Specific examples thereof include the adhesiveness-imparting agent described in paragraph [0184] of JP-A-2005-232419.

  In addition, in the range that does not inhibit the hydrosilylation reaction, carbon atoms such as epoxy groups, isocyanate groups, isocyanurate groups, carbamate groups, amino groups, mercapto groups, carboxyl groups, halogen groups, (meth) acryl groups and the like in the molecule A silane coupling agent having both an organic group having an atom other than a hydrogen atom and a crosslinkable silyl group can be used. Specific examples thereof include a silane coupling agent having both a crosslinkable silyl group and an organic group having an atom other than a carbon atom and a hydrogen atom described in paragraph [0185] of JP-A-2005-232419. Among these, alkoxysilanes having an epoxy group or a (meth) acryl group in the molecule are more preferable from the viewpoint of curability and adhesiveness.

  These may be used alone or in combination of two or more.

  Specific examples of the adhesion-imparting agent other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resins, phenol resins, sulfur, alkyl titanates, and aromatic polyisocyanates.

  Moreover, in order to further improve adhesiveness, a crosslinkable silyl group condensation catalyst can be used in combination with the above-mentioned adhesiveness-imparting agent. Examples of the crosslinkable silyl group condensation catalyst include those described in paragraph [0187] of JP-A-2005-232419.

The adhesiveness-imparting agent is preferably blended in an amount of 0.01 to 20 parts by weight per 100 parts by weight of component (A). If the amount is less than 0.01 part by weight, the effect of improving the adhesiveness is small, and if it exceeds 20 parts by weight, the physical properties of the cured product tend to be lowered. More preferably, it is 0.1-10 weight part, More preferably, it is 0.5-5 weight part.
The adhesiveness-imparting agent may be used alone or in combination of two or more.

<Antioxidant>
In the curable composition of the present invention, various antioxidants may be used as necessary in order to increase the heat resistance of the resulting cured product. Examples of these antioxidants include phenol-based antioxidants and amine-based antioxidants, and secondary antioxidants include phosphorus-based antioxidants and sulfur-based antioxidants.

  The phenolic antioxidant is not particularly limited and any one can be used. From the viewpoint of heat aging resistance, a phenolic antioxidant having a hindered phenol structure or a one-hindered phenol structure in the molecule is preferable. Specific examples of these compounds include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono (or di or tri) (α Methylbenzyl) phenol, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3- Methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, tris -[N- (3,5-di-t-butyl-4-hydroxybenzyl)] isocyanurate, 1,1,3-tris- ( -Methyl-4-hydroxy-5-tert-butylphenyl) butane, butylidene-1,1-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], octadecyl-3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis- [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, triethylene glycol-bis- [3- (3-tert-butyl-4hydroxy-5-methylphenyl) propionate], 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,3,5-tri Til-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), benzenepropanoic acid, 3,5-bis (1,1- Dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3 5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] 1,3,5-triazine-2,4,6-trione, 2,4-bis- (n-octylthio) -6 -(4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2-tert-butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxy Benzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) -ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,6- Bis [(octylthio) methyl] o-cresol, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 1,6-hexanediol-bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], and the like.

  These phenolic antioxidants may be used alone or in combination of two or more. Tetrakis- [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, tris having a molecular weight of phenolic antioxidant of 600 or more from the viewpoint of further improving heat aging resistance -[N- (3,5-di-t-butyl-4-hydroxybenzyl)] isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl- 4-hydroxybenzyl) benzene, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4 More preferred is 8,10-tetraoxaspiro [5,5] undecane.

  Although there is no restriction | limiting in particular as the usage-amount of a phenolic antioxidant, Preferably it is 0.1-10 weight part with respect to 100 weight part of (A) component, More preferably, it is 0.5-5 weight part. If the blending amount is less than 0.1 parts by weight, the effect of improving the heat aging resistance may not be sufficient, and if it exceeds 10 parts by weight, it is not only economically disadvantageous, but conversely the heat resistance deteriorates. May end up.

There is no restriction | limiting in particular about amine type antioxidant, Arbitrary things can be used. Examples of amine antioxidants include amine-ketone compounds, aromatic amine compounds, and phenylenediamine compounds. Examples of amine-ketone compounds include 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, a reaction product of diphenylamine and acetone. Etc. Examples of aromatic amine compounds include naphthylamine antioxidants, diphenylamine antioxidants, and p-phenylenediamine antioxidants. Specific examples of these compounds include phenyl-α-naphthylamine and the like. Naphthylamine antioxidants: p- (p-toluenesulfonylamido) diphenylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, 4,4′-distyryldiphenylamine, 4,4′-dioctyldiphenylamine , Octylated diphenylamine, reaction product of diphenylamine and diisobutylene, alkylated diphenylamine, p-isopropoxy-diphenylamine, bis (phenyl-isopropylidene) -4,4-diphenylamine, 4- (α-phenylethyl) diphenylamine, 4, Diphenylamine antioxidants such as '-bis (α-phenylethyl) diphenylamine, styrenated diphenylamine, di-tert-butyldiphenylamine, diphenylamine derivatives; N, N'-diphenyl-p-phenylenediamine, N-isopropyl-N' -Phenyl-p-phenylenediamine, N, N'-di-2-naphthyl-p-phenyldiamine, N-phenyl-N '-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, 4- (Anilinophenyl) methacrylamide, 4- (mercaptoacetamido) diphenylamine, 2-[(mercaptoacetyl) oxy] ethyl-3-[[4- (phenylamino) phenyl] amino] butanate, N, N′-bis ( 1-methylheptyl) -p-phenylenediamine N, N-bis (1,4-dimethylpentyl) -p-phenylenediamine, N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, N-cyclohexyl-N′- Phenyl-p-phenylenediamine, 2,4,6-tris (N-1,4-dimethylpentyl-p-phenylenediamino) 1,3,5-triazine, diallyl-p-phenylenediamine mixture, phenyl-octyl-p And p-phenylenediamine-based antioxidants such as -phenylenediamine.
Among these, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, 4,4′-dioctyl from the viewpoint of excellent heat resistance. Diphenylamine, N, N′-diphenyl-p-phenylenediamine, N, N′-di-2-naphthyl-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N-phenyl-N ′ -(3-Methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine and the like are preferred, and 4,4′-bis (α, α-dimethylbenzyl) diphenylamine is preferred because of its availability and low bleed to the cured product surface. N, N′-di-2-naphthyl-p-phenylenediamine, N-phenyl-N ′-(3-methacryloyloxy-2-hydroxyl Pills)-p-phenylenediamine are more preferred.

Although there is no restriction | limiting in particular as the usage-amount of an amine antioxidant, 0.1-10 weight part is preferable with respect to 100 weight part of (A) component, and it is more preferable to use 0.5-5 weight part. If the blending amount is less than 0.1 parts by weight, the effect of improving the heat resistance may not be sufficient, and if it exceeds 10 parts by weight, it is not only economically disadvantageous but also inferior in curability, and conversely Heat resistance may deteriorate. The amine-based antioxidant may be used alone or in combination of two or more. The phosphorus-based antioxidant and sulfur-based antioxidant used as secondary antioxidants are particularly Although there is no restriction | limiting and arbitrary things can be used, Since the sulfur type antioxidant and a thiol containing compound affect sclerosis | hardenability, the sulfur type antioxidant which has a thioether structure in a molecule | numerator is preferable. Specific examples of these compounds include 4,4′-thiobis (3-methyl-6-tert-butylphenol), dilauryl-thiodipropionate, bis {2-methyl-4- [3-n-alkyl. (C ₁₂ or C ₁₄ ) thiopropionyloxy] -5-tert-butylphenyl} sulfide, pentaerythrityl-tetrakis (3-laurylthiopropionate), ditridecyl-3,3′-thiodipropionate, distearyl -Thiodipropionate, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,6-bis [(octylthio) methyl] o-cresol 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3 5-Triazine, dimyristyl-3,3′-thiodipropionate, dibutylmethylene-bis-thioglucolate and the like.

  These sulfur-based antioxidants may be used alone or in combination of two or more. From the viewpoint of further improving heat aging resistance, pentaerythrityl-tetrakis (3-laurylthiopropionate) in which the molecular weight of the sulfur-based antioxidant is 1000 or more is more preferable.

  Although there is no restriction | limiting in particular as the usage-amount of a sulfur type antioxidant, 0.1-10 weight part is preferable with respect to 100 weight part of (A) component, and it is more preferable to use 0.5-5 weight part. When the blending amount is less than 0.1 parts by weight, the effect of improving the heat aging resistance may not be sufficient, and when it exceeds 10 parts by weight, the curability may be affected.

  There are no particular restrictions on the ratio of phenolic antioxidants, which are primary antioxidants, and amine-based antioxidants, and sulfur-based antioxidants, which are secondary antioxidants, but more effectively improves heat aging resistance. In this respect, the ratio of phenolic antioxidant or amine antioxidant / sulfur antioxidant is preferably in the range of 0.1 to 10, particularly preferably 0.3 to 3.

<< Method for producing curable composition >>
The production method of the present invention is a method for producing a curable composition containing the components (A) to (D) described above, wherein the components (A) and (D) are heated to 90 ° C. or higher under reduced pressure. And a step of mixing while mixing (hereinafter sometimes simply referred to as “heating and vacuum mixing”). By performing this heating and vacuum mixing, a curable composition capable of giving a cured product having a small compression set can be produced.

  In the heating and vacuum mixing of the production method of the present invention, mixing under reduced pressure and heating conditions, specifically, heating and mixing while reducing the pressure inside the kneader is necessary.

  The heating in the heating and vacuum mixing of the production method of the present invention (heating in the heating and vacuum mixing after adding the components (A) and (D)) may be performed at a temperature in the kneader of 90 ° C. or higher, preferably It is 130 ° C. or higher, more preferably 150 ° C. or higher, and further preferably 180 ° C. or higher. When it is heated to 130 ° C. or higher, the compression set characteristic is improved even when the cured product of the resulting curable composition does not perform secondary heating, and when heated to 180 ° C. or higher, secondary heating is not performed. In this case, the compression set characteristics are further improved. When heated to a temperature lower than 90 ° C., since the viscosity of the mixture of the component (A) and the component (D) is high, a stronger mixing blade is required, and the power for the stirrer at the time of kneading is increased. Moreover, productivity becomes inferior, such as time required for mixing becoming long. Since the higher the temperature, the lower the viscosity of the component (A), the more heat and vacuum mixing is performed, the smaller the energy required for kneading and the shorter the processing time. Then, the component (A) itself may start to decompose by heat, and the cooling step necessary for the preparation step for kneading other compounding agents after the heating and decompression mixing operation becomes long, so the temperature is 250 ° C. or less. It is preferable to implement.

  The heating and vacuum mixing step of the production method of the present invention may be carried out under reduced pressure conditions (pressure reduction during heating and vacuum mixing after adding the components (A) and (D)), but is not particularly limited. Speaking of specific decompression conditions, the degree of decompression with respect to normal pressure is preferably −0.090 MPa or less, more preferably −0.100 MPa or less, and further preferably −0.1005 MPa or less. If the degree of vacuum is higher than -0.090 MPa, the resulting cured product tends to be insufficiently cured to improve compression set.

  The “mixing” in the heating and vacuum mixing of the production method of the present invention may be an operation of mixing different components. For example, mixing by rotating a container, mixing by stirring, and applying mechanical shearing force uniformly A kneading operation for mixing is also included. In order to mix (A) and (D), a known kneader generally used in preparing a curable composition can be used. Although it is not particularly limited, for example, a batch kneader such as a Banbury mixer, a demixer (a kneader mixer), a planetary mixer, a Shinagawa stirrer, or a sealable kneader such as a uniaxial or biaxial continuous mixer. Can be used.

  In the heating and vacuum mixing step of the production method of the present invention, other conditions such as mixing time during operation can be appropriately set according to the capacity, heating capacity, mixing capacity, etc. of the apparatus within the range not impairing the effects of the present invention.

  In the heating and vacuum mixing step of the production method of the present invention, the component (A) and the component (D) are mixed (kneaded), and the component (B), the component (C), and the additives described above are added. And may be mixed. However, in the heating and vacuum mixing step, when the components (B) and (C) are further added and mixed, it is preferable to adjust the temperature in the kneader so that the hydrosilylation reaction does not proceed.

  In the production method of the present invention, it is preferable to cool the mixture after the heating and vacuum mixing. Specifically, it is preferable to cool the temperature in the kneader after heating and decompression mixing. Since the temperature in the kneading machine has increased after mixing under heating and reduced pressure, the temperature of the mixture has also increased. When (C) component or (B) component is added to the mixture, the hydrosilyl of component (C) In some cases, the catalyst is deactivated, or the addition of the component (B) and the component (C) causes thickening or gelation in the kneader due to the reaction between the component (A) and the component (B). Because there is. The cooling temperature after mixing under heating and reduced pressure in the production method of the present invention is not particularly limited as long as it does not cause the above-mentioned problems. However, in terms of specific temperature conditions, it is preferably 130 ° C. or lower. Preferably it is 120 degrees C or less, More preferably, it is 100 degrees C or less.

  In the production method of the present invention, the heating and depressurization step may be included in the step of preparing the curable composition, and the mixing and kneading operation of the component (B), the component (C) and other components, or the defoaming of the mixture What is necessary is just to perform the process and operation performed at the time of preparation of normal curable compositions, such as operation, as needed.

  As a preferred embodiment of the production method of the present invention, the components (A) and (D) are charged into a kneader, heated at 90 ° C. or higher, and under a reduced pressure of −0.09 MPa or lower with respect to normal pressure. A method of cooling to 130 ° C. or lower after mixing and charging and mixing the component (B) or the component (C) can be mentioned.

  As one preferred embodiment of the production method of the present invention, when the heating and vacuum mixing is carried out at 130 ° C. or higher, in addition to the component (A) and the component (D), the component (B) or the component (C) is present. There are cases where problems such as thickening or gelation in the kneader due to the reaction between the component (B) and the component (A) occur, or the component (C) is deactivated. Therefore, when carrying out heating and vacuum mixing at 130 ° C. or higher, it is necessary to cool to 130 ° C. or lower before adding the component (B) or the component (C). On the other hand, when carrying out heating and vacuum mixing at 130 ° C. or lower, in addition to the components (A) and (D), the components (B) or (C) are added, and then heating and vacuum mixing is performed. Alternatively, the component (B) or the component (C) may be added after the component (A) and the component (D) are heated and decompressed and mixed. However, if the (A) component, (B) component, and (C) component are heated in a mixed state, the curing reaction proceeds. Therefore, in the mixed state of these three components, heat to 90 ° C or higher. Should be avoided.

<< Method for producing cured product >>
The hardened | cured material obtained from the said curable composition obtained by the manufacturing method of this invention is demonstrated below.

  In the present invention, the curable composition is cured by the addition reaction of the SiH group to the alkenyl group using a hydrosilylation catalyst, so that the curing rate is very fast, which is advantageous for line production. In particular, the temperature for thermosetting is preferably in the range of 100 ° C to 180 ° C. Since the curable composition of the present invention is excellent in storage stability, the curing reaction hardly proceeds at a temperature lower than 100 ° C. However, when the temperature is about 100 ° C. or higher, the hydrosilylation reaction proceeds rapidly and takes a short time. A cured product can be obtained.

  Since the curable composition of the present invention is excellent in storage stability even at a relatively high temperature, the composition can be handled with a lower viscosity, and is suitable for liquid injection molding at a high temperature.

  When the curable composition of the present invention is flowed, it is preferably performed at a temperature of 20 ° C. or more and less than 100 ° C., but more preferably 40 ° C. or more and less than 80 ° C.

  Moreover, while making the curable composition of this invention flow at the temperature of 20 degreeC or more and less than 100 degreeC, it can perform hardening reaction, making it flow further at 20 degreeC or more. That is, the curable composition of the present invention can be used as a resin for liquid injection molding (LIM or the like).

  The curable composition used in the present invention may be prepared as a one-component type in which all the ingredients are pre-blended and stored and heated by curing at the time of curing, to ensure long-term storage stability. May be prepared in the form of two liquids or three liquids or more and mixed before curing.

  In the case of preparing as a two-part form, there is no particular limitation on how to divide the ingredients, but when long-term storage stability is required, (B) a hydrosilyl group-containing compound and (C) hydrosilylation The catalyst is divided, and one compounded liquid (referred to as liquid a) is mixed with a mixture of (A) component polyoxyalkylene polymer and / or vinyl polymer and (D) filler (C). ) Component hydrosilylation catalyst is blended, and the other compounded liquid (referred to as liquid b) comprises (A) component polyoxyalkylene polymer and / or vinyl polymer and (D) component filler. It is desirable to add the hydrosilyl group-containing compound of component (B) to the mixture. The curing modifier, metal soap, plasticizer, anti-aging agent, etc. may be blended in either the liquid a or liquid b. In consideration of the stability of each component, it may be better to mix a curing regulator and metal soap in the liquid b. Since the workability at the time of mixing is improved, it is preferable to adjust the compounding materials of each liquid so that the liquids a and b may be mixed in an equivalent amount, and the viscosity of both liquids should be adjusted to the same level. Is more preferable.

<< Molding method >>
The molding method when the curable composition of the present invention is used as a molded body is not particularly limited, and various commonly used molding methods can be used. Examples thereof include cast molding, compression molding, transfer molding, injection molding, extrusion molding, rotational molding, hollow molding, and thermoforming. In particular, from the viewpoint of being able to be automated and continuous and being excellent in productivity, the one by injection molding is preferable.

<< Usage >>
The curable composition of the present invention is not particularly limited, but is electrically insulating materials such as automotive materials, electric / electronic component materials, electric wire / cable insulating coating materials, coating materials, foams, electric and electronic potting materials, It can be used for various applications such as films, gaskets, oil seals, O-rings, packings, hoses and tubes, rolls, diaphragms, casting materials, and various molding materials.

  Furthermore, the molded body showing rubber elasticity obtained from the curable composition of the present invention can be applied to sealing materials mainly for gaskets and packings.

  For example, in the automobile field, it can be used as a body part as a sealing material for maintaining airtightness, an anti-vibration material for glass, an anti-vibration material for vehicle body parts, particularly a wind seal gasket and a door glass gasket. As chassis parts, it can be used for vibration-proof and sound-proof engines and suspension rubbers, especially engine mount rubbers. Engine parts include transmission oil cooler hose, engine oil cooler hose, air duct hose, turbo intercooler hose, hot air hose, radiator hose, power steering hose, fuel hose, drain hose, etc. for cooling, fuel supply, intake and exhaust Hoses, engine cam covers and oil pan gaskets, oil pump gaskets, power steering vane pump gaskets, intake manifold gaskets, throttle body gaskets, compressor gaskets, timing belt cover gaskets, crankshaft seal gaskets, Camshaft seal gaskets, transmission seal gaskets, etc., various O-rings, oil seals Power steering seal belt cover seal, seal washer, oil receiver, plug tube seal, squeeze seal, lip seal seal, bore plug, injection pipe seal, brake drum seal, connector seal for wire harness, oil level gauge, breather, Various rubber parts such as valves and diaphragms, fuel injection devices, fuel heating devices, air dampers, pressure detection devices, oil coolers for resin tanks for heat exchangers, variable compression ratio engines, cylinder devices, regulators for compressed natural gas, pressure vessels, in-cylinder Fuel injection system for direct injection internal combustion engine or high pressure pump O-ring, igniter HIC or automotive hybrid IC botting material, constant velocity joint boot material and rack and pinion boot material, The coating material for emission gin control board, it is possible to use molding, head lamp lens, the adhesive for a sunroof seal or mirror. It can also be used for exhaust gas cleaning device parts and brake parts.

  In the electrical field, it can be used for coating, potting, packing, O-rings, belts and the like. Specifically, high-voltage thick film resistors, hybrid IC circuit elements, HICs, electrical insulation components, semiconductive components, conductive components, modules, printed circuits, ceramic substrates, diodes, transistors or buffer materials for bonding wires, Semi-conductor element or coating material such as optical fiber for optical communication, transformer high-voltage circuit, printed circuit board, high-voltage transformer with variable resistance, electrical insulation component, semi-conductive component, conductive component, solar cell or TV flyback Potting materials such as transformers, heavy electrical components, weak electrical components, solar cell backside sealing, sealing materials for circuits and boards of electrical and electronic equipment, decorations for lighting fixtures, waterproof packings, anti-vibration rubbers, insect protection Anti-vibration / sound absorption and air sealant for packing, drip-proof cover for electric water heater, heater , Electrode packing, safety valve diaphragm, hoses for sake cans, waterproof packing, solenoid valves, waterproof packing for steam microwave ovens and jar rice cookers, water supply tank packing, water absorption valve, water receiving packing, connection hose, belt, heat insulation Oil packing for combustion equipment such as heater packing, steam outlet seal, etc., O-ring, drain packing, pressure tube, blower tube, feed / intake packing, anti-vibration rubber, oil filler packing, oil meter packing, oil feed tube Rubber parts such as speaker valves, speaker edges, turntable seats, belts, pulleys, etc. for acoustic devices such as diaphragm valves and air pipes. Also, cathode ray tube wedges, necks, electrical insulation parts, adhesives for semi-conductive parts or conductive parts, wire covering repair materials, insulation joints for wire joint parts, rolls for office automation equipment, ink wipers, vibration absorbers, gels It can also be used for etc.

  In the construction field, it can be used for structural gaskets (zipper gaskets), air membrane roof materials, waterproof materials, fixed sealing materials, vibration-proof materials, sound-proof materials, setting blocks, sliding materials, and the like.

  In the sports field, it can be used for all-weather pavement materials and gymnasium floors as sports floors, shoe sole materials and midsole materials as sports shoes, and golf balls as ball for ball games.

  In the field of anti-vibration rubber, it can be used as anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, anti-vibration materials, and the like.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

In the examples and comparative examples below, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
(Production Example 1)
Table 1 shows the amount of each raw material used.

(1) Polymerization step Acrylic acid ester (in the case of copolymerization, a predetermined amount of acrylic acid ester mixed in advance) was deoxygenated. The inside of the stainless steel reaction vessel equipped with a stirrer was deoxygenated, and cuprous bromide and a part of the total acrylic ester (described as the initial charge monomer in Table 1) were charged and stirred with heating. Acetonitrile (described as “Acetonitrile for polymerization” in Table 1) and diethyl 2,5-dibromoadipate as an initiator were added and mixed. At the stage where the temperature of the mixture was adjusted to about 80 ° C., pentamethyldiethylenetriamine (hereinafter abbreviated as triamine). ) Was added to initiate the polymerization reaction. The remaining acrylic ester (described as an additional monomer in Table 1) was sequentially added to proceed the polymerization reaction. During the polymerization, triamine was appropriately added to adjust the polymerization rate. The total amount of triamine used during the polymerization is shown in Table 1 as a triamine for polymerization. As the polymerization proceeds, the internal temperature rises due to the heat of polymerization, so the polymerization was allowed to proceed while adjusting the internal temperature to about 80 ° C to about 90 ° C. When the monomer conversion rate (polymerization reaction rate) was about 95% or more, volatile components were removed by devolatilization under reduced pressure to obtain a polymer concentrate.

(2) Diene reaction step 1,7-octadiene (hereinafter abbreviated as diene or octadiene) and acetonitrile (referred to as acetonitrile for diene reaction in Table 1) were added to the concentrate, and a triamine (in Table 1, triamine for diene reaction) Added). While adjusting the internal temperature to about 80 ° C. to about 90 ° C., the mixture was heated and stirred for several hours to react the octadiene with the polymer terminal. Acetonitrile and unreacted octadiene were removed by devolatilization under reduced pressure to obtain a concentrate containing a polymer having an alkenyl group at the terminal.

(3) Rough purification step The above concentrate is diluted with toluene, and a filter aid, an adsorbent (KYOWARD 700SEN: manufactured by Kyowa Chemical), hydrotalcite (KYOWARD 500SH: manufactured by Kyowa Chemical)) are added, and 80 to After stirring at about 100 ° C., the solid component was filtered off. The filtrate was concentrated to obtain a crude polymer product.

(4) High-temperature heat treatment / adsorption purification process Crude polymer product, heat stabilizer (Sumilyzer GS: manufactured by Sumitomo Chemical Co., Ltd.), adsorbent (KYOWARD 700SEN, KYOWARD 500SH) are added, and devolatilization under reduced pressure. The temperature was raised while heating and stirring, and heating and stirring and vacuum devolatilization were performed for several hours at a high temperature of about 170 ° C to about 200 ° C. Adsorbents (Kyoward 700SEN, Kyoward 500SH) were added, about 10 parts by weight of toluene was added to the polymer, and the mixture was further heated and stirred at a high temperature of about 170 ° C. to about 200 ° C. for several hours.

  The treatment liquid was further diluted with toluene, and the adsorbent was filtered off. The filtrate was concentrated to obtain a polymer [P1] having alkenyl groups at both ends. Table 1 shows the number of alkenyl groups introduced per molecule of the obtained polymer, the number average molecular weight, and the molecular weight distribution.

（製造例２）
５Ｌの二口フラスコにトルエン１８００ｇ、１，３，５，７−テトラメチルシクロテトラシロキサン１４４０ｇを入れ、１２０℃のオイルバス中で窒素下、加熱攪拌した。この溶液に、トリアリルイソシアヌレート２００ｇ、トルエン２００ｇ及び白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）１４４μｌの混合液を、５０分かけて滴下した。得られた溶液をそのまま６時間加温、攪拌した。１−エチニル−１−シクロヘキサノール２．９５ｍｇを加えた後、未反応の１，３，５，７−テトラメチルシクロテトラシロキサン及びトルエンを減圧留去し、ヒドロシリル基含有化合物[Ｂ１]を得た。

(Production Example 2)
1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in a 5 L two-necked flask, and the mixture was heated and stirred under nitrogen in a 120 ° C. oil bath. To this solution, a mixed solution of 200 g of triallyl isocyanurate, 200 g of toluene and 144 μl of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was dropped over 50 minutes. The resulting solution was heated and stirred as it was for 6 hours. After adding 2.95 mg of 1-ethynyl-1-cyclohexanol, unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a hydrosilyl group-containing compound [B1]. .

Hydrosilyl group-containing compound [B1] is a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane, as determined by ¹ H-NMR analysis (manufactured by Varian Technologies Japan Limited, 300 MHz NMR apparatus). Was reacted with triallyl isocyanurate (hydrosilyl group-containing compound [B1] is a mixture, but contains the following compound having 9 SiH groups in one molecule as a main component).

（実施例１）
製造例１で得られたアルケニル末端共重合体［Ｐ１］１００部と、充填剤としてシリカ（商品名：ニップシールＬＰ、東ソー・シリカ製）を２０部、アミン系酸化防止剤として、４，４’−ビス（α，α−ジメチルベンジル）ジフェニルアミン（商品名：ノクラックＣＤ、大内新興化学工業製）を２部配合し、井上製作所製２Ｌ２軸プラネタリーミキサーを用いてジャケット温度約９０℃、減圧度−０．０９５ＭＰａ以下の加熱減圧下１時間混合した（以下、「ジャケット温度約９０℃、減圧度−０．０９５ＭＰａ以下の加熱減圧下１時間混合」を単に「加熱減圧下１時間混合」と称することがある。）。その後、ジャケット温度６０℃、常圧下の条件で、硬化調整剤として３，５−ジメチル−１−へキシン−３−オール（商品名：サーフィノール６１、日信化学工業製）を、アルケニル末端共重合体［Ｐ１］のアルケニル基の７．５×１０^−２モル当量添加添加し１５分攪拌した。続いて、０価白金の１，１，３，３−テトラメチル−１，３−ジビニルジシロキサン錯体のイソプロパノール溶液（白金として３ｗｔ％含有）を白金換算でアルケニル末端共重合体［Ｐ１］のアルケニル基の５×１０^−４モル当量添加し１５分攪拌した。さらに、ヒドロシリル基含有化合物［Ｂ１］を、［Ｂ１］のＳｉＨ基がアルケニル末端共重合体［Ｐ１］のアルケニル基の２．２モル当量分となる量を添加し１５分攪拌した。最後にジャケット温度６０℃、減圧度−０．０９５ＭＰａ以下の条件で減圧攪拌脱泡を５分間実施し、系中の気泡を除去した後、窒素で常圧に戻し硬化性組成物を得た。

Example 1
100 parts of the alkenyl-terminated copolymer [P1] obtained in Production Example 1, 20 parts of silica (trade name: Nipseal LP, manufactured by Tosoh Silica) as a filler, and 4,4 ′ as an amine-based antioxidant 2 parts of bis (α, α-dimethylbenzyl) diphenylamine (trade name: NOCRACK CD, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) is blended, and the jacket temperature is about 90 ° C. and the degree of vacuum is reduced using a 2L 2-axis planetary mixer manufactured by Inoue Seisakusho. The mixture was mixed for 1 hour under a heating reduced pressure of −0.095 MPa or less (hereinafter referred to as “mixing for 1 hour under a heating reduced pressure with a jacket temperature of about 90 ° C. and a degree of vacuum of −0.095 MPa” is simply referred to as “mixing for 1 hour under a heated reduced pressure”). Sometimes.). Thereafter, 3,5-dimethyl-1-hexyn-3-ol (trade name: Surfynol 61, manufactured by Nissin Chemical Industry Co., Ltd.) was used as a curing regulator under conditions of jacket temperature of 60 ° C. and normal pressure. 7.5 × 10 ⁻² molar equivalent of the alkenyl group of the polymer [P1] was added and stirred for 15 minutes. Subsequently, an alkenyl of an alkenyl-terminated copolymer [P1] using an isopropanol solution (containing 3 wt% as platinum) of a 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zero-valent platinum in terms of platinum 5 × 10 ⁻⁴ molar equivalent of the group was added and stirred for 15 minutes. Further, the hydrosilyl group-containing compound [B1] was added in an amount such that the SiH group of [B1] was 2.2 molar equivalents of the alkenyl group of the alkenyl-terminated copolymer [P1] and stirred for 15 minutes. Finally, vacuum stirring and defoaming was carried out for 5 minutes under conditions of a jacket temperature of 60 ° C. and a degree of vacuum of −0.095 MPa or less, and after removing bubbles in the system, the pressure was returned to normal pressure with nitrogen to obtain a curable composition.

(Example 2)
A curable composition was obtained in the same manner as in Example 1 except that the jacket temperature was raised to about 130 ° C. instead of heating to about 90 ° C. with a planetary mixer.

(Example 3)
After mixing with a planetary mixer for 1 hour under heating and decompression, the mixture is taken out and heated at 180 ° C. and the degree of decompression is −0.095 MPa or less for 1 hour using an evaporator, and the mixture is again put into the planetary mixer. It returned and the curable composition was obtained like Example 1 except having performed subsequent operation.

Example 4
After mixing with a planetary mixer for 1 hour under reduced pressure, the mixture is transferred to a separable flask and heated in an oil bath at 180 ° C. and a reduced pressure of −0.095 MPa or less for 4 hours. A curable composition was obtained in the same manner as in Example 1 except that the operation was performed after returning to the planetary mixer.

(Example 5)
After mixing with a planetary mixer for 1 hour under heating and decompression, the mixture was taken out and allowed to stand in an oven at 180 ° C. for 22 hours, after which the mixture was returned to the planetary mixer and the subsequent operations were performed. In the same manner as in Example 1, a curable composition was obtained.

(Comparative Example 1)
In the planetary mixer, instead of mixing for 1 hour under heating and reduced pressure with a jacket temperature of about 90 ° C. and a degree of vacuum of −0.095 MPa or less, except for mixing for 1 hour without performing a pressure reduction operation at a jacket temperature of about 60 ° C. In the same manner as in Example 1, a curable composition was obtained.

(Comparative Example 2)
In Example 1, instead of mixing at a jacket temperature of 130 ° C. for 1 hour with a planetary mixer, the jacket temperature was about 90 ° C., and the degree of vacuum was -0.095 MPa or less for 1 hour without performing a pressure reduction operation for 1 hour. Attempts were made to mix, but the internal pressure in the mixer increased, resulting in a dangerous situation. As a result, a curable composition was not obtained.

  About the curable composition obtained in the said Examples 1-5 and Comparative Examples 1-2, the moisture content and viscosity of each curable composition, and the compression set of the cured material produced from these curable compositions The hardness was measured by the method described below. Table 2 shows the measurement results of each curable composition.

(amount of water)
The moisture in the obtained curable composition was measured by the Karl Fischer volumetric titration method using a Karl Fischer moisture meter MKA-610-ST manufactured by Kyoto Electronics Industry.

(viscosity)
The viscosity of the obtained curable composition was measured using a cone plate viscometer (Tokyo Keiki E-type viscometer EHD, 3 ° × 28φ cone) under the conditions of a rotation speed of 0.5 rpm and a measurement temperature of 50 ° C. Measurements were taken from readings after 10 minutes.

(Compression set)
The obtained curable composition was press-molded at 180 ° C. for 10 minutes to prepare a large test piece for compression set test measurement according to JIS K 6262. The obtained test piece group was divided into two, one was subjected to secondary vulcanization at 180 ° C. for 22 hours, and the other was prepared without performing secondary vulcanization. The two types of obtained test pieces were subjected to a compression set test at 150 ° C. for 70 hours according to JIS K 6262.

(hardness)
Using two types of test pieces (secondary added test piece and second non-added test piece) obtained in the above measurement of compression set, hardness was measured with a Shimadzu type A durometer according to JIS K 6253. It was measured.

実施例と比較例の比較から以下のことが明らかである。（Ａ）成分であるアルケニル基を両末端に有するビニル系重合体と（Ｄ）成分であるシリカ（ニップシールＬＰ）を混合するにあたり、９０℃で混合した場合（比較例１）では、得られる硬化物は発泡が著しく成形物としての用を成さない。さらに、１３０℃で混合した場合（比較例２）には、シリカ中の水分の揮発に起因すると思われる内圧の高まりが生じその後の操作が不可能であり、硬化性組成物を得ることすらできない。一方、加温と同時に減圧操作を実施した場合（実施例１、５）には、低水分量の硬化性組成物を得ることが可能で、得られる硬化物も硬度・圧縮永久歪特性に優れる。また、１３０℃以上で加熱減圧混合操作を実施すること（実施例２）により、二次加硫を実施しない場合の圧縮永久歪特性が改善される。さらに、１８０℃の高温下で、加熱減圧混合操作を実施すること（実施例３、４）により、二次加硫を実施しない場合の圧縮永久歪特性がさらに改善される。

The following is clear from the comparison between Examples and Comparative Examples. When mixing at 90 ° C. when mixing a vinyl polymer having an alkenyl group as component (A) at both ends and silica (nip seal LP) as component (D), the resulting cured product (Comparative Example 1) The product is extremely foamed and cannot be used as a molded product. Further, when mixed at 130 ° C. (Comparative Example 2), the internal pressure is increased due to the volatilization of moisture in the silica, the subsequent operation is impossible, and it is not possible to obtain a curable composition. . On the other hand, when decompression operation is carried out simultaneously with heating (Examples 1 and 5), it is possible to obtain a curable composition having a low moisture content, and the obtained cured product is also excellent in hardness and compression set characteristics. . Further, by carrying out the heating and decompression mixing operation at 130 ° C. or higher (Example 2), the compression set characteristics when the secondary vulcanization is not carried out are improved. Furthermore, by carrying out the heating and decompression mixing operation at a high temperature of 180 ° C. (Examples 3 and 4), the compression set characteristics when the secondary vulcanization is not performed are further improved.

  Regarding the compression set characteristics when this secondary vulcanization is not performed, when the mixture is heated to 180 ° C. and mixed under reduced pressure (Examples 3 and 4), the vacuum mixing operation is performed only by heating at 180 ° C. Since the compression set is greatly improved as compared with the case (Example 5) when not, it is possible not only to heat-treat at a high temperature but also to perform a vacuum mixing operation in addition to heating to a high temperature. It can be seen that excellent characteristics can be exhibited not only in compression set characteristics after secondary vulcanization but also in compression set characteristics when secondary vulcanization is not performed.

  According to the method for producing a curable composition of the present invention, a curable composition capable of giving a cured product having a small compression set is obtained in a curable composition that can be cured by a hydrosilylation reaction.

Claims (19)

(A) a polyoxyalkylene polymer and / or a vinyl polymer containing at least one alkenyl group capable of hydrosilylation reaction in the molecule,
(B) Hydrosilyl group-containing compound (II),
(C) a hydrosilylation catalyst, and
(D) A method for producing a curable composition containing a filler,
A step of mixing the component (A) and the component (D) while heating to 90 ° C. or higher under reduced pressure conditions;
A method for producing a curable composition.   The manufacturing method of the curable composition of Claim 1 whose said heating is 180 degreeC or more.   The curing according to claim 1 or 2, wherein the vinyl polymer containing at least one alkenyl group capable of hydrosilylation reaction in a molecule is a hydrocarbon polymer and / or a (meth) acrylic polymer. Method for producing a composition.   The curable composition according to any one of claims 1 to 3, wherein a molecular weight distribution of a vinyl polymer containing at least one alkenyl group capable of hydrosilylation reaction in a molecule is less than 1.8. Production method.   The main chain of the vinyl polymer containing at least one alkenyl group capable of hydrosilylation reaction in the molecule is a (meth) acrylic monomer, acrylonitrile monomer, aromatic vinyl monomer, fluorine-containing vinyl monomer and silicon-containing The manufacturing method of the curable composition as described in any one of Claims 1-4 manufactured mainly by superposing | polymerizing at least 1 sort (s) chosen from the group which consists of a vinyl-type monomer.   The curable composition according to any one of claims 1 to 5, wherein the vinyl polymer containing at least one alkenyl group capable of hydrosilylation reaction in a molecule is a (meth) acrylic polymer. Production method.   The method for producing a curable composition according to any one of claims 1 to 6, wherein the vinyl polymer containing at least one alkenyl group capable of hydrosilylation reaction in the molecule is an acrylic polymer.   The production of the curable composition according to any one of claims 1 to 7, wherein the vinyl polymer containing at least one alkenyl group capable of hydrosilylation reaction in a molecule is an acrylate ester polymer. Method.   The vinyl polymer containing at least one alkenyl group capable of hydrosilylation in the molecule is ethyl acrylate, butyl acrylate, 2-methoxyethyl acrylate, 2-methoxybutyl acrylate, 2-ethylhexyl acrylate, The method for producing a curable composition according to any one of claims 1 to 8, which is produced mainly by polymerizing at least one selected from the group consisting of stearyl acrylate.   The main chain of the vinyl polymer containing at least one alkenyl group capable of hydrosilylation reaction in the molecule is produced by a living radical polymerization method, according to any one of claims 1 to 9. A method for producing a curable composition.   The manufacturing method of the curable composition of Claim 10 whose said living radical polymerization is atom transfer radical polymerization. The vinyl polymer containing in the molecule at least one alkenyl group capable of hydrosilylation reaction includes the following steps:
(1a) By polymerizing a vinyl monomer by an atom transfer radical polymerization method, the general formula (1)
-C (R ¹ ) (R ² ) (X) (1)
(In the formula, R ¹ and R ² represent a group bonded to an ethylenically unsaturated group of a vinyl monomer. X represents chlorine, bromine or iodine.)
A vinyl polymer having a terminal structure represented by
(2a) converting the terminal halogen of the polymer into a substituent having an alkenyl group capable of hydrosilylation reaction;
The manufacturing method of the curable composition as described in any one of Claims 1-11 obtained by these. The vinyl polymer containing in the molecule at least one alkenyl group capable of hydrosilylation reaction includes the following steps:
(1b) A vinyl polymer is produced by polymerizing a vinyl monomer by a living radical polymerization method,
(2b) reacting the polymer with a compound having at least two alkenyl groups having low polymerizability;
The manufacturing method of the curable composition as described in any one of Claims 1-11 obtained by these.   The method for producing a curable composition according to any one of claims 1 to 13, wherein the alkenyl group capable of hydrosilylation reaction is at the end of a molecular chain.   The manufacturing method of the curable composition as described in any one of Claims 1-14 whose said (B) hydrosilyl group containing compound (II) is organohydrogenpolysiloxane.   The manufacturing method of the curable composition as described in any one of Claims 1-15 whose said (D) filler is a silica.   The manufacturing method of the curable composition as described in any one of Claims 1-16 whose said (D) filler is surface untreated silica.   The curable composition obtained by the manufacturing method as described in any one of Claims 1-17.   A cured product obtained by curing the curable composition according to claim 18.