JP2014024958A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a room-temperature-curable heat-conductive composition excellent in terms of curability, storage stability, heat conductivity, and endurance, unlikely to entail contact faults attributed to cyclosiloxanes, etc. deemed problematic in the prior art, facilitating such operations as coating, etc. due to the low viscosity thereof, and rapidly curable at room temperature and a heat-conductive material provided by curing the composition.SOLUTION: The heat-conductive material is provided by coating, in-between a heat generator and a radiator, a fluid composition curable at room temperature which includes (A) a reactive silicon-containing oxyalkylene organic polymer having, atop a single silicon atom, three hydroxyl groups or at least one hydrolyzable group, (B) a (meth)acrylic acid ester-type organic polymer having, atop a single silicon atom, at least two hydroxyl groups or at least one hydrolyzable group, (C) a plasticizer, (D) a heat-conductive filler, (E) a metal carboxylate, (F) a carboxylic acid, and (G) a methyl ester-type compound and which exhibits a post-curing heat conductivity of 0.5 W/mK or above and by subsequently curing the composition in-between the heat generator and radiator.

Description

  The present invention relates to a curable composition used for heat dissipation of various devices such as electronic devices such as personal computers, mobile phones, and PDAs, and lighting and display devices such as LEDs and EL. More specifically, (A) a reactive silicon-containing oxyalkylene organic polymer having at least one hydroxyl group or hydrolyzable group on one silicon atom, and (B) at least one silicon atom. (Meth) acrylic ester organic polymer having at least one hydroxyl group or hydrolyzable group, (C) plasticizer, (D) thermally conductive filler, (E) carboxylic acid metal salt, (F A composition containing a carboxylic acid and (G) a methyl ester compound, having a heat conductivity after curing of 0.5 W / mK or more and having fluidity at room temperature, a heating element and a radiator A curable resin obtained by curing between a heating element and a heat radiator after application between the two.

  In recent years, the performance of electronic devices such as personal computers, mobile phones, and PDAs, and lighting and display devices such as LEDs and EL has been remarkably improved, which is due to the significant performance improvements of arithmetic elements and light emitting elements. As described above, the amount of heat generation is remarkably increased with the improvement of the performance of the arithmetic element and the light emitting element, and how to dissipate heat in electronic devices, lighting, and display devices is an important issue. As a countermeasure against heat, the method of radiating heat by spreading heat generated by arithmetic elements and light-emitting elements over a wide area as quickly as possible is intended to increase cooling efficiency, but does not actively cool. It is the most realistic cooling method for small electronic devices such as mobile phones and personal computers and lighting.

  As a heat conductive material used for the purpose of heat dissipation and heat transfer, for example, a soft heat dissipation sheet in which a heat conductive filler is highly filled and cured in a base rubber such as silicone rubber is known. A technique based on a combination of a thermally conductive filler and silicone rubber is disclosed (see Patent Documents 1 to 3).

  The heat-dissipating sheet for the purpose of such heat conduction requires not only the heat conduction of the material itself, but also the heat resistance with the heat-generating body and the heat-dissipating element, so the adhesion with the heat-generating body and the heat dissipating element Is considered important. For the adhesion to the heating element and the radiator, the adhesion to the heating element and the surface of the radiator and the followability to the shape and deformation of the heating element and the radiator are important. However, if the heat conductive filler is highly filled to increase the thermal conductivity of the heat radiating sheet, the hardness of the sheet becomes hard, and the adhesiveness to the heating element and the surface of the heat radiating body and the shape followability are reduced. There was a problem that.

  In order to solve these problems, for example, Patent Document 4 discloses a room temperature curing type heat conduction that can be cured at room temperature after applying a liquid material in which a silicone rubber before curing is highly filled with a heat conductive filler. An adhesive silicone rubber composition has been disclosed, and since it is a liquid material, the adhesiveness to a heat body and a heat radiating body is very good, which is preferable. However, since it is an uncured silicone rubber composition, there is a problem that volatilization of low molecular siloxane components and cyclic siloxane components increases during use. Problems have been pointed out that silicone resins often cause poor contact of electrical components and poor reading of precision devices such as hard disks due to volatilization of cyclic siloxane, which is a low molecular component.

  On the other hand, for example, Patent Document 5 discloses a heat conductive grease in which a poly α-olefin oligomer is highly filled with a heat conductive filler. If such a composition is used, since it is a liquid substance, the adhesiveness with a heat body and a heat radiator becomes very good, and there is little possibility that a low molecular weight siloxane component volatilizes at the time of use. However, since such a composition does not cure at room temperature, when the heating element reaches a high temperature, the liquid grease having a low viscosity flows out and may contaminate surrounding electronic devices. There is a problem of being.

  Patent Document 6 includes a hydrolyzable silyl group-containing oligomer having a hydrolyzable silyl group, such as polyalkylene glycol and polyisobutylene, which is blended with a heat conductive filler and has excellent strength and adhesion. It is disclosed that it is a resin composition possessed together. However, hydrolyzable silyl group-containing polyalkylene glycol-based oligomers may not have sufficient heat resistance, and hydrolyzable silyl group-containing polyisobutylene-based oligomers are relatively viscous and difficult to handle, and have a curing rate. Since it is slow, it is often difficult to use it as a one-component composition.

  Patent Documents 7 to 8 show a composition for a heat radiation sheet in which a vinyl polymer produced by a living radical polymerization method having a molecular weight distribution of 1.8 or less is filled with a heat conductive filler. In addition, there is no description regarding a method of using the liquid material as a room temperature curable thermal conductive composition.

Japanese Patent Publication No. 6-55891 Japanese Examined Patent Publication No. 6-38460 Japanese Patent Publication No. 7-91468 JP 2004-352947 A JP 2008-19319 A JP 2001-302936 A JP 2006-274094 A JP 2006-278476 A

  The present invention has excellent curability, storage stability, heat resistance, and durability, and has a low possibility of contact failure due to cyclic siloxane, which has been regarded as a problem in the prior art. An object of the present invention is a room temperature curable heat conductive composition that is easy to operate and can be rapidly cured at room temperature, and a heat conductive material obtained by curing the composition.

The inventor has the following configuration.
(A) a reactive silicon-containing oxyalkylene organic polymer having at least one hydroxyl group or hydrolyzable group on one silicon atom, (B) at least two hydroxyl groups on one silicon atom Or (meth) acrylic ester organic polymer having at least one hydrolyzable group, (C) plasticizer, (D) thermally conductive filler, (E) carboxylic acid metal salt, (F) carboxylic acid, (G) A composition containing a methyl ester compound and having a thermal conductivity after curing of 0.5 W / mK or more and having fluidity, which can be cured at room temperature, is applied between the heating element and the heat dissipation element. Then, a curable resin is cured between the heating element and the heat dissipation element.

The curable composition obtained by curing the thermally conductive composition that can be rapidly cured at room temperature according to the present invention has excellent storage stability, durability, and the like, and is a cyclic siloxane that is regarded as a problem in the prior art. It has the characteristic that the contact failure by etc. is improved.

The curable composition of this invention is explained in full detail below.
(A) About vinyl polymer << Polyether polymer >>
In the present invention, a reactive silicon-containing oxyalkylene having at least three hydroxyl groups or hydrolyzable groups on one silicon atom in order to obtain a fluidly curable composition that can be rapidly cured at room temperature. An organic polymer (A) is used. The amount of the vinyl polymer (A) used is preferably 1% by weight to 99% by weight, more preferably 1% by weight to 60% by weight, based on the balance of curability. It is especially preferable to set it as 5 to 50 weight%.

In the present invention, a polyether polymer can also be used.
<< Polyether polymer having a crosslinkable functional group >>
The main chain of the main chain polyether polymer is not particularly limited, and examples thereof include polyethylene oxide, polypropylene oxide, polybutylene oxide, and polyphenylene oxide. Of these, it is preferably essentially polyoxyalkylene, and more preferably essentially polypropylene oxide, which may contain ethylene oxide, butylene oxide, phenylene oxide and the like in addition to propylene oxide. Moreover, the polyether polymer may or may not contain a urethane bond in the main chain. Here, “the main chain is essentially polypropylene oxide” means that propylene oxide units occupy 50% or more, preferably 70% or more, more preferably 90% or more of the repeating units constituting the main chain. Say. The lower the viscosity, the better the handleability, so that the molecular weight distribution (Mw / Mn) of the polypropylene oxide polymer is more preferably 1.5 or less.

The crosslinkable functional group in the crosslinkable functional group polyether polymer is not particularly limited, and preferably has a crosslinkable silyl group, an alkenyl group, a hydroxyl group, an amino group, and a polymerizable carbon-carbon double bond. Group and epoxy group. In particular, a crosslinkable silyl group is preferable.

  The polyether polymer preferably has at least one crosslinkable functional group, but may be 1 or less. From the viewpoint of curability of the composition, it is preferably more than 1, more preferably 1.1 to 4.0 on average, and even more preferably 1.5 to 2.5 on average. Moreover, it is preferable from a viewpoint of rubber elasticity of hardened | cured material that a crosslinkable functional group exists in the terminal of a polyether-type polymer. More preferably, there are functional groups at both ends of the polymer.

Molecular weight The polyether polymer having at least one crosslinkable functional group preferably has a number average molecular weight of 7500 or more, but may be 7500 or less. In particular, it is more preferable to use an organic polymer having a number average molecular weight of 7500 to 25000. When the number average molecular weight of the polyether polymer is lower than 7500, the cured product is hard and the elongation is low, and when the number average molecular weight exceeds 25,000, there is no problem in the flexibility and elongation of the cured product. The adhesiveness of itself will become remarkably low, and practicality will become low. However, even if the molecular weight is low, flexibility and elongation may be improved if the number of crosslinkable functional groups is small, and adhesion may be improved if the number of crosslinkable functional groups is large even if the molecular weight is high. There is. The number average molecular weight is particularly preferably 8000 to 20000 from the viewpoint of viscosity, but it may be 8000 or less or 20,000 or more.

Use amount of the polyether polymer The use amount when the polyether polymer is added may be any amount, but the weight is relative to the vinyl polymer (I) having at least one crosslinkable silyl group. The ratio is preferably in the range of 100/1 to 1/100, more preferably in the range of 100/5 to 5/100, and still more preferably in the range of 100/10 to 10/100. The addition amount can be set according to each application and purpose. However, if the addition amount is too large, the excellent heat resistance and weather resistance, which are one of the effects of the present invention, may be lowered.

  A (meth) acrylic polymer produced by a general radical polymerization method or a high-temperature continuous bulk polymer (for example, an SGO oligomer produced by Toa Gosei Co., Ltd. or a silylated product thereof in advance in the above-mentioned polyether polymer. What was mixed may be used for mixing with the vinyl polymer.

<Polyether polymer having a crosslinkable silyl group>
The polyether polymer having a crosslinkable silyl group will be described below.

The main chain structure of the polyether polymer having a main chain crosslinkable silyl group is the same as described above. The main chain may be linear or branched, or a mixture thereof. Of these, a main chain derived from polyoxypropylene diol, polyoxypropylene triol or a mixture thereof is particularly preferable. Further, other monomer units and the like may be contained, but the monomer unit represented by the above formula is preferably present in the polymer in an amount of 50% by weight or more, preferably 80% by weight or more.

  The main chain may or may not contain a urethane bond or urea bond.

  The molecular structure of the polyether-based polymer varies depending on the intended use and intended properties, and those described in JP-A-63-112642 can be used. Such polyoxyalkylenes can be obtained by conventional polymerization methods (anionic polymerization methods using caustic), cesium metal catalysts, JP-A 61-197631, JP-A 61-215622, JP-A 61-215623, and Porphyrin / aluminum complex catalysts exemplified in JP-A-61-218632 and the like, double metal cyanide complex catalysts exemplified in JP-B-46-27250 and JP-B-59-15336, etc., exemplified in JP-A-10-273512 It can be obtained by a method using a catalyst comprising a polyphosphazene salt.

  In a method using a porphyrin / aluminum complex catalyst, a double metal cyanide complex catalyst or a catalyst comprising a polyphosphazene salt, the molecular weight distribution (Mw / Mn) is 1.6 or less, and further a small value of oxy such as 1.5 or less. When an alkylene polymer can be obtained and the molecular weight distribution is small, there is an advantage that the viscosity of the composition can be reduced while maintaining the low modulus and high elongation of the cured product.

As the crosslinkable silyl group, the group represented by the general formula (1) can be used as in the vinyl polymer, and the group represented by the general formula (7) is preferable. The explanation about the group represented by the general formula (1) or the general formula (7) is similarly applied to the polyether polymer having a crosslinkable silyl group. The crosslinkable silyl group in the polyether polymer may have the same structure as the crosslinkable silyl group in the vinyl polymer having a crosslinkable silyl group, or may have a different structure.

  The bond between the crosslinkable silyl group and the polyether moiety is resistant to hydrolysis, so that there are at least 3 carbon atoms between the silicon atom of the silyl group and the ether oxygen atom of the polyether moiety. In addition, an alkylene group such as trimethylene and tetramethylene is preferable.

The number of crosslinkable silyl groups and the number of position crosslinkable silyl groups are preferably more than 1.2 from the viewpoint of the curability of the composition, and more preferably 1.2 or more and 4.0 or less. Preferably, it is 1.5-2.5 or less more preferably. Moreover, it is preferable that the crosslinkable silyl group of a polyether-type polymer exists in the terminal of a molecular chain from a viewpoint of the rubber elasticity of hardened | cured material, More preferably, it has a functional group in the both ends of a polymer.

  A polyether polymer having an average of less than 1.2 crosslinkable silyl groups can also be used. In this case, a cured product having high elongation at break, low bleeding, low surface contamination, and excellent paint adhesion can be obtained. Moreover, the viscosity of a composition can be reduced by setting the molecular weight of this polymer smaller. The lower limit of the number of crosslinkable silyl groups is preferably at least 0.1, more preferably 0.3 or more, and even more preferably 0.5 or more. The crosslinkable silyl group is preferably at the end of the molecular chain. Further, the crosslinkable silyl group of this polyether polymer is preferably only at one end in the main chain and not at the other end, but if it is 1.2 or less on average It is not particularly limited. In the case of reducing the viscosity by using a polyether polymer having an average of less than 1.2 crosslinkable silyl groups, the preferred molecular weight is less than 10,000, and further less than 5,000.

Introduction Method of Crosslinkable Silyl Group The introduction of the crosslinkable silyl group may be performed by a known method. That is, for example, the following method can be mentioned. For example, in the case of an oxyalkylene polymer obtained using a double metal cyanide complex catalyst, JP-A-3-72527, and in the case of an oxyalkylene polymer obtained using a polyphosphazene salt and active hydrogen as a catalyst, JP-A-11-60723 is disclosed. It is described in.

  (1) An oxyalkylene polymer having a functional group such as a hydroxyl group at the terminal is reacted with an organic compound having an active group and an unsaturated group which are reactive with the functional group, or an unsaturated group-containing epoxy compound To obtain an unsaturated group-containing oxyalkylene polymer. Next, hydrosilylation is performed by allowing hydrosilane having a crosslinkable silyl group to act on the obtained reaction product.

  (2) An unsaturated group-containing oxyalkylene polymer obtained in the same manner as in the method (1) is reacted with a compound having a mercapto group and a crosslinkable silyl group.

  (3) A functional group (hereinafter referred to as Y ′) having reactivity with this Y functional group to an oxyalkylene polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group (hereinafter referred to as Y functional group) at the terminal. And a compound having a crosslinkable silyl group).

  Examples of the silicon compound having a Y ′ functional group include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, 3- Amino, 2-methylpropyltrimethoxysilane, N-ethyl-3-amino, 2-methylpropyltrimethoxysilane, 4-amino, 3-methylpropyltrimethoxysilane, 4-amino, 3-methylpropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and amino group-containing silanes such as partial Michael addition reaction products of various amino group-containing silanes with maleic esters and acrylate compounds; γ-mercaptopropyltrimethoxysilane Γ-mercaptopropylmethyl Mercapto group-containing silanes such as dimethoxysilane; epoxy-silanes such as γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; vinyltriethoxysilane, γ -Vinyl-type unsaturated group-containing silanes such as methacryloyloxypropyltrimethoxysilane and γ-acryloyloxypropylmethyldimethoxysilane; Chlorine atom-containing silanes such as γ-chloropropyltrimethoxysilane; γ-isocyanatopropyl Isocyanate-containing silanes such as triethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyltrimethoxysilane; methyldimethoxysilane, trimethoxysilane, methyldiethoxy Specific examples include hydrosilanes such as silane and triethoxysilane, but are not limited thereto.

  In addition, when producing a polymer having an average number of crosslinkable silyl groups of 1.2 or less, a polyether polymer having only one functional group in the molecule when introducing the crosslinkable silyl group. And a method for obtaining a polyether polymer having an average of 1.2 or less crosslinkable silyl groups by reacting the functional group with a compound having a crosslinkable silyl group in an equivalent amount or a smaller amount. By using a polyether polymer having an average of one or more functional groups in the molecule and reacting a compound having a crosslinkable silyl group that is less than the functional group, There is a method for obtaining a polyether polymer having an average of 1.2 or less.

Use amount of the polyether polymer having a crosslinkable silyl group The use amount of the polyether polymer having a crosslinkable silyl group may be any amount, but at least one crosslinkable silyl group is present. The weight ratio of the vinyl polymer (I) is preferably 100/1 to 1/100, more preferably 100/5 to 5/100, and more preferably 100/10 to 10/100. More preferably, it is in the range. The addition amount can be set according to each application and purpose. However, if the addition amount is too large, the excellent heat resistance and weather resistance, which are one of the effects of the present invention, may be lowered.

  When using a polyether polymer having an average of 1.2 or less crosslinkable silyl groups, the amount used is preferably 1 part by weight or more and 200 parts by weight or less with respect to 100 parts by weight of the vinyl polymer, The amount is more preferably 3 parts by weight or more and 100 parts by weight or less, and further preferably 5 parts by weight or more and 80 parts by weight or less. If it is less than 1 part by weight, the effect of addition is difficult to obtain, and if it exceeds 200 parts by weight, the physical properties of the cured product tend to become unstable.

  As an aspect to be used in combination, 1) vinyl polymer having a crosslinkable silyl group represented by the general formula (1), and an average of 1.2 or less with a polyether polymer having a crosslinkable silyl group Adding a polyether polymer having a crosslinkable silyl group of 2) adding a polyether polymer having a crosslinkable silyl group and a vinyl polymer having a crosslinkable silyl group at one end; 3) When a polyether polymer having a crosslinkable silyl group and a vinyl polymer having a crosslinkable functional group and a molecular weight distribution of 1.8 or more are added, the crosslinkability is 1.2 or less on average. Adding a polyether polymer having a silyl group and a vinyl polymer having a crosslinkable silyl group at one end; and 4) a polyether polymer having an average of 1.2 or less crosslinkable silyl groups. Coalescence and cross-linking It like molecular weight have a functional group distribution is added 1.8 or more of the vinyl polymer and the like without limitation.

<< Arbitrary Polymer Components Having Various Crosslinkable Functional Groups >>
In the curable composition of the present invention, polymers having various crosslinkable functional groups may be added as optional components. Examples of the polymer having a crosslinkable functional group include (i) a polyisobutylene polymer having a crosslinkable functional group, particularly a polyisobutylene polymer having a crosslinkable silyl group, and (ii) polysiloxane. . These polymers can be added using 1 type (s) or 2 or more types.

  When these polymer optional components are added to the vinyl polymer having a crosslinkable silyl group of the present invention, the polymer has a hydrolyzable silicon group formed by bonding two hydrolyzable groups per silicon atom. A vinyl polymer and a polymer arbitrary component formed by bonding three hydrolyzable groups per crosslinkable functional group may be combined. Conversely, three hydrolyzable groups per silicon atom are combined. You may combine the vinyl polymer which has a hydrolysable silicon group formed by combining, and the polymer arbitrary component formed by combining two hydrolyzable groups per crosslinkable functional group. Also, any polymer may be a combination having a crosslinkable functional group formed by bonding three hydrolyzable groups, or a combination having a crosslinkable functional group formed by bonding two hydrolyzable groups. . Furthermore, one to three things may be mixed.

  (B) The (meth) acrylic acid ester organic polymer will be described.

<Main chain>
The present inventors have so far made numerous inventions relating to vinyl polymers having various crosslinkable functional groups at the ends of the polymer, production methods thereof, curable compositions, and uses (Japanese Patent Application Laid-Open No. 11-1990). 080249, JP-A-11-080250, JP-A-11-005815, JP-A-11-116617, JP-A-11-116606, JP-A-11-080571, JP-A-11-080570, JP-A-11-130931, JP-A-11-100033, JP-A-11-116763, JP-A-9-272714, JP-A-9-272715, etc.). Although it does not specifically limit as vinyl-type polymer (I) of this invention, All the polymers disclosed by the invention illustrated above can be used suitably.

It does not specifically limit as a vinyl-type monomer which comprises the principal chain of the vinyl-type polymer of this invention, Various things can be used. To illustrate,
(Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n-butyl, (meth) Isobutyl acrylate, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid-n-heptyl , (Meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid isononyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, ( (Meth) acrylic acid phenyl, (meth) acrylic acid tolyl, (meth) acrylic acid benzyl, (meth) acrylic acid-2-methyl Xylethyl, (meth) acrylate-3-methoxybutyl, (meth) acrylate-2-hydroxyethyl, (meth) acrylate-2-hydroxypropyl, stearyl (meth) acrylate, glycidyl (meth) acrylate, ( (Meth) acrylic acid 2-aminoethyl, γ- (methacryloyloxypropyl) trimethoxysilane, (meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethyl methyl, (meth) acrylic acid 2-trifluoro Methyl ethyl, perfluoroethyl methyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, perfluoroethyl perfluorobutyl methyl (meth) acrylate, 2-perfluoroethyl-2 (meth) acrylate -Perfluorobutylethyl, (meth) aqua Perfluoroethyl laurate, perfluoromethyl (meth) acrylate, diperfluoromethyl methyl (meth) acrylate, 2,2-diperfluoromethyl ethyl (meth) acrylate, perfluoromethyl per (meth) acrylate Fluoroethylmethyl, 2-perfluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylmethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, (meth) acrylic (Meth) such as 2-perfluorodecylmethyl acid, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylmethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate Acrylic monomers; styrene, vinyl toluene, α-methyl Aromatic vinyl monomers such as styrene, chlorostyrene, styrene sulfonic acid, and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; silicon such as vinyltrimethoxysilane and vinyltriethoxysilane Containing vinyl monomers; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexyl Maleimide monomers such as maleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; acrylonitrile, meta Acrylonitrile monomers such as acrylonitrile; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate; Ethylene, propylene, etc. Alkenes; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or a plurality of these may be copolymerized.

  The main chain of the vinyl polymer is mainly polymerized with at least one monomer selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. It is preferable that it is manufactured. Here, “mainly” means that 30 mol% or more, preferably 50 mol% or more of the monomer units constituting the vinyl polymer are the above monomers.

  Of these, a styrene monomer and a (meth) acrylic acid monomer are preferable from the physical properties of the product. More preferred are acrylic ester monomers and methacrylic ester monomers, and particularly preferred are acrylic ester monomers. In this application, a butyl acrylate monomer is more preferable because physical properties such as a low viscosity of the blend and a heat resistance of the cured product are required. On the other hand, in applications where oil resistance is required, a copolymer mainly composed of ethyl acrylate is more preferable. This polymer mainly composed of ethyl acrylate is excellent in oil resistance but tends to be slightly inferior in low temperature characteristics (cold resistance). Therefore, in order to improve the low temperature characteristics, a part of ethyl acrylate is converted into butyl acrylate. It is also possible to replace it. However, as the ratio of butyl acrylate is increased, the good oil resistance is impaired, so that the ratio is preferably 80 mol% or less depending on the application for which oil resistance is required, and 60 mol% or less. More preferably, it is 40 mol% or less, more preferably 30 mol% or less. It is also preferable to use 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, or the like in which oxygen is introduced into the side chain alkyl group in order to improve low-temperature characteristics and the like without impairing oil resistance. However, since heat resistance tends to be inferior due to the introduction of an alkoxy group having an ether bond in the side chain, when heat resistance is required, the ratio is preferably 60 mol% or less, and 40% or less. Is more preferable. In accordance with various uses and required purposes, it is possible to obtain suitable polymers by changing the ratio in consideration of required physical properties such as oil resistance, heat resistance and low temperature characteristics. For example, although not limited, examples of excellent physical property balance such as oil resistance, heat resistance, and low-temperature characteristics include ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (molar ratio of 40-50 / 20- 30 / 20-30).

In addition, in the case of adding an epoxy resin to the vinyl polymer of the present invention, in order to obtain a transparent cured product when the curable composition is cured, the vinyl polymer is an epoxy. Resins that are compatible with the resin are preferred, and polymers or copolymers having a higher polarity than the butyl acrylate homopolymer are preferred, and the main chain of the vinyl polymer is represented by the general formula (2). A polymer or copolymer having a unit structure is more preferable.
_{- [CH 2 -CR (COOR '} )] - (2)
(In the formula, R is hydrogen or a methyl group, and R ′ is the same or different and is an alkoxyalkyl group or an alkyl group having 1 to 3 carbon atoms.)
The polymer or copolymer having a higher polarity than the butyl acrylate homopolymer is not particularly limited, and examples thereof include a copolymer of butyl acrylate and a monomer having a higher polarity than butyl acrylate. Here, examples of the monomer having higher polarity than butyl acrylate include ethyl acrylate and 2-methoxyethyl acrylate. For example, a copolymer of ethyl acrylate / butyl acrylate / acrylic acid 2-methoxyethyl (molar ratio 40-50 / 20-30 / 20-30) is easily compatible with various epoxy resins, and is a transparent cured product. It is preferable because it is easy to obtain.

  Copolymerizes monomers with long-chain alkyl groups such as stearyl groups and lauryl groups to improve compatibility with other polymers such as modified silicone resins (oxyalkylene polymers having crosslinkable silyl groups) You may let them. Although there is no particular limitation, for example, 5-30 mol% of stearyl acrylate or lauryl acrylate is copolymerized so that the compatibility with the modified silicone resin becomes very good. Since the compatibility varies depending on the molecular weight of each polymer, it is preferable to select the proportion of the monomer to be copolymerized accordingly. In this case, block copolymerization may be performed. The effect may be manifested in a small amount.

  The curable composition containing a vinyl polymer having a functional silyl group may have a slow curability upon storage, that is, a poor storage stability. For example, it may be possible to suppress such a decrease by copolymerizing methyl acrylate. Moreover, you may use when you want to improve the intensity | strength of hardened | cured material. Also in this case, the ratio of monomers to be copolymerized may be selected according to the molecular weight and / or may be block copolymerized.

  In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in that case, these preferred monomers are preferably contained in a weight ratio of 40% or more. . In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  The molecular weight distribution of the vinyl polymer of 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 is not particularly limited. A distribution of less than 1.8, particularly less than 1.3 is preferred from the viewpoint of workability. In the GPC measurement in the present invention, chloroform is usually 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 vinyl polymer in the present invention is not particularly limited. In addition, when measured by gel permeation chromatography, 500 to 1,000,000, particularly 5,000 to 50,000 are preferable from the viewpoint of workability and physical properties. Of course, the smaller the molecular weight, the easier it is to be compatible with other resins (various polymers), and the resulting cured product tends to have a high modulus and low elongation. Conversely, if the molecular weight is large, the opposite is true. Show the trend.

<Method of synthesizing the main chain>
The method for synthesizing the vinyl polymer in the present invention is not limited and may be free radical polymerization. However, controlled radical polymerization is preferable, living radical polymerization is more preferable, and atom transfer radical polymerization is particularly preferable. These will be described below.

Controlled radical polymerization The radical polymerization method is a “general radical polymerization method” in which a monomer having a specific functional group and a vinyl monomer are simply copolymerized using an azo compound or a peroxide as a polymerization initiator. Can be classified into “controlled radical polymerization methods” in which a specific functional group can be introduced at a controlled position such as a terminal.

  The “general radical polymerization method” is a simple method. However, in this method, a monomer having a specific functional group is introduced into the polymer only in a probabilistic manner, so an attempt is made to obtain a polymer having a high functionalization rate. In such a case, it is necessary to use this monomer in a considerably large amount. On the contrary, if the monomer is used in a small amount, there is a problem that the proportion of the polymer in which this specific functional group is not introduced becomes large. Moreover, since it is free radical polymerization, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

  The “controlled radical polymerization method” further includes a “chain transfer agent method” in which a vinyl polymer having a functional group at a terminal is obtained by polymerization using a chain transfer agent having a specific functional group, It can be classified as “living radical polymerization method” in which a polymer having a molecular weight almost as designed can be obtained by growing the terminal without causing a termination reaction or the like.

  In the “chain transfer agent method”, a polymer having a high functionalization rate can be obtained, but a chain transfer agent having a considerably large amount of a specific functional group with respect to the initiator is required. There is an economic problem. Further, like the above-mentioned “general radical polymerization method”, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained because of free radical polymerization.

  Unlike these polymerization methods, the “living radical polymerization method” is a radical polymerization that is difficult to control because the polymerization rate is high and a termination reaction due to coupling between radicals is likely to occur. It is difficult to obtain a polymer having a narrow molecular weight distribution (Mw / Mn is about 1.1 to 1.5), and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

  Accordingly, the “living radical polymerization method” can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and a monomer having a specific functional group can be introduced at almost any position of the polymer. The method for producing the vinyl polymer having the specific functional group is more preferable.

  In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. It also includes pseudo-living polymerization that grows in an equilibrium state. The definition in the present invention is also the latter.

  The “living radical polymerization method” has been actively researched by various groups in recent years. Examples thereof include those using a cobalt porphyrin complex as shown in, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943, Macromolecules. (Macromolecules), 1994, Vol. 27, p. 7228, using a radical capping agent such as a nitroxide compound, “atom transfer radical polymerization” using an organic halide as an initiator and a transition metal complex as a catalyst ( Atom Transfer Radical Polymerization (ATRP).

  Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing vinyl monomers using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above “living radical polymerization method”. In addition to the features of ”, it has a halogen, which is relatively advantageous for functional group conversion reaction, at the end, and has a high degree of freedom in designing initiators and catalysts, so the production of vinyl polymers having specific functional groups More preferable as a method. As this atom transfer radical polymerization method, for example, Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614, Macromolecules 1995, 28, 7901, Science 1996, 272, 866, WO96 / 30421, WO97 / 18247, WO98 / 01480, WO98 / 40415, or Sawamoto et al., Macromolecules. Macromolecules 1995, 28, 1721, JP-A-9-208616, JP-A-8-41117, and the like.

  In the present invention, there is no particular restriction as to which of these living radical polymerization methods is used, but an atom transfer radical polymerization method is preferred.

  The living radical polymerization will be described in detail below, but before that, one of the controlled radical polymerizations that can be used for the production of vinyl polymers described later, the polymerization using a chain transfer agent will be described. To do. Although it does not specifically limit as radical polymerization using a chain transfer agent (telomer), The following two methods are illustrated as a method of obtaining the vinyl polymer which has the terminal structure suitable for this invention.

  JP-A-4-132706 discloses a method for obtaining a halogen-terminated polymer by using a halogenated hydrocarbon as a chain transfer agent, JP-A-61-271306, JP-A-2594402, This is a method for obtaining a hydroxyl-terminated polymer by using a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent as disclosed in JP-A-54-47782.

  Below, living radical polymerization is demonstrated.

  First, a method using a radical capping agent such as a nitroxide compound will be described. In this polymerization, a stable nitroxy free radical (= N—O.) Is generally used as a radical capping agent. Examples of such compounds include, but are not limited to, 2,2,6,6-substituted-1-piperidinyloxy radical, 2,2,5,5-substituted-1-pyrrolidinyloxy radical, and the like. Nitroxy free radicals from cyclic hydroxyamines are preferred. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable. Specific nitroxy free radical compounds include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1- Piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1, Examples include 1,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical, and the like. Instead of the nitroxy free radical, a stable free radical such as a galvinoxyl free radical may be used.

  The radical capping agent is used in combination with a radical generator. It is considered that the reaction product of the radical capping agent and the radical generator serves as a polymerization initiator and the polymerization of the addition polymerizable monomer proceeds. The combination ratio of both is not particularly limited, but 0.1 to 10 mol of the radical generator is suitable for 1 mol of the radical capping agent.

  Although various compounds can be used as the radical generator, a peroxide capable of generating a radical under polymerization temperature conditions is preferred. Examples of the peroxide include, but are not limited to, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, diisopropyl peroxydicarbonate, bis There are peroxycarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, alkyl peresters such as t-butylperoxyoctate and t-butylperoxybenzoate. Benzoyl peroxide is particularly preferable. Furthermore, radical generators such as radical-generating azo compounds such as azobisisobutyronitrile may be used instead of peroxide.

  Macromolecules 1995, 28, P.M. As reported in 2993, instead of using a radical capping agent and a radical generator in combination, an alkoxyamine compound may be used as an initiator.

  When an alkoxyamine compound is used as an initiator, if it has a functional group such as a hydroxyl group as shown in the above figure, a polymer having a functional group at the terminal can be obtained. When this is used in the method of the present invention, a polymer having a functional group at the terminal can be obtained.

  Polymerization conditions such as monomers, solvents, polymerization temperature and the like used in polymerization using a radical capping agent such as the above nitroxide compound are not limited, but may be the same as those used for atom transfer radical polymerization described below.

Atom Transfer Radical Polymerization Next, a more preferred atom transfer radical polymerization method as the living radical polymerization of the present invention will be described.

In this 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 halogenated compound. A sulfonyl compound or the like is used as an initiator.
For example,
_{C 6 H 5 -CH 2 X,} C 6 H 5 -C (H) (X) CH 3, C 6 H 5 -C (X) (CH 3) 2
(However, in the above chemical formula, C ₆ H ₅ is a phenyl group, X is chlorine, bromine, or iodine)
^{R 3 -C (H) (X} ) -CO 2 R 4, R 3 -C (CH 3) (X) -CO 2 R 4, R 3 -C (H) (X) -C (O) R 4 R ³ —C (CH ₃ ) (X) —C (O) R ⁴ ,
(Wherein R ³ and R ⁴ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine)
R ³ —C ₆ H ₄ —SO ₂ X
(Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine).

  As an initiator of atom transfer radical polymerization, an organic halide or a sulfonyl halide compound having a functional group other than the functional group for initiating polymerization can also be used. In such a case, a vinyl polymer having a functional group at one end of the main chain and a growth terminal structure of atom transfer radical polymerization at the other main chain end is produced. Examples of such functional groups include alkenyl groups, crosslinkable silyl groups, hydroxyl groups, epoxy groups, amino groups, amide groups, and the like.

It does not limit as an organic halide which has an alkenyl group, For example, what has a structure shown in General formula (3) is illustrated.
R ⁶ R ⁷ C (X) —R ⁸ —R ⁹ —C (R ⁵ ) ═CH ₂ (3)
(Wherein R ⁵ is hydrogen or a methyl group, R ⁶ and R ⁷ are hydrogen, or a monovalent alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, or interconnected at the other end. things, R ⁸ is, -C (O) O- (ester group), - C (O) - ( keto group), or o-, m-, p-phenylene, R ⁹ is a direct bond or carbon atoms 1 to 20 divalent organic groups which may contain one or more ether bonds, X is chlorine, bromine or iodine)
Specific examples of the substituents R ⁶ and R ⁷ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, pentyl group, hexyl group and the like. R ⁶ and R ⁷ may be linked at the other end to form a cyclic skeleton.

Specific examples of the organic halide having an alkenyl group represented by the general formula (3) include
_{XCH 2 C (O) O (} CH 2) n CH = CH 2, H 3 CC (H) (X) C (O) O (CH 2) n CH = CH 2, (H 3 C) 2 C (X ) C (O) O (CH ₂ ) _n CH═CH ₂ , CH ₃ CH ₂ C (H) (X) C (O) O (CH ₂ ) _n CH═CH ₂ , (in the above formulas, X Is chlorine, bromine, or iodine, n is an integer of 0-20)
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m CH = CH 2, H 3 CC (H) (X) C (O) O (CH 2) n O (CH 2) m CH = _{CH 2, (H 3 C)} 2 C (X) C (O) O (CH 2) n O (CH 2) m CH = CH 2, CH 3 CH 2 C (H) (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m CH═CH ₂ (in the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1-20, m is an integer of 0-20) o, _{m, p-XCH 2 -C 6} H 4 - (CH 2) n -CH = CH 2, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2) n - _{CH = CH 2, o, m} , p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2,
(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 C (H) (X) -C _{6 H 4 - (CH 2)} n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) _{n -O- (CH 2) m CH} = CH 2,
(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -CH = CH 2, o, m, p-CH 3 C (H) (X) -C 6 H 4 -O- _{(CH 2) n -CH = CH} 2, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2,
(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 C (H) (X) —C ₆ H ₄ —O— (CH ₂ ) _n —O— (CH ₂ ) _m —CH═CH ₂ , o, m, p—CH ₃ CH ₂ C (H) (X) —C ₆ H ₄ — O— (CH ₂ ) _n —O— (CH ₂ ) _m —CH═CH ₂ ,
(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
Examples of the organic halide having an alkenyl group further include a compound represented by the general formula (4).
^{_{H 2 C = C (R 5}} ) -R 9 -C (R 6) (X) -R 10 -R 7 (4)
Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ and X are the same as above, R ¹⁰ is a direct bond, —C (O) O— (ester group), —C (O) — (keto group Or an o-, m-, p-phenylene group)
R ⁹ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds), and in the case of a direct bond, carbon to which a halogen is bonded Is a halogenated allylic compound. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, it is not always necessary to have a C (O) O group or a phenylene group as R ¹⁰ , and a direct bond may be used. In the case where R ⁹ is not a direct bond, R ¹⁰ is preferably a C (O) O group, a C (O) group or a phenylene group in order to activate the carbon-halogen bond.

If the compound of general formula (4) is specifically illustrated,
_{CH 2 = CHCH 2 X, CH} 2 = C (CH 3) CH 2 X, CH 2 = CHC (H) (X) CH 3, CH 2 = C (CH 3) C (H) (X) CH 3, CH ₂ = CHC (X) (CH ₃ ) ₂ , CH ₂ = CHC (H) (X) C ₂ H ₅ , CH ₂ = CHC (H) (X) CH (CH ₃ ) ₂ , CH ₂ = CHC ( _{H) (X) C 6 H} 5, CH 2 = CHC (H) (X) CH 2 C 6 H 5, CH 2 = CHCH 2 C (H) (X) -CO 2 R, CH 2 = CH (CH _{2) 2 C (H) (} X) -CO 2 R, CH 2 = CH (CH 2) 3 C (H) (X) -CO 2 R, CH 2 = CH (CH 2) 8 C (H) ( _{X) -CO 2 R, CH 2} = CHCH 2 C (H) (X) -C 6 H 5, CH 2 = CH (CH 2) 2 C (H) (X) -C 6 H 5, CH 2 = _{CH (CH 2) 3 C (} H) (X) -C 6 H 5,
(In the above formulas, X is chlorine, bromine, or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group).

If the specific example of the sulfonyl halide compound which has an alkenyl group is given,
_{o-, m-, p-CH 2} = CH- (CH 2) n -C 6 H 4 -SO 2 X, o-, m-, p-CH 2 = CH- (CH 2) n -O-C ₆ H ₄ —SO ₂ X,
(In the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20).

It does not specifically limit as said organic halide which has a crosslinkable silyl group, For example, what has a structure shown to General formula (5) is illustrated.
^{R 6 R 7 C (X)} -R 8 -R 9 -C (H) (R 5) CH 2 - [Si (R 11) 2-b (Y) b O] m -Si (R 12) 3- _a (Y) _a (5)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are the same as above, and R ¹¹ and R ¹² are all alkyl groups, aryl groups, aralkyl groups, or those having 1 to 20 carbon atoms, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). Represents an organosiloxy group, and when two or more R ¹¹ or R ¹² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and Y represents two or more When present, they may be the same or different, a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer from 0 to 19. (Provided that a + mb ≧ 1)
If the compound of the general formula (5) is specifically exemplified,
_{XCH 2 C (O) O (} CH 2) n Si (OCH 3) 3, CH 3 C (H) (X) C (O) O (CH 2) n Si (OCH 3) 3, (CH 3) 2 C (X) C (O) O (CH 2) n Si (OCH 3) 3, XCH 2 C (O) O (CH 2) n Si (CH 3) (OCH 3) 2, CH 3 C (H) (X) C (O) O (CH 2) n Si (CH 3) (OCH 3) 2, (CH 3) 2 C (X) C (O) O (CH 2) n Si (CH 3) (OCH ₃ ) ₂ ,
(In the above formulas, X is chlorine, bromine, iodine, n is an integer of 0-20)
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (OCH 3) 3, H 3 CC (H) (X) C (O) O (CH 2) n O (CH 2) m Si (OCH ₃ ) ₃ , (H ₃ C) ₂ C (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m Si (OCH ₃ ) ₃ , CH ₃ CH ₂ C (H) (X ) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3, XCH 2 C (O) O (CH 2) n O (CH 2) m Si (CH 3) (OCH 3 ) ₂ , H ₃ CC (H) (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m —Si (CH ₃ ) (OCH ₃ ) ₂ , (H ₃ C) ₂ C (X) _{C (O) O (CH 2} ) n O (CH 2) m -Si (CH 3) (OCH 3) 2, CH 3 CH 2 C (H) (X) C (O) O (CH 2) n O _{(CH 2) m -Si (CH} 3) (OCH 3) 2,
(In the above formulas, X is chlorine, bromine, iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2 _{) 2 Si (OCH 3) 3} , o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3, o, m, p- _{XCH 2 -C 6 H 4 - (} CH 2) 3 Si (OCH 3) 3, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3 _{) 3, o, m, p} -CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3, o, m, p-XCH 2 -C 6 H _{4 - (CH 2) 2 -O-} (CH 2) 3 Si (OCH 3) 3, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2) 2 -O _{- (CH 2) 3 Si (} OCH 3) 3, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H _{4 - (CH 2) 2 -O-} (CH 2) 3 Si (OCH 3) 3, o, m, p-XCH 2 -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3, _{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3, o, m, p-CH 3 CH 2 C (H) ( _{X) -C 6 H 4 -O- (} CH 2) 3 -Si (OCH 3) 3, o, m, p-XCH 2 -C 6 H 4 -O- (CH 2) 2 -O- (CH 2 _{) 3 -Si (OCH 3) 3} , o, m, p-CH 3 C (H) (X) -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 Si (OCH 3 _{) 3, o, m, p} -CH 3 CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
(In the above formulas, X is chlorine, bromine, or iodine).

Examples of the organic halide having a crosslinkable silyl group further include those having a structure represented by the general formula (6).
^{_{(R 12) 3-a (}} Y) a Si- [OSi (R 11) 2-b (Y) b] m -CH 2 -C (H) (R 5) -R 9 -C (R 6) ( X) -R ¹⁰ -R ⁷ (6)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , a, b, m, X, Y are the same as above)
If such a compound is specifically illustrated,
_{(CH 3 O) 3 SiCH 2} CH 2 C (H) (X) C 6 H 5, (CH 3 O) 2 (CH 3) SiCH 2 CH 2 C (H) (X) C 6 H 5, (CH _{3 O) 3 Si (CH 2} ) 2 C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si (CH 2) 2 C (H) (X) -CO 2 R, _{(CH 3 O) 3 Si (} CH 2) 3 C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si (CH 2) 3 C (H) (X) -CO 2 _{R, (CH 3 O) 3} Si (CH 2) 4 C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si (CH 2) 4 C (H) (X) - _{CO 2 R, (CH 3 O} ) 3 Si (CH 2) 9 C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si (CH 2) 9 C (H) (X _{) -CO 2 R, (CH 3} O) 3 Si (CH 2) 3 C (H) (X) -C 6 H 5, (C _{3 O) 2 (CH 3)} Si (CH 2) 3 C (H) (X) -C 6 H 5, (CH 3 O) 3 Si (CH 2) 4 C (H) (X) -C 6 H _{5, (CH 3 O) 2} (CH 3) Si (CH 2) 4 C (H) (X) -C 6 H 5,
(In each of the above formulas, X is chlorine, bromine, or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group).

The organic halide having a hydroxyl group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
_{HO- (CH 2) n -OC (} O) C (H) (R) (X)
(In the formula, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
The organic halide having an amino group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
_{H 2 N- (CH 2) n} -OC (O) C (H) (R) (X)
(In the formula, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
The organic halide having the epoxy group or the sulfonyl halide compound is not particularly limited.
(In the formula, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
In order to obtain a polymer having two or more growth terminal structures in one molecule, it is preferable to use an organic halide having two or more starting points or a sulfonyl halide compound as an initiator.

  There is no restriction | limiting in particular as a vinyl-type monomer used in this superposition | polymerization, All already illustrated 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, 8, 9, 10, or 11 element as a central metal. More preferable examples include a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. is there. When a copper compound is used, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity A ligand such as a polyamine is added. A preferred ligand is a nitrogen-containing compound, a more preferred ligand is a chelate-type nitrogen-containing compound, and a more preferred ligand is N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine. It is. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine A complex (NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

  The polymerization can be carried out without solvent or in various solvents. Solvent types include hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, halogenated hydrocarbon solvents such as methylene chloride and chloroform, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Solvents, alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol, nitrile solvents such as acetonitrile, propionitrile, benzonitrile, ester solvents such as ethyl acetate, butyl acetate, Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate, and these can be used alone or in admixture of two or more.

  Moreover, although not limited, superposition | polymerization can be performed in the range of 0 to 200 degreeC, Preferably it is 50 to 150 degreeC.

  The atom transfer radical polymerization of the present invention includes so-called reverse atom transfer radical polymerization. Reverse atom transfer radical polymerization is a high oxidation state when a normal atom transfer radical polymerization catalyst generates radicals, for example, a peroxide relative to Cu (II) when Cu (I) is used as a catalyst. And the like, and as a result, an equilibrium state similar to that of atom transfer radical polymerization is produced (see Macromolecules 1999, 32, 2872).

<Functional group>
Number of crosslinkable silyl groups The number of crosslinkable silyl groups in the vinyl polymer is not particularly limited, but from the viewpoint of the curability of the composition and the physical properties of the cured product, it should have an average of 1 or more in the molecule. More preferably, it is 1.1 or more and 4.0 or less, More preferably, it is 1.2 or more and 3.5 or less.

Position of the crosslinkable silyl group When a rubber-like property is particularly required for a cured product obtained by curing the curable composition of the present invention, the molecular weight between crosslinking points that greatly affects rubber elasticity can be taken. At least one of the crosslinkable functional groups is preferably at the end of the molecular chain. More preferably, it has all crosslinkable functional groups at the molecular chain ends.

  A method for producing a vinyl polymer having at least one crosslinkable silyl group at the molecular chain end, in particular, a (meth) acrylic polymer is disclosed in Japanese Patent Publication No. 3-14068, Japanese Patent Publication No. 4-55444, This is disclosed in, for example, Kaihei 6-221922. 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 crosslinkable silyl groups at the molecular chain ends, while Mw / Mn The value of the molecular weight distribution represented by 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 a crosslinkable silyl group at the molecular chain terminal at a high ratio, the above “living radical polymerization method” is used. However, it is not limited to a polymer having a narrow molecular weight distribution.

  These functional groups will be described below.

The crosslinking silyl group of the crosslinkable silyl group present invention, the general formula (1);
_{^{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
{Wherein R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R 'Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different), and represents a triorganosiloxy group represented by R ¹ or When two or more R ² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }
The group represented by these is mention | raise | lifted.

  Examples of the hydrolyzable group include commonly used groups such as a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, an alkoxy group, an amide group, and an aminooxy group are preferable, but an alkoxy group is particularly preferable in terms of mild hydrolyzability and easy handling. Among the alkoxy groups, those having fewer carbon atoms have higher reactivity, and the reactivity decreases in the order of methoxy group> ethoxy group> propoxy group, and can be selected according to the purpose and application.

Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3, and (a + Σb) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silyl group, they may be the same or different. The number of silicon atoms forming the crosslinkable silyl group is one or more, but in the case of silicon atoms linked by a siloxane bond or the like, it is preferably 20 or less. In particular, the general formula (7)
-Si (R ² ) _3-a (Y) _a (7)
A crosslinkable silyl group represented by the formula (wherein R ² and Y are the same as described above, and a is an integer of 1 to 3) is preferable because it is easily available.

  Although not particularly limited, a is preferably 2 or more in consideration of curability.

  As such a vinyl polymer having a crosslinkable silyl group, a polymer having a hydrolyzable silicon group formed by bonding two hydrolyzable groups per silicon atom is often used. When a very fast curing rate is required, such as when used at low temperatures, etc., the curing rate is not sufficient, and if it is desired to provide flexibility after curing, it is necessary to reduce the crosslinking density. For this reason, the crosslink density is not sufficient, and stickiness (surface tack) may occur. In that case, it is preferable that a is 3 (for example, trimethoxy functional group).

  Further, those having a of 3 (for example, trimethoxy functional group) cure faster than those having 2 (for example, dimethoxy functional group), but those having 2 are superior in terms of storage stability and mechanical properties (elongation, etc.). There is a case. In order to balance the curability and physical properties, two (for example, dimethoxy functional group) and three (for example, trimethoxy functional group) may be used in combination.

  For example, when Y is the same, the greater the a, the higher the reactivity of Y. Therefore, by variously selecting Y and a, it is possible to control the curability and the mechanical properties of the cured product. It can be selected according to the application. A compound having a of 1 is used as a chain extender mixed with a polymer having a crosslinkable silyl group, specifically, at least one polymer comprising a polysiloxane, polyoxypropylene or polyisobutylene. it can. It is possible to obtain a composition having low viscosity before curing, high elongation at break after curing, low bleeding, low surface contamination, and excellent paint adhesion.

The following method of introducing the crosslinkable silyl group, will be described method of introducing the crosslinkable silyl group into the vinyl polymer of the present invention, but is not limited thereto.

  First, a method for introducing a crosslinkable silyl group, alkenyl group, and hydroxyl group by terminal functional group conversion will be described. Since these functional groups can be precursors to each other, they are described in the order from the crosslinkable silyl group.

As a method for synthesizing a vinyl polymer having at least one crosslinkable silyl group,
(A) Method of adding a hydrosilane compound having a crosslinkable silyl group to a vinyl polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst (B) One molecule per vinyl polymer having at least one hydroxyl group A method of reacting a compound having a group capable of reacting with a hydroxyl group, such as a compound having a crosslinkable silyl group and an isocyanate group therein. (C) When synthesizing a vinyl polymer by radical polymerization, polymerization is performed in one molecule. (D) Method of using a chain transfer agent having a crosslinkable silyl group when synthesizing a vinyl polymer by radical polymerization (E) A vinyl polymer having at least one high carbon-halogen bond having a crosslinkable silyl group and a stable carbanion in one molecule And a method of reacting the compound.

  The vinyl polymer having at least one alkenyl group used in the method (A) can be obtained by various methods. Although the synthesis method is illustrated below, it is not necessarily limited to these.

(Aa) When synthesizing a vinyl polymer by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule as shown in the following general formula (9) To react as a second monomer.
^{_{H 2 C = C (R 14}} ) -R 15 -R 16 -C (R 17) = CH 2 (9)
(Wherein R ¹⁴ represents hydrogen or a methyl group, R ¹⁵ represents —C (O) O—, or o-, m-, p-phenylene group, R ¹⁶ represents a direct bond, or a carbon number of 1 to 20 represents a divalent organic group having 20 and may contain one or more ether bonds, R ¹⁷ is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 carbon atoms. Represents -20 aralkyl groups)
There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule. It is preferable to react as the second monomer at the end or after completion of the reaction of the predetermined monomer.

  (Ab) When synthesizing a vinyl polymer by living radical polymerization, for example, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. A method of reacting a compound having at least two alkenyl groups having low polymerizability, such as

  (Ac) Various organometallic compounds having an alkenyl group such as organotin such as allyltributyltin and allyltrioctyltin on a vinyl polymer having at least one highly reactive carbon-halogen bond A method of replacing halogen by reaction.

(Ad) A method of substituting halogen by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a stabilized carbanion having an alkenyl group as shown in the general formula (10). .
^{M + C - (R 18)} (R 19) -R 20 -C (R 17) = CH 2 (10)
(Wherein, R ¹⁷ is as defined above, R ^18, R ¹⁹ together carbanion C ^- a is an electron withdrawing group stabilizing or one of the other is hydrogen or a 1 to 10 carbon atoms in the electron-withdrawing group Represents an alkyl group or a phenyl group, R ²⁰ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms, and may contain one or more ether bonds, M ⁺ represents an alkali metal ion, Or a quaternary ammonium ion)
As the electron withdrawing group for R ¹⁸ and R ¹⁹ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

  (Ae) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with, for example, a single metal such as zinc or an organometallic compound. A method of reacting with an electrophilic compound having an alkenyl group, such as an alkenyl group-containing compound having a leaving group such as an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, an acid halide having an alkenyl group .

(Af) For example, an oxyanion or carboxylate anion having an alkenyl group represented by the general formula (11) or (12) is added to a vinyl polymer having at least one carbon-halogen bond having high reactivity. A method of replacing halogen by reaction.
^{_{H 2 C = C (R 17}} ) -R 21 -O - M + (11)
(Wherein R ¹⁷ and M ⁺ are the same as above. R ²¹ is a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds)
H ₂ C═C (R ¹⁷ ) −R ²² —C (O) O ⁻ M ⁺ (12)
(Wherein, R ¹⁷ and M ⁺ are the same as above. R ²² is a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds). .

  The method for synthesizing a vinyl polymer having at least one highly reactive carbon-halogen bond is an atom transfer radical polymerization method using an organic halide as described above as an initiator and a transition metal complex as a catalyst. For example, but not limited to.

Further, the vinyl polymer having at least one alkenyl group can be obtained from a vinyl polymer having at least one hydroxyl group, and the methods exemplified below can be used, but are not limited thereto. In the hydroxyl group of a vinyl polymer having at least one hydroxyl group,
(Ag) A method of reacting a base such as sodium methoxide with an alkenyl group-containing halide such as allyl chloride.

  (Ah) A method of reacting an alkenyl group-containing isocyanate compound such as allyl isocyanate.

  (Ai) A method in which an alkenyl group-containing acid halide such as (meth) acrylic acid chloride is reacted in the presence of a base such as pyridine.

  (Aj) A method in which an alkenyl group-containing carboxylic acid such as acrylic acid is reacted in the presence of an acid catalyst;

  In the present invention, when a halogen is not directly involved in a method for introducing an alkenyl group such as (Aa) and (Ab), it is preferable to synthesize a vinyl polymer using a living radical polymerization method. The method (Ab) is more preferable from the viewpoint of easier control.

  When an alkenyl group is introduced by converting the halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide having at least one highly reactive carbon-halogen bond, or A vinyl heavy polymer having at least one highly reactive carbon-halogen bond at the terminal, obtained by radical polymerization of a vinyl monomer using a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst (atom transfer radical polymerization method). It is preferable to use coalescence. In view of easier control, the method (Af) is more preferable.

Moreover, there is no restriction | limiting in particular as a hydrosilane compound which has a crosslinkable silyl group, When a typical thing is shown, the compound shown by General formula (13) will be illustrated.
_{^{H- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (13)
{Wherein R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R 'Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different), and represents a triorganosiloxy group represented by R ¹ or When two or more R ² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }
Among these hydrosilane compounds, in particular, the general formula (14)
H-Si (R ² ) _3-a (Y) _a (14) (wherein R ² , Y and a are the same as above)
The compound which has a crosslinkable group shown by is preferable from a point with easy acquisition.

When the hydrosilane compound having a crosslinkable silyl group is added to an alkenyl group, a transition metal catalyst is usually used. Examples of the transition metal catalyst include platinum simple substance, alumina, silica, carbon black and the like in which a platinum solid is dispersed, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc., platinum-olefin. Complex, platinum (0) -divinyltetramethyldisiloxane complex is mentioned. Examples of the catalyst other than platinum _{compounds, RhCl (PPh 3) 3,} RhCl 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 · H 2 O, NiCl 2, TiCl 4 , and the like.

  Examples of the method for producing a vinyl polymer having at least one hydroxyl group used in the methods (B) and (Ag) to (Aj) include the following methods, but are limited to these methods. It is not something.

(Ba) When synthesizing a vinyl polymer by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule as shown in the following general formula (15) is used as the second monomer. To react as.
^{_{H 2 C = C (R 14}} ) -R 15 -R 16 -OH (15)
(Wherein R ¹⁴ , R ¹⁵ and R ¹⁶ are the same as above)
There is no limitation on the timing of reacting the compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule. However, particularly in the case of living radical polymerization, when the rubber-like properties are expected, the end of the polymerization reaction or a predetermined monomer. After completion of the reaction, it is preferable to react as the second monomer.

  (Bb) When a vinyl polymer is synthesized by living radical polymerization, an alkenyl alcohol such as 10-undecenol, 5-hexenol or allyl alcohol is reacted at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. How to make.

  (Bc) A method in which a vinyl monomer is radically polymerized using a large amount of a hydroxyl group-containing chain transfer agent such as a hydroxyl group-containing polysulfide described in JP-A-5-262808.

  (Bd) A method of radical polymerization of a vinyl monomer using hydrogen peroxide or a hydroxyl group-containing initiator as disclosed in, for example, JP-A-6-239912 and JP-A-8-283310.

  (Be) A method of radical polymerization of a vinyl monomer by using an excessive amount of alcohol as disclosed in, for example, JP-A-6-116312.

  (Bf) Hydrolysis of a vinyl polymer having at least one highly reactive carbon-halogen bond or reaction with a hydroxyl group-containing compound by a method such as disclosed in JP-A-4-132706. To introduce a hydroxyl group into the terminal.

(Bg) A method in which a vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having a hydroxyl group as listed in the general formula (16) to substitute the halogen.
M ⁺ C ⁻ (R ¹⁸ ) (R ¹⁹ ) —R ²⁰ —OH (16)
(Wherein R ¹⁸ , R ¹⁹ and R ²⁰ are the same as above)
As the electron withdrawing group for R ¹⁸ and R ¹⁹ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

  (Bh) An enolate anion is prepared by allowing a metal polymer such as zinc or an organometallic compound to act on a vinyl polymer having at least one highly reactive carbon-halogen bond, and then aldehydes. Or a method of reacting ketones.

(Bi) A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with, for example, an oxyanion or carboxylate anion having a hydroxyl group as shown in the general formula (17) or (18). To replace the halogen.
HO—R ²¹ —O ⁻ M ⁺ (17)
(Wherein R ²¹ and M ⁺ are the same as above)
HO—R ²² —C (O) O ⁻ M ⁺ (18)
(Wherein R ²² and M ⁺ are the same as above)
(Bj) When synthesizing a vinyl polymer by living radical polymerization, as the second monomer after the completion of the polymerization reaction or after the completion of the reaction of the predetermined monomer, an alkenyl group and a hydroxyl group having low polymerization in one molecule A method of reacting a compound having

Although it does not specifically limit as such a compound, The compound etc. which are shown by General formula (19) are mentioned.
^{_{H 2 C = C (R 14}} ) -R 21 -OH (19)
(Wherein R ¹⁴ and R ²¹ are the same as described above.)
Although it does not specifically limit as a compound shown by the said General formula (19), From an easy acquisition, alkenyl alcohol like 10-undecenol, 5-hexenol, allyl alcohol is preferable.

  In the present invention, when halogen is not directly involved in the method of introducing a hydroxyl group such as (Ba) to (Be) and (Bj), a vinyl polymer is obtained by using a living radical polymerization method. It is preferable to synthesize. The method (Bb) is more preferable in terms of easier control.

  When introducing a hydroxyl group by converting halogen in a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide or a sulfonyl halide compound is used as an initiator, and a transition metal complex is used as a catalyst. It is preferable to use a vinyl polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by radical polymerization of a vinyl monomer (atom transfer radical polymerization method). The method (Bi) is more preferable from the viewpoint of easier control.

  Examples of the compound having a crosslinkable silyl group and a group capable of reacting with a hydroxyl group such as an isocyanate group in one molecule include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and γ-isocyanate. Examples thereof include natopropyltriethoxysilane, and a generally known catalyst for urethanization reaction can be used if necessary.

As a compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule used in the method (C), for example, trimethoxysilylpropyl (meth) acrylate, methyldimethoxysilylpropyl (meth) acrylate, etc., What is shown by the following general formula (20) is mentioned.
^{_{H 2 C = C (R 14}} ) -R 15 -R 23 - [Si (R 1) 2-b (Y) b O] m -Si (R 2) 3-a (Y) a (20)
(In the formula, R ¹ , R ² , R ¹⁴ , R ¹⁵ , Y, a, b and m are the same as above. R ²³ is a direct bond or one divalent organic group having 1 to 20 carbon atoms. The above ether bond may be included.)
There is no particular limitation on the timing of reacting the compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule. However, particularly in the case of living radical polymerization, when a rubber-like property is expected, the end of the polymerization reaction or a predetermined value is determined. It is preferable to make it react as a 2nd monomer after completion | finish of reaction of this monomer.

  Examples of the chain transfer agent having a crosslinkable silyl group used in the chain transfer agent method of (D) include mercaptans having a crosslinkable silyl group and crosslinkable silyl as shown in, for example, Japanese Patent Publication Nos. 3-14068 and 4-55444. And hydrosilane having a group.

The method for synthesizing a vinyl polymer having at least one highly reactive carbon-halogen bond, which is used in the method (E), uses an organic halide as described above as an initiator, and a transition metal complex. Examples thereof include, but are not limited to, an atom transfer radical polymerization method using a catalyst. Examples of the compound having both a crosslinkable silyl group and a stabilized carbanion in one molecule include those represented by the general formula (21).
^{M + C - (R 18)} (R 19) -R 24 -C (H) (R 25) -CH 2 - [Si (R 1) 2-b (Y) b O] m -Si (R 2) _3-a (Y) _a (21)
(In the formula, R ¹ , R ² , R ¹⁸ , R ¹⁹ , Y, a, b, m are the same as above. R ²⁴ is a direct bond or one divalent organic group having 1 to 10 carbon atoms. R ²⁵ which may contain the above ether bond represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.
As the electron withdrawing group for R ¹⁸ and R ¹⁹ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

<Use of multiple vinyl polymers>
Only one kind of the above-mentioned vinyl polymers can be used, or two or more kinds of vinyl polymers can be used in combination. When only one kind is used, it is preferable to use a vinyl polymer having a molecular weight of 5,000 to 50,000 and a number of crosslinkable silyl groups of 1.2 to 3.5. When two or more vinyl polymers are combined, the first polymer is a vinyl polymer having a molecular weight of 5,000 to 50,000 and a number of crosslinkable silyl groups of 1.2 to 3.5. When the second polymer is a polymer having a small number of crosslinkable silyl groups, a cured product having high elongation at break, low bleeding, low surface contamination, and excellent paint adhesion can be obtained. Moreover, the viscosity of a composition can be reduced by setting the molecular weight of a 2nd polymer smaller. The preferred molecular weight of the polymer to be the low molecular weight component is less than 10,000, more preferably less than 5,000, and the preferred number of crosslinkable silyl groups is less than 1.2, further 1 or less. Further, since the viscosity can be further reduced, the molecular weight distribution is preferably less than 1.8. When a vinyl polymer having a crosslinkable functional group and a molecular weight distribution of 1.8 or more and a vinyl polymer having a crosslinkable silyl group at one end are added, the effect of reducing the viscosity is remarkable.

  As a polymer having such a low molecular weight and a small number of crosslinkable silyl groups, it is definitely possible to use a vinyl polymer having a crosslinkable silyl group at one end obtained by the following production method. It is preferable because it can be introduced.

  A vinyl polymer having a crosslinkable silyl group at one end has approximately one crosslinkable silyl group per molecule at the end of the polymer. Use of the above-mentioned living radical polymerization method, particularly the atom transfer radical polymerization method, has a high proportion of crosslinkable silyl groups at the molecular chain ends, a molecular weight distribution of less than 1.8, a narrow molecular weight distribution, and a low viscosity. Since a vinyl polymer is obtained, it is preferable.

About the method of introduce | transducing a crosslinkable silyl group into one terminal, the method shown below can be used, for example. In the method of introducing a crosslinkable silyl group, an alkenyl group, and a hydroxyl group by terminal functional group conversion, these functional groups can be precursors to each other, and therefore, they are described in the order starting from the method of introducing the crosslinkable silyl group.
(1) A method of adding a hydrosilane compound having a crosslinkable silyl group to a polymer having one alkenyl group per molecule at the molecular chain end in the presence of a hydrosilylation catalyst,
(2) A method of reacting a polymer having one hydroxyl group per molecular chain end with a compound having both a crosslinkable silyl group and a group capable of reacting with a hydroxyl group such as an isocyanate group in one molecule,
(3) A method of reacting a polymer having one highly reactive carbon-halogen bond per molecule at the end of a molecular chain with a compound having a crosslinkable silyl group and a stable carbanion in one molecule,
Etc.

  Polymers having one alkenyl group per molecule chain end in the method (1) can be obtained by various methods. Although a manufacturing method is illustrated below, it is not necessarily limited to these.

  (1-1) Various polymers having an alkenyl group such as organotin such as allyltributyltin and allyltrioctyltin in a polymer having one highly reactive carbon-halogen bond per molecular chain end A method of replacing halogen by reacting an organometallic compound.

(1-2) A polymer having one highly reactive carbon-halogen bond per molecule per molecule is reacted with a stabilized carbanion having an alkenyl group as shown in the general formula (10) to form a halogen. How to replace
^{M + C - (R 18)} (R 19) -R 20 -C (R 17) = CH 2 (10)
(Wherein, R ^18, R ¹⁹ together carbanion C ^- or an electron withdrawing group stabilizing, or one of the other is hydrogen or an alkyl group having 1 to 10 carbon atoms in the electron-withdrawing group or a phenyl group, R ²⁰ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms and may contain one or more ether bonds R ¹⁷ represents hydrogen or an alkyl group having 1 to 20 carbon atoms Represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and M ⁺ represents an alkali metal ion or a quaternary ammonium ion.
As the electron withdrawing group for R ¹⁸ and R ¹⁹ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

  (1-3) An enolate anion is prepared by reacting a polymer having one highly reactive carbon-halogen bond per molecule chain molecule with a single metal such as zinc or an organometallic compound, for example, Thereafter, an electrophilic compound having an alkenyl group, such as an alkenyl group-containing compound having a leaving group such as a halogen or an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, an acid halide having an alkenyl group, etc. How to react with.

(1-4) A polymer having one highly reactive carbon-halogen bond per molecule at the end of the molecule chain, for example, an oxyanion having an alkenyl group as shown in the general formula (11) or (12) A method of substituting halogen by reacting a carboxylate anion.
^{_{H 2 C = C (R 17}} ) -R 21 -O - M + (11)
(In the formula, R ¹⁷ and M ⁺ are the same as above. R ²¹ is a divalent organic group having 1 to 20 carbon atoms, and may contain one or more ether bonds.)
H ₂ C═C (R ¹⁷ ) −R ²² —C (O) O ⁻ M ⁺ (12)
(In the formula, R ¹⁷ and M ⁺ are the same as described above. R ²² is a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds.)
Etc.

  The above-described method for synthesizing a polymer having one highly reactive carbon-halogen bond per molecule at the end of a molecule chain is an atom transfer using an organic halide as described above as an initiator and a transition metal complex as a catalyst. Examples include, but are not limited to, radical polymerization methods.

  Further, a polymer having one alkenyl group per molecule at the molecular chain end can be obtained from a polymer having at least one hydroxyl group at the molecular chain end, and the methods exemplified below can be used, but are not limited thereto. It is not done.

In the polymer hydroxyl group having at least one hydroxyl group at the molecular chain end,
(1-5) a method of reacting a base such as sodium methoxide with an alkenyl group-containing halide such as allyl chloride;
(1-6) a method of reacting an alkenyl group-containing isocyanate compound such as allyl isocyanate,
(1-7) a method of reacting an alkenyl group-containing acid halide such as (meth) acrylic acid chloride in the presence of a base such as pyridine,
(1-8) a method of reacting an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst,
Etc.

  When an alkenyl group is introduced by converting a halogen of a polymer having one highly reactive carbon-halogen bond per molecule at the end of the molecule chain, one highly reactive carbon-halogen bond per molecule A highly reactive carbon-halogen bond is formed at the terminal obtained by radical polymerization (atom transfer radical polymerization) of a vinyl monomer using an organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst. It is preferable to use a polymer having one molecule per molecule chain end.

Moreover, there is no restriction | limiting in particular as a hydrosilane compound which has a crosslinkable silyl group, When a typical thing is shown, the compound shown by General formula (13) will be illustrated.
_{^{H- [Si (R 1 2-}} b) (Y b) O] m -Si (R 2 3-a) Y a (13)
(In the formula, R ¹ , R ² , Y, a, b and m are the same as described above. When two or more R ¹ or R ² are present, they may be the same or different. However, it shall be satisfied that a + mb ≧ 1.)
Among these hydrosilane compounds, in particular, the general formula (14)
H-Si (R ² _3-a ) Y _a (14)
(Wherein R ² , Y and a are the same as above)
The compound which has a crosslinkable silyl group shown by is preferable from a point with easy acquisition.

When the hydrosilane compound having a crosslinkable silyl group is added to an alkenyl group, a transition metal catalyst is usually used. Examples of the transition metal catalyst include platinum simple substance, alumina, silica, carbon black and the like in which a platinum solid is dispersed, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc., platinum-olefin. Complex, platinum (0) -divinyltetramethyldisiloxane complex is mentioned. Examples of the catalyst other than platinum _{compounds, RhCl (PPh 3) 3,} RhCl 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 · H 2 O, NiCl 2, TiCl 4 and the like.

  The amount of vinyl polymer having a crosslinkable silyl group at one end, preferably a polymer having a molecular weight distribution of less than 1.8, is 5 in terms of modulus and elongation with respect to 100 parts by weight of the vinyl polymer. It is preferable that it is -400 weight part.

  As a second embodiment in which two or more kinds of vinyl polymers are used in combination, a vinyl polymer having a molecular weight distribution of 1.8 or more and a vinyl polymer having a molecular weight distribution of less than 1.8 can be used in combination. . A vinyl polymer having a molecular weight distribution of 1.8 or more may or may not have a crosslinkable silicon group, but having a crosslinkable silicon group is preferred because weather resistance, adhesive strength, and strength at break are further improved. Moreover, the improvement of the tear strength of the hardened | cured material of a composition can be anticipated. As the main chain of the vinyl polymer having a molecular weight distribution of less than 1.8, used as the first polymer, the vinyl polymer having a molecular weight distribution of 1.8 or more, or the second polymer, Polymers derived from the vinyl monomers mentioned can be used, and both polymers are preferably acrylate polymers.

  A vinyl polymer having a molecular weight distribution of 1.8 or more can be obtained by a usual vinyl polymerization method, for example, a solution polymerization method by radical reaction. The polymerization is usually carried out by adding the above-mentioned monomer, a radical initiator, a chain transfer agent and the like and reacting at 50 to 150 ° C. In this case, generally a molecular weight distribution of 1.8 or more is obtained.

  Examples of the radical initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 4,4′-azobis (4-cyanovaleric) acid. 1,1′-azobis (1-cyclohexanecarbonitrile), azobisisobutyric acid amidine hydrochloride, 2,2′-azobis (2,4-dimethylvaleronitrile) and other azo initiators, benzoyl peroxide, diperoxide Organic peroxide-based initiators such as -tert-butyl are exemplified, but use of azo-based initiators is preferable in that they are not affected by the solvent used for polymerization and have a low risk of explosion and the like.

  Examples of chain transfer agents include n-dodecyl mercaptan, tert-dodecyl mercaptan, lauryl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyl Examples include mercaptans such as diethoxysilane and halogen-containing compounds.

  The polymerization may be performed in a solvent. Examples of the solvent are preferably nonreactive solvents such as ethers, hydrocarbons, and esters.

Examples of the method for introducing a crosslinkable silyl group include a method of copolymerizing a compound having both a polymerizable unsaturated bond and a crosslinkable silyl group with a (meth) acrylate monomer unit. As a compound having both a polymerizable unsaturated bond and a crosslinkable silyl group, the general formula (26):
^{_{CH 2 = C (R 28)}} COOR 30 - [Si (R 1 2-b) (Y b) O] m Si (R 2 3-a) Y a (26)
(In the formula, R ²⁸ is the same as above. R ³⁰ represents a divalent alkylene group having 1 to 6 carbon atoms. R ¹ , R ² , Y, a, b and m are the same as above.)
Or general formula (27):
^{_{CH 2 = C (R 28)}} - [Si (R 1 2-b) (Y b) O] m Si (R 2 3-a) Y a (27)
(In the formula, R ²⁸ , R ¹ , R ² , Y, a, b and m are the same as above.)
Monomers such as γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyl polyalkoxysilane such as γ-methacryloxypropyltriethoxysilane, and γ-acrylic. Γ-acryloxypropyl polyalkoxysilane such as loxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, etc. Examples thereof include vinyl alkyl polyalkoxysilane. Further, when a compound having both a mercapto group and a crosslinkable silyl group is used as a chain transfer agent, the crosslinkable silyl group can be introduced into the polymer terminal. Examples of such chain transfer agents include mercaptans such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldiethoxysilane. .

  A vinyl polymer having a crosslinkable functional group and having a molecular weight distribution of 1.8 or more preferably has a number average molecular weight in terms of polystyrene by GPC measurement of 500 to 100,000 from the viewpoint of ease of handling. Furthermore, the thing of 1,500-30,000 is more preferable from the weather resistance of a hardened | cured material, and workability | operativity being favorable.

(C) Plasticizer component Various plasticizers may be used in the curable composition of the present invention as required. When a plasticizer is used in combination with a filler to be described later, it becomes more advantageous because the elongation of the cured product can be increased or a large amount of filler can be mixed, but it is not necessarily added. Although it does not specifically limit as a plasticizer, For purposes, such as adjustment of physical properties and adjustment of properties, for example, phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate Non-aromatic dibasic esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate and isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl ricinoleate; diethylene glycol dibenzoate, triethylene glycol di Polyalkylene glycol esters such as benzoate and pentaerythritol ester; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Polystyrenes such as re-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; Polyether glycol such as polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide copolymer, polytetramethylene glycol, etc., one end or both ends or all ends of the hydroxyl groups of these polyether polyols to alkyl ester groups or alkyl ether groups Polyethers such as converted alkyl derivatives; Epoxy group-containing plasticizers such as epoxidized soybean oil, benzyl epoxy stearate, E-PS; sebacic acid, adipic acid, azela Polyester plasticizers obtained from dibasic acids such as inic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; pyromellitic acid esters, acrylic plasticizer And vinyl polymers obtained by polymerizing vinyl monomers including the above by various methods.

  In particular, a polymer plasticizer which is a polymer having a number average molecular weight of 500 to 15,000 is added, whereby the viscosity and slump property of the curable composition and the tensile strength of the cured product obtained by curing the composition are obtained. Mechanical properties such as strength and elongation can be adjusted, and the initial physical properties are maintained over a long period of time compared to the case of using a low molecular plasticizer that is a plasticizer that does not contain a polymer component in the molecule. It is possible to improve the drying property (also referred to as paintability) when an alkyd paint is applied. Although not limited, the polymer plasticizer may or may not have a functional group.

  Although the number average molecular weight of the polymer plasticizer was described as 500 to 15,000 above, it is preferably 800 to 10,000, and more preferably 1,000 to 8,000. If the molecular weight is too low, the plasticizer flows out over time due to heat, and the initial physical properties cannot be maintained over a long period of time, and if the molecular weight is too high, the viscosity increases and workability deteriorates.

  Among these polymer plasticizers, polyether plasticizers and (meth) acrylic polymer plasticizers are preferable from the viewpoint of high elongation characteristics or high weather resistance. Examples of the synthesis method of the acrylic polymer include those obtained by conventional solution polymerization and solvent-free acrylic polymers. The latter acrylic plasticizer is prepared by a high temperature continuous polymerization method (USP 4414370, JP 59-6207, JP-B-5-58005, JP 1-313522, USP 5010166) without using a solvent or a chain transfer agent. More preferred for the purposes of the present invention. Examples thereof include, but are not particularly limited to, for example, ARUFON UP series (UP-1000, UP-1110, UP-2000, UP-2130) (referred to as SGO) of Toagosei Co., Ltd. (waterproof journal, June 2002 issue) reference). 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 from the viewpoint of viscosity, and 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.

  From the viewpoint of viscosity, it is preferable to have a branched structure in the main chain because the viscosity becomes lower at the same molecular weight. The high temperature continuous polymerization method mentioned above is mentioned as this example.

  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. In addition, for example, in the case of a composition in which the vinyl polymer of the present invention and a polyether polymer which is one of optional polymers having a crosslinkable functional group are mixed, from the point of compatibility of the mixture Polyesters, pyromellitic acid esters, phthalic acid esters, and acrylic polymers are particularly preferable.

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

  The amount of the plasticizer used is not limited, but is preferably 5 to 200 parts by weight, more preferably 10 to 120 parts by weight, more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group. Is more preferable. If it is less than 5 parts by weight, the effect as a plasticizer is hardly exhibited, and if it exceeds 200 parts by weight, the mechanical strength of the cured product tends to be insufficient.

(D) About a heat conductive filler component The heat conductive filler of this invention can use the general good heat conductive filler marketed. Among them, carbon compounds such as graphite, diamond, etc .; aluminum oxide, magnesium oxide from the viewpoint of being able to impart specific electrical characteristics such as thermal conductivity, availability, insulation, electromagnetic shielding, and electromagnetic absorption , Metal oxides such as beryllium oxide, titanium oxide, zirconium oxide, and zinc oxide; metal nitrides such as boron nitride, aluminum nitride, and silicon nitride; metal carbides such as boron carbide, aluminum carbide, and silicon carbide; aluminum hydroxide, water Metal hydroxides such as magnesium oxide; metal carbonates such as magnesium carbonate and calcium carbonate; crystalline silica: calcined acrylonitrile polymer, calcined furan resin, calcined cresol resin, calcined polyvinyl chloride, calcined sugar Baked organic polymer such as fired charcoal; composite with Zn ferrite Ferrite; Fe-Al-Si ternary alloy; metal powders, and the like preferably.

Further, from the viewpoint of availability and thermal conductivity, graphite, aluminum oxide, magnesium oxide, boron nitride, aluminum nitride, silicon carbide, aluminum hydroxide, magnesium carbonate, and crystallized silica are more preferable, graphite, α-alumina, hexagonal More preferred are crystalline boron nitride, aluminum nitride, aluminum hydroxide, Mn—Zn soft ferrite, Ni—Zn soft ferrite, Fe—Al—Si ternary alloy (Sendust), carbonyl iron, iron nickel alloy (Permalloy) Spheroidized graphite, round or spherical α-alumina, spheroidized hexagonal boron nitride, aluminum nitride, aluminum hydroxide, Mn—Zn soft ferrite, Ni—Zn soft ferrite, spherical Fe—Al—Si three Original alloy (Sendust), Carbo Nyl iron is particularly preferred.
When carbonyl iron is used in the present invention, reduced carbonyl iron powder is desirable. The reduced carbonyl iron powder is not a standard grade but a carbonyl iron powder classified into a reduced grade, and is characterized by a low carbon and nitrogen content compared to the standard grade.

  In addition, these thermally conductive fillers are silane coupling agents (vinyl silane, epoxy silane, (meth) acryl silane, isocyanate silane, chloro silane, amino silane from the viewpoint of improving dispersibility with respect to the vinyl polymer (I). Etc.), titanate coupling agents (alkoxy titanate, amino titanate, etc.), or fatty acids (caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and other saturated fatty acids, sorbic acid , Elaidic acid, oleic acid, linoleic acid, linolenic acid, erucic acid and other unsaturated fatty acids) and resin acids (abietic acid, pimaric acid, levopimaric acid, neoapitic acid, parastrinic acid, dehydroabietic acid, isopimaric acid, sandaracopi Maric acid, cormic acid, secodehydride Abietic acid, the dihydroabietic acid, etc.) or the like, it is preferable that the surface has been treated.

  Among these, some of the thermal conductivities are, for example, 1.5 W / mK for silica, 20 W / mK for alumina, 40 W / mK for magnesium oxide, 60 W / mK for boron nitride, and 70 W / mK for aluminum nitride. , Copper has a good thermal conductivity of 398 W / mK, aluminum has a thermal conductivity of 237 W / mK, and the like.

  The amount of the heat conductive filler used is such that the heat conductivity of the heat conductive material obtained from the composition of the present invention can be increased, so that the volume ratio (%) of the heat conductive filler is high. Is preferably 25% by volume or more of the total composition. If it is less than 25% by volume, the thermal conductivity tends to be insufficient. When a higher thermal conductivity is desired, the amount of the thermally conductive filler used is more preferably 40% by volume or more in the total composition.

Here, the volume fraction (%) of the thermally conductive filler is calculated from the weight fraction and specific gravity of the resin component and the thermally conductive filler, and is obtained by the following equation. In the following formula, the thermally conductive filler is simply referred to as “filler”.
Filler volume ratio (volume%) = (filler weight ratio / filler specific gravity) ÷ [(resin weight ratio / resin weight specific gravity) + (filler weight ratio / filler specific gravity)] × 100
Here, the resin component refers to all components excluding the heat conductive filler, and specifically, vinyl polymers (A) and (B), (C) plasticizer, (E) carboxylic acid metal salt. , (F) carboxylic acid, (G) various additives such as methyl ester compounds and other tackifying resins.

  Further, as one method for increasing the filling rate of the heat conductive filler with respect to the vinyl polymers (A) and (B), it is preferable to use two or more kinds of heat conductive fillers having different particle diameters in combination. In this case, it is preferable that the heat conductive filler having a large particle diameter exceeds 10 μm, and the heat conductive filler having a small particle diameter is 10 μm or less.

  Moreover, these heat conductive fillers can use not only the same kind of heat conductive filler but also two or more kinds of different kinds in combination. Moreover, you may use various fillers other than a heat conductive filler as needed to such an extent that the effect of this invention is not prevented. Various fillers other than the heat conductive filler are not particularly limited, but wood powder, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice husk powder, diatomaceous earth, white clay, silica (Fumed silica, precipitated silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid, amorphous spherical silica, etc.), reinforcing filler such as carbon black; diatomaceous earth, calcined clay, clay, talc, Titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, activated zinc white, zinc powder, calcium carbonate, chemibest, zinc carbonate and shirasu balloon, glass microballoon, phenol resin and vinylidene chloride resin organic Fillers such as microballoons, PVC powder, PMMA powder and other resin powders; asbestos, glass fiber And glass filaments, carbon fibers, Kevlar fibers, fibrous fillers such as polyethylene fiber and the like. Of these fillers, precipitated silica, fumed silica, fused silica, dolomite, carbon black, titanium oxide, talc and the like are preferable. Some of these fillers have a slightly function as a heat conductive filler, and the composition, such as carbon fiber, various metal powders, various metal oxides, various organic fibers, Some synthesis methods, crystallinity, and crystal structures can be used as excellent heat conductive fillers.

(E) Carboxylic acid metal salt component A polymer having a crosslinkable silyl group is crosslinked and cured by forming a siloxane bond in the presence or absence of a carboxylic acid metal salt catalyst. The properties of the cured product can be broadly created from rubbery to resinous depending on the molecular weight and main chain skeleton of the polymer.

  As such a condensation catalyst, for example, a carboxylic acid metal salt in which the carbon atom adjacent to the carbonyl group is a quaternary carbon is preferable because of these effects as well as improving effects such as curability and storage stability.

Examples of carboxylic acid metal salts include tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, manganese carboxylate , Iron carboxylate, cobalt carboxylate, nickel carboxylate, cerium carboxylate are preferable because of their high catalytic activity, and further, tin carboxylate, lead carboxylate, bismuth carboxylate, titanium carboxylate, iron carboxylate, zirconium carboxylate Is more preferable, especially tin carboxylate, and divalent tin carboxylate is most preferable from the viewpoint of adhesiveness.
Examples of the carboxylic acid having an acid group of a carboxylic acid metal salt include those exemplified for the carboxylic acid (F) described later.

  The effects relating to the compatibility, workability, and volatility described above can be similarly applied to carboxylic acid metal salts having an acid group. Therefore, as the carboxylic acid metal salt, the metal salt of neodecanoic acid, versatic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid is most preferable.

  Specific examples of carboxylic acid metal salts include tin pivalate, tin neodecanoate, tin versatate, tin 2,2-dimethyloctanoate, tin 2-ethyl-2,5-dimethylhexanoate, lead versatate, neodecane Bismuth oxide, bismuth versatate, potassium versatate, calcium versatate, barium versatate, titanium versatate, zirconium versatate, hafnium versatate, vanadium versatate, manganese versatate, iron versatate, cobalt versatate, nickel versatate And cerium versatate. Among these, tin neodecanoate, tin versatate, tin 2,2-dimethyloctanoate, tin 2-ethyl-2,5-dimethylhexanoate, lead versatate, bismuth versatate, titanium versatate, iron versatate, Zircon versatate is preferable because of its high catalytic activity, and in particular, from the viewpoint of adhesion, neodecanoic acid tin, versaic acid tin, tin 2,2-dimethyloctanoate, and 2-ethyl-2,5-dimethylhexanoate are more preferred. preferable.

  Carboxylic acid metal salts may be used alone or in combination of two or more. A combination system with (F) carboxylic acid may also be used. The blending amount of these carboxylic acid metal salts is preferably about 0.1 to 30 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group, and the blending amount of the carboxylic acid metal salt is less than 0.1 parts by weight. If it is, the curing rate may be extremely slow, and the curing reaction may not proceed sufficiently. On the other hand, when the compounding amount of the carboxylic acid metal salt exceeds 30 parts by weight, the pot life may become too short, which is not preferable from the viewpoint of workability.

(F) Carboxylic acid component The carboxylic acid (F) is not limited to carboxylic acid, but also includes carboxylic acid derivatives that generate carboxylic acid by hydrolysis of carboxylic acid anhydrides, esters, amides, nitriles, acyl chlorides, and the like. . The carboxylic acid (bF) is particularly preferably a carboxylic acid because of its high catalytic activity.

Carboxylic acid (F) has the effect of improving curing activity when used in combination with a carboxylic acid metal salt, in addition to functioning alone as a catalyst. Moreover, when a carboxylic acid metal salt is used as a curing catalyst, curability may decrease after storage, but by adding carboxylic acid (F), a decrease in curability after storage can be suppressed.
(Wherein R13 is a substituted or unsubstituted organic group, R14 is a substituted or unsubstituted divalent organic group, each of which may contain a carboxyl group) and general formula (13)
(Wherein, R15 is a substituted or unsubstituted trivalent organic group, which may contain a carboxyl group), and a cyclic carboxylic acid containing a structure represented by Specific examples include pivalic acid, 2,2-dimethylbutyric acid, 2-ethyl-2-methylbutyric acid, 2,2-diethylbutyric acid, 2,2-dimethylvaleric acid, 2-ethyl-2-methylvaleric acid, 2,2-diethylvaleric acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, neodecanoic acid, versatic acid, Chain monocarboxylic acids such as 2,2-dimethyl-3-hydroxypropionic acid, dimethylmalonic acid, ethylmethylmalonic acid, diethylmalonic acid, 2,2-dimethylsuccinic acid, 2,2-diethylsuccinic acid, 2, Chain dicarboxylic acids such as 2-dimethylglutaric acid, chain tricarboxylic acids such as 3-methylisocitric acid and 4,4-dimethylaconitic acid, 1-methylcyclopentane Rubonic acid, 1,2,2-trimethyl-1,3-cyclopentanedicarboxylic acid, 1-methylcyclohexanecarboxylic acid, 2-methylbicyclo [2.2.1] -5-heptene-2-carboxylic acid, 2- Methyl-7-oxabicyclo [2.2.1] -5-heptene-2-carboxylic acid, 1-adamantanecarboxylic acid, bicyclo [2.2.1] heptane-1-carboxylic acid, bicyclo [2.2. 2] Cyclic carboxylic acids such as octane-1-carboxylic acid. Many compounds containing such structures exist in natural products, but of course they can also be used.

  As the carboxylic acid, a monocarboxylic acid is more preferable, and a chain monocarboxylic acid is more preferable from the viewpoint of good compatibility with the component (A) and the component (B). In addition, pivalic acid, neodecanoic acid, versatic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid and the like are particularly preferable because they are easily available.

Further, when the melting point of the carboxylic acid (b1) is high (high crystallinity), it becomes difficult to handle (poor workability). Therefore, the melting point of the carboxylic acid is preferably 65 ° C. or less, more preferably −50 to 50 ° C., and particularly preferably −40 to 35 ° C.
Furthermore, the carboxylic acid preferably has 5 to 20 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 8 to 12 carbon atoms. When the number of carbon atoms exceeds this range, it tends to become solid and it becomes difficult to achieve compatibility with the component (A) and the component (B), and the activity tends not to be obtained. On the other hand, when the number of carbon atoms is small, the volatility increases and the odor tends to increase. From these points, neodecanoic acid, versatic acid, 2,2-dimethyloctanoic acid, and 2-ethyl-2,5-dimethylhexanoic acid are most preferred as the carboxylic acid having a quaternary carbon atom adjacent to the carbonyl group.
Carboxylic acid may be used independently and may use 2 or more types together.
Carboxylic acid may be used independently and may use 2 or more types together. Moreover, you may use also in the combined use system with the carboxylic acid metal salt of (E) component. The blending amount of these carboxylic acids is preferably about 0.1 to 30 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group, and the blending amount of the carboxylic acid metal salt is less than 0.1 parts by weight. The curing speed may be extremely slow, and the curing reaction may not proceed sufficiently. On the other hand, when the compounding amount of the carboxylic acid metal salt exceeds 30 parts by weight, the pot life may become too short, which is not preferable from the viewpoint of workability.

(G) stored in the storage in stability improving agent, especially one-component curable composition for component, polymer C ₂ or higher alcohols are terminal functional groups generated from the ester of the side chain of having a plasticizer or a crosslinking silyl group It may be delayed by transesterification. More stable storage stability can be ensured by adding a methyl ester compound for ensuring the storage stability of the curable composition. Specific examples of the component (G) include dimethyl sebacate, dimethyl oleate, dimethyl adipate, dimethyl stearate, dimethyl laurate, and dimethyl carboxylate, and dimethyl adipate (DMA) is particularly preferable. The addition amount is preferably about 0.1 to 30 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group, and the storage stability is maintained when the amount of the carboxylic acid metal salt is less than 0.1 parts by weight. In addition, the addition of 30 parts by weight or more results in poor workability balance, and drooping and stringiness.

<< Curable composition >>
In the curable composition of the present invention, various compounding agents may be added according to the intended physical properties.
In the curable composition of the present invention, a silane coupling agent having an amino group can be used as a cocatalyst in order to further increase the activity of the condensation catalyst. This amino group-containing silane coupling agent is a compound having a group containing a silicon atom to which a hydrolyzable group is bonded (hereinafter referred to as hydrolyzable silyl group) and an amino group, and the groups already exemplified as this hydrolyzable group A methoxy group, an ethoxy group, and the like are preferable from the viewpoint of hydrolysis rate. The number of hydrolyzable groups is preferably 2 or more, particularly 3 or more.

  The compounding amount of these amine compounds is preferably about 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group. If the compounding amount of the amine compound is less than 0.01 parts by weight, the curing rate may be slow, and the curing reaction may not proceed sufficiently. On the other hand, when the compounding amount of the amine compound exceeds 30 parts by weight, the pot life may become too short, which is not preferable from the viewpoint of workability.

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

  Furthermore, a silicon compound having no amino group or silanol group may be added as a promoter. These silicon compounds are not limited, but phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane and the like are preferable. In particular, diphenyldimethoxysilane and diphenyldiethoxysilane are most preferable because of low cost and easy availability.

  The amount of the silicon compound is preferably about 0.01 to 20 parts, more preferably 0.1 to 10 parts, based on 100 parts of the polymer having a crosslinkable silyl group. When the compounding amount of the silicon compound is below this range, the effect of accelerating the curing reaction may be reduced. On the other hand, when the compounding amount of the silicon compound exceeds this range, the hardness and tensile strength of the cured product may decrease.

<< Tackifying resin >>
The tackifying resin of the present invention is not particularly limited, and those usually used can be used. Specific examples include phenolic resins, modified phenolic resins (eg cashew oil-modified phenolic resin, tall oil-modified phenolic resin, etc.), terpene phenolic resin, xylene-phenolic resin, cyclopentadiene-phenolic resin, xylene resin, petroleum resin, phenol Examples thereof include modified petroleum resins, rosin ester resins, low molecular weight polystyrene resins, and terpene resins. These may be used alone or in combination of two or more. The amount of tackifying resin used is preferably 10 to 140 parts by weight, more preferably 15 to 80 parts by weight, based on 100 parts by weight of the polymer having a crosslinkable silyl group.

<Dehydrating agent>
The curable composition increases in viscosity and gelation during storage due to moisture at the time of production, etc., causing difficulty in workability during use, and also increases in viscosity and gelation. By using an advanced curable composition, the physical properties of the cured product after curing may be deteriorated, resulting in a problem that the original intended adhesion or the like is impaired. That is, the storage stability of the curable composition may be a problem.

  In order to improve the storage stability of this curable composition, there is a method of reducing the moisture content of the curable composition by azeotropic dehydration. For example, about 0.1 to 10 parts by weight of a volatile organic compound having a minimum azeotropic point with respect to water is added and mixed uniformly, and then heated to about 50 to 90 ° C. and sucked with a vacuum pump. The method of taking out the azeotropic composition of a compound out of the system is mentioned. Volatile organic compounds having a minimum azeotropic point with respect to water include halides such as methylene chloride, chloroform, carbon tetrachloride, and trichloroethylene; alcohols such as ethanol, allyl alcohol, 1-propanol, and butanol; ethyl acetate, propionic acid Examples thereof include esters such as methyl; ketones such as methyl ethyl ketone and 3-methyl-2-butanone; ethers such as ethyl ether and isopropyl ether; hydrocarbons such as benzene, toluene, xylene and hexane. However, since this method involves a devolatilization operation, it is necessary to devise other volatile compounding agents, or it is necessary to treat, recover, etc., the volatile organic compound to be azeotroped. Therefore, it may be preferable to add the following dehydrating agents.

  As described above, a dehydrating agent for removing moisture in the composition can be added to the composition of the present invention for the purpose of improving storage stability. Examples of the dehydrating agent include inorganic solids such as phosphorus pentoxide, sodium hydrogen carbonate, sodium sulfate (anhydrous bow glass), and molecular sieves. These solid dehydrating agents may be used, but the liquidity after addition tends to be acidic or basic, condensing easily, resulting in poor storage stability and workability such as removing the solid later. In some cases, the liquid hydrolyzable ester compound described below is preferable. Examples of hydrolyzable ester compounds include trialkyl orthoformate such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate. And trialkyl orthoacetate such as tributyl orthoacetate, and those selected from the group consisting of these compounds.

Other hydrolyzable ester compounds may further include the formula R _4-n SiY _n (wherein Y is a hydrolyzable group, R is an organic group and may or may not contain a functional group). n is an integer of 1 to 4, preferably 3 or 4, and specific examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, and methyltrimethoxy. Silane, methyltriethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, methyltriacetoxysilane, tetramethyl orthosilicate (tetramethoxysilane or methyl silicate), tetraethyl orthosilicate (tetraethoxysilane or ethyl silicate), tetra orthosilicate Silanes such as propyl and tetrabutyl orthosilicate Compound or partial hydrolysis condensate thereof, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-acryloxy Propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, etc. Examples thereof include silane coupling agents or partial hydrolysis condensates thereof. One or more of these can be used in combination.

  The dehydrating agent not only prevents hydrolysis of the vinyl polymer during storage and forms a three-dimensional network structure by silanol condensation reaction, but also decomposes the ketimine with water and reacts with the epoxy resin to cure. Therefore, it is more preferable as a storage stability improver.

  As a usage-amount of a storage stability improving agent, 0.1-30 weight part is preferable with respect to 100 weight part of polymers which have a crosslinkable silyl group, 0.3-20 weight part is more preferable, 0.5- 10 parts by weight is more preferable.

  In addition, when adding these storage stability improving agents, it is preferable to carry out after making a curable composition anhydrous, but you may add in the state containing a water | moisture content.

<Adhesive agent>
A silane coupling agent or an adhesion-imparting agent other than the silane coupling agent can be added to the curable composition of the present invention. When an adhesion imparting agent is added, it is possible to simultaneously impart a function as an adhesive for adhering the heat generating element and the heat radiating element to the heat conducting material. Further, in some cases, it is not necessary to use a primer used for improving adhesiveness, and simplification of work is expected. Specific examples of silane coupling agents include silane coupling agents having functional groups such as amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, halogens, and the like. As γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and other isocyanate group-containing silanes; γ-aminopropyltrimethoxysilane Γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) amino Propyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ -(2-aminoethyl) aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl -Amino group-containing silanes such as γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, etc. Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Epoxy group-containing silanes such as silane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- Carboxysilanes such as (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyltrieth Vinyl-type unsaturated group-containing silanes such as xysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate, bis (3-triethoxysilylpropyl) Examples thereof include polysulfanes such as tetrasulfane. In addition, a reaction product of the amino group-containing silane and the epoxy group-containing silane, a reaction product of an amino group-containing silane and an acroyloxy group-containing silane, an amino group-containing silane and an isocyanate group-containing silane These reactants can also be used. In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, blocked isocyanate silanes, silylated polyesters, etc., which are derivatives of these, are also used as silane coupling agents. Can be used. Moreover, the ketimine compound etc. which are obtained by reaction of said amino group containing silanes and ketone compounds, such as methyl isobutyl ketone, can also be used as a silane coupling agent.

  In general, the silane coupling agent is preferably used in the range of 0.1 to 20 parts with respect to 100 parts of the polymer having a crosslinkable silyl group. In particular, it is more preferable to use in the range of 0.5 to 10 parts. The effects of the silane coupling agent added to the curable composition of the present invention are various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, mortar, vinyl chloride, acrylic, polyester, When used on an organic substrate such as polyethylene, polypropylene, and polycarbonate, it exhibits a remarkable adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable. Moreover, if the usage-amount is about 1 part with respect to 100 parts of polymers which have a crosslinkable silyl group, it will hardly affect transparency of hardened | cured material.

  Specific examples other than the silane coupling agent are not particularly limited. For example, epoxy resin, phenol resin, polystyrene-polybutadiene-polystyrene, polystyrene-polyisoprene-polystyrene, polystyrene-polyisoprene / butadiene copolymer-polystyrene, polystyrene. -Polyethylene / propylene copolymer-Polystyrene, polystyrene-polyethylene / butylene copolymer-Linear or branched block copolymers such as polystyrene, polystyrene-polyisobutene-polystyrene, alkyl sulfonates, sulfur, alkyl titanates And aromatic polyisocyanate. The epoxy resin can be used by reacting with the above amino group-containing silanes.

  The adhesiveness-imparting agent may be used alone or in combination of two or more. By adding these adhesion-imparting agents, the adhesion to the adherend can be improved. Although not particularly limited, it is preferable to use 0.1 to 20 parts by weight of a silane coupling agent among the above-mentioned adhesion-imparting agents in order to improve adhesion, particularly adhesion to a metal-coated surface.

  The type and amount of the adhesion-imparting agent can be selected depending on, for example, the crosslinkable silyl group of the polymer having a crosslinkable silyl group of the present invention, the type of Y in the general formula (1), and the number of a. Thus, it is possible to control the curability and mechanical properties of the present invention according to the purpose and application. In particular, care must be taken in selecting it because it affects curability and elongation.

<Physical property modifier>
You may add the physical property modifier which adjusts the tensile characteristic of the hardened | cured material produced | generated as needed to the curable composition of this invention.

Furthermore, minute hollow particles may be used in combination with these reinforcing fillers for the purpose of reducing the weight and cost without causing a significant decrease in physical properties. However, the addition of a large amount of fine hollow particles may cause a decrease in thermal conductivity. The fine hollow particles (hereinafter referred to as balloons) are not particularly limited, but as described in “The latest technology of functional filler” (CMC), the diameter is 1 mm or less, preferably 500 μm or less, more preferably 200 μm or less. The hollow body comprised with the inorganic or organic material of these. 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 it is more preferable to use a micro hollow body having a specific gravity of 0.5 g / cm ³ or less.

  Other physical property modifiers are not particularly limited, but examples include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropeno Alkyl isopropenoxy silane such as xysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethyl Methoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldi Alkoxysilanes having a functional group such as Tokishishiran; silicone varnishes; polysiloxanes and the like. By using the physical property modifier, the hardness when the composition of the present invention is cured can be increased, the hardness can be decreased, and the elongation can be increased. The said physical property modifier may be used independently and may be used together 2 or more types.

<Silanol-containing compound>
You may add a silanol containing compound to the curable composition of this invention as needed, such as changing the physical property of hardened | cured material. The silanol-containing compound refers to a compound having one silanol group in the molecule and / or a compound capable of producing a compound having one silanol group in the molecule by reacting with moisture. Only one of these may be used, or both compounds may be used simultaneously.

The compound having one silanol group in the molecule which is one of the silanol-containing compounds is not particularly limited, and the compounds shown below,
(CH ₃ ) ₃ SiOH, (CH ₃ CH ₂ ) ₃ SiOH, (CH ₃ CH ₂ CH ₂ ) ₃ SiOH, (n-Bu) ₃ SiOH, (sec-Bu) ₃ SiOH, (t-Bu) ₃ SiOH , (T-Bu) Si (CH ₃ ) ₂ OH, (C ₅ H ₁₁ ) ₃ SiOH, (C ₆ H ₁₃ ) ₃ SiOH, (C ₆ H ₅ ) ₃ SiOH, (C ₆ H ₅ ) ₂ Si ( _{CH 3) OH, (C 6} H 5) Si (CH 3) 2 OH, (C 6 H 5) 2 Si (C 2 H 5) OH, C 6 H 5 Si (C 2 H 5) 2 OH, C ₆ H ₅ CH ₂ Si (C ₂ H ₅ ) ₂ OH, C ₁₀ H ₇ Si (CH ₃ ) ₂ OH
(In the above formula, C ₆ H ₅ represents a phenyl group, and C ₁₀ H ₇ represents a naphthyl group.)
(R ″) ₃ SiOH (wherein R ″ is the same or different substituted or unsubstituted alkyl group or aryl group), cyclic polysiloxane compounds containing silanol groups, silanols, etc. A chain polysiloxane compound containing a group, a main chain of silicon, a compound having a silanol group bonded to a polymer end composed of carbon, a compound having a main chain of silicon, carbon, a compound having a silanol group bonded to a polysilane main chain end, Examples thereof include a compound in which a silanol group is bonded to a polymer terminal composed of oxygen. Of these, (CH ₃ ) ₃ SiOH, which is easy to obtain and has a low molecular weight, is preferable from the viewpoint of effects.

  The compound having one silanol group in the molecule reacts with a crosslinkable silyl group of a polymer having a crosslinkable silyl group or a siloxane bond formed by crosslinking, thereby reducing the number of crosslinking points and curing. It gives a composition with flexibility and low surface tack and excellent dust resistance.

In addition, a compound that can generate a compound having one silanol group in the molecule by reacting with moisture, which is one of the components of the present invention, is not particularly limited, but N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, bistrimethylsilylurea, N- (t-butyldimethylsilyl) N-methyltrifluoroacetamide, (N, N -Dimethylamino) trimethylsilane, (N, N-diethylamino) trimethylsilane, hexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, N- (trimethylsilyl) imidazole, trimethylsilyltrifluoromethanesulfonate, tri Tylsilylphenoxide, trimethylsilylated product of n-octanol, trimethylsilylated product of 2-ethylhexanol, tris (trimethylsilyl) ated product of glycerin, tris (trimethylsilyl) ated product of trimethylolpropane, tris (trimethylsilyl) ated product of pentaerythritol, tetra of pentaerythritol (trimethylsilyl) _{ated, (CH 3) 3 SiNHSi (} CH 3) 3, (CH 3) 3 SiNSi (CH 3) 2, allyloxy trimethylsilane, N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide Bis (trimethylsilyl) trifluoroacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, bistrimethylsilylurea, N- (t-butyldimethylsilane N) N-methyltrifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (N, N-diethylamino) trimethylsilane, hexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, N- (Trimethylsilyl) imidazole, trimethylsilyl trifluoromethanesulfonate, trimethylsilylphenoxide, trimethylsilylated product of n-octanol, trimethylsilylated product of 2-ethylhexanol, tris (trimethylsilyl) ated product of glycerol, tris (trimethylsilyl) ated product of trimethylolpropane, pentaerythritol Tris (trimethylsilyl), pentaerythritol tetra (trimethylsilyl), (CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ , (CH ₃ ) ₃ SiNSi ( CH ₃ ) ₂ , etc. can be preferably used, but (CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ is particularly preferred from the amount of silanol groups contained in the hydrolysis product.

Furthermore, the compound that can generate a compound having one silanol group in the molecule by reacting with moisture, which is one of the components of the present invention, is not particularly limited. ) Is preferred.
((R ⁵⁸ ) ₃ SiO) _n R ⁵⁹ (46)
(In the formula, R ⁵⁸ is the same as described above. N represents a positive number, and R ⁵⁹ represents a group obtained by removing some or all of the active hydrogen from the active hydrogen-containing compound.)
R ⁵⁸ is preferably a methyl group, an ethyl group, a vinyl group, a t-butyl group, or a phenyl group, and more preferably a methyl group.
The (R ⁵⁸ ) ₃ Si group is particularly preferably a trimethylsilyl group in which all three R ⁵⁸ are methyl groups. N is preferably 1 to 5.

The active hydrogen-containing compound from which R ⁵⁹ is derived is not particularly limited. For example, methanol, ethanol, n-butanol, i-butanol, t-butanol, n-octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol , Alcohols such as diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propanediol, tetramethylene glycol, polytetramethylene glycol, glycerin, trimethylolpropane, pentaerythritol; phenol, cresol, bisphenol A, hydroquinone, etc. Phenols: formic acid, acetic acid, propionic acid, lauric acid, palmitic acid, stearic acid, behenic acid, acrylic acid, methacrylic acid Carboxylic acids such as oleic acid, linoleic acid, linolenic acid, sorbic acid, oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, benzoic acid, phthalic acid, terephthalic acid, trimellitic acid; ammonia; methylamine, dimethyl Amines such as amine, ethylamine, diethylamine, n-butylamine and imidazole; acid amides such as acetamide and benzamide; ureas such as urea and N, N′-diphenylurea; acetone, acetylacetone and 2,4-heptadione Examples include ketones.

A compound capable of generating a compound having one silanol group in the molecule by reacting with the water represented by the general formula (46) is, for example, trimethylsilyl chloride or dimethyl (t It can be obtained by reacting a compound having a group capable of reacting with an active hydrogen such as a halogen group together with (R ⁵⁸ ) ₃ Si group, which is also called a silylating agent such as -butyl) chloride, but is not limited thereto. (However, R ⁵⁸ is the same as described above.)

Specific examples of the compound represented by the general formula (46) include
Allyloxytrimethylsilane, N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, bistrimethylsilylurea, N- (t- Butyldimethylsilyl) N-methyltrifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (N, N-diethylamino) trimethylsilane, hexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, N- (trimethylsilyl) imidazole, trimethylsilyl trifluoromethanesulfonate, trimethylsilyl phenoxide, trimethylsilylated product of n-octanol, trimethylsilylated 2-ethylhexanol , Tris (trimethylsilyl) product of glycerin, tris (trimethylsilyl) product of trimethylolpropane, tris (trimethylsilyl) product of pentaerythritol, tetra (trimethylsilyl) product of pentaerythritol, trimethylsilylated product of polypropylene glycol, trimethylsilylated product of polypropylene triol, etc. Examples thereof include, but are not limited to, a trimethylsilyl product of polyether polyol, a trimethylsilyl product of polypropylene tetraol, and a trimethylsilyl product of acrylic polyol. These may be used alone or in combination of two or more.

In addition, a compound represented by the general formula (((R ⁶⁰ ) ₃ SiO) (R ⁶¹ O) _s ) _t Z, CH ₃ O (CH ₂ CH (CH ₃ ) O) ₅ Si (CH ₃ ) ₃ ,
_{CH 2 = CHCH 2 (CH 2} CH (CH 3) O) 5 Si (CH 3) 3,
(CH ₃ ) ₃ SiO (CH ₂ CH (CH ₃ ) O) ₅ Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO (CH ₂ CH (CH ₃ ) O) ₇ Si (CH ₃ ) ₃
(Wherein R ⁶⁰ is the same or different substituted or unsubstituted monovalent hydrocarbon group or hydrogen atom, R ⁶¹ is a divalent hydrocarbon group having 1 to 8 carbon atoms, and s and t are positive integers. , S is 1 to 6, s × t is 5 or more, Z is a 1 to 6-valent organic group)
Etc. can also be used suitably. These may be used alone or in combination of two or more.

  Among the compounds that can produce a compound having one silanol group in the molecule by reacting with moisture, the active hydrogen compound produced after hydrolysis is not adversely affecting storage stability, weather resistance, etc. Phenols, acid amides and alcohols are preferred, and phenols and alcohols whose active hydrogen compounds are hydroxyl groups are more preferred.

  Among the above compounds, N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, trimethylsilylphenoxide, trimethylsilylated product of n-octanol, trimethylsilylated product of 2-ethylhexanol, tris (trimethylsilyl) ated product of glycerin, A tris (trimethylsilyl) product of trimethylolpropane, a tris (trimethylsilyl) product of pentaerythritol, a tetra (trimethylsilyl) product of pentaerythritol and the like are preferable.

  A compound that can generate a compound having one silanol group in the molecule by reacting with moisture has one silanol group in the molecule by reacting with moisture during storage, curing or after curing. A compound is produced. The compound having one silanol group in the molecule thus produced reacts with the crosslinkable silyl group of the vinyl polymer or the siloxane bond formed by crosslinking as described above, thereby reducing the number of crosslinking points. It is presumed that it is reduced and the cured product is given flexibility.

  The structure of the silanol-containing compound can be selected depending on the type of Y and the number of a in the vinyl polymer of the present invention, and controls the curability and mechanical properties of the present invention according to the purpose and application. It is possible.

  The silanol-containing compound may be used in combination with an air oxidation curable material described later, and by using it together, the modulus of the cured product is kept low, and the curability and dust adhesion of the alkyd paint coated on the surface are improved. Therefore, it is preferable.

  The addition amount of the silanol-containing compound can be appropriately adjusted according to the expected physical properties of the cured product. The silanol-containing compound can be added in an amount of 0.1 to 50 parts by weight, preferably 0.3 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group. If the amount is less than 0.1 parts by weight, the effect of addition does not appear. If the amount exceeds 50 parts by weight, the crosslinking becomes insufficient, and the strength and gel fraction of the cured product are too low.

Moreover, the time which adds a silanol containing compound is not specifically limited, You may add at the time of manufacture of a polymer, and you may add at the time of preparation of a curable composition.
<Thixotropic agent (anti-sagging agent)>
A thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability.

  A thixotropic agent (anti-sagging agent) is also called a thixotropic agent. Thixotropy imparts fluidity when a strong force is applied, such as when extruding from a cartridge into a bead, applying with a spatula, or spraying with a spray, etc., until it hardens after application or construction. It imparts the property of not flowing down.

  The thixotropy imparting agent (anti-sagging agent) is not particularly limited, and examples thereof include amide waxes, hydrogenated castor oil, hydrogenated castor oil derivatives, fatty acid derivatives, stears represented by Disparon (manufactured by Enomoto Kasei). Metal soap such as calcium phosphate, aluminum stearate, barium stearate, organic compounds such as 1,3,5-tris (trialkoxysilylalkyl) isocyanurate, calcium carbonate and fine powder surface-treated with fatty acids and resin acids Examples thereof include inorganic compounds such as silica and carbon black.

  Fine powder silica means a natural or artificial inorganic filler mainly composed of silicon dioxide. Specific examples include kaolin, clay, activated clay, silica sand, silica stone, diatomaceous earth, anhydrous aluminum silicate, hydrous magnesium silicate, talc, perlite, white carbon, mica fine powder, bentonite, and organic bentonite. it can.

Among these, ultrafine anhydrous silica or organic bentonite produced by reacting a volatile compound containing silicon in the gas phase is preferable. At least 50 m ² / g, and more preferably it has a specific surface area of 50 to 400 m ² / g. Either hydrophilic silica or hydrophobic silica can be used. Hydrophobic silica whose surface is hydrophobically treated with silazane, chlorosilane, alkoxysilane, or polysiloxane having only a methyl group as an organic substituent bonded to a silicon atom is preferable. .

  Specific examples of the surface treatment agent include silazanes such as hexamethyldisilazane; halogenated silanes such as trimethylchlorosilane, dimethyldichlorosilane, and methyltrichlorosilane; trimethylalkoxysilane and dimethyldialkoxysilane. Alkoxysilanes such as methyltrialkoxysilane (wherein alkoxy groups include methoxy, ethoxy, propoxy, butoxy, etc.); cyclic or linear polydimethylsiloxane, etc. Examples thereof include siloxanes, and these may be used alone or in combination of two or more. Among these, hydrophobic fine powder silica subjected to a surface treatment with siloxanes (dimethylsilicone oil) is preferable from the viewpoint of thixotropic effect.

  Moreover, thixotropy is increased when a polyether compound such as diethylene glycol, triethylene glycol, or polyethylene glycol, a reaction product of a polyether compound and a functional silane, or a nonionic surfactant having an ethylene oxide chain is used in combination with fine powder silica. . These nonionic surfactants may be used alone or in combination of two or more.

  Specific examples of the fine powder silica include, for example, trade names Aerosil R974, R972, R972V, R972CF, R805, R812, R812S, RY200, RX200, RY200S, # 130, # 200, # 300, R202, etc., manufactured by Nippon Aerosil. And trade name Nippon Sil SS series made by Nippon Silica, trade names Rheorosil MT-10, MT-30, QS-102, QS-103, made by Soda Tokuyama, trade names made by Cabot, Cabosil TS-720, MS-5, MS -7, commercial products such as Sven and Organite manufactured by Toyoshiro Yoko.

  The organic bentonite is a powdery substance obtained by finely pulverizing montmorillonite ore, which is surface-treated with various organic substances. As the organic compound, an aliphatic primary amine, an aliphatic quaternary amine (all of which preferably have 20 or less carbon atoms) are used. Specific examples of the organic bentonite include, for example, trade names Orven D, New D Orven, manufactured by Shiraishi Kogyo, trade name Hard Sil, manufactured by Kaolin Tsuchiya, clay # 30 manufactured by Bergess Pigment, Southern Cray # 33, manufactured by National Lead, USA. “Bentone 34” (dimethyloctadecyl ammonium bentonite) and the like.

  The thixotropic index means a ratio of apparent viscosity at a low rotation speed (for example, 0.5 to 12 rpm) and a high speed (for example, 2.5 to 60 rpm) in viscosity measurement using a rotational viscometer (however, The ratio of the high speed rotation speed to the low speed rotation speed is preferably at least 5 and more preferably in the range of 5-10.

  These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more.

<Photo-curing substance>
You may add a photocurable substance to the curable composition of this invention as needed. A photo-curing substance is a substance that undergoes a chemical change in the molecular structure in a short period of time due to the action of light, resulting in a change in physical properties such as curing. By adding this photocurable substance, the adhesiveness (also referred to as residual tack) of the cured product surface when the curable composition is cured can be reduced. This photo-curable substance is a substance that can be cured by exposure to light, but a typical photo-curable substance is allowed to stand at room temperature for one day, for example, in an indoor location where the sun is exposed (near the window). It is a substance that can be cured by. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and the type is not particularly limited. For example, unsaturated acrylic compounds, polycinnamic acid Examples thereof include vinyls or azide resins, epoxy compounds, vinyl ether compounds and the like.

  Specific examples of unsaturated acrylic compounds include (meth) acrylic acid esters (oligoester acrylates) of low molecular weight alcohols such as ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, and neopentyl alcohol; bisphenol A (Meth) acrylic acid esters of alcohols obtained by modifying acids such as isocyanuric acid or the above-mentioned low molecular weight alcohols with ethylene oxide or propylene oxide; polyether polyols whose main chain is a polyether and having a hydroxyl group at the terminal; Polymer polyols obtained by radical polymerization of vinyl monomers in polyols that are ethers, polyester polyols with a main chain of polyester and a hydroxyl group at the terminal, and main chains of vinyl or (meth) acrylic (Meth) acrylic acid esters such as polyols with hydroxyl groups in the main chain; the main chain is a vinyl or (meth) acrylic polymer and a polyfunctional acrylate is copolymerized in the main chain (Meth) acrylic esters obtained by reacting epoxy resins such as bisphenol A type and novolac type with (meth) acrylic acid; polyol, polyisocyanate and hydroxyl group-containing (meta ) Urethane acrylate oligomers having a urethane bond and a (meth) acryl group in the molecular chain obtained by reacting acrylate or the like.

  Polyvinyl cinnamate is a photosensitive resin having a cinnamoyl group as a photosensitive group, and includes many polyvinyl cinnamate derivatives other than those obtained by esterifying polyvinyl alcohol with cinnamic acid.

  Azide resin is known as a photosensitive resin having an azide group as a photosensitive group. In general, in addition to a rubber photosensitive solution in which an azide compound is added as a photosensitive agent, “photosensitive resin” (published March 17, 1972). , Published by the Printing Society Press, page 93 to page 106 to page 117), these are detailed examples, and these can be used alone or in combination, and a sensitizer can be added if necessary.

  Examples of the epoxy compound and vinyl ether compound include epoxy group-terminated or vinyl ether group-terminated polyisobutylene.

  Among the above-mentioned photocurable materials, unsaturated acrylic compounds are preferable because they are easy to handle.

  The photocurable material is preferably added in an amount of 0.01 to 20 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group. If the amount is less than 0.01 parts by weight, the effect is small. If the amount exceeds 20 parts by weight, the physical properties may be adversely affected. Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect.

<Air oxidation curable substance>
If necessary, an air oxidation curable material may be added to the curable composition of the present invention. The air oxidation curable substance is a compound having an unsaturated group that can be crosslinked and cured by oxygen in the air. By adding this air oxidation curable substance, the tackiness (also referred to as residual tack) of the cured product surface when the curable composition is cured can be reduced. The air oxidation curable substance in the present invention is a substance that can be cured by contact with air, and more specifically, has a property of curing by reacting with oxygen in the air. A typical air oxidation curable substance can be cured by, for example, standing in air indoors for 1 day.

  Examples of air oxidative curable substances include drying oils such as tung oil and linseed oil; various alkyd resins obtained by modifying these drying oils; acrylic polymers modified with drying oil, epoxy resins, silicone resins, Urethane resin: 1,2-polybutadiene, 1,4-polybutadiene, C5 to C8 diene polymers and copolymers, and various modified products of the polymers and copolymers (maleinized modified products, boil oil modified products) A specific example is a thing etc.). Of these, paulownia oil, diene polymer liquid (liquid diene polymer) and modified products thereof are particularly preferred.

  Specific examples of the liquid diene polymer include a liquid polymer obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene, and copolymerizable with these diene compounds. Polymers such as NBR and SBR obtained by copolymerizing monomers such as acrylonitrile and styrene having a main component with a diene compound, and various modified products thereof (maleinized modified products, boiled oils) Modified products, etc.). These may be used alone or in combination of two or more. Of these liquid diene compounds, liquid polybutadiene is preferred.

  The air oxidation curable substance may be used alone or in combination of two or more. In addition, the effect may be enhanced if a catalyst that promotes the oxidative curing reaction or a metal dryer is used together with the air oxidative curable substance. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, and zirconium octylate, amine compounds, and the like.

  The air oxidation curable substance may be used in combination with the above-described photocurable substance, and further, the above-mentioned silanol-containing compound may be used in combination. Combined use of these two components or combination of the three components further demonstrates its effect, especially when exposed to a long period of time, and in a severely contaminated area with a lot of dust and fine earth and sand. This is particularly preferable.

  The air oxidation curable substance is preferably added in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the polymer having a crosslinkable silyl group. If the amount is less than 0.01 parts by weight, the effect is small. If the amount exceeds 20 parts by weight, the physical properties may be adversely affected.

<Antioxidant>
You may add antioxidant to the curable composition of this invention as needed. Various types of antioxidants are known, and are described in, for example, “Antioxidant Handbook” published by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242) published by CM Chemical Co., Ltd. Although various things are mentioned, it is not necessarily limited to these. For example, phosphoethers such as thioethers such as MARK PEP-36 and MARK AO-23 (all manufactured by Asahi Denka Kogyo), Irgafos 38, Irgafos 168, Irgafos P-EPQ (all manufactured by Ciba Specialty Chemicals) An inhibitor etc. are mentioned. Of these, hindered phenol compounds as shown below are preferred.

  Specific examples of the hindered phenol compound include the following. 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 (4methyl-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, triethylene glycol-bis- [3- (3-t- Butyl-5-methyl-4hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3 5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3 5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t- Butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl -2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium, tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4-2,4-bis [(octylthio) methyl] o-cresol, N, N′-bis [3- (3 5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris (2,4-di-t-butylphenyl) phosphite, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) Benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) -benzotriazole, methyl-3- [3 -T-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-condensate with polyethylene glycol (molecular weight about 300), hydroxyphenylbenzotriazole derivative, 2- (3,5- Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl) -4-piperidyl), 2,4-di -t- butyl-3,5-di -t- butyl-4-hydroxybenzoate, and the like.

  In terms of product names, Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7, Nocrack DAH (all above Also manufactured by Ouchi Shinsei Chemical Industry), MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO-616, MARK AO-635, MARK AO-658, MARK AO-80, MARK AO-15, MARK AO-18, MARK 328, MARK AO-37 (all manufactured by Asahi Denka Kogyo), IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, IRGANOX-1024, IRGANOX 1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all of these are manufactured by Ciba Specialty Chemicals), Sumizer GM, and Sumilizer GA-80 (all of which are manufactured by Sumitomo Chemical) However, the present invention is not limited to these examples.

  Antioxidants may be used in combination with the light stabilizers described later, and are particularly preferred because they can further exert their effects and improve heat resistance in particular. Tinuvin C353, Tinuvin B75 (both manufactured by Ciba Specialty Chemicals) and the like in which an antioxidant and a light stabilizer are mixed in advance may be used.

  It is preferable that the usage-amount of antioxidant is the range of 0.1-10 weight part with respect to 100 weight part of polymers which have a crosslinkable silyl group. If it is less than 0.1 parts by weight, the effect of improving the weather resistance is small, and if it exceeds 5 parts by weight, there is no great difference in the effect, which is economically disadvantageous.

<Light resistance stabilizer>
You may add a light-resistant stabilizer to the curable composition of this invention as needed. Various types of light-resistant stabilizers are known and described in, for example, “Antioxidant Handbook” published by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242), issued by CMC Chemical, and the like. There are various types. Although it is not necessarily limited to these, in a light-resistant stabilizer, a ultraviolet absorber and a hindered amine light stabilizer compound are preferable. Specifically, benzotriazole compounds such as Tinuvin P, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 329, Tinuvin 213 (all of which are manufactured by Ciba Specialty Chemicals), Tinuvin 1577, etc. Examples thereof include triazine-based compounds, benzophenone-based compounds such as CHIMASSORB 81, and benzoate-based compounds such as Tinuvin 120 (manufactured by Ciba Specialty Chemicals).

Hindered amine compounds are also preferred, and such compounds are described below.
Dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate of succinate, poly [{6- (1,1,3,3-tetramethylbutyl) Amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N′-bis (3aminopropyl) ethylenediamine- 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperidinyl) ester and the like.

  In terms of product names, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 944LD, CHIMASSORB 119FL, Irgafos 168 (all of which are manufactured by Ciba Specialty Chemicals), MARK LA-52, MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68, MARK LA-82, MARK LA-87 (all manufactured by Asahi Denka Kogyo), Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Examples include, but are not limited to, sanol LS-1114, sanol LS-744, and sanol LS-440 (all of which are manufactured by Sankyo).

  The light-resistant stabilizer may be used in combination with the above-mentioned antioxidant, and is particularly preferable because the effect is further exhibited by using it together, and the weather resistance may be improved. The combination is not particularly limited, but a combination of the above-mentioned hindered phenol-based antioxidant and, for example, a benzotriazole-based ultraviolet absorber or a combination of the above-mentioned hindered phenol-based antioxidant and a hindered amine-based light stabilizer compound is preferable. . Or the combination of the above-mentioned hindered phenolic antioxidant, for example, a benzotriazole type ultraviolet absorber and a hindered amine light stabilizer compound is preferable. Tinuvin C353, Tinuvin B75 (both manufactured by Ciba Specialty Chemicals) and the like in which a light stabilizer and an antioxidant are mixed in advance may be used.

  The hindered amine light stabilizer may be used in combination with the above-mentioned photo-curing substance, and it is particularly preferable because the hindered amine light stabilizer further exerts its effect and particularly the weather resistance may be improved. The combination is not particularly limited, but in this case, a hindered amine light stabilizer containing a tertiary amine is preferable because the increase in viscosity during storage is small and the storage stability is good.

  It is preferable that the usage-amount of a light stabilizer is the range of 0.1-10 weight part with respect to 100 weight part of polymers which have a crosslinkable silyl group. If it is less than 0.1 parts by weight, the effect of improving the weather resistance is small, and if it exceeds 5 parts by weight, there is no great difference in the effect, which is economically disadvantageous.

<Epoxy resin>
You may add an epoxy resin to the curable composition of this invention as needed. Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, novolac type epoxy resin, bisphenol A propylene oxide Adduct glycidyl ether type epoxy resin, hydrogenated bisphenol A type (hydrogenated bisphenol A type) epoxy resin, fluorinated epoxy resin, rubber modified epoxy resin containing polybutadiene or NBR, glycidyl ether of tetrabromobisphenol A, etc. Flame retardant epoxy resin, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane series Xylene resin, urethane-modified epoxy resin having urethane bond, various alicyclic epoxy resins, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycerin Examples thereof include glycidyl ethers of polyhydric alcohols, epoxidized products of unsaturated polymers such as hydantoin type epoxy resins, petroleum resins, etc., but are not limited thereto, and are generally used epoxies Resins can be used. These epoxy resins may be used alone or in combination of two or more.

  Among these epoxy resins, those having at least two epoxy groups in one molecule are preferable from the viewpoint of high reactivity and easy formation of a three-dimensional network upon curing.

  In order to obtain a transparent cured product when the mixture of the vinyl polymer of the present invention and the epoxy resin is cured, the epoxy resin is preferably compatible with the vinyl polymer. Hydrogenated bisphenol A type epoxy resins are easily compatible with various vinyl polymers, and easily obtain a transparent cured product.

  A curable composition having a combination of good compatibility between the vinyl polymer and the epoxy resin tends to take a modulation structure when cured, and as a result, a transparent cured product is easily obtained. Furthermore, the mechanical properties may be remarkably improved.

  For example, a combination of a vinyl polymer or vinyl copolymer whose main chain is more polar than butyl acrylate homopolymer and an epoxy resin having an aromatic ring, or a vinyl polymer or vinyl copolymer And a preferable combination such as a combination with an epoxy resin having no aromatic ring.

  Although it does not specifically limit as an example of the epoxy resin which does not have an aromatic ring, An alicyclic epoxy resin is preferable and the epoxy resin in which a glycidyl group is not directly attached to an alicyclic ring is more preferable.

The vinyl polymer or vinyl copolymer whose main chain is higher in polarity than the butyl acrylate homopolymer is not limited to this, but is represented by the general formula (2) as a preferred example. , Polymers or copolymers.
_{- [CH 2 -CR (COOR '} )] m - (2)
(In the formula, R is hydrogen or a methyl group, and R ′ is the same or different and is an alkoxyalkyl group or an alkyl group having 1 to 3 carbon atoms.)
Specifically, a copolymer of ethyl acrylate / butyl acrylate / acrylic acid 2-methoxyethyl (molar ratio 40-50 / 20-30 / 30-20) and bisphenol A type epoxy resin or bisphenol F type epoxy resin Preferred combinations include, but are not limited to, combinations of hydrogenated bisphenol A type epoxy resins and the like, and combinations of butyl acrylate acrylate homopolymer and hydrogenated bisphenol A type epoxy resins and hexahydrophthalic acid diglycidyl ester. It is not a thing.

Addition amount of epoxy resin As an addition amount when adding an epoxy resin, the mixing ratio of the polymer having a crosslinkable silyl group and the epoxy resin is preferably in the range of 100/1 to 1/100 by weight. More preferably in the range of 100/5 to 5/100, still more preferably in the range of 100/10 to 10/100, but the mixing ratio is not limited and depends on each application and purpose. Can be set. Due to its characteristics, this curable composition can be used as an elastic adhesive for bonding materials with different linear expansion coefficients or for members that are repeatedly displaced by a heat cycle. Taking advantage of its properties, it can be used as a coating agent in applications where the substrate can be seen. For example, in this elastic adhesive application, if the mixing ratio of the epoxy resin is too large, the cured product becomes hard and the peel strength decreases, and if it is too small, the adhesive strength and water resistance decrease conversely, It is usually used in the range of about 10 to 150 parts by weight, preferably in the range of 20 to 100 parts by weight with respect to 100 parts by weight of the polymer having a silyl group.

Epoxy resin curing catalyst / curing agent If necessary, a curing agent for epoxy resin can be included. A conventionally well-known thing can be widely used as a hardening | curing agent for epoxy resins. For example, aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, methylpentamethylenediamine, trimethylhexamethylenediamine, guanidine, tetramethylguanidine, oleylamine; Diamine, isophorone diamine, norbornane diamine, piperidine, N, N′-dimethylpiperazine, N-aminoethylpiperazine, BASF Ramilon C-260, CIBA Araldit HY-964, Rohm and Haas Mensendiamine, , 2-diaminocyclohexane, diaminodicyclohexylmethane, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocycline) Hexyl) alicyclic amines such as methane, polycyclohexylpolyamine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU); m-xylylenediamine, m-phenylenediamine, 4, 4′- Aromatic amines such as diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone; (CH ₃ ) ₂ N (CH ₂ ) _n N (CH ₃ ) ₂ (where n is an integer of 1 to 10) A linear tertiary amine represented by a chain diamine, (CH ₃ ) ₂ —N (CH ₂ ) _n —CH ₃ (where n is an integer of 0 to 10), N {(CH ₂ ) _n CH ₃ } ₃ (wherein n is an integer from 1 to 10) alkyl tertiary monoamines; fats such as benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol Aromatic Mines; 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (ATU), morpholine, N-methylmorpholine, polyoxypropylenediamine, polyoxy Amines having ether bonds such as propylenetriamine and polyoxyethylenediamine; hydroxyl-containing amines such as diethanolamine and triethanolamine; triethylenediamine, pyridine, picoline, diazabicycloundecene, phthalic anhydride, trimellitic anhydride, anhydrous Acid anhydrides such as pyromellitic acid, benzophenone anhydride tetracarboxylic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, dodecyl succinic anhydride; diethylenetriamine as dimer acid Polyamides obtained by reacting polyamines such as triethylenetetramine, various polyamide resins, polyamide amines such as polyamides using polycarboxylic acids other than dimer acid; various imidazoles such as 2-ethyl-4-methylimidazole; dicyandiamide And derivatives thereof; polyoxypropylene-based amines such as polyoxypropylene-based diamine and polyoxypropylene-based triamine; phenols; epoxy-modified amine obtained by reacting an epoxy compound with the above amines; Modified amines such as Mannich modified amine, Michael addition modified amine, ketimine obtained by condensation reaction of amine compound and carbonyl compound; 2,4,6-tris (dimethylaminomethyl) Examples include amine salts such as 2-ethylhexanoate of phenol; compounds having an amino group and a hydrolyzable silyl group in one molecule such as N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane. . Specific examples of the ketimine compound include, for example, JP-A-7-242737.

  These curing agents may be used alone or in combination of two or more. Although not particularly limited, among these curing agents for epoxy resins, 2,4,6-tris (dimethylaminomethyl) phenol and polyoxypropylene-based diamine are preferable from the viewpoint of curability and physical property balance.

  Such a curing agent for epoxy resins is usually in the range of about 1 to 60 parts by weight, preferably 2 to 50 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group, depending on the amount of the epoxy resin. It is good to be used within a range. If it is less than 1 part by weight, the epoxy resin is insufficiently cured and the adhesive strength is lowered. On the other hand, when the amount exceeds 60 parts by weight, bleeding to the interface occurs and the adhesiveness is lowered, which is not preferable.

  In addition, it is preferable to add a compound having a group capable of reacting to both the crosslinkable silyl group of the polymer (I) and the epoxy group of the epoxy resin to the curable resin composition because the strength is further improved. Specific examples thereof include N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane. Etc.

<Compatibilizer>
A compatibilizing agent can be added to the curable composition of the present invention. As specific examples of such additives, for example, copolymers of a plurality of vinyl monomers described in the specification of JP-A-2001-329025 can be used.

<Compound having an α, β diol structure or an α, γ diol structure in the molecule>
A compound having an α, β diol structure or an α, γ diol structure may be added to the molecule contained in the curable composition of the present invention. As the compound having an α, β diol structure or an α, γ diol structure, generally well-known compounds can be used. In the present specification, the α, β diol structure represents a structure having two hydroxyl groups at adjacent carbon atoms, and the α, γ diol structure has two hydroxyl groups at adjacent carbon atoms. In addition, as represented by glycerin and the like, both α and β diol structures and α and γ diol structures, or polyols such as triols and tetraols containing either structure are also included.

The compound having an α, β diol structure or an α, γ diol structure in the molecule is not particularly limited. For example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3 Diols such as butanediol, 2,3-butanediol, pinacol, 2,2-dimethyl-1,3-propanediol, 2-methyl-2-hydroxymethyl-1,3-propanediol; glycerin, 1, Triols such as 2,6-hexanetriol, 1,1,1-tris (hydroxymethyl) propane, 2,2-bis (hydroxymethyl) butanol; pentaerythritol, D-sorbitol, D-mannitol, diglycerin, poly Tetravalent or higher polyols such as glycerin; glycerin monostearate, glyce Emissions monoisostearate, glycerin monooleate, glycerin monolaurate, glycerin monopalmitate, glycerin monocaprylate, glycerin monoacetate, glycerin monocarboxylic acid esters such as glycerin monobehenate;
Diglycerol monostearate, diglycerol monooleate, diglycerol monolaurate, tetraglycerol monostearate, tetraglycerol monooleate, tetraglycerol monolaurate, tetraglycerol distearate, tetraglycerol dioleate, tetraglycerol Polyglycerol carboxylates such as dilaurate, decaglycerol monostearate, decaglycerol monooleate, decaglycerol monolaurate, decaglycerol distearate, decaglycerol dioleate, decaglycerol dilaurate; pentaerythritol monostearate, Pentaerythritol such as pentaerythritol monoisostearate, pentaerythritol monooleate, pentaerythritol monolaurate Nokarubon esters; pentaerythritol distearate, pentaerythritol dioleate, pentaerythritol dicarboxylic acid esters such as pentaerythritol dilaurate;
Sorbitan monocarboxylic esters such as sorbitan monostearate, sorbitan monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monobehenate; sorbitan distearate, sorbitan dioleate, sorbitan dilaurate, sorbitan dipalmitate Sorbitan dicarboxylic acid esters such as sorbitan dibehenate; glycerol monoalkyl ethers such as glycerol monostearyl ether, glycerol monooleyl ether, glycerol monolauryl ether, glycerol mono-2-ethylhexyl ether; diglycerol monostearyl ether, di Glycerol monooleyl ether, diglycerin monolauryl ether, tetraglycerin monostearyl ether, tetraglyceride Monooleyl ether, tetraglycerin monolauryl ether, tetraglycerin distearyl ether, tetraglycerin dioleyl ether, tetraglycerin dilauryl ether, decaglycerin monostearyl ether, decaglycerin monooleyl ether, decaglycerin monolauryl ether, decaglycerin di Polyglycerin alkyl ethers such as stearyl ether, decaglycerin dioleyl ether, decaglycerin dilauryl ether;
Pentaerythritol monoalkyl ethers such as pentaerythritol monostearyl ether, pentaerythritol monooleyl ether and pentaerythritol monolauryl ether; pentaerythritol dialkyl ethers such as pentaerythritol distearyl ether, pentaerythritol dioleyl ether and pentaerythritol dilauryl ether Sorbitan monoalkyl ethers such as sorbitan monostearyl ether, sorbitan monooleyl ether, sorbitan monolauryl ether; sorbitan dialkyl ethers such as sorbitan distearyl ether, sorbitan dioleyl ether, sorbitan dilauryl ether, and the like.

  Many of the above compounds are readily available as many general-purpose compounds such as emulsifiers, surfactants, dispersants, antifoaming agents, antifogging agents, solubilizers, thickeners, and lubricants.

  The above compounds may be used alone or in combination of two or more. The amount of the compound used is preferably 0.01 to 100 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group. If the amount is less than 0.01 parts by weight, the intended effect cannot be obtained. If the amount exceeds 100 parts by weight, the mechanical strength of the cured product is insufficient, which is not preferable. More preferably, it is 0.1-20 weight part.

<Other additives>
Various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include flame retardants, curability modifiers, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents and the like. These various additives may be used alone or in combination of two or more.

  Specific examples of such additives are described in, for example, the specifications of JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, and JP-A-64-22904. Yes.

  The curable composition of the present invention can be used substantially without a solvent. Although a solvent may be used from the viewpoint of workability and the like, it is desirable not to use it because of environmental influences.

  The curable composition of the present invention may be prepared as a one-component type in which all compounding components are preliminarily blended and stored and cured by moisture in the air after coating, and a polymer having a crosslinkable silyl group and its curing Separately, a component such as a filler, a plasticizer, and water may be added separately from the agent and the curing catalyst, and the mixture may be adjusted as a two-component type that is mixed before use.

  For example, but not limited to, as an agent A, a polymer having a crosslinkable silyl group is adjusted, and as a agent B, a tin compound as a curing catalyst for a polymer having a crosslinkable silyl group, water, etc. is adjusted. In addition, the above-mentioned A agent and B agent can be mixed and used immediately before application.

  In the case of the one-component type, there is no need for mixing and kneading at the time of application, and at the same time, there is no weighing error (mixing ratio error), and thus errors such as poor curing can be prevented.

<Viscosity before curing of curable composition>
The curable resin composition has a viscosity before curing at room temperature of 30 Pa.s. It is preferable to apply a resin composition having fluidity of s or more but relatively high viscosity. The viscosity before curing is 30 Pa. If the viscosity is less than about s, the cured product between the heating element and the heat radiating body will be washed away after application, resulting in a problem that workability during application is reduced. The viscosity before curing is preferably 40 Pa. s or more, more preferably 50 Pa. s or more. As the viscosity before curing, a value measured under the condition of 2 rpm using a BS type viscometer in an atmosphere of 23 ° C./50% RH is used. The upper limit of the viscosity before curing is not particularly limited, but if the viscosity is too high, application may be difficult, or air may be entrained during application, which may cause a decrease in thermal conductivity. Therefore, in general, 3000 Pa. s or less, preferably 2000 Pa.s. Those below s are used.

<< Usage and usage >>
The composition of the present invention can be used as a thermal interface that transfers heat between the heat generating material and the heat spreader, or between the heat spreader and the cooling member. It can also be used as a heat spreader itself. Although it does not specifically limit as a heat-generating material, Electronic components, such as a heater with a heat_generation | fever, a temperature sensor, an arithmetic element, a transistor, and a light emitting element, etc. are mentioned. The cooling member is not particularly limited, and examples of the heat radiating material include a heat sink such as a heat radiating fin, a graphite sheet (graphite film), liquid ceramics, a Peltier element, and the like. It is preferably used as a thermally conductive material that dissipates heat from these heat generating materials to a cooling member or the like, and may be used as the heat radiating material itself. Moreover, you may serve as a heat spreader and a cooling member. Recently, it can also be used as a heat dissipation material by filling a sealing material on a thin base chip in a mobile phone or a shielding can.

  Since the composition of the present invention uses a vinyl polymer as a base resin, it is excellent in heat resistance, weather resistance, chemical resistance and water resistance, and can withstand severe use. In addition, when an electrically insulating filler is mainly used, it is excellent in electrical insulation and can be used in a site where electrical insulation is required. On the other hand, when an electrically conductive filler is mainly used, it is excellent in electrical conductivity and can also be used in a site where electrical conductivity is required.

  Furthermore, since the composition of the present invention is applied between the heat generating body and the heat radiating body and then cured between the heat generating body and the heat radiating body, it is in close contact with these heat generating materials and heat radiating materials. It has excellent properties and can sufficiently transfer heat even with some unevenness.

  Although it is not limited as a use utilizing thermal conductivity, it is particularly suitable for a small electronic device such as a mobile phone or a personal computer because a contact failure due to cyclic siloxane does not occur. Furthermore, it can be used for various applications such as electric and electronic component materials such as automobiles and home appliances, electric insulating materials such as insulating coating materials for electric wires and cables, and potting agents for electric and electronic devices.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples.

  In the following synthesis examples, examples and comparative examples, “part” and “%” represent “part by weight” and “% by weight”, respectively.

  Synthesis examples of the polymer in the present invention are shown below.

  In the following synthesis examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column packed with polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko) and chloroform as a GPC solvent were used.

(Synthesis Example 1)
Polyoxypropylene diol having a number average molecular weight of about 2,000 is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst. A TOS-GEL H type manufactured by Tosoh was used as the column, and a polypropylene oxide (polystyrene equivalent value measured using THF) was obtained as the solvent. Subsequently, a 1.2-fold equivalent NaOMe methanol solution was added to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide to distill off the methanol, and allyl chloride was added to convert the terminal hydroxyl group into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polypropylene oxide, water was removed by centrifugation, and the resulting hexane solution was further added. 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by vacuum devolatilization. Thus, a bifunctional polypropylene oxide having a number average molecular weight of about 25,500 having an allyl group at the end was obtained.

To 100 parts by weight of the obtained allyl-terminated polypropylene oxide, 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt% was added as a catalyst, and reacted with 0.95 parts by weight of trimethoxysilane at 90 ° C. for 5 hours. A methoxysilyl group-terminated polyoxypropylene polymer (I-2) was obtained. As described above, 1H-NMR measurement showed that the number of terminal trimethoxysilyl groups was 1.3 on average per molecule.

Synthesis Example 2 Synthesis Example of Poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate) copolymer having a crosslinkable silyl group CuBr (1.21 kg) in a 250 L reactor under a nitrogen atmosphere ), Acetonitrile (10.8 kg), butyl acrylate (7.19 kg), ethyl acrylate (10.3 kg), 2-methoxyethyl acrylate (8.47 kg) and diethyl 2,5-dibromoadipate (3. 37 kg) was added and stirred at 70-80 ° C. for about 30 minutes. To this was added pentamethyldiethylenetriamine to initiate the reaction. A mixture of butyl acrylate (28.8 kg), ethyl acrylate (41.3 kg), and 2-methoxyethyl acrylate (33.9 kg) was continuously added over 2 hours after 30 minutes from the start of the reaction. During the reaction, pentamethyldiethylenetriamine was appropriately added so that the internal temperature became 70 ° C to 90 ° C. The total amount of pentamethyldiethylenetriamine used so far was 243 g. Four hours after the start of the reaction, volatile components were removed by heating and stirring at 80 ° C. under reduced pressure. Acetonitrile (32.5 kg), 1,7-octadiene (30.9 kg) and pentamethyldiethylenetriamine (486 g) were added thereto, and stirring was continued for 4 hours. The mixture was heated and stirred at 80 ° C. under reduced pressure to remove volatile components.

  Toluene was added to this concentrate to dissolve the polymer, diatomaceous earth was added as a filter aid, aluminum silicate and hydrotalcite were added as adsorbents, and the mixture was heated and stirred in an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%). . The solid content in the mixed solution was removed by filtration, and the filtrate was heated and stirred at an internal temperature of 100 ° C. under reduced pressure to remove volatile components.

  Furthermore, aluminum silicate, hydrotalcite, and a heat deterioration inhibitor were added as adsorbents to this concentrate, and the mixture was heated and stirred under reduced pressure (average temperature of about 175 ° C., reduced pressure of 10 Torr or less).

  Furthermore, aluminum silicate and hydrotalcite were added as adsorbents, an antioxidant was added, and the mixture was heated and stirred in an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%).

  Toluene was added to this concentrate to dissolve the polymer, and then the solid content in the mixed solution was removed by filtration. The filtrate was heated and stirred under reduced pressure to remove volatile matter, and the polymer having an alkenyl group was removed. Obtained.

Polymer having this alkenyl group, dimethoxymethylsilane (2.0 molar equivalents relative to alkenyl group), methyl orthoformate (1.0 molar equivalents relative to alkenyl group), platinum catalyst [bis (1,3-divinyl -1,1,3,3-tetramethyldisiloxane) platinum complex catalyst xylene solution: hereinafter referred to as platinum catalyst] (10 mg as platinum relative to 1 kg of polymer) is mixed and heated and stirred at 100 ° C. in a nitrogen atmosphere. did. After confirming the disappearance of the alkenyl group, the reaction mixture was concentrated to obtain a poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate) copolymer [P1] having a dimethoxysilyl group at the terminal. Obtained. The number average molecular weight of the obtained copolymer was about 18000, and the molecular weight distribution was 1.2. When the average number of silyl groups introduced per molecule of the copolymer was determined by ¹ H NMR analysis, it was about 1.9.

Example 1
Polymer obtained in Synthesis Example 1: 50 parts by weight, polymer obtained in Synthesis Example 2: 50 parts by weight, plasticizer W-7010 (manufactured by DIC): 95 parts by weight, antioxidant Irganox 1010 (manufactured by BASF) ): 1 part by weight, heat conductive filler BF083 (alumina hydroxide, made by Nippon Light Metal): 440 parts by weight, zinc oxide type 1 (manufactured by Sakai Chemical Industry)): 108 parts by weight were sufficiently stirred and kneaded. Later, vacuum dehydration was performed while heating and kneading using a 5 L biaxial butterfly mixer. Cooled after completion of dehydration, storage stability improver DMA: (manufactured by Taoka Chemical Co., Ltd.) 5 parts by weight, dehydrant A171 (manufactured by Momentive Performance Materials): 2 parts by weight, curing catalyst, tin neodecanoate U-50 (manufactured by Nitto Kasei) ): 4 parts by weight, versatic 10 (manufactured by Hexion Specialty Chemicals): mixed with 4 parts by weight to obtain a one-component curable resin composition. The evaluation results are shown in Table-1.

(Example 2)
10 parts by weight of the polymer obtained in Synthesis Example 1, 90 parts by weight of the polymer obtained in Synthesis Example 2, 95 parts by weight of plasticizer W-7010 (manufactured by DIC), Irganox 1010 antioxidant (manufactured by BASF) ): 1 part by weight, heat conductive filler BF083 (alumina hydroxide, made by Nippon Light Metal): 440 parts by weight, zinc oxide type 1 (manufactured by Sakai Chemical Industry)): 108 parts by weight were sufficiently stirred and kneaded. Later, vacuum dehydration was performed while heating and kneading using a 5 L biaxial butterfly mixer. Cooled after completion of dehydration, storage stability improver (DMA: manufactured by Taoka Chemical Co., Ltd.) 5 parts by weight, dehydrating agent A171 (produced by Momentive Performance Materials): 2 parts by weight, curing catalyst, tin neodecanoate U-50 (manufactured by Nitto Kasei) : 4 parts by weight, Versatic 10 (manufactured by Hexion Specialty Chemicals): mixed with 4 parts by weight to obtain a curable resin composition. The evaluation results are shown in Table-1.

(Comparative Example 1)
Polymer obtained in Synthesis Example 1: 50 parts by weight, polymer obtained in Synthesis Example 2: 50 parts by weight, plasticizer (manufactured by W-7010DIC): 95 parts by weight, antioxidant (Irganox 1010 (manufactured by BASF) )): 1 part by weight, 108 parts by weight of thermally conductive filler (BF083 (alumina hydroxide, Nippon Light Metal)), 108 parts by weight of zinc oxide (manufactured by Sakai Chemical Industry), and kneaded with sufficient stirring. Later, vacuum dehydration was performed while heating and kneading using a 5 L biaxial butterfly mixer. Cooled after completion of dehydration, storage stability improver (DMA: manufactured by Taoka Chemical Co., Ltd.) 5 parts by weight, dehydrating agent (A171 (produced by Momentive Performance Materials)): 2 parts by weight, curing catalyst (U-220H (manufactured by Nitto Kasei)) The curable resin composition was obtained by mixing with 2 parts by weight, and the evaluation results are shown in Table 1.

(Comparative Example 2)
Polymer obtained in Synthesis Example 1: 10 parts by weight, polymer obtained in Synthesis Example 2: 90 parts by weight, plasticizer (manufactured by W-7010DIC): 95 parts by weight, antioxidant (Irganox 1010 (manufactured by BASF) )): 1 part by weight, 108 parts by weight of thermally conductive filler (BF083 (alumina hydroxide, Nippon Light Metal)), 108 parts by weight of zinc oxide (manufactured by Sakai Chemical Industry), and kneaded with sufficient stirring. Later, vacuum dehydration was performed while heating and kneading using a 5 L biaxial butterfly mixer. Cooled after completion of dehydration, storage stability improver (DMA: manufactured by Taoka Chemical Co., Ltd.) 5 parts by weight, dehydrating agent (A171 (produced by Momentive Performance Materials)): 2 parts by weight, curing catalyst (U-220H (manufactured by Nitto Kasei)) The curable resin composition was obtained by mixing with 2 parts by weight, and the evaluation results are shown in Table 1.

(Curability measurement)
The composition obtained in a temperature-controlled room (23 ° C./50% RH) was applied onto an aluminum plate so as to have a thickness of about 3 mm, and the time until the surface was cured was determined to be curable.
(Viscosity measurement)
The viscosity before curing of the obtained composition was measured at 2 rpm using a BS type viscometer manufactured by Tokyo Keiki Co., Ltd. in a thermostatic chamber (23 ° C./50% RH).
[Storage stability measurement]
The obtained composition was filled in a 50 cc aluminum tube and stored in a 50 ° C. dryer.
(Thermal conductivity measurement)
The thermal conductivity of the curable composition was measured using a hot disk method thermal conductivity measuring device TPA-501 manufactured by Kyoto Electronics Industry Co., Ltd., using a cured product sheet of about 3 mm thickness in advance, a 4φ size sensor having a thickness of 3 mm and a diameter of 20 mm. The measurement was performed in an atmosphere at 23 ° C. by sandwiching the two disk-shaped samples.

Claims (11)

(A) a reactive silicon-containing oxyalkylene organic polymer having at least one hydroxyl group or hydrolyzable group on one silicon atom, and (B) at least two water molecules on one silicon atom. A (meth) acrylic acid ester-based organic polymer having at least one acid group or hydrolyzable group, (C) a plasticizer, and (D) a thermally conductive filler, having a thermal conductivity of 0 after curing. A curable resin composition of 5 W / mK or more. The curable composition according to claim 1, further comprising a carboxylic acid tin salt as the component (E) and a carboxylic acid as the component (F). Furthermore, the curable composition of Claim 1 and 2 which contains a storage stability improving agent as (G) component. The weight ratio of (A) component / (B) component is 1 / 99-50 / 50, The curable composition of Claim 1-3. The curable composition according to claim 1-4, wherein the volume ratio of the total amount of the organic polymer of component (A) and the organic polymer of component (B) in the composition is 50% or less. The curable composition according to claim 1, wherein the molecular weight distribution of the organic polymer of component (A) and the organic polymer of component (B) is less than 1.8. The reactive silicon group of the component (A) is represented by the general formula (1) and the reactive silicon group of the component (B) (2), and the curable composition according to claim 1-5 object.
_{^{- [Si (R 1) 2}} -a (Y) a O] m -Si (X) 3 ··· (1)
(In the formula, R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group represented by (R ′) ₃ SiO—. (wherein, R 'is a monovalent represents a hydrocarbon group. multiple R C20' may be different may or be the same) are shown there .R ¹ is two or more When they are, they may be the same or different, Y or X represents a hydroxyl group or a hydrolyzable group, and when two or more Y or X are present, they may be the same. A represents 1 or 2, a represents 0, 1, or 2. m represents an integer of 0 to 19.)
-[Si (R ³ ) _2-c (W) _c O] _n -Si (R ² ) _3-b (Z) _b (2)
(Wherein R ² and R ³ are the same or different and are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ″) ₃ SiO. (Wherein R ″ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. A plurality of R ″ may be the same or different). When ^two or more R ² or R ³ are present, they may be the same or different, Z and W each represent a hydroxyl group or a hydrolyzable group, and Z and W are When two or more each exist, they may be the same or different, b represents 1 or 2, c represents 0, 1, or 2. n represents an integer of 0 to 19. Show.) The curable composition according to Claims 1-7, wherein the plasticizer as component (C) is at least one selected from polyester compounds, pyromellitic acid compounds, and the like. The thermally conductive filler as component (D) is at least one selected from graphite, aluminum nitride, boron nitride, aluminum oxide, zinc oxide, magnesium oxide, aluminum hydroxide, nanofiller mainly composed of silver or copper The curable composition according to claim 1-8. The curable composition according to claim 1-9, wherein the storage stability improving agent as component (G) is a methyl ester compound. A heat dissipation member obtained by integrating and curing the curable composition according to claim 1-11 with a heating element and / or a heat dissipation element.