JP2009144103A - Curable composition and corrosion prevention method for metal surface using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition containing an organic compound having a carbon-carbon double bond reactive with an SiH group, a silicon compound containing at least two SiH groups in one molecule, and a hydrosilylation catalyst, the composition suppressing corrosion on a metal surface, and to provide a treatment method for preventing corrosion on a metal surface by using the curable composition. <P>SOLUTION: The curable composition contains: (A) an organic compound having at least two carbon-carbon double bonds reactive with the SiH groups, in one molecule; (B) a silicon compound having at least two SiH groups in one molecule; (C) a hydrosilylation catalyst; and (D) at least one selected from a group consisting of anion exchangers, amine compounds and adsorbents. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a curable composition. More specifically, the present invention provides a curable composition capable of preventing corrosion of a metal surface, and a treatment method for preventing corrosion of a metal surface using the curable composition. is there.

Electrical and electronic equipment parts must have corrosion resistance in long-term use. However, halogen ions or halogen compounds that may be contained in materials used in electrical and electronic equipment, and corrosive substances (SO _x , H ₂ S, NO _x , sea salt particles) in the atmosphere are electrodes, etc. In some cases, the corrosion of the metal surface may cause a failure of the electronic device (Non-patent Document 1).

For example, as a method for preventing corrosion of a metal surface due to a sulfur source in the atmosphere, inventions have been proposed in which a metal powder that is easily sulfided by a sulfur-containing gas is blended with a silicone rubber composition (Patent Documents 1 and 2). However, the present invention has disadvantages such that it cannot be used in places where transparency is required, and that when it is highly filled with metal powder, it may not be used in places where there is a risk of short circuit between electrodes or where insulation is required. .
JP2003-096301 JP-A-2005-113115 Nikkei Electronics, October 24, 2005, P32

  An object of the present invention is to contain an organic compound containing a carbon-carbon double bond reactive with SiH groups, a silicon compound containing at least two SiH groups in one molecule, and a hydrosilylation catalyst. To provide a curable composition capable of suppressing corrosion of a metal surface in a curable composition, and to provide a treatment method for preventing corrosion of a metal surface using the curable composition. It is.

  The present inventors have disclosed a composition containing an organic compound containing a carbon-carbon double bond reactive with SiH groups, a silicon compound containing at least two SiH groups in a molecule, and a hydrosilylation catalyst. Faced with the fact that the metal surface may be corroded in the case where the metal surface is coated with a cured product of the above, and as a result of intensive investigation of the cause of the phenomenon, the excellent heat resistance and light resistance exhibited by the composition are maintained. In addition, the present inventors have succeeded in producing a composition effective for suppressing metal corrosion and have completed the present invention.

That is, the present invention
(A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, (B) a silicon compound containing at least two SiH groups in one molecule, (C And (D) a curable composition containing at least one selected from the group consisting of an anion exchanger, an amine compound, and an adsorbent.

  The curable composition according to claim 1, wherein the anion exchanger is a hydrotalcite-like compound and / or a calcined product of a hydrotalcite-like compound (claim 2).

  The curable composition according to claim 1 or 2, wherein the amine compound is a benzotriazole derivative and / or an aminoalkoxysilane (claim 3).

  The curable composition according to any one of claims 1 to 3, wherein the adsorbent is zeolite (Claim 4).

  The curable composition according to any one of claims 1 to 4, wherein the component (A) is a compound composed of an element selected from the group consisting of C, H, N, O, S and halogen. Claim 5).

  The component (A) is represented by the following general formula (I)

（式中、Ｒ^１は炭素数１〜５０の一価の有機基を表し、それぞれのＲ^１は異なっていても同一であってもよい。）で表される有機化合物である、請求項１〜５のいずれか一項に記載の硬化性組成物（請求項６）。

(Wherein R ¹ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ¹ may be different or the same). The curable composition as described in any one of -5 (Claim 6).

  The component (B) comprises (α) an organic compound containing one or more carbon-carbon double bonds reactive with SiH groups in one molecule, and (β) at least two SiH groups in one molecule. The curable composition according to any one of claims 1 to 6, wherein the curable composition is a compound obtainable by hydrosilylation reaction with a linear and / or cyclic polyorganosiloxane having a hydrogen atom (claim 7).

  The curable composition according to claim 7, wherein the component (α) is an aliphatic compound (claim 8).

  The component (β) is represented by the following general formula (II)

（式中、Ｒ^２は炭素数１〜６の有機基を表し、ｎは３〜１０の数を表す。）で表される、１分子中に少なくとも３個のＳｉＨ基を有する環状ポリオルガノシロキサンである、請求項７又は８に記載の硬化性組成物（請求項９）。

(Wherein R ² represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10). Cyclic polyorganosiloxane having at least 3 SiH groups in one molecule. The curable composition according to claim 7 or 8 (claim 9).

  Hardened | cured material obtained by hardening the curable composition as described in any one of Claims 1-9 (Claim 10).

A treatment method for preventing corrosion of a metal surface, wherein the curable composition according to any one of claims 1 to 9 is applied to a metal surface and then cured.
About.

  According to the curable composition of the present invention, it is possible to prevent corrosion of the metal surface even in extremely severe environments and to use electric / electronic devices for a long period of time. Moreover, it can be applied to a member that requires transparency and insulation.

  The present invention relates to (A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and (B) silicon containing at least two SiH groups in one molecule. A curable composition containing at least one selected from the group consisting of a compound, (C) a hydrosilylation catalyst, and (D) an anion exchanger, an amine compound, and an adsorbent, the cured product, and corrosion of the metal surface The present invention relates to a processing method for preventing the problem.

  The components (A), (B), (C) and (D) will be described below.

((A) component)
The component (A) is not particularly limited as long as it is an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule. The organic compound does not contain a siloxane unit (Si-O-Si) like polysiloxane-organic block copolymer or polysiloxane-organic graft copolymer, and is composed of C, H, N, O, S and halogen as constituent elements. It is preferable that it contains only an element selected from the group consisting of Those containing siloxane units have gas permeability and repelling problems.

  The bonding position of the carbon-carbon double bond having reactivity with the SiH group is not particularly limited, and may be present anywhere in the molecule.

  The organic compound (A) can be classified into an organic polymer compound and an organic monomer compound.

  Examples of organic polymer compounds include polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, polyacrylate ester, polyamide, phenol-formaldehyde (phenolic resin) ) And polyimide compounds.

  Examples of organic monomer compounds include aromatic hydrocarbons such as phenols, bisphenols, benzene and naphthalene: aliphatic hydrocarbons such as linear and alicyclic: heterocyclic compounds and their A mixture etc. are mentioned.

  Although it does not specifically limit as a carbon-carbon double bond which has reactivity with SiH group of (A) component, The following general formula (III)

（式中Ｒ^３は水素原子あるいはメチル基を表す。）で示される基が反応性の点から好適である。また、原料の入手の容易さからは、

A group represented by the formula (wherein R ³ represents a hydrogen atom or a methyl group) is preferred from the viewpoint of reactivity. In addition, from the availability of raw materials,

で示される基が特に好ましい。

Is particularly preferred.

  As the carbon-carbon double bond having reactivity with the SiH group of the component (A), the following general formula (IV)

（式中Ｒ^４は水素原子あるいはメチル基を表す。）で示される部分構造を環内に有する脂環式の基が、硬化物の耐熱性が高いという点から好適である。また、原料の入手の容易さからは、

An alicyclic group having a partial structure represented by the formula (wherein R ⁴ represents a hydrogen atom or a methyl group) in the ring is preferable from the viewpoint of high heat resistance of the cured product. In addition, from the availability of raw materials,

で示される脂環式の基が特に好ましい。

The alicyclic group represented by is particularly preferable.

  The carbon-carbon double bond having reactivity with the SiH group may be directly bonded to the skeleton portion of the component (A) or may be covalently bonded via a divalent or higher valent substituent. The divalent or higher valent substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms, but includes only elements selected from the group consisting of C, H, N, O, S, and halogen as constituent elements. Is preferred. Examples of these substituents include

が挙げられる。また、これらの２価以上の置換基の２つ以上が共有結合によりつながって１つの２価以上の置換基を構成していてもよい。

Is mentioned. Moreover, two or more of these divalent or higher valent substituents may be connected by a covalent bond to constitute one divalent or higher valent substituent.

  Examples of the group covalently bonded to the skeleton as described above include vinyl group, allyl group, methallyl group, acrylic group, methacryl group, 2-hydroxy-3- (allyloxy) propyl group, 2-allylphenyl group, 3 -Allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group, 2,2-bis (allyl) Oxymethyl) butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group,

が挙げられる。

Is mentioned.

  Specific examples of the component (A) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2, -tetraallyloxy. Ethane, diarylidene pentaerythritol, triallyl cyanurate, triallyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzenes (having a purity of 50 to 100%, preferably having a purity of 80 to 100% ), Divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof, 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1,2) (The ratio is 50 to 100%) Allyl ether rack phenol, allylated polyphenylene oxide,

の他、従来公知のエポキシ樹脂のグルシジル基の一部あるいは全部をアリル基に置き換えたもの等が挙げられる。

In addition, there may be mentioned those in which part or all of the glycidyl group of a conventionally known epoxy resin is replaced with an allyl group.

  As the component (A), low molecular weight compounds that are difficult to express separately as described above for the skeleton portion and the alkenyl group can also be used. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene, fats such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene. Examples thereof include aromatic cyclic polyene compound systems and substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.

  The component (A) preferably contains 0.001 mol or more of a carbon-carbon double bond having reactivity with the SiH group per 1 g of the component (A) from the viewpoint of further improving the heat resistance. What contains 0.005 mol or more per is more preferable, and what contains 0.008 mol or more is still more preferable.

  The number of carbon-carbon double bonds having reactivity with the SiH group of component (A) should be on average at least two per molecule, but may exceed 2 if it is desired to further improve the mechanical strength. Preferably, it is 3 or more. When the number of carbon-carbon double bonds having reactivity with the SiH group of component (A) is 1 or less per molecule, only a graft structure is formed even if it reacts with component (B). Don't be.

  From the viewpoint of good reactivity as the component (A), it is preferable that one or more vinyl groups are contained in one molecule, and two or more vinyl groups are contained in one molecule. Is more preferable. Further, from the viewpoint that the storage stability tends to be good, it is preferable that 6 or less vinyl groups are contained in one molecule, and it is more preferable that 4 or less vinyl groups are contained in one molecule.

  The component (A) preferably has a molecular weight of less than 900, preferably less than 700, from the viewpoint of high mechanical heat resistance and from the viewpoint of low formability of the raw material liquid and good moldability and handleability. More preferably, those less than 500 are more preferable.

  As the component (A), in order to obtain uniform mixing with other components and good workability, the viscosity is preferably less than 100 Pa · s at 23 ° C., more preferably less than 30 Pa · s. Those less than 3 Pa · s are more preferred. The viscosity can be measured with an E-type viscometer.

  As the component (A), those having a low content of a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group are preferable from the viewpoint of suppressing coloring, particularly yellowing. What does not contain the compound which has a derivative is preferable. In the present invention, the phenolic hydroxyl group means a hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by a benzene ring, naphthalene ring, anthracene ring, etc., and a phenolic hydroxyl group derivative means a hydrogen atom of the above-mentioned phenolic hydroxyl group. A group substituted by an alkyl group such as a methyl group or an ethyl group, an alkenyl group such as a vinyl group or an allyl group, an acyl group such as an acetoxy group, or the like.

  Further, from the viewpoint of good optical properties such as low birefringence and low photoelastic coefficient, and good light resistance, the component (A) is preferably an aliphatic compound. . In this case, the aliphatic compound means a compound that does not contain an aromatic ring or has a small content. Specifically, the weight ratio of the component (A) in the aromatic ring is preferably 50% by weight or less, more preferably 40% by weight or less, and even more preferably 30% by weight or less. Most preferred are those that do not contain an aromatic hydrocarbon ring.

  From the viewpoint that the obtained cured product is less colored, has high optical transparency, and has high light resistance, the component (A) includes vinylcyclohexene, dicyclopentadiene, triallyl isocyanurate, 2,2-bis (4 -Hydroxycyclohexyl) propane diallyl ether, 1,2,4-trivinylcyclohexane is preferred, triallyl isocyanurate, 2,2-bis (4-hydroxycyclohexyl) propane diallyl ether, 1,2,4-trivinyl Cyclohexane is particularly preferred.

  (A) As a component, you may have reactive groups other than the carbon-carbon double bond which has reactivity with SiH group. Examples of the reactive group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. When it has these functional groups, the adhesiveness of the resulting curable composition tends to be high, and the strength of the resulting cured product tends to be high. Of these functional groups, an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased. Moreover, it is preferable to have 1 or more reactive groups in one molecule on average from the point that the heat resistance of the obtained cured product tends to be high.

(General formula (I))
As the component (A), from the viewpoint of high heat resistance and transparency, the following general formula (I)

（式中Ｒ^１は炭素数１〜５０の一価の有機基を表し、それぞれのＲ^１は異なっていても同一であってもよい。）で表される化合物が好ましい。

(Wherein R ¹ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ¹ may be different or the same).

As R < ¹ > of the said general formula (I), it is preferable that it is a C1-C20 monovalent organic group from a viewpoint that the heat resistance of the hardened | cured material obtained can become higher, and C1-C1 10 monovalent organic groups are more preferable, and monovalent organic groups having 1 to 4 carbon atoms are more preferable. Examples of these preferable R ¹ are methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,

等が挙げられる。

Etc.

R ^{1 in the} general formula (I) is a carbon in which at least one of the three R ^{1 s} contains one or more epoxy groups from the viewpoint that adhesion of the obtained cured product to various materials can be improved. A monovalent organic group of 1 to 50 is preferable,

で表されるエポキシ基を１個以上含む炭素数１〜５０の一価の有機基であることがより好ましい。これらの好ましいＲ^１の例としては、グリシジル基、

It is more preferable that it is a C1-C50 monovalent organic group containing 1 or more of epoxy groups represented by these. Examples of these preferred R ¹ include a glycidyl group,

等が挙げられる。

Etc.

As R ¹ of the above general formula (I), from the viewpoint that the chemical thermal stability of the resulting cured product can be improved, it contains 2 or less oxygen atoms, and C, H, and A monovalent organic group having 1 to 50 carbon atoms containing only an element selected from the group consisting of O is preferable, and a monovalent hydrocarbon group having 1 to 50 carbon atoms is more preferable. Examples of these preferable R ¹ are methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,

等が挙げられる。

Etc.

As R ^{1 in the} general formula (I), at least one of the three R ¹ groups is from the viewpoint of improving the reactivity.

で表される基を１個以上含む炭素数１〜５０の一価の有機基であることが好ましく、下記一般式（ＩＩＩ）

It is preferable that it is a C1-C50 monovalent organic group containing 1 or more groups represented by general formula (III) below.

（式中Ｒ^３は水素原子あるいはメチル基を表す。）で表される基を１個以上含む炭素数１〜５０の一価の有機基であることがより好ましく、
３つのＲ^１のうち少なくとも２つが下記一般式（Ｖ）

(Wherein R ³ represents a hydrogen atom or a methyl group), and more preferably a monovalent organic group having 1 to 50 carbon atoms containing at least one group represented by:
At least two of the three R ¹ are represented by the following general formula (V)

（式中Ｒ^５は直接結合あるいは炭素数１〜４８の二価の有機基を表し、Ｒ^６は水素原子あるいはメチル基を表す。）で表される有機基（複数のＲ^５およびＲ^６はそれぞれ異なっていても同一であってもよい。）であることがさらに好ましい。

(Wherein R ⁵ represents a direct bond or a divalent organic group having 1 to 48 carbon atoms, and R ⁶ represents a hydrogen atom or a methyl group) (a plurality of R ⁵ and R ⁶ are More preferably, they may be the same or different.

R ^{5 in the} general formula (V) is a direct bond or a divalent organic group having 1 to 48 carbon atoms. From the viewpoint that the obtained cured product can have higher heat resistance, the direct bond or carbon It is preferably a divalent organic group having 1 to 20 carbon atoms, more preferably a direct bond or a divalent organic group having 1 to 10 carbon atoms, and a direct bond or a divalent organic group having 1 to 4 carbon atoms. More preferably, it is a group. Examples of these preferred R ⁵ include

等が挙げられる。

Etc.

As R ⁵ of the general formula (V), from the viewpoint that the chemical thermal stability of the resulting cured product can be improved, it is a direct bond or contains two or less oxygen atoms and contains C as a constituent element. It is preferably a C1-C48 divalent organic group containing only an element selected from the group consisting of H and O, and may be a direct bond or a C1-C48 divalent hydrocarbon group. More preferred. Examples of these preferred R ⁵ include

が挙げられる。

Is mentioned.

R ^{6 in the} general formula (V) is a hydrogen atom or a methyl group, and a hydrogen atom is preferable from the viewpoint of good reactivity.

  However, in the preferred examples of the organic compound represented by the general formula (I) as described above, it is necessary to contain at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule. is there. From the viewpoint that heat resistance can be further improved, an organic compound containing three or more carbon-carbon double bonds having reactivity with SiH groups in one molecule is more preferable.

  Preferred specific examples of the organic compound represented by the above general formula (I) include triallyl isocyanurate,

等が挙げられる。
本発明の硬化性組成物においては、（Ａ）成分を、単独もしくは２種以上のものを混合して用いることが可能である。

Etc.
In the curable composition of this invention, it is possible to use (A) component individually or in mixture of 2 or more types.

((B) component)
Next, the silicon compound containing at least two SiH groups in one molecule as the component (B) will be described.

  The component (B) is not particularly limited as long as it is a compound containing at least two SiH groups in one molecule. For example, the compound described in International Publication WO 96/15194 is at least two SiH groups in one molecule. Those having a group can be used.

  Among these, from the viewpoint of availability, a linear and / or cyclic organopolysiloxane having at least two SiH groups in one molecule is preferable. In particular,

が挙げられる。なかでも、（Ａ）成分との相溶性が良いという観点からは、さらに、下記一般式（ＩＩ）

Is mentioned. Among these, from the viewpoint of good compatibility with the component (A), the following general formula (II)

（式中、Ｒ^２は炭素数１〜６の有機基を表し、ｎは３〜１０の数を表す。）で表される、１分子中に少なくとも３個のＳｉＨ基を有する環状オルガノポリシロキサンが好ましい。

(Wherein R ² represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10). Cyclic organopolysiloxane having at least 3 SiH groups in one molecule. Is preferred.

The substituent R ² in the compound represented by the general formula (II) is preferably composed only of an element selected from the group consisting of C, H and O, and is preferably a hydrocarbon group. More preferably, it is a methyl group.

  The compound represented by the general formula (II) is preferably 1,3,5,7-tetramethylcyclotetrasiloxane from the viewpoint of availability.

  The molecular weight of the component (B) is not particularly limited and any one can be suitably used, but a low molecular weight is preferably used from the viewpoint of easier expression of fluidity. In this case, the lower limit of the preferred molecular weight is 50, and the upper limit of the preferred molecular weight is 100,000, more preferably 1,000, and still more preferably 700.

  From the viewpoint of having good compatibility with the component (A), and from the viewpoint that the problem of outgas from the cured product that can be reduced in the volatility of the component (B) is less likely to occur, the component (B) is a SiH group. An organic compound (α) containing at least one carbon-carbon double bond having reactivity with one molecule, and a linear and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule (Β) is preferably a compound that can be obtained by a hydrosilylation reaction.

((Α) component)
The component (α) may be an organic compound containing one or more carbon-carbon double bonds having reactivity with the SiH group in one molecule. Here, about an organic compound, it is the same as that of the above-mentioned (A) component, and the preferable aspect of (A) component is similarly preferable also about ((alpha)) component. The same applies to a carbon-carbon double bond having reactivity with the SiH group. In addition, as long as the carbon-carbon double bond having reactivity with the SiH group included in the component (α) includes only elements composed of C, H, N, O, S, and halogen as constituent elements, The (B) component tends to be better compatible with the (A) component.

  As the component (α), the same component as the organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group, which is the component (A), can be used. The preferred compound for component (A) is also suitable for component (α). When an organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group is used in a molecule, the resulting cured product has a high crosslink density and tends to have a high mechanical strength and a highly reliable cured product. .

As the component (α), an organic compound containing one carbon-carbon double bond having reactivity with the SiH group in one molecule can also be used. When an organic compound containing one carbon-carbon double bond having reactivity with the SiH group in one molecule is used, the obtained cured product tends to have low elasticity, and can be used as a highly reliable cured product due to low stress. .
Specific examples of the organic compound containing one carbon-carbon double bond reactive with the SiH group in one molecule include propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-undecene, Idemitsu Petrochemical's linearene, 4,4-dimethyl-1-pentene, 2-methyl-1-hexene, 2,3,3 -Chain aliphatic hydrocarbon compounds such as trimethyl-1-butene, 2,4,4-trimethyl-1-pentene, cyclohexene, methylcyclohexene, methylenecyclohexane, norbornylene, ethylidenecyclohexane, vinylcyclohexane, camphene, Cyclic aliphatic hydrocarbon compounds such as Karen, α-pinene, β-pinene, styrene, α-methylstyrene, indene Aromatic hydrocarbon compounds such as phenylacetylene, 4-ethynyltoluene, allylbenzene, 4-phenyl-1-butene, allyl ethers such as alkyl allyl ether, allyl phenyl ether, glycerin monoallyl ether, ethylene glycol mono Aliphatic compounds such as allyl ether, 4-vinyl-1,3-dioxolan-2-one, aromatic compounds such as 1,2-dimethoxy-4-allylbenzene, o-allylphenol, monoallyldi Examples thereof include substituted isocyanurates such as benzyl isocyanurate and monoallyl diglycidyl isocyanurate, and silane compounds such as vinyltrimethylsilane, vinyltrimethoxysilane and vinyltriphenylsilane.

  Among these, the chain aliphatic hydrocarbon compounds and cyclic aliphatic hydrocarbon compounds described above, which are aliphatic hydrocarbons, are particularly preferable from the viewpoint of light resistance.

  Furthermore, polyether resins such as one-end allylated polyethylene oxide and one-end allylated polypropylene oxide, hydrocarbon resins such as one-end allylated polyisobutylene, one-end allylated polybutyl acrylate, one-end allylated polymethyl methacrylate Examples thereof also include polymers or oligomers having a vinyl group at one end, such as acrylic resins.

  The structure may be linear or branched, and the molecular weight is not particularly limited, and various types can be used. The molecular weight distribution is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, and more preferably 1.5 or less in that the viscosity of the mixture is low and the moldability is likely to be good. More preferably it is.

  When there is a glass transition temperature of an organic compound containing at least one carbon-carbon double bond having reactivity with SiH group in one molecule, there is no particular limitation on this, and various compounds can be used. The glass point transition temperature is preferably 100 ° C. or less, more preferably 50 ° C. or less, and even more preferably 0 ° C. or less in that the cured product to be obtained tends to be tough. Examples of preferred resins include polybutyl acrylate resins. Conversely, the glass transition temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 150 ° C. or higher, in that the heat resistance of the cured product obtained is increased. Most preferably, it is 170 ° C. or higher. The glass transition temperature can be determined as a temperature at which tan δ exhibits a maximum in the dynamic viscoelasticity measurement.

  The organic compound containing at least one carbon-carbon double bond having reactivity with the SiH group in one molecule is a hydrocarbon compound in that the heat resistance of the resulting cured product is increased. preferable. In this case, the preferable lower limit of the carbon number is 7, and the preferable upper limit of the carbon number is 10.

  The organic compound containing at least one carbon-carbon double bond having reactivity with the SiH group in one molecule has a reactive group other than the carbon-carbon double bond having reactivity with the SiH group. May be. Examples of the reactive group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. When it has these functional groups, the adhesiveness of the resulting curable composition tends to be high, and the strength of the resulting cured product tends to be high. Of these functional groups, an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased. Moreover, it is preferable to have 1 or more reactive groups in one molecule on average from the point that the heat resistance of the obtained cured product tends to be high. Specific examples include monoallyl diglycidyl isocyanurate, allyl glycidyl ether, allyloxyethyl methacrylate, allyloxyethyl acrylate, vinyltrimethoxysilane, and the like.

  As the above (α) component, a single component may be used, or a plurality of components may be used in combination.

((Β) component)
The component (β) is a linear and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule.

  Specifically, for example

が挙げられる。

Is mentioned.

  Here, from the viewpoint of easy compatibility with the component (α), the following general formula (II)

（式中、Ｒ^２は炭素数１〜６の有機基を表し、ｎは３〜１０の数を表す。）で表される、１分子中に少なくとも３個のＳｉＨ基を有する環状ポリオルガノシロキサンが好ましい。

(Wherein R ² represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10). Cyclic polyorganosiloxane having at least 3 SiH groups in one molecule. Is preferred.

The substituent R ² in the compound represented by the general formula (II) is preferably composed of an element selected from the group consisting of C, H, and O, and more preferably a hydrocarbon group. Preferably, it is a methyl group.

  In view of availability, 1,3,5,7-tetramethylcyclotetrasiloxane is preferable.

  Various (β) components as described above can be used alone or in admixture of two or more.

(Reaction of (α) component and (β) component)
Next, hydrosilylation of (α) component and (β) component in the case of using a compound obtained by hydrosilylation reaction of (α) component and (β) component as component (B) of the present invention The reaction will be described.

  In addition, when the (α) component and the (β) component are subjected to a hydrosilylation reaction, a mixture of a plurality of compounds containing the (B) component of the present invention may be obtained, but without separating the (B) component therefrom. The curable composition of the present invention can also be produced using the mixture as it is.

  The mixing ratio of the (α) component and the (β) component when the (α) component and the (β) component are subjected to a hydrosilylation reaction is not particularly limited, but the hydrosilylation of the obtained (B) component and (A) component is not limited. In view of the strength of the cured product due to the above, since it is preferable that the component (B) has a larger amount of SiH groups, the total number of carbon-carbon double bonds having reactivity with the SiH groups in the component (α) to be mixed ( The ratio of X) to the total number of SiH groups (Y) in the (β) component to be mixed is preferably Y / X ≧ 2, and more preferably Y / X ≧ 3. Moreover, it is preferable that it is 10> = Y / X from the point that compatibility with the (A) component of (B) component becomes easy, and it is more preferable that it is 5> = Y / X.

When the (α) component and the (β) component are subjected to a hydrosilylation reaction, an appropriate hydrosilylation catalyst may be used. As the catalyst, for example, the following can be used. Platinum simple substance, alumina, silica, carbon black or the like supported on solid platinum, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone or the like, platinum-olefin complex (for example, Pt (CH _{2 = CH 2) 2 (PPh} 3) 2, Pt (CH 2 = CH 2) 2 Cl 2), platinum - vinylsiloxane complex _{(e.g., Pt (ViMe 2 SiOSiMe 2 Vi} ) n, Pt [(MeViSiO) 4] m), platinum-phosphine complexes (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phosphite complexes (eg, Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) _{3 4} ) (In the formula, Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent integers), dicarbonyldi. Chloroplatinum, Karstedt catalyst, and platinum-hydrocarbon complexes described in Ashby US Pat. Nos. 3,159,601 and 3,159,622, and Lamoreaux, US Pat. No. 3,220,972. Examples include platinum alcoholate catalysts described in the text. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _4. , Etc.

  Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. Moreover, these catalysts may be used independently and may be used together 2 or more types.

The addition amount of the catalyst is not particularly limited, but the lower limit of the preferred addition amount is sufficient with respect to 1 mole of SiH group of the (β) component in order to have sufficient curability and keep the cost of the curable composition relatively low. 10 ^-8 mol, more preferably ^{10 -6} mole, preferable amount of the upper limit is ^{10 -1} moles per mole of the SiH group (beta) component, more preferably ^{10 -2} moles.
The hydrosilylation catalyst used in the hydrosilylation reaction between the (α) component and the (β) component can also act as a hydrosilylation catalyst that is the (C) component of the curable composition of the present invention.

In addition, a cocatalyst can be used in combination with the above catalyst. Examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl maleate, 2-hydroxy-2-methyl-1 -Acetylene alcohol compounds such as butyne, sulfur compounds such as simple sulfur, amine compounds such as triethylamine, and the like. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount relative to 1 mol of the hydrosilylation catalyst is 10 ⁻² mol, more preferably 10 ⁻¹ mol, and the upper limit of the preferable addition amount is 10 ^2. Mol, more preferably 10 mol.

  Various methods can be used to mix the (α) component, the (β) component, and the catalyst in the reaction. The (α) component mixed with the catalyst and the (β) component are mixed. Is preferred. If the catalyst is mixed with the mixture of the component (α) and the component (β), it is difficult to control the reaction. When the method of mixing the (β) component with the catalyst and the (α) component is used, the (β) component is reactive in the presence of the catalyst, and therefore it may be altered. is there.

  The reaction temperature can be variously set. In this case, the lower limit of the preferable temperature range is 30 ° C., more preferably 50 ° C., and the upper limit of the preferable temperature range is 200 ° C., more preferably 150 ° C. If the reaction temperature is low, the reaction time for sufficiently reacting becomes long, and if the reaction temperature is high, it is not practical. The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required.

  Various reaction times and pressures during the reaction can be set as required.

  A solvent may be used during the hydrosilylation reaction. Solvents that can be used are not particularly limited as long as they do not inhibit the hydrosilylation reaction. Specific examples include hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1, Ether solvents such as 3-dioxolane and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used. The solvent can also be used as a mixed solvent of two or more types. As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable. The amount of solvent to be used can also be set as appropriate.

  In addition, various additives may be used for the purpose of controlling reactivity.

  After reacting the (α) component and the (β) component, the solvent, the unreacted (α) component and / or the (β) component can also be removed. By removing these volatile components, the component (B) obtained does not have volatile components, so that the problem of voids and cracks due to volatilization of the volatile components hardly occurs in the case of curing with the component (A). Examples of the removal method include treatment with activated carbon, aluminum silicate, silica gel and the like in addition to vacuum devolatilization. When devolatilizing under reduced pressure, it is preferable to treat at a low temperature. The upper limit of the preferable temperature in this case is 100 ° C, more preferably 60 ° C. When treated at high temperatures, it tends to be accompanied by alterations such as thickening.

Examples of the component (B) that is a reaction product of the component (α) and the component (β) as described above include the reaction of bisphenol A diallyl ether with 1,3,5,7-tetramethylcyclotetrasiloxane. Product, reaction product of vinylcyclohexene and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane, dicyclopentadiene and 1, Reaction product of 3,5,7-tetramethylcyclotetrasiloxane, reaction product of triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, diallyl monoglycidyl isocyanurate and 1,3,5 , 7-Tetramethylcyclotetrasiloxane reaction product, allyl glycidyl ether and 1,3,5,7-tetramethylsilane Reaction product of clotetrasiloxane, reaction product of α-methylstyrene and 1,3,5,7-tetramethylcyclotetrasiloxane, monoallyl diglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane And the like, and the like.
(Mixing of component (A) and component (B))
Regarding combinations of component (A) and component (B), various combinations of those listed as examples of component (A) and their various mixtures / examples of component (B) and their various mixtures are listed. be able to.

  The mixing ratio of the component (A) and the component (B) is not particularly limited as long as the necessary strength is not lost, but the number of SiH groups in the component (B) (Y) is the carbon-carbon in the component (A). In the ratio to the number of double bonds (X), the lower limit of the preferred range is Y / X ≧ 0.3, more preferably Y / X ≧ 0.5, and even more preferably Y / X ≧ 0.7, which is preferable. The upper limit of the range is 3 ≧ Y / X, more preferably 2 ≧ Y / X, and even more preferably 1.5 ≧ Y / X. When it deviates from the preferred range, sufficient strength may not be obtained or thermal deterioration may easily occur.

((C) component)
Next, the hydrosilylation catalyst as component (C) will be described.

  The hydrosilylation catalyst is not particularly limited as long as it has catalytic activity for the hydrosilylation reaction, and examples thereof include the same hydrosilylation catalysts as those used in the hydrosilylation reaction of the component (α) and the component (β). In the component (C), the preferred hydrosilylation catalysts described above are also suitable. Moreover, these catalysts may be used independently and may be used together 2 or more types.

Although the addition amount of (C) component is not specifically limited, in order to have sufficient sclerosis | hardenability and hold down the cost of a curable composition comparatively low, the minimum of preferable addition amount is 1 mol of SiH groups of (B) component ^{10 -8} mol relative to, more preferably ^{10 -6} mole, preferable amount upper limit ^{10 -1} moles per mole of the SiH group (beta) component, more preferably ^{10 -2} mol .

In addition, a co-catalyst can be used in the same manner as the hydrosilylation catalyst used in the hydrosilylation reaction of the component (α) and the component (β).
((D) component)
Examples of the component (D) include at least one selected from the group consisting of an anion exchanger, an amine compound, and an adsorbent.

Anion exchangers are highly corrosive anions such as halogen ions and sulfur ions (for example, sulfate ion, sulfite ion, thiosulfate ion, sulfide ion) mixed in the resin and from the environment. There is no particular limitation as long as it can capture and exchange, and not only anions but also cations can be captured and exchanged at the same time. As an anion exchanger, a polystyrene type anion exchange resin, _a hydrotalcite-like compound (M ²⁺ ) represented by the general formula M ²⁺ _a M ³⁺ _b (OH ⁻ ) _c (CO ₃ ²⁻ ) _d · nH ₂ O Divalent metal, M ³⁺ represents a trivalent metal, a, b, c, d and n are positive _numbers ), general formula M ²⁺ _x M ³⁺ _y O _{x + 1.5y} (M ²⁺ is a divalent metal, M ³⁺ represents a trivalent metal, and x and y are positive numbers). A fired product of activated hydrotalcite-like compound, activated alumina, and the like can be exemplified. You may use together.

  As the polystyrene-based anion exchange resin, Diaion (manufactured by Mitsubishi Chemical Corporation) is preferably used under the trade name. Specific product names include Diaion SA Series (SA10A, SA11A, SA12A, NSA100, SA20A, SA21A), Diaion PA Series (PA308, PA312, PA316, PA406, PA412, PA418), Diaion Examples thereof include HPA series (HPA25), Diaion WA series (WA10, WA20, WA21J, WA30).

The hydrotalcite-like compound and the fired product of the hydrotalcite-like compound are trade names of DHT-4A, DHT-4C (aluminum magnesium hydrotalcite, manufactured by Kyowa Chemical Industry Co., Ltd.), and the KYOWARD series (Kyowa Chemical). Industrial Co., Ltd.) and IXE series (Toagosei Co., Ltd.) are preferably used.
In particular, in the cured product of the curable composition, a hydrotalcite-like compound and / or a fired product of the hydrotalcite-like compound is preferable as the anion exchanger from the viewpoint of heat resistance and light resistance, and the transparency of the cured product is preferred. Aluminum magnesium hydrotalcite is more preferable from the point of having.
As the addition amount of the anion exchanger, the upper limit of the preferable addition amount with respect to 100 parts by weight of [(A) component + (B) component] (total amount of (A) component and (B) component) is 20 parts by weight. More preferably, it is 10 parts by weight. The lower limit of the preferable addition amount with respect to 100 parts by weight of [(A) component + (B) component] is 0.01 parts by weight with respect to 100 parts by weight of [(A) component + (B) component], more preferably 0.1 parts by weight. If the amount of the anion exchanger added is too large, corrosion of the metal may be promoted conversely, and if it is too small, the effect of preventing corrosion of the metal may not be obtained.

  As the amine compound, a primary amine, a secondary amine, or a tertiary amine can be used within a range where a cured product can be obtained, and one kind may be used alone, or two or more kinds may be used in combination. In addition, since primary amines greatly inhibit the hydrosilylation reaction, for example, those that are capped with a protecting group as ketimines or those that are deprotected by light or electron beams such as photobase generators to become amine compounds may be used. Good.

  Examples of amine compounds include triazole and triazole derivatives, benzotriazole and benzotriazole derivatives, imidazole and imidazole derivatives, pyrazole and pyrazole derivatives, triazine and triazole derivatives, organic amines such as pentamethyldiethylenetriamine and tetramethylethylenediamine, and triethanolamine. Alcoholamine, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) -γ-aminopropyltri Methoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane 3-triethoxysilyl-N-(1,3-dimethyl - butylidene) amino alkoxysilanes such as propylamine can be suitably used.

  In particular, triazole derivatives and aminoalkoxysilanes can be suitably used because they have low volatility during curing and can impart corrosion resistance by adding a relatively small amount. Further, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3), which is used as a benzotriazole-based ultraviolet absorber because it is easily available among triazole derivatives. , 4,5,6-tetrahydrophthalimido-methyl) -5-methylphenyl] benzothiazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- ( 2-hydroxy-5-t-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-pentylphenyl) benzotriazole, and N, N used as metal deactivators -Bis (2-ethylhexyl)-(4 or 5) -methyl-1H-benzotriazole-1-methylamine is preferred. It can be used for.

  As the addition amount of the amine compound, the upper limit of a preferable addition amount with respect to 100 parts by weight of [(A) component + (B) component] (total amount of (A) component and (B) component) is 10 parts by weight, More preferably, it is 5 parts by weight. The lower limit of the preferable addition amount with respect to 100 parts by weight of [(A) component + (B) component] is 0.01 parts by weight with respect to 100 parts by weight of [(A) component + (B) component], more preferably 0.1 parts by weight. If the amount of the amine compound added is too large, a cured product may not be obtained or the corrosion of the metal may be accelerated, and if it is too small, the effect of preventing the corrosion of the metal may not be obtained.

The adsorbent is not particularly limited as long as it can adsorb hydrogen sulfide, sulfur oxide and nitrogen oxide which are corrosive components derived from the atmosphere, but generally used activated carbon, zeolite, metal zeolite, silica gel Activated alumina or the like can be used.
In particular, zeolite can be suitably used because of the high transparency of the cured product and the addition of a relatively small amount of corrosion resistance.

As a trade name of zeolite, ABSENTS1000, ABSENTS2000, ABSENTS3000, molecular sieve 4A, molecular sieve 5A, molecular sieve 13X (manufactured by Union Showa Co., Ltd.) and the like can be suitably used.
As the addition amount of the adsorbent, the upper limit of a preferable addition amount with respect to 100 parts by weight of [(A) component + (B) component] (total amount of (A) component and (B) component) is 20 parts by weight. The amount is preferably 10 parts by weight. The lower limit of the preferable addition amount with respect to 100 parts by weight of [(A) component + (B) component] is 0.01 parts by weight with respect to 100 parts by weight of [(A) component + (B) component], more preferably 0.1 parts by weight. If the amount of adsorbent added is too large, the corrosion of the metal may be accelerated, and if too small, the effect of preventing the corrosion of the metal may not be obtained.
(Compound containing at least one epoxy group in one molecule)
The curable composition of the present invention is not particularly limited as long as it contains the above components (A), (B), (C) and (D), but (E) at least 1 in one molecule. A compound containing one epoxy group may be contained.
A compound containing at least one epoxy group in one molecule, which is the component (E) that can be used in the curable composition of the present invention, will be described.

  As the component (E), various compounds can be used without particular limitation as long as they are compounds containing at least one epoxy group in one molecule. Examples of such component (E) include epoxy silanes, epoxy compounds, epoxy resins and the like.

  (E) The epoxy silane which is an example of a component is a compound which has at least 1 each of an epoxy group and a hydrolyzable silicon group in a molecule | numerator. Examples of hydrolyzable silicon groups include chlorosilyl groups, acylsilyl groups, alkoxysilyl groups, etc., but alkoxysilyl groups are preferred in terms of ease of handling, and methoxysilyl groups, ethoxysilyl groups are preferred in terms of reactivity. Is particularly preferred.

  Specific examples of the epoxy silanes that are examples of the component (E) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl. Examples include trimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

  Examples of the epoxy compound which is an example of the component (E) include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 2,2′-bis (4-glycidyloxycyclohexyl) propane, and 3,4-epoxycyclohexylmethyl- 3,4-epoxycyclohexanecarboxylate, 4-vinylcyclohexene dioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, 4-vinyl cyclohexyl 1,2-epoxide, glycidyl methacrylate, allyl glycidyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, 4-vinylcyclohexene 1,2-epoxide and 1,3,5,7-tetra Examples include a reaction product of methylcyclotetrasiloxane.

  Examples of the epoxy resin as an example of the component (E) include copolymerization of bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, and glycidyl methacrylate. Examples thereof include olefin polymers contained as components.

  Of these compounds containing at least one epoxy group in one molecule, epoxy silanes are preferred as the component (E) from the viewpoint that adhesion is likely to be higher.

  In addition, the component (E) is reactive with SiH groups in that it is likely to have high adhesiveness by being incorporated into the main chain skeleton by a hydrosilylation reaction, or that volatilization during curing is easily suppressed. A compound containing a carbon-carbon double bond and / or a SiH group is preferred.

  The amount of component (E) added can be variously set, but the lower limit of the preferred amount added per 100 parts by weight of [(A) component + (B) component] (total amount of (A) component and (B) component) Is 0.1 part by weight, more preferably 0.5 part by weight, and the upper limit of the preferable addition amount is 80 parts by weight, more preferably 50 parts by weight, and further preferably 25 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

  In addition, these compounds containing at least one epoxy group in one molecule may be used alone or in combination of two or more.

(mixture)
As a method of mixing the component (A), the component (B), the component (C), and the component (D), various methods can be used, but the storage stability of the intermediate raw material of the curable composition is improved. In terms of ease, a method of mixing the component (A), the component (C) and the component (D) with a method of mixing the component (B), a method of mixing the component (A) and (C), The method of mixing the component (B) and the component (D) and the component (A) and the component (C) are mixed with the component (B) and the component (D). A method in which the component (B) and the component (C) are not directly mixed is preferable.

  A solvent may be appropriately added for the purpose of improving dispersibility during mixing. Solvents that can be used are not particularly limited as long as they do not inhibit the hydrosilylation reaction. Specific examples include hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1, Ether solvents such as 3-dioxolane and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used. The solvent can also be used as a mixed solvent of two or more types. The amount of the solvent to be used can also be set as appropriate, and when it has an adverse effect on the physical properties of the cured product, it may be distilled off under reduced pressure after mixing to obtain a curable composition.

(Additive)
(Curing retarder)
In the composition of the present invention, a curing retarder can be used for the purpose of improving the storage stability or adjusting the reactivity of the hydrosilylation reaction during the production process.

  Examples of the curing retarder include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide, and these may be used in combination. Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, and maleate esters. Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. Examples of organic sulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, benzothiazole disulfide and the like. Examples of nitrogen-containing compounds include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and tert-butyl perbenzoate.

  Among these curing retarders, from the viewpoint of good retarding activity and good raw material availability, benzothiazole, thiazole, dimethyl malate, 3-hydroxy-3-methyl-1-butyne, 1-ethynyl-1- Cyclohexanol is preferred.

The addition amount of the curing retarder can be selected at various levels, the preferred amount of the lower limit is 10 ^-1 moles with respect to hydrosilylation catalyst 1mol used, more preferably 1 mol, the upper limit of the preferable amount is 10 ³ mol, more preferably Is 50 moles.

  Moreover, these hardening retarders may be used independently and may be used together 2 or more types.

(Adhesion improver)
An adhesion improver can also be added to the curable composition of the present invention. In addition to commonly used adhesives as adhesion improvers, for example, various coupling agents, phenol resins, coumarone-indene resins, rosin ester resins, terpene-phenol resins, α-methylstyrene-vinyltoluene copolymers , Polyethylmethylstyrene, aromatic polyisocyanate and the like.

  An example of the coupling agent is a silane coupling agent. The silane coupling agent is a compound having at least one functional group reactive with an organic group and at least one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from a methacryl group, an acryl group, an isocyanate group, an isocyanurate group, a vinyl group and a carbamate group from the viewpoint of handleability. From the viewpoint of properties, a methacryl group and an acryl group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Preferred silane coupling agents include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane. And alkoxysilanes having a methacrylic group or an acrylic group such as methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane.

  The addition amount in the case of using the above-mentioned adhesion improver is not particularly limited and can be variously set, but [(A) component + (B) component] (total amount of (A) component and (B) component) 100 parts by weight The lower limit of the preferred addition amount is 0.1 parts by weight, more preferably 0.5 parts by weight, and the upper limit of the preferred addition amount is 50 parts by weight, more preferably 25 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

  Moreover, these coupling agents, silane coupling agents, etc. may be used independently and may be used together 2 or more types.

  In the present invention, in order to enhance the effect of the coupling agent, silane coupling agent, and epoxy compound, a silanol condensation catalyst can be further used, and the adhesion can be improved and / or stabilized. Such a silanol condensation catalyst is not particularly limited, but aluminum compounds, titanium compounds, boric acid esters, and acid anhydrides are preferable.

  Examples of the aluminum compound used as a silanol condensation catalyst include aluminum alkoxides such as aluminum triisopropoxide, sec-butoxyaluminum diisopropoxide, aluminum trisec-butoxide, ethyl acetoacetate aluminum diisopropoxide, aluminum tris (ethyl). Acetoacetate), aluminum chelate M (manufactured by Kawaken Fine Chemicals, alkyl acetoacetate aluminum diisopropoxide), aluminum tris (acetylacetonate), aluminum monoacetylacetonate bis (ethylacetoacetate) and other aluminum chelates Aluminum chelates are more preferable from the viewpoint of handleability.

  Titanium compounds that serve as silanol condensation catalysts include tetraalkoxy titaniums such as tetraisopropoxy titanium and tetrabutoxy titanium, titanium chelates such as titanium tetraacetylacetonate, and residues having residues such as oxyacetic acid and ethylene glycol. And titanate coupling agents.

  Further, as boric acid ester as a silanol condensation catalyst, tri-2-ethylhexyl borate, normal trioctadecyl borate, tri-octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, boric acid Examples include tri-normal butyl, tri-sec-butyl borate, tri-tert-butyl borate, triisopropyl borate, trinormal propyl borate, triallyl borate, triethyl borate, trimethyl borate, and boron methoxyethoxide. From the viewpoint of availability, trimethyl borate, triethyl borate, and trinormal butyl borate are preferable.

  In addition, the acid anhydrides that serve as the silanol condensation catalyst are not particularly limited,

２−エチルヘキサン酸、シクロヘキサンカルボン酸、シクロヘキサンジカルボン酸、メチルシクロヘキサンジカルボン酸、テトラヒドロフタル酸、メチルテトラヒドロフタル酸、メチルハイミック酸、ノルボルネンジカルボン酸、水素化メチルナジック酸、マレイン酸、アセチレンジカルボン酸、乳酸、リンゴ酸、クエン酸、酒石酸、安息香酸、ヒドロキシ安息香酸、桂皮酸、フタル酸、トリメリット酸、ピロメリット酸、ナフタレンカルボン酸、ナフタレンジカルボン酸等の単独あるいは複合酸無水物が挙げられる。

2-ethylhexanoic acid, cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, methylcyclohexanedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylheimic acid, norbornene dicarboxylic acid, hydrogenated methylnadic acid, maleic acid, acetylenedicarboxylic acid, Examples thereof include lactic acid, malic acid, citric acid, tartaric acid, benzoic acid, hydroxybenzoic acid, cinnamic acid, phthalic acid, trimellitic acid, pyromellitic acid, naphthalene carboxylic acid, naphthalene dicarboxylic acid and the like alone or in combination.

  Among these acid anhydrides, carbon-reactive with SiH groups in that it has a hydrosilylation reactivity and hardly impairs the physical properties of the resulting cured product. Those containing a carbon double bond are preferred. Preferred acid anhydrides include, for example,

テトラヒドロフタル酸、メチルテトラヒドロフタル酸等の単独あるいは複合酸無水物等が挙げられる。

Examples thereof include tetrahydrophthalic acid and methyltetrahydrophthalic acid alone or in combination.

  The addition amount in the case of using the silanol condensation catalyst is not particularly limited and can be variously set. However, the lower limit of the preferable addition amount with respect to 100 parts by weight of component (E) is 0.1 parts by weight, more preferably 1 part by weight. The upper limit of the preferable addition amount is 50 parts by weight, more preferably 10 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

  Moreover, these adhesive improvement agents may be used independently and may be used together 2 or more types.

(Thermosetting resin)
Various thermosetting resins can be added to the composition of the present invention for the purpose of modifying the properties. Examples of the thermosetting resin include, but are not limited to, cyanate ester resins, phenol resins, polyimide resins, urethane resins, bismaleimide resins, and the like.

  The addition amount of the thermosetting resin is not particularly limited, but the lower limit of the preferable use amount is 5% by weight of the entire curable composition, more preferably 10% by weight, and the upper limit of the preferable use amount is the curable composition. The content is 50% by weight, more preferably 30% by weight. If the addition amount is small, it is difficult to obtain the intended effects such as adhesiveness, and if the addition amount is large, the addition tends to be brittle.

  The said thermosetting resin may be used independently and may be used combining several things.

When the thermosetting resin is blended in the curable composition of the present invention, the resin raw material of the thermosetting resin and / or the cured resin is dissolved in the component (A) or / and the component (B) to be uniform. The mixture may be mixed as it is, or may be pulverized and mixed in a particle state, or may be dispersed by dissolving in a solvent and mixing. In the point that the obtained hardened | cured material tends to become more transparent, it is preferable to melt | dissolve in (A) component or / and (B) component, and to mix as a uniform state. Also in this case, the thermosetting resin may be directly dissolved in the component (A) or / and the component (B), or may be uniformly mixed using a solvent or the like. It is good also as a dispersed state or / and a mixed state.

  When the thermosetting resin is used in a dispersed state, the average particle diameter can be variously set, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 10 μm. There may be a distribution of the particle system, which may be monodispersed or have a plurality of peak particle diameters, but from the viewpoint that the viscosity of the curable composition is low and the moldability tends to be good. The coefficient of variation is preferably 10% or less.

(Thermoplastic resin)
Various thermoplastic resins may be added to the composition of the present invention for the purpose of modifying the properties. Various thermoplastic resins can be used. For example, a homopolymer of methyl methacrylate or a polymethyl methacrylate resin such as a random, block or graft polymer of methyl methacrylate and other monomers (for example, Hitachi Chemical) Optretz, etc.), acrylic resins represented by polybutyl acrylate resins such as butyl acrylate homopolymers or random, block or graft polymers of butyl acrylate and other monomers, bisphenol A, 3, A polycarbonate resin such as a polycarbonate resin containing 3,5-trimethylcyclohexylidenebisphenol or the like as a monomer structure (for example, APEC manufactured by Teijin Limited), a norbornene derivative, a vinyl monomer, or the like is copolymerized alone or copolymerized. Cycloolefin resins such as resins obtained by ring-opening metathesis polymerization of fats and norbornene derivatives, or hydrogenated products thereof (for example, APEL manufactured by Mitsui Chemicals, ZEONOR, ZEONEX manufactured by Nippon Zeon, ARTON manufactured by JSR, etc.), ethylene and Olefin-maleimide resins such as maleimide copolymers (eg, TI-PAS manufactured by Tosoh Corporation), bisphenols such as bisphenol A and bis (4- (2-hydroxyethoxy) phenyl) fluorene, and diols such as diethylene glycol Polyester resins such as polyester obtained by polycondensation of phthalic acids and aliphatic dicarboxylic acids such as terephthalic acid and isophthalic acid (eg O-PET manufactured by Kanebo Co., Ltd.), polyethersulfone resins, polyarylate resins, polyvinyl acetal resins, Polyethylene resin Polypropylene resins, polystyrene resins, polyamide resins, silicone resins, other like fluorine resin, not natural rubber, but the rubber-like resin is exemplified such EPDM is not limited thereto.

  As a thermoplastic resin, you may have the carbon-carbon double bond or / and SiH group which have a reactivity with SiH group in a molecule | numerator. In the point that the obtained cured product tends to be tougher, the molecule has one or more carbon-carbon double bonds or / and SiH groups having reactivity with SiH groups in the molecule on average. It is preferable.

  The thermoplastic resin may have other crosslinkable groups. Examples of the crosslinkable group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. From the viewpoint that the heat resistance of the obtained cured product tends to be high, it is preferable to have one or more crosslinkable groups in one molecule on average.

  The molecular weight of the thermoplastic resin is not particularly limited, but the number average molecular weight is preferably 10,000 or less in that the compatibility with the component (A) or the component (B) tends to be good. The following is more preferable. On the contrary, the number average molecular weight is preferably 10,000 or more, and more preferably 100,000 or more in that the obtained cured product tends to be tough. The molecular weight distribution is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, in that the viscosity of the mixture tends to be low and the moldability tends to be good. More preferably, it is as follows.

  The blending amount of the thermoplastic resin is not particularly limited, but a preferable lower limit of the amount used is 5% by weight of the entire curable composition, more preferably 10% by weight, and a preferable upper limit of the amount used is in the curable composition. Is 50% by weight, more preferably 30% by weight. When the addition amount is small, the obtained cured product tends to be brittle, and when it is large, the heat resistance (elastic modulus at high temperature) tends to be low.

  A single thermoplastic resin may be used, or a plurality of thermoplastic resins may be used in combination.

  The thermoplastic resin may be dissolved in the component (A) or / and the component (B) and mixed in a uniform state, pulverized and mixed in a particle state, or dissolved in a solvent and mixed. It may be in a dispersed state. In the point that the obtained hardened | cured material tends to become more transparent, it is preferable to melt | dissolve in (A) component or / and (B) component, and to mix as a uniform state. Also in this case, the thermoplastic resin may be directly dissolved in the component (A) or / and the component (B), or may be mixed uniformly using a solvent or the like, and then the solvent is removed and uniform dispersion is performed. It is good also as a state or / and a mixed state.

  When the thermoplastic resin is dispersed and used, the average particle diameter can be variously set, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 10 μm. There may be a distribution of the particle system, which may be monodispersed or have a plurality of peak particle diameters, but from the viewpoint that the viscosity of the curable composition is low and the moldability tends to be good. The coefficient of variation is preferably 10% or less.

(Filler)
A filler may be added to the composition of the present invention.

  Various fillers are used. For example, silica-based fillers such as quartz, fume silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine powder amorphous silica, silicon nitride, silver powder, etc. Inorganic fillers such as alumina, aluminum hydroxide, titanium oxide, glass fiber, carbon fiber, mica, carbon black, graphite, diatomaceous earth, clay, clay, talc, calcium carbonate, magnesium carbonate, barium sulfate, inorganic balloon As a filler for a conventional sealing material such as an epoxy-based filler, generally used and / or proposed fillers can be mentioned.

  The filler may be appropriately surface treated. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a coupling agent, and the like.

  Examples of the coupling agent in this case include a silane coupling agent. The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling. From the viewpoints of adhesiveness and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacrylic or acrylic groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Alkoxysilanes which can be exemplified.

  In addition, there is a method of adding a filler. For example, a hydrolyzable silane monomer or oligomer such as alkoxysilane, acyloxysilane, or halogenated silane, or an alkoxide, acyloxide, or halide of a metal such as titanium or aluminum is added to the composition of the present invention. There can also be mentioned a method in which a filler is produced in the composition by reacting in a partial reactant in the composition or in the composition.

  Among the fillers as described above, a silica-based filler is preferable from the viewpoint that the curing reaction is hardly inhibited and the effect of reducing the linear expansion coefficient is large.

  The average particle diameter of the filler is preferably 10 μm or less and more preferably 5 μm or less in terms of easy penetration into a narrow gap of the sealing material.

  The shape of the filler is preferably a spherical filler from the viewpoint of easily reducing the viscosity of the sealing material.

  A filler may be used independently and may be used together 2 or more types.

  The addition amount of the filler is not particularly limited, but from the viewpoint that the effect of reducing the linear expansion coefficient is high and the fluidity of the composition is good, the preferred lower limit of the addition amount is 30% by weight in the total composition, More preferably, it is 50% by weight, and the upper limit of the preferable addition amount is 80% by weight in the total composition, more preferably 70% by weight.

(Antioxidant)
An antioxidant may be added to the composition of the present invention. The antioxidant is not particularly limited. For example, triethylene glycol bis (3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate), 1,6-hexanediol bis (3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate), 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3, 5-triazine, pentaerythrityltetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), 2,2-thiodiethylenebis (3- (3,5-di-tert-butyl) -4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphene) L) propionate, N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl Ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-tert-butyl-4-hydroxy) Ethyl benzylphosphonate) calcium / polyethylene wax (50 wt% / 50 wt% mixture), tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,4-bis (octylthiomethyl) -o -Cresol, isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propio Hindered phenols such as over preparative, 2,5,7,8-tetramethyl-2- (4,8,12-trimethyltridecyl) include chroman-6-ol and the like.
The addition amount of the antioxidant can be variously set, but the lower limit of the preferable addition amount with respect to 100 parts by weight of [(A) component + (B) component] is 0.01 part by weight, more preferably 0.1 part by weight. The upper limit of the preferable addition amount is 10 parts by weight, more preferably 5 parts by weight. If the amount added is less than 0.01 parts by weight, the antioxidant effect at high temperature may not be sufficiently obtained. If the amount added is more than 5 parts by weight, it may adversely affect bleeding from the cured product. .

  Moreover, these antioxidants may be used alone or in combination of two or more.

(UV absorber)
You may add the ultraviolet absorber generally used to the composition of this invention. An ultraviolet absorber may be used independently and may be used together 2 or more types.

(Other additives)
The composition of the present invention includes, in addition to those used or / and proposed as a filler for conventional sealing materials such as epoxy, colorants, mold release agents, flame retardants, flame retardant aids, Surfactant, antifoaming agent, emulsifier, leveling agent, anti-repellent agent, ion trap agent, thixotropic agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plastic Agent, reactive diluent, anti-aging agent, heat stabilizer, radical inhibitor, conductivity-imparting agent, antistatic agent, radiation blocking agent, nucleating agent, phosphorus peroxide decomposing agent, lubricant, pigment, heat conduction A property-imparting agent, a physical property modifier and the like can be added within a range that does not impair the object and effect of the present invention.

(solvent)
The composition of the present invention can be used by dissolving in a solvent. Solvents that can be used are not particularly limited, and specific examples include hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether, and the like. An ether solvent, a ketone solvent such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and a halogen solvent such as chloroform, methylene chloride, and 1,2-dichloroethane can be preferably used.

  As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable.

  Although the amount of solvent to be used can be set as appropriate, the lower limit of the preferred amount of use with respect to 1 g of the curable composition to be used is 0.1 mL, and the upper limit of the preferred amount of use is 10 mL. If the amount used is small, it is difficult to obtain the effect of using a solvent such as a low viscosity, and if the amount used is large, the solvent tends to remain in the material, causing problems such as thermal cracks, and also from a cost standpoint. It is disadvantageous and the industrial utility value decreases.

  These solvents may be used alone or as a mixed solvent of two or more.

(Curing)
In the present invention, a cured product is prepared by curing the cured composition and may be used for various applications. In particular, after the curable composition is applied to the metal surface, the metal surface is corroded by curing. Can be prevented.

  As a curing method, the reaction can be performed by simply mixing, or the reaction can be performed by heating. A method of heating and reacting is preferable from the viewpoint that the reaction is fast and generally a material having high heat resistance is easily obtained.

  Although the curing temperature can be variously set, the lower limit of the preferable temperature is 30 ° C., more preferably 100 ° C., and the upper limit of the preferable temperature is 300 ° C., more preferably 200 ° C. If the reaction temperature is low, the reaction time for sufficient reaction will be long, and if the reaction temperature is high, molding will tend to be difficult.

  Curing may be performed at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. It is preferable to carry out the reaction while raising the temperature in a multistage manner or continuously, as compared with the case where the temperature is constant, in that a uniform cured product without distortion can be easily obtained.

  Although various curing times can be set, it is preferable to react at a relatively low temperature for a long time rather than reacting at a high temperature for a short time because a uniform cured product without distortion can be easily obtained.

  The pressure during the reaction can be variously set as required, and the reaction can be carried out at normal pressure, high pressure, or reduced pressure. It is preferable to cure in a reduced pressure state in that it is easy to remove volatile matter generated in some cases, and when it is used as a sealant or the like, the filling property to the details is good.

  In the manufacturing process in which the composition of the present invention is used, the weight loss during curing is not more than 5% by weight from the viewpoint that voids in the composition and process problems due to outgas from the composition hardly occur. Preferably, it is 3% by weight or less, more preferably 1% or less.

  The weight loss during curing is examined as follows. Using a thermogravimetric analyzer, 10 mg of the composition of the present invention is heated from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, and can be determined as the ratio of the initial weight of the reduced weight.

  Further, in terms of hardly causing the problem of silicone contamination, the content of Si atoms in the volatile component in this case is preferably 1% or less.

(Curing property)
From the viewpoint of good heat resistance, the cured product obtained by curing the composition of the present invention preferably has a Tg of 100 ° C or higher, more preferably 150 ° C or higher. On the other hand, from the viewpoint of low stress and high thermal stress resistance, the cured product obtained by curing the composition of the present invention preferably has a Tg of less than 100 ° C, and is 80 ° C or less. More preferred.

  In this case, Tg is examined as follows. Dynamic viscoelasticity measurement using a 3 mm x 5 mm x 30 mm prismatic test piece under the conditions of tensile mode, measurement frequency 10 Hz, strain 0.1%, static / power ratio 1.5, temperature rising side 5 ° C / min ( Let Tg be the peak temperature of tan δ of DVA-200 manufactured by IT Measurement & Control Co.).

  In addition, it is preferable that the extracted ion content from the cured product is less than 100 ppm in that the wiring contacted when used as an electronic material is less likely to cause problems such as ion migration and has high reliability. More preferably, it is less than 50 ppm, and still more preferably less than 10 ppm.

  In this case, the extracted ion content is examined as follows. 1 g of the cut cured product is put in a Teflon (registered trademark) container together with 50 ml of ultrapure water and sealed, and treated under conditions of 121 ° C., 2 atm and 20 hours. The obtained extract was analyzed by ICP mass spectrometry (using HP-4500 manufactured by Yokogawa Analytical Systems), and the obtained Na and K content values were converted to the concentration in the cured product used. Ask. On the other hand, the same extract was analyzed by ion chromatography (using Dionex DX-500, column: AS12-SC), and the resulting Cl and Br content values were converted to the concentration in the cured product used. Ask. The contents of the cured Na, K, Cl, and Br obtained as described above are totaled to obtain the extracted ion content.

  The method for preventing corrosion of the curable composition, the cured product and the metal surface of the present invention can be used for the purpose of protecting the metal electrode part and the conductive wire in the electric / electronic device from corrosive substances. It can also be used as a corrosion-resistant paint and a corrosion-resistant adhesive in the fields of automobiles and transportation equipment and construction, and the range of use is not limited.

  Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.

The SiH group content in Synthesis Example 1 was measured as follows.
(NMR)
A 300 MHz NMR apparatus manufactured by Varian Technologies Japan Limited was used. (B) The reaction tracking in component synthesis was measured by adding a reaction solution diluted to about 1% with deuterated chloroform to an NMR tube, and measuring the peak of the methylene group derived from the unreacted allyl group and the reaction allyl group. From the peak of the methylene group. Moreover, the functional group value of (B) component calculated | required SiH group value (mmol / g) in conversion of dibromoethane.

(Synthesis Example 1)
A stirrer, a dropping funnel, and a condenser tube were set in a 5 L four-necked flask. Into this flask, 1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, heated and stirred in an oil bath at 120 ° C. A mixed solution of 200 g of triallyl isocyanurate, 200 g of toluene and 1.44 ml of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 50 minutes. The resulting solution was heated and stirred as it was for 6 hours, and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. ^{By 1} H-NMR, it was found that the reaction product was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with triallyl isocyanurate (referred to as reactant A). ). Further, when the content of SiH groups was determined by ¹ H-NMR using 1,2-dibromoethane as an internal standard, it was found to contain 8.08 mmol / g SiH groups. Although the product is a mixture, it contains as a main component the following component (B) of the present invention. Moreover, the platinum vinylsiloxane complex which is (C) component of this invention is contained.

（実施例１〜４、比較例１）
（Ａ）成分としてトリアリルイソシアヌレートを用い、（Ｂ）成分として合成例１で合成した反応物Ａを用い、（Ｃ）成分として白金ビニルシロキサン錯体を用い、（Ｄ）成分として表１記載の成分を用いて硬化性組成物を作製した。

(Examples 1-4, Comparative Example 1)
The triallyl isocyanurate is used as the component (A), the reactant A synthesized in Synthesis Example 1 is used as the component (B), the platinum vinylsiloxane complex is used as the component (C), and the components shown in Table 1 are used as the component (D). A curable composition was prepared using the components.

(transparency)
The produced curable composition is heated stepwise at 60 ° C./6 hours, 70 ° C./1 hour, 80 ° C./1 hour, 120 ° C./1 hour, 150 ° C./1 hour to produce a cured product. Then, the transparency on the appearance of the obtained cured product was visually evaluated.

(Metal corrosion prevention)
The corrosion resistance of metals was evaluated by the following two methods. The degree of corrosion was evaluated visually. The case where the degree of corrosion was very severe was rated as XX, the case where corrosion was severe, X, where the degree of corrosion was small, and the case where corrosion did not progress at all.

(Na hypochlorite treatment)
The surface of the silver-plated metal plate was immersed in an aqueous solution of sodium hypochlorite having an effective chlorine concentration of 0.01% for 10 seconds, immediately removed, washed with pure water, and the surface water was gently wiped off, followed by room temperature. It was made to dry and it was set as the silver plating metal plate by which the surface was oxidized. The cured composition shown in Table 1 was thinly applied to this metal plate and cured by heating at 150 ° C./30 minutes to produce a silver-plated metal plate whose surface was coated with a cured product. A metal plate whose surface is coated with a cured product is measured with a sample fixing type metering weather meter tester (manufactured by Suga Test Instruments, model: M6T, light source: metal halide lamp), sample surface irradiance is 1.55 kW / m ² , integrated radiation A corrosion acceleration test was performed in an environment with an illuminance of 150 MJ / m ² and a sample surface temperature of 100 ° C., and whether the corrosion of the surface of the silver-plated metal plate was further progressed was visually evaluated.
(SO ₂ treatment)
The cured composition shown in Table 1 was thinly applied to a metal plate whose surface was silver-plated, and was heated and cured at 150 ° C./30 minutes to obtain a silver-plated metal plate whose surface was coated with a cured product. A metal plate whose surface is coated with a cured product is exposed to an SO ₂ atmosphere of about 5% concentration for 1 hour, and then a sample-fixed metaling weather meter tester (manufactured by Suga Test Instruments, model: M6T, light source: metal halide lamp) In order to check whether the surface of the silver-plated metal plate is corroded by conducting a corrosion acceleration test in an environment with a sample surface irradiance of 1.55 kW / m ² , an integrated irradiance of 150 MJ / m ² , and a sample surface temperature of 100 ° C. Visual evaluation was performed.

  According to the curable composition of the present invention, since it has heat resistance and light resistance, corrosion of the metal surface can be prevented even in extremely severe environments, and long-term use of electric / electronic devices becomes possible. Further, it can be applied to various uses such as a member requiring transparency and insulation, and the use range is not limited.

Claims (11)

(A) an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule;
(B) a silicon compound containing at least two SiH groups in one molecule;
(C) a hydrosilylation catalyst, and
(D) at least one selected from the group consisting of an anion exchanger, an amine compound and an adsorbent;
A curable composition containing   The curable composition according to claim 1, wherein the anion exchanger is a hydrotalcite-like compound and / or a fired product of a hydrotalcite-like compound.   The curable composition according to claim 1 or 2, wherein the amine compound is a benzotriazole derivative and / or an aminoalkoxysilane.   The curable composition according to any one of claims 1 to 3, wherein the adsorbent is zeolite.   The curable composition according to any one of claims 1 to 4, wherein the component (A) is a compound composed of an element selected from the group consisting of C, H, N, O, S, and halogen. The component (A) is represented by the following general formula (I)

(Wherein R ¹ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ¹ may be different or the same). The curable composition as described in any one of -5. The component (B) is
(Α) an organic compound containing at least one carbon-carbon double bond having reactivity with a SiH group in one molecule;
(Β) a linear and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule;
The curable composition according to any one of claims 1 to 6, which is a compound obtainable by hydrosilylation reaction.   The curable composition according to claim 7, wherein the component (α) is an aliphatic compound. The component (β) is represented by the following general formula (II)

(Wherein R ² represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10). Cyclic polyorganosiloxane having at least 3 SiH groups in one molecule. The curable composition according to claim 7 or 8, wherein   Hardened | cured material obtained by hardening the curable composition as described in any one of Claims 1-9. The processing method which prevents the corrosion of the metal surface characterized by making it harden, after apply | coating the curable composition as described in any one of Claims 1-9 to a metal surface.