JP2008260894A - Curing agent and adhesive curing composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curing agent having good workability and high adhesiveness for a long period of time and able to produce a cured product having strengths, heat resistance, light resistance and optical transparency, a curable composition using the curing agent and a cured product produced by curing the composition. <P>SOLUTION: The curing agent is a reaction product of (α1) a silicon compound having 3 SiH groups in one molecule with (α2) an organic compound having one carbon-carbon double bond having reactivity with the SiH group in one molecule and a heterocyclic skeleton containing at least one polar group, and has ≤1,000 Pa s viscosity at 23°C and 2 SiH groups in one molecule. The curing composition containing the curing agent and the cured product of the same are provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a curing agent having excellent workability and a cured product having high adhesiveness, a curable composition using the same, and a cured product obtained by curing the curable composition. Specifically, the present invention relates to a curing agent and a curable composition that can provide a cured product having adhesiveness, strength, weather resistance, and optical transparency.

  In recent years, in order to reduce the load on the environment by extending the product life, long-term reliability of members has been required. In particular, in sealing electrical and electronic parts and in-vehicle parts, there is an increasing demand for reliability with respect to the external environment such as light and heat.

  As a composition resistant to environmental degradation, a curable composition composed of a compound containing a carbon-carbon double bond, a compound containing a SiH group, and a hydrosilylation catalyst has been proposed. For example, as disclosed in Patent Document 1, a curable composition that improves the adhesive force by adding an isocyanuric acid ester having an epoxy group to a silicone resin is mentioned. Sex is not enough. Moreover, there was no description regarding hardness and transparency. Moreover, although patent document 2 has mentioned the curable composition which has optical transparency and toughness, there was no description regarding long-term adhesiveness with a base material.

One method for improving the adhesion of the cured product is to introduce a polar group into the cured product. However, in general, when a compound having a polar group is introduced, the viscosity becomes high or becomes a solid, so that there are problems such as insufficient handling and workability. Further, unless a compound having a polar group to be introduced was selected, sufficient adhesive strength could not be obtained, or a transparent cured product could not be obtained.
JP 2006-137797 A JP 2004-292779 A

  The present invention relates to a curing agent having good workability and capable of giving a cured product having high adhesiveness, a curable composition using the curing agent, and a cured product obtained by curing the same. , A curing agent that can realize good adhesion over a long period of time, has excellent adhesion, and can give a cured product having strength, heat resistance, light resistance, and optical transparency, and a curable composition using the same Is to provide.

  As a result of intensive studies, the present inventors have used a reaction product of a specific SiH group-containing silicon compound and an organic compound containing a carbon-carbon double bond reactive with a specific SiH group as a curing agent. The present inventors have found that the above problems can be solved, and have reached the present invention.

That is, the present invention relates to a curing agent having at least two SiH groups in one molecule, which is a reaction product of the following components and has a viscosity at 23 ° C. of 1000 Pa · s or less:
(Α1) a silicon compound having at least three SiH groups in one molecule (hereinafter sometimes referred to as “(α1) component”), and (α2) a carbon-carbon double having reactivity with SiH groups. An organic compound having a heterocyclic skeleton containing one bond in one molecule and containing at least one polar group (hereinafter sometimes referred to as “(α2) component”).

  The heterocyclic skeleton of the component (α2) is preferably isocyanurate, and at least one of the polar groups of the component (α2) is preferably an epoxy group.

  The component (α1) is preferably a cyclic polyorganosiloxane.

  The mixing ratio of the (α1) component and the (α2) component is (the number of moles of SiH groups contained in α1) / (number of moles of carbon-carbon double bond groups having reactivity with SiH groups contained in α2). It is preferably 3 or more.

  The component (α2) is preferably monoallyl diglycidyl isocyanurate.

  The component (α1) is preferably 1,3,5,7-tetramethyltetracyclosiloxane.

  The adhesive curable composition of the present invention comprises (A) the curing agent, (B) an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups, and (C ) A hydrosilylation catalyst is an essential component.

  The adhesive curable composition may further contain (D) a silicon compound having at least two SiH groups in one molecule and (E) an adhesion promoter.

  The 3 mm-thick cured product of the adhesive curable composition preferably has a transmittance of 60% or more at a wavelength of 400 nm.

  The cured product of the adhesive curable composition has a transmittance of 45% or more at 400 nm of a cured product having a thickness of 3 mm after irradiation with 50 MJ per square meter by a metal halide lamp, and the adhesive strength of the cured product is It is preferable that it is 70% or more compared with the adhesive force of the hardened | cured material before irradiation.

  Moreover, the hardened | cured material of this invention hardens the said curable composition.

  The adhesive curable composition of the present invention can be applied to a coating material or an optical material.

The curing agent of the present invention has good workability and the cured product has high adhesiveness. Therefore, the curable composition using the curing agent of the present invention and the cured product obtained by curing the composition have good adhesiveness after the environmental test and are excellent in strength, weather resistance, optical properties, and the like. Excellent transparency.

Hereinafter, preferred modes for carrying out the present invention will be described.

(Curing agent)
The curing agent of the present invention will be described.

  The curing agent of the present invention contains (α1) a silicon compound having at least three SiH groups in one molecule and (α2) one carbon-carbon double bond having reactivity with SiH groups in one molecule. And a reaction product with an organic compound having a heterocyclic skeleton containing at least one polar group, having a viscosity at 23 ° C. of 1000 Pa · s or less and having at least two SiH groups in one molecule. If so, it can be used without any particular limitation.

  First, the (α1) component will be described.

  The (α1) silicon compound having at least 3 SiH groups in one molecule that can be used in the present invention is not particularly limited, and is, for example, a compound described in International Publication No. 96/15194 pamphlet. Those having at least 3 SiH groups can be used.

  Among these, from the viewpoint of availability, a linear and / or cyclic and / or network polyorganosiloxane having at least three SiH groups in one molecule is preferable. From the viewpoint of adhesive strength, a cyclic polyorganosiloxane having at least three SiH groups in one molecule is preferable.

  Specific examples of the chain organopolysiloxane include the following general formula (I):

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２は、同一又は異なって、水素あるいは炭素数１〜５０の一価の有機基を表すが、少なくとも３個は水素である。ｐ、ｑ、ｒはそれぞれ１〜３００の数を表す。）で表される化合物が挙げられる。なお、ここでいう有機基は、特に限定されないが、エーテル結合、エステル結合、アセタール結合、イミド結合、アミド結合、ハロゲン化合物を有していてもよい炭化水素系の官能基であることが好ましい。以下に挙げられる「有機基」についても同様である。

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² are the same or different and are hydrogen or carbon number. 1 to 50 monovalent organic groups, at least three being hydrogen, p, q, and r each represent a number of 1 to 300). The organic group herein is not particularly limited, but is preferably a hydrocarbon-based functional group that may have an ether bond, an ester bond, an acetal bond, an imide bond, an amide bond, or a halogen compound. The same applies to the “organic groups” listed below.

As R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , the resulting cured product can have higher heat resistance. From the viewpoint, it is preferably a monovalent organic group having 1 to 20 carbon atoms, more preferably a monovalent organic group having 1 to 15 carbon atoms, and a monovalent organic group having 1 to 10 carbon atoms. More preferably, it is a group. Examples of these preferred R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² are methyl, ethyl, propyl Group, butyl group, phenyl group, benzyl group, phenethyl group, methoxy group, ethoxy group, vinyl group, allyl group, glycidyl group and the like.

  Examples of the cyclic polyorganosiloxane include the following general formula (II):

（式中、Ｒ^１３、Ｒ^１４は水素あるいは炭素数１〜６の有機基を表し、ｎは２〜１０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等が挙げられる。なお、上記一般式（ＩＩ）におけるＲ^１３、Ｒ^１４は、Ｃ、Ｈ、Ｏから構成される炭素数１〜６の有機基であることが好ましく、炭素数１〜６の炭化水素基であることがより好ましく、炭素数１〜６のアルキル基であることがさらに好ましい。また、ｎは３〜１０の数であることが好ましい。

(Wherein R ¹³ and R ¹⁴ represent hydrogen or an organic group having 1 to 6 carbon atoms, and n represents a number of 2 to 10), and at least three SiH groups are represented in one molecule. Examples thereof include cyclic polyorganosiloxane. In addition, it is preferable that R <^13> , R < ¹⁴ > in the said general formula (II) is a C1-C6 organic group comprised from C, H, and O, and is a C1-C6 hydrocarbon group. It is more preferable that the alkyl group has 1 to 6 carbon atoms. N is preferably a number of 3 to 10.

  Preferable specific examples of the cyclic polyorganosiloxane represented by the general formula (II) include 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5 , 7,9-pentamethylcyclopentasiloxane and the like.

  Regarding the silicon compound having at least three SiH groups in one molecule used for obtaining the curing agent, the number average molecular weight is not particularly limited and any one can be suitably used, but the viewpoint that the fluidity is more easily expressed. Are preferably those having a low molecular weight. In this case, the lower limit of the preferred number average molecular weight is 50, and the upper limit of the preferred number average molecular weight is 100,000, more preferably 1,000, and still more preferably 700. In this specification, the number average molecular weight indicates the number average molecular weight in terms of styrene by GPC.

  Moreover, about the silicon compound which has at least 3 SiH group in 1 molecule used in order to obtain the said hardening | curing agent, it is possible to use individually or in mixture of 2 or more types.

  Next, the (α2) component will be described.

  (Α2) An organic compound having a heterocyclic skeleton containing one carbon-carbon double bond having reactivity with SiH group in one molecule and containing at least one polar group is a heterocyclic ring. And an organic skeleton portion, a group having a carbon-carbon double bond reactive with the SiH group covalently bonded to the organic skeleton portion, and at least one polar group. When expressed in this way, the group or polar group having a carbon-carbon double bond having reactivity with the SiH group may be covalently bonded to any part of the organic skeleton. At this time, the group having a carbon-carbon double bond having reactivity with the SiH group is not particularly limited as long as it has reactivity with the SiH group. In addition, the polar group is not particularly limited as long as it is a functional group in which a bias of charge occurs due to bonding of a group of atoms having different electronegativity such as a hetero atom or a halogen atom to a hydrocarbon group. Excluding those with

  Examples of the group having a carbon-carbon double bond having reactivity with the SiH group include the following general formula (III):

（式中Ｒ^１５は水素原子又はメチル基を表す。）で示されるアルケニル基が反応性の点から好適である。

An alkenyl group represented by the formula (wherein R ¹⁵ represents a hydrogen atom or a methyl group) is preferred from the viewpoint of reactivity.

  From the availability of raw materials,

が特に好ましい。

Is particularly preferred.

  (A) As an alkenyl group which the organic compound of a component contains, following general formula (IV)

（式中Ｒ^１６、Ｒ^１７は、同一又は異なって、水素原子又はメチル基を表す。）で示されるアルケニル基が、硬化物の耐熱性が高いという点から好適である。

(In the formula, R ¹⁶ and R ¹⁷ are the same or different and each represents a hydrogen atom or a methyl group.) An alkenyl group represented by the formula is preferred from the viewpoint that the heat resistance of the cured product is high.

  In addition, from the availability of raw materials,

が特に好ましい。

Is particularly preferred.

  The alkenyl group may be covalently bonded to the organic skeleton through 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. Examples of such substituents include

等が挙げられる。

Etc.

  Two or more of these substituents may be connected by a covalent bond to form one divalent or higher substituent.

  Examples of the group having a carbon-carbon double bond reactive with the SiH group covalently bonded to the organic skeleton as described above include a vinyl group, an allyl group, a methallyl group, an acrylic group, a methacryl 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, 3- (Allyloxy) propyl group, 2,2-bis (allyloxymethyl) butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group,

等が挙げられる。
極性基とは、例えば、カルボニル基やニトロ基、スルホン基、環状エーテル基、ハロゲン基といった活性水素を持たない官能基は反応性の点から好適である。

Etc.
As the polar group, for example, a functional group having no active hydrogen such as a carbonyl group, a nitro group, a sulfone group, a cyclic ether group, or a halogen group is preferable from the viewpoint of reactivity.

  From the viewpoint that the adhesiveness of the obtained cured product with various materials can be good, it is preferably a monovalent organic group having 1 to 50 carbon atoms containing one or more epoxy groups,

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。これらの好ましい極性基の例としては、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 polar groups include glycidyl groups,

等が挙げられる。
次に、複素環を含む有機骨格部分について述べる。
有機骨格とは、主に炭素、水素、酸素、ニクトゲン原子、カルコゲン原子、ハロゲン原子から構成される骨格であり、上記元素からなるものであれば特に限定されない。例えば、飽和炭化水素系、ポリエーテル系、ポリエステル系、ポリアクリル酸エステル系、ポリカーボネート系、ポリアリレート系、ポリアミド系、ポリイミド系、フェノール−ホルムアルデヒド系（フェノール樹脂系）等の有機重合体骨格や、フェノール系、ビスフェノール系、ベンゼン、ナフタレン等の芳香族炭化水素系、脂肪族炭化水素系、脂肪族アルコール系、環状炭化水素系等及びこれらの２種以上からなる有機単量体骨格が挙げられる。
数平均分子量についても特に限定はないが、取扱い性の観点から、数平均分子量が１万以下のものが好ましい。

Etc.
Next, the organic skeleton part containing a heterocyclic ring will be described.
The organic skeleton is a skeleton mainly composed of carbon, hydrogen, oxygen, nictogen atoms, chalcogen atoms, and halogen atoms, and is not particularly limited as long as it is composed of the above elements. For example, organic polymer skeletons such as saturated hydrocarbons, polyethers, polyesters, polyacrylates, polycarbonates, polyarylates, polyamides, polyimides, phenol-formaldehydes (phenolic resins), Examples thereof include aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene, aliphatic hydrocarbons, aliphatic alcohols, cyclic hydrocarbons, and the like, and organic monomer skeletons composed of two or more of these.
The number average molecular weight is not particularly limited, but from the viewpoint of handleability, a number average molecular weight of 10,000 or less is preferable.

The heterocyclic ring is not particularly limited as long as it is a cyclic compound having a hetero element in the cyclic skeleton. However, those in which Si is contained in the atoms forming the ring are excluded. The number of atoms forming the ring is not particularly limited and may be 3 or more. From availability, it is preferable that it is 10 or less.
Specific examples of the heterocyclic ring include epoxy, oxetane, furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, imidazole, pyrazole, furazane, triazole, tetrazole, There are pyran series, thiine series, pyridine series, oxazine series, thiazine series, pyridazine series, pyrimidine series, pyrazine series and piperazine series. Among them, isocyanurate is preferable as the heterocyclic ring.
In addition, the above heterocyclic ring may be condensed with other carbocyclic rings or a plurality of heterocyclic rings.

An organic compound having a heterocyclic skeleton containing one carbon-carbon double bond reactive with the SiH group in one molecule and containing at least one polar group has other reactive groups. You may do it. 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 these reactive groups are included, the strength of the resulting cured product tends to increase. 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 of the component (α2) include allyl glycidyl ether, vinyl dioxolane, 4-vinyl-1-cyclohexene-1,2-epoxide, 4-vinyl-1,3-dioxolane, N-vinyl caprolactam, and N-vinyl phthalamide. 1-vinylpyrrolidone, monoallyl diglycidyl isocyanurate, and the like.

  As an organic compound (α2) component having a heterocyclic skeleton containing one carbon-carbon double bond reactive with the SiH group as described above in one molecule and containing at least one polar group May use a single thing, and may use combining several things.

(Preliminary reaction)
The reaction for obtaining the curing agent will be described.

  A silicon compound (α1) having at least three SiH groups in one molecule, one carbon-carbon double bond reactive with the SiH group in one molecule, and at least one polar group SiH group-containing silicon compound (α1), a carbon-carbon double bond reactive with SiH group, and at least one polarity when hydrosilylation reaction is performed with the organic compound (α2) having a heterocyclic skeleton. The mixing ratio of the heterocyclic organic compound (α2) component having a group is such that two or more SiH groups remain in one molecule, and the viscosity measured with an E-type viscometer at 23 ° C. is 1000 Pa · s or less. If it is a range, it will not specifically limit.

  Considering the strength of the cured product obtained by using the curing agent of the present invention, it is preferable that the curing agent component has a larger amount of SiH groups. Therefore, one molecule of carbon-carbon double bond having reactivity with SiH groups to be mixed is present. The number of moles of carbon-carbon double bonds having reactivity with SiH groups in the organic compound (α2) component having a heterocyclic skeleton containing one and having at least one polar group (Y ) And the number of moles (X) of SiH groups in the silicon compound (α1) having SiH groups to be mixed is preferably X / Y ≧ 2, more preferably X / Y ≧ 3. preferable.

  Considering the handleability of the curing agent of the present invention, it is necessary that the viscosity of the curing agent at 23 ° C. is 1000 Pa · s or less. At this time, an organic compound (α2) component having a heterocyclic skeleton containing one carbon-carbon double bond reactive with the SiH group to be mixed in one molecule and containing at least one polar group The ratio between the number of moles (Y) of carbon-carbon double bonds having reactivity with SiH groups in the silicon compound and the number of moles (X) of SiH groups in the silicon compound (α1) having SiH groups to be mixed is X / Y ≧ 3 is preferable, and X / Y ≧ 4 is more preferable. From the economical viewpoint, X / Y ≦ 100 is preferable, and X / Y ≦ 30 is more preferable.

  In the case of hydrosilylation, an appropriate catalyst may be used. As the catalyst, for example, the component (C) described later can be used.

The addition amount of the catalyst is not particularly limited, but the lower limit of the preferred addition amount is sufficient to have sufficient curability and keep the cost of the curable composition relatively low. The SiH group of the silicon compound (α1) having a SiH group The upper limit of the preferable addition amount is 10 ⁻¹ mol relative to 1 mol of SiH groups in the silicon compound (α1) having SiH groups, more preferably 10 ⁻⁸ mols, more preferably 10 ⁻⁶ mols per mol. Is 10 ⁻² mol.

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 malate, 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 as a catalyst mixing method at the time of reaction, and it contains one carbon-carbon double bond reactive with SiH group in one molecule, and at least one polar group. A method of mixing the organic compound (α2) having a heterocyclic skeleton and a catalyst mixed with the silicon compound (α1) having a SiH group is preferable. Organic having a heterocyclic skeleton containing a silicon compound (α1) having a SiH group and one carbon-carbon double bond reactive with the SiH group in one molecule and containing at least one polar group In the method of mixing the catalyst with the mixture with the compound (α2), it tends to be difficult to control the reaction. Further, a mixture of a silicon compound having an SiH group (α1) and a catalyst contains one carbon-carbon double bond reactive with the SiH group in one molecule, and at least one polar group In the method of mixing the organic compound (α2) having a heterocyclic skeleton containing, there is a possibility that the silicon compound (α1) having a SiH group in the presence of the catalyst is reactive with moisture mixed therein and may be altered.

  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, 1,4-dioxane, and chloroform are preferable. The amount of solvent to be used can also be set as appropriate. An organic compound (α2) having a heterocyclic skeleton containing one carbon-carbon double bond reactive with a SiH group in one molecule and containing at least one polar group is monoallyl diglycidyl isocyanate. In the case of nurate, a cyclic ether solvent such as tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane is preferable from the viewpoint of solubility.

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

  After the hydrosilylation reaction, a silicon compound (α1) having a solvent and / or an unreacted SiH group and / or one carbon-carbon double bond reactive with the SiH group is contained in one molecule, and at least The organic compound (α2) having a heterocyclic skeleton containing one polar group can also be removed. By removing these volatile components, the resulting curing agent does not have volatile components, so that problems of voids and cracks due to volatilization of volatile components are unlikely to occur during curing. 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 120 ° C, more preferably 60 ° C. When treated at high temperatures, it tends to be accompanied by alterations such as thickening.

  The viscosity of the curing agent of the present invention is not particularly limited as long as the viscosity measured with an E-type viscometer at 23 ° C. is 1000 Pa · s or less. When the viscosity exceeds 1000 Pa · s, it becomes difficult to measure at the time of blending, or the viscosity is different from other materials at the time of mixing, and it becomes difficult to mix.

  As an example of the curing agent as described above, a reaction product of monoallyl diglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane is more preferable. At this time, in order to obtain a viscosity of 1000 Pa · s or less, the molar ratio of monoallyl diglycidyl isocyanurate (X) to 1,3,5,7-tetramethylcyclotetrasiloxane (Y) is Y / X ≧ 0. .75 reactant is preferred.

  The curing agent of the present invention may be used alone or in combination of two or more.

  Since the curing agent of the present invention has at least two SiH groups in one molecule, the curing agent is intended for curing by a hydrosilylation reaction with a compound having a carbon-carbon double bond that is reactive with SiH groups. It is suitable as. The preferred use form of the curing agent of the present invention, that is, the adhesive curable composition of the present invention is a carbon-carbon double bond having reactivity with the above-described curing agents (A) and (B) SiH groups of the present invention. Is contained as an essential component and an organic compound containing at least two per molecule in the molecule and (C) a hydrosilylation catalyst.

  Each component contained in the adhesive curable composition of the present invention will be described below.

((B) component)
Next, (B) component at the time of producing a curable composition in this invention is demonstrated.

  The component (B) 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 (B) containing at least two carbon-carbon double bonds having reactivity with the SiH group is reactive with the organic skeleton part and the SiH group covalently bonded to the organic skeleton part. And a group having a carbon-carbon double bond. When expressed in this way, the group having a carbon-carbon double bond that is reactive with the SiH group may be covalently bonded to any part of the organic skeleton.

  The group having a carbon-carbon double bond reactive with the SiH group contained in the organic compound (B) is not particularly limited as long as it has reactivity with the SiH group. Of these, a group having a carbon-carbon double bond having reactivity with the SiH group of the component (α2) described in the curing agent (A) component is also preferable.

  Next, the organic skeleton part of the component (B) will be described. The organic skeleton of the component (B) is not particularly limited as long as it is a skeleton mainly composed of carbon, hydrogen, oxygen, nictogen atoms, chalcogen atoms, and halogen atoms. Especially, the organic frame | skeleton part demonstrated by the ((alpha) 2) component demonstrated by the said hardening | curing agent (A) component is preferable.

  Specific examples of the organic compound (B) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2-tetra Allyloxyethane, diarylidenepentaerythritol, triallyl cyanurate, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzenes (having a purity of 50 to 100%, preferably Has a purity of 80 to 100%), divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof, 1,2-polybutadiene (1,2 ratio 10 to 100%) Things Preferably 1, 2 Ratio 50-100% of those), allyl ether of novolak phenol, allylated polyphenylene oxide,

が挙げられる。
（Ｂ）成分の有機化合物としては、耐熱性の観点からは、イソシアヌレート骨格を有する有機化合物（イソシアヌレート化合物）が好ましい。イソシアヌレートとは、下記一般式（Ｖ）

Is mentioned.
The organic compound (B) is preferably an organic compound having an isocyanurate skeleton (isocyanurate compound) from the viewpoint of heat resistance. Isocyanurate is the following general formula (V)

（式中Ｒ^１８、Ｒ^１９、Ｒ^２０は、同一又は異なって、炭素数１〜５０の一価の有機基を表すが、少なくとも二つはＳｉＨ基と反応性を有する炭素−炭素二重結合を有する基である。）で表される。

(In the formula, R ¹⁸ , R ¹⁹ and R ²⁰ are the same or different and each represent a monovalent organic group having 1 to 50 carbon atoms, at least two of which are reactive with a SiH group.) It is a group having

From the viewpoint that the heat resistance of the resulting cured product can be higher, it is preferably a monovalent organic group having 1 to 20 carbon atoms as R ¹⁸ , R ¹⁹ , and R ^{20 in the} general formula (V). The monovalent organic group having 1 to 10 carbon atoms is more preferable, and the monovalent organic group having 1 to 4 carbon atoms is further preferable. Examples of these preferable R ¹⁸ , R ¹⁹ and R ²⁰ include one methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group and epoxy group. C1-C50 monovalent organic group (other than glycidyl group) containing above,

等が挙げられる。

Etc.

From the viewpoint of improving the reactivity, at least one of these as R ¹⁸ , R ¹⁹ and R ^{20 in the} general formula (V) is

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（ＶＩ）

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

（式中Ｒ^２１は水素原子又はメチル基を表す。）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、Ｒ^１８、Ｒ^１９、Ｒ^２０のうち少なくとも２つが下記一般式（ＶＩＩ）

(Wherein R ²¹ represents a hydrogen atom or a methyl group) is more preferably a monovalent organic group having 1 to 50 carbon atoms and containing at least one group represented by R ¹⁸ , R ¹⁹ , R ^At least two of ²⁰ are represented by the following general formula (VII)

（式中Ｒ^２２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^２３は水素原子又はメチル基を表す。）で表される１価の有機基（複数のＲ^２２及びＲ^２３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 ²² represents a direct bond or a divalent organic group having 1 to 48 carbon atoms, and R ²³ represents a hydrogen atom or a methyl group) (a plurality of R ²² and More preferably, R ²³ may be different or the same.

From the viewpoint that the adhesiveness of the obtained cured product with various materials can be improved, as R ¹⁸ , R ¹⁹ and R ^{20 in the} general formula (V), at least one of them has one or more epoxy groups. It is preferable that it is a C1-C50 monovalent organic group to contain.

  Preferable specific examples of the organic compound represented by the general formula (V) are triallyl isocyanurate, diallyl monoglycidyl isocyanurate and derivatives thereof. Among them, diallyl monoglycidyl isocyanurate is preferable as the component (B) for improving the adhesiveness of the cured product.

  A mixture of triallyl isocyanurate and diallyl monoglycidyl isocyanurate is preferred in order to achieve both improved adhesion and light resistance of the cured product. Since the mixture has an isocyanuric ring skeleton, it is also effective from the viewpoint of heat resistance. The mixing ratio can be arbitrarily set, but in order to achieve the above object, triallyl isocyanurate / allyl monoglycidyl isocyanurate (molar ratio) is preferably 99/1 to 1/99, more preferably 95/5 to 5/95. 90/10 to 10/90 is particularly preferable.

  In addition, as the organic compound of component (B), a compound in which a group containing a carbon-carbon double bond having reactivity with the SiH group is covalently bonded to the organic polymer skeleton is also preferable.

  Examples of the organic polymer skeleton include polyether polymers such as polyoxyethylene, polyoxypropylene, polyoxytetramethylene, and polyoxyethylene-polyoxypropylene copolymer. More specific examples:

（式中、Ｒ^２４、Ｒ^２５は炭素数１〜２００の二価の有機基、ｐ、ｑ、ｒはそれぞれ１〜３００の数を表す。）等が挙げられる。

(Wherein R ²⁴ and R ²⁵ are divalent organic groups having 1 to 200 carbon atoms, and p, q, and r each represent a number of 1 to 300).

R ²⁴ and R ²⁵ are preferably a divalent hydrocarbon group having 1 to 200 carbon atoms, more preferably an alkylene group having 1 to 200 carbon atoms.

  Examples of other polymers used as the organic polymer skeleton include dibasic acids such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydrophthalic acid, and ethylene glycol, diethylene glycol, propylene glycol, tetramethylene glycol, Polyester polymers obtained by condensation with glycols such as neopentyl glycol or ring-opening polymerization of lactones; ethylene-propylene copolymers; polyisobutylene, copolymers of isobutylene and isoprene, etc .; polychloroprene; polyisoprene , Copolymers of isoprene and butadiene, acrylonitrile, styrene, etc .; copolymers of polybutadiene, butadiene and styrene, acrylonitrile, etc .; polyolefins obtained by hydrogenating polyisoprene (saturated hydrocarbons) Polymers, polyolefin polymers obtained by hydrogenating polybutadiene, polyolefin polymers obtained by hydrogenating copolymers of isoprene and acrylonitrile, styrene, etc., copolymers of butadiene and acrylonitrile, styrene, etc. Polyolefin polymer obtained by hydrogenation of polyacrylic acid ester obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate; acrylic acid ester such as ethyl acrylate and butyl acrylate, vinyl acetate, acrylonitrile, methyl Acrylate ester copolymer with methacrylate, styrene, etc .; Graft polymer obtained by polymerizing vinyl monomer in the organic polymer; Polysulfide polymer; Nylon 6, hexene by ring-opening polymerization of ε-caprolactam Nylon 66 by polycondensation of samethylenediamine and adipic acid, nylon 610 by polycondensation of hexamethylenediamine and sebacic acid, nylon 11 by polycondensation of 11-aminoundecanoic acid, nylon 12 by ring-opening polymerization of laurolactam, Polyamide polymer such as copolymer nylon having two or more components of nylon; polycarbonate polymer produced by polycondensation from bisphenol A and carbonyl chloride; diallyl phthalate polymer; novolac type phenol resin, resole Examples thereof include phenolic resins such as type phenolic resin, ammonia resol type phenolic resin, and benzylic ether type phenolic resin.

  Moreover, the thing of the said description is mentioned about the group (alkenyl group) containing the carbon-carbon double bond reactive with SiH group.

  Various methods for introducing an alkenyl group into the polymer skeleton can be used. However, the method can be roughly divided into a method for introducing an alkenyl group after polymerization and a method for introducing an alkenyl group during polymerization. Can do.

  As a method for introducing an alkenyl group after polymerization, for example, an organic polymer having a functional group such as a hydroxyl group, an alkoxide group, a carboxyl group, or an epoxy group at the terminal, main chain, or side chain is reactive with the functional group. By reacting an organic compound having both an active group having an alkenyl group and an alkenyl group, the alkenyl group can be introduced into the terminal, main chain or side chain.

Examples of organic compounds having both an active group and an alkenyl group that are reactive with respect to the functional group include 3 to 20 carbon atoms such as acrylic acid, methacrylic acid, vinyl acetic acid, acrylic acid chloride, and acrylic acid bromide. unsaturated fatty acids, acid halides, acid anhydrides and the like; allyl chloroformate _{(CH 2 = CHCH 2 OCOCl)} , allyl bromo formate _{(CH 2} = CHCH ₂ OCOBr) unsaturated aliphatic 3 to 20 carbon atoms such as alcohol Substituted carbonates; allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ) Ether, 1-hexenyl (chloromethoxy) ) Benzene, allyloxy (chloromethyl) benzene, allyl isocyanate.

  There is also a method of introducing an alkenyl group using a transesterification method. This method is a method in which an alcohol residue in an ester portion of a polyester resin or an acrylic resin is transesterified with an alkenyl group-containing alcohol or an alkenyl group-containing phenol derivative using a transesterification catalyst.

  The alkenyl group-containing alcohol or alkenyl group-containing phenol derivative used for exchange with an alcohol residue may be any alcohol or phenol derivative having at least one alkenyl group and having at least one hydroxyl group. It is preferable to have one. The catalyst may or may not be used, but when used, a titanium-based and tin-based catalyst is preferable.

  Examples of the alcohol or phenol derivative having an alkenyl group and a hydroxyl group include allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, and 6-heptene-1-. All, 7-octen-1-ol, 8-nonen-1-ol, 9-decen-1-ol, 2- (allyloxy) ethanol, neopentyl glycol monoallyl ether, glyceryl diallyl ether, trimethylolpropane triallyl ether , Trimethylolethane triallyl ether, pentaerythritol tetraallyl ether, 1,2,6-hexanetriol triallyl ether, sorbitan triallyl ether,

等が挙げられる。この中でも、入手の容易さから、アリルアルコール、３−ブテン−１−オール、２−（アリルオキシ）エタノール、及び、

Etc. Among these, because of availability, allyl alcohol, 3-buten-1-ol, 2- (allyloxy) ethanol, and

が好ましい。

Is preferred.

  Further, the ester residue of the above alcohol or phenol derivative such as acetate ester and the ester portion of the polyester resin or acrylic resin are transesterified using a transesterification catalyst, and the alcohol residue in the ester portion of the polyester resin or acrylic resin to be produced is obtained. There is also a method of introducing an alkenyl group by a method in which a low molecular weight esterified product such as an acetic ester with a group is distilled out of the system by vacuum devolatilization or the like.

  Moreover, after polymerizing methyl (meth) acrylate etc. by living polymerization, an alkenyl group can also be introduce | transduced into the terminal by the method of stopping a living terminal with the compound which has an alkenyl group.

  As a method for introducing an alkenyl group during the polymerization, for example, in the case of producing the organic polymer skeleton of the component (B) used in the present invention by radical polymerization, radical reactivity in molecules such as allyl methacrylate and allyl acrylate By using a vinyl monomer having a low alkenyl group or a radical chain transfer agent having a low alkenyl group such as allyl mercaptan, an alkenyl group can be introduced into the side chain or terminal of the organic polymer skeleton. .

  As a specific example of the organic compound of the component (B) in which an alkenyl group is introduced into the side chain or the terminal of the organic polymer skeleton,

（式中、Ｒ^２６は水素原子又はメチル基、Ｒ^２７、Ｒ^２８は、同一又は異なって、炭素数１〜２００の二価の有機基、Ｘ、Ｙは、同一又は異なって、直接結合又は炭素数１〜４８の二価の有機基、ｐ、ｑ、ｒはそれぞれ１〜３００の数を表す。）

(Wherein R ²⁶ is a hydrogen atom or a methyl group, R ²⁷ and R ²⁸ are the same or different, a divalent organic group having 1 to 200 carbon atoms, X and Y are the same or different, and are directly bonded or (C1-C48 divalent organic group, p, q, and r represent the number of 1-300, respectively.)

（式中、Ｒ^２９は水素原子又はメチル基、Ｒ^３０、Ｒ^３１は、同一又は異なって、炭素数１〜２００の二価の有機基、Ｘ、Ｙは、同一又は異なって、直接結合又は炭素数１〜４８の二価の有機基、ｎは１〜３００の数を表す。）

(Wherein R ²⁹ is a hydrogen atom or a methyl group, R ³⁰ and R ³¹ are the same or different, a divalent organic group having 1 to 200 carbon atoms, X and Y are the same or different, and are directly bonded or C1-C48 divalent organic group, n represents the number of 1-300.)

（式中、Ｒ^３２は水素原子又はメチル基、Ｒ^３３、Ｒ^３４は、同一又は異なって、炭素数１〜２００の二価の有機基、Ｘ、Ｙは、同一又は異なって、直接結合又は炭素数１〜４８の二価の有機基、ｐ、ｑ、ｒはそれぞれ１〜３００の数を表す。）

(Wherein R ³² is a hydrogen atom or a methyl group, R ³³ and R ³⁴ are the same or different, a divalent organic group having 1 to 200 carbon atoms, X and Y are the same or different, a direct bond or (C1-C48 divalent organic group, p, q, and r represent the number of 1-300, respectively.)

（式中、Ｒ^３５は水素原子又はメチル基、Ｒ^３６、Ｒ^３７は、同一又は異なって、炭素数１〜６の二価の有機基、Ｘ、Ｙは、同一又は異なって、直接結合又は炭素数１〜４８の二価の有機基、ｐ、ｑ、ｒはそれぞれ１〜３００の数を表す。）

(Wherein R ³⁵ is a hydrogen atom or a methyl group, R ³⁶ and R ³⁷ are the same or different, a divalent organic group having 1 to 6 carbon atoms, X and Y are the same or different, and are directly bonded or (C1-C48 divalent organic group, p, q, and r represent the number of 1-300, respectively.)

（式中、Ｒ^３８は水素原子又はメチル基、Ｒ^３９、Ｒ^４０、Ｒ^４１は、同一又は異なって、炭素数１〜６の二価の有機基、Ｘ、Ｙは、同一又は異なって、直接結合又は炭素数１〜４８の二価の有機基、ｐ、ｑ、ｒ、ｓはそれぞれ１〜３００の数を表す。）
等が挙げられる。

Wherein R ³⁸ is a hydrogen atom or a methyl group, R ³⁹ , R ⁴⁰ and R ⁴¹ are the same or different, a divalent organic group having 1 to 6 carbon atoms, X and Y are the same or different, (Direct bond or divalent organic group having 1 to 48 carbon atoms, p, q, r, and s each represent a number of 1 to 300.)
Etc.

Note that R ²⁷ , R ²⁸ , R ³⁰ , R ³¹ , R ³³ , and R ³⁴ are preferably a divalent hydrocarbon group having 1 to 200 carbon atoms, more preferably an alkylene group having 1 to 200 carbon atoms. R ³⁶ , R ³⁷ , R ³⁹ , R ⁴⁰ , and R ⁴¹ are preferably a divalent hydrocarbon group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms. X and Y are preferably a direct bond or a divalent hydrocarbon group having 1 to 48 carbon atoms, more preferably a direct bond or an alkylene group having 1 to 48 carbon atoms.

  As the component (B), it is also possible to use low molecular weight compounds that are difficult to express separately as described above for the skeleton and alkenyl groups. 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 (B) 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 (B) 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 that are reactive with the SiH group of the component (B) should be on average at least two per molecule, but it may exceed 2 if it is desired to further improve the mechanical strength. Preferably, it is 3 or more.

(B) As a component, you may have another reactive 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 these reactive groups are included, 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 reactive groups, an epoxy group is preferred 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.
(B) A component can be used individually or in mixture of 2 or more types.

((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. For example, platinum alone; solid platinum supported on a support such as alumina, silica, carbon black; chloroplatinic acid; platinum chloride Complexes of acids with alcohols, aldehydes, ketones, etc .; platinum-olefin complexes (eg Pt (CH ₂ ═CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ ═CH ₂ ) ₂ Cl ₂ ); platinum-vinyl Siloxane complexes (eg, Pt (ViMe ₂ SiOSiMe ₂ Vi) _a , Pt [(MeViSiO) ₄ ] _b ); platinum-phosphine complexes (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ); platinum-phos Fight complexes _{(e.g., Pt [P (OPh) 3} ] 4, Pt [P (OBu) 3] 4) ( in the formula, Me represents a methyl group, B Is a butyl group, Vi is a vinyl group, Ph is a phenyl group, a and b are integers.); Dicarbonyldichloroplatinum; Karstedt catalyst; Ashby U.S. Pat. And the platinum-alcohol complex described in US Pat. No. 3,159,662; the platinum alcoholate catalyst described in US Pat. No. 3,220,972 of Lamoreaux. 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.

  In addition, a cocatalyst can be used in combination with the catalyst. Examples of the cocatalyst include a sulfur-based compound such as simple sulfur, and an amine-based compound such as triethylamine.

The addition amount of the cocatalyst is not particularly limited, but a lower limit of 10 ⁻² mol and an upper limit of 10 ² mol are preferable with respect to 1 mol of the hydrosilylation catalyst, and a lower limit of 10 ⁻¹ mol and an upper limit of 10 mol are more preferable. It is.

(Curable composition)
The ratio of the component (A) to the component (B) in the curable composition is [carbon-carbon double bond (alkenyl group) having reactivity with the SiH group of the component (B) in the curable composition]. The ratio of the number of moles / the number of moles of the SiH group of the component (A) in the curable composition] is preferably a ratio such that the lower limit is 0.05 and the upper limit is 10, and the lower limit is 0.1 and the upper limit is 5. It is more preferable that the ratio be in the range. When the above value is less than 0.05, the effect of crosslinking by the reaction between the alkenyl group and the SiH group tends to be insufficient, and when it is more than 10, the unreacted component (B) is bleed from the cured product. Tend to come.

The addition amount of the hydrosilylation catalyst of component (C) in the curable composition is not particularly limited, but in order to have sufficient curability and keep the cost of the curable composition relatively low, component (A) A lower limit of 10 ⁻⁸ mol and an upper limit of 10 ⁻¹ mol are preferable, and a lower limit of 10 ⁻⁶ mol and an upper limit of 10 ⁻² mol are more preferable.

  The catalyst does not necessarily need to be added if the remaining amount used at the synthesis of the component (A) shows sufficient curability, but it is newly added in the above range in order to adjust curability. It can also be added.

((D) component)
A compound having at least two SiH groups in one molecule as component (D) will be described. The curable composition of the present invention is a hydrosilylation reaction product of the curing agent (A) of the present invention, that is, the above (α1) component and (α2) component, and has a molecular weight of 1000 Pa · s or less. In addition to the compound having at least two SiH groups therein, a compound having at least two SiH groups per molecule (component (D)) can be contained. The component (D) is not particularly limited as long as it is a compound having at least two SiH groups in one molecule.

  The (D) silicon compound having at least two SiH groups in one molecule that can be used in the curable composition of the present invention is not particularly limited, and is described in, for example, WO 96/15194. A compound having at least two SiH groups in one molecule can be used.

  Especially, the compound demonstrated by the silicon compound ((alpha) 1) which has SiH group which was demonstrated by the said (A) component is similarly suitable also in (D) component.

  In addition, from the viewpoint of having good compatibility with the component (A) and the component (B), and from the viewpoint that the problem of outgas from the composition that can reduce the volatility of the component (D) is unlikely to occur. Reacting a silicon compound (d1) having at least two SiH groups in one molecule with an organic compound (d2) containing at least two carbon-carbon double bonds having reactivity with the SiH group. It is preferable that it is the compound obtained by this. As (d1), a silicon compound having at least two SiH groups in one molecule can be used, and a chain and / or cyclic and / or network polyorgano having at least two SiH groups in one molecule. Siloxane is more preferable, and cyclic polyorganosiloxane is more preferable. As (d2), the same organic compound as the component (B) described above can be used. When the hydrosilylation reaction of (d1) and (d2) is performed, a mixture of a plurality of compounds containing the component (D) of the present invention may be obtained. The curable composition of the present invention can also be produced by using it as it is. Further, after the hydrosilylation reaction, the solvent and / or unreacted (d1) and / or (d2) may be removed. By removing these volatile components, the component (D) obtained does not have volatile components, so that problems of voids and cracks due to volatilization of volatile components are unlikely to occur in the case of curing. Examples of the removal method include, for example, treatment with activated carbon, aluminum silicate, silica gel and the like in addition to devolatilization under reduced pressure, as in the synthesis of the component (A) described above. Also about the temperature in the case of carrying out vacuum devolatilization, the preferable temperature of the above-mentioned (A) component vacuum devolatilization can be applied preferably similarly.

  Although there is no restriction | limiting in particular in the reaction method, It is preferable that it is the same as the synthesis method of (A) component.

The mixing ratio of the silicon compound (d1) having a SiH group and the organic compound (d2) containing at least two carbon-carbon double bonds reactive with the SiH group in one molecule is SiH group in one molecule. As long as there are two or more, there is no particular limitation, but considering the strength of the cured product obtained by the present invention, it is preferable that the component (D) has a larger amount of SiH groups. SiH to be mixed with the number of moles (X) of carbon-carbon double bonds having reactivity with SiH groups in the organic compound (d2) component containing at least two carbon-carbon double bonds in one molecule The ratio with the number of moles (Y) of SiH groups in the silicon compound (d1) having a group 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 (A) and (B) component of (D) component becomes easy, and it is more preferable that it is 5> = Y / X.
Examples of the above component (D) include a reaction product of bisphenol A diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, divinylbenzene and 1,3,5,7-tetramethylcyclohexane. Reaction product of tetrasiloxane, reaction product of triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of diallyl monoglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane Etc.

  The upper limit of the component (D) that can be added to the curable composition of the present invention is preferably 95% by weight and more preferably 90% by weight of the total amount of the component (A) and the component (D). When (D) component of the addition amount exceeding 95 weight% is added, there exists a tendency for the adhesive force of hardened | cured material to fall.

  In the present invention, the above component (D) may be used alone or in combination of two or more.

((E) component)
(E) A component is demonstrated. The adhesiveness imparting agent is not particularly limited as long as it improves the adhesiveness of the curable composition. For example, in addition to commonly used adhesives, various coupling agents, epoxy compounds, phenol resins, coumarone-indene resins, rosin ester resins, terpene-phenol resins, α-methylstyrene-vinyltoluene copolymers, poly Examples include ethyl methyl styrene and aromatic polyisocyanate.

  An example of the coupling agent is 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.

  The addition amount of the silane coupling agent 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 (+ (D) component)] is 0.1 part by weight. More preferably, the amount is 0.5 parts by weight, and the upper limit of the preferable 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.

  Examples of the epoxy compound include novolak phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and 2,2′-bis (4-glycidyloxycyclohexyl). Propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinyl cyclohexylene 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 iso Cyanurate, mention may be made of diallyl monoglycidyl isocyanurate and the like.

  The addition amount of the epoxy compound 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 (+ (D) component)] is 1 part by weight, more preferably The upper limit of the preferred amount added 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.

  These coupling agents, silane coupling agents, epoxy compounds, etc. may be used alone or in combination of two or more.

  In the present invention, a silanol condensation catalyst can be further used to enhance the effect of the coupling agent or the epoxy compound, and the adhesion can be improved and / or stabilized.

  Such a silanol condensation catalyst is not particularly limited, but boron compounds, aluminum compounds, titanium compounds, and zirconium compounds are preferable.

  Boron compounds that can be used in the curable composition of the present invention include tri-2-ethylhexyl borate, normal trioctadecyl borate, trinormal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, boric acid. Examples thereof include boric esters such as trinormal butyl, tri-sec-butyl borate, tri-tert-butyl borate, triisopropyl borate, trinormal propyl borate, triallyl borate, triethyl borate, trimethyl borate and boron methoxyethoxide.

  These boric acid esters may be used alone or in combination of two or more. Mixing may be performed in advance or may be performed at the time of producing a cured product.

  Of these boric acid esters, trimethyl borate, triethyl borate, and trinormal butyl borate are preferable, and trimethyl borate is more preferable among them because it is easily available and has high industrial utility.

  From the point that the volatility at the time of curing can be suppressed, normal trioctadecyl borate, trinormal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, trinormal butyl borate, tri-sec-butyl borate, boric acid Tri-tert-butyl, triisopropyl borate, tripropylpropyl borate, triallyl borate, and boron methoxyethoxide are preferred. Among these, normal trioctadecyl borate, tri-tert-butyl borate, triphenyl borate, and tributyl normal borate are more preferred. preferable.

  From the viewpoint of suppression of volatility and good workability, trinormal butyl borate, triisopropyl borate and trinormal propyl borate are preferable, and trinormal butyl borate is more preferable.

  From the viewpoint of low colorability at high temperatures, trimethyl borate and triethyl borate are preferred, and trimethyl borate is more preferred.

  Examples of aluminum compounds that can be used in the curable composition of the present invention include aluminum alkoxides such as aluminum triisopropoxide, sec-butoxyaluminum diisoflopoxide, aluminum trisec-butoxide, and ethyl acetoacetate aluminum diisopropoxy. Aluminum tris (ethyl acetoacetate), aluminum chelate M (manufactured by Kawaken Fine Chemicals, alkyl acetoacetate aluminum diisopropoxide), aluminum tris (acetylacetonate), aluminum monoacetylacetonate bis (ethyl acetoacetate), etc. Aluminum chelates can be exemplified, and aluminum chelates are more preferable from the viewpoint of handleability.

  Examples of titanium compounds that can be used in the curable composition of the present invention include tetraalkoxy titaniums such as tetraisopropoxy titanium and tetrabutoxy titanium, titanium chelates such as titanium tetraacetylacetonate, oxyacetic acid and ethylene glycol. A typical titanate coupling agent having a residue can be exemplified.

  Zirconium-based compounds that can be used in the curable composition of the present invention include tetraalkoxyzirconium compounds such as zirconium tetranormal propoxide and zirconium tetranormal butoxide, zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium mono Examples thereof include zirconium chelates such as butoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate), zirconium tetraacetylacetonate, and zirconium acylates.

  The amount used in the case of using a silanol condensation catalyst can be variously set, but the lower limit of the preferred addition amount with respect to 100 parts by weight of the coupling agent and / or epoxy compound 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 30 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.

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

  Further, in the present invention, a silanol source compound can be further used in order to further enhance the effect of improving adhesiveness, and the adhesiveness can be improved and / or stabilized. Examples of such silanol source compounds include silanol compounds such as triphenylsilanol and diphenyldihydroxysilane, and alkoxysilanes such as diphenyldimethoxysilane, tetramethoxysilane, and methyltrimethoxysilane.

  The amount used in the case of using a silanol source compound can be variously set, but the lower limit of the preferred amount added relative to 100 parts by weight of the coupling agent and / or epoxy compound 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 30 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 silanol source compounds may be used independently and may be used together 2 or more types.

  In the present invention, carboxylic acids and / or acid anhydrides can be used to enhance the effect of the coupling agent and the epoxy compound, and the adhesion can be improved and / or stabilized. Such carboxylic acids and acid anhydrides 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、およびそれら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 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 single or complex acid anhydrides thereof It is done.

  Of these carboxylic acids and / or acid anhydrides, they react with SiH groups in that they have hydrosilylation reactivity and are unlikely to impair the physical properties of the resulting cured product with a low possibility of seepage from the cured product. What contains the carbon-carbon double bond which has property is preferable. Preferred carboxylic acids and / or 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およびそれら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, methyltetrahydrophthalic acid, and single or complex acid anhydrides thereof.

  The amount used in the case of using carboxylic acids and / or acid anhydrides can be variously set, but the lower limit of the preferred addition amount with respect to 100 parts by weight of the coupling agent and / or epoxy compound is 0.1 parts by weight, more preferably Is 1 part by weight, and 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.

  Further, these carboxylic acids and / or acid anhydrides may be used alone or in combination of two or more.

(Other additives)
In the curable composition of the present invention, it is possible to adjust the viscosity by adding a solvent to improve workability. Solvents that can be used are not particularly limited, but specific examples include hydrocarbon solvents such as benzene, toluene, hexane, and heptane; ether solvents such as tetrahydrofuran, 1,4-dioxane, and diethyl ether. Solvents; Ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone; ester solvents such as n-butyl acetate, ethyl cellosolve acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; chloroform, methylene chloride, 1,2-dichloroethane, etc. These halogen solvents can be suitably used. Moreover, the said solvent may be used independently and can also be used as 2 or more types of mixed solvents.

  The amount of the solvent to be used is preferably 0.1 parts by weight and 100 parts by weight with respect to 100 parts by weight of [(A) component + (B) component + (D) component]. More preferably, it is used in a range of 0.5 parts by weight and an upper limit of 50 parts by weight, and more preferably in a range of a lower limit of 1 part by weight and an upper limit of 30 parts by weight. If the amount used is less than 0.1 parts by weight, the effect of lowering the viscosity tends to be difficult to obtain. If the amount used is more than 100 parts by weight, the solvent remains in the material, causing problems such as a decrease in heat resistance. And tends to be disadvantageous in terms of cost.

  A curing retarder can be used for the purpose of improving the storage stability of the curable composition of the present invention 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 compound, and an organic peroxide. These may be used alone or in combination of two or more.

  Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, maleate esters and the like. Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide and the like. Examples of the nitrogen-containing compound 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.

Amount of the curing retarder, towards hydrosilylation catalyst 1 mole to be used, the lower limit 10 ^-1 mol, the range of the upper limit 10 ³ moles and preferably, more preferably the lower limit 1 mol, the range of the upper limit 50 mol.

  Next, various resins that can be added for the purpose of modifying the characteristics of the curable composition of the present invention will be described. Examples of the resin include polycarbonate resin, polyethersulfone resin, polyarylate resin, epoxy resin, cyanate resin, phenol resin, acrylic resin, polyimide resin, polyvinyl acetal resin, urethane resin, polyester resin, and the like. It is not limited.

  You may add an inorganic filler to the curable composition of this invention as needed. Addition of an inorganic filler is effective in increasing the strength of the material and improving flame retardancy. The inorganic filler is preferably in the form of fine particles, and examples thereof include alumina, aluminum hydroxide, fused silica, crystalline silica, ultrafine amorphous silica, hydrophobic ultrafine silica, talc, and barium sulfate.

Examples of the method for adding the filler include hydrolyzable silane monomers or oligomers such as alkoxysilanes, acyloxysilanes, and halogenated silanes, and metal alkoxides, acyloxides, and halides such as titanium and aluminum. Examples of the method include adding to the curable composition and reacting in the composition or a partial reaction product of the composition to form an inorganic filler in the composition.
You may add antioxidant to the curable composition obtained by this invention. Examples of the anti-aging agent include citric acid, phosphoric acid, sulfur-based anti-aging agent and the like in addition to the anti-aging agents generally used such as hindered phenol type.

  As the hindered phenol-based anti-aging agent, various types such as Irganox 1010 available from Ciba Specialty Chemicals are used.

  Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylic acid esters, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.

  Moreover, these anti-aging agents may be used independently and may be used together 2 or more types.

  A radical inhibitor may be added to the curable composition of the present invention. Examples of the radical inhibitor include 2,6-di-t-butyl-3-methylphenol (BHT), 2,2′-methylene-bis (4-methyl-6-t-butylphenol), tetrakis (methylene- Phenol radical inhibitors such as 3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane, phenyl-β-naphthylamine, α-naphthylamine, N, N′-secondary butyl-p- Examples include amine radical inhibitors such as phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine, and the like.

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

  An ultraviolet absorber may be added to the curable composition of the present invention. Examples of the ultraviolet absorber include 2 (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate and the like. Can be mentioned.

  Moreover, these ultraviolet absorbers may be used independently and may be used together 2 or more types.

  The curable composition of the present invention includes other flame retardants, surfactants, antifoaming agents, emulsifiers, leveling agents, anti-fogging agents, ion trapping agents such as antimony-bismuth, thixotropic agents, and tackifiers. , Ozone degradation inhibitor, light stabilizer, thickener, plasticizer, antioxidant, heat stabilizer, processing stabilizer, reactive diluent, antistatic agent, radiation blocker, nucleating agent, phosphorus peroxide Decomposing agents, lubricants, pigments, metal deactivators, physical property modifiers, and the like can be added as long as the objects and effects of the present invention are not impaired.

  The curable composition of this invention is obtained by mixing said each component.

  Moreover, it does not specifically limit as a method of hardening the curable composition of this invention, It can also make it react only by mixing each component, It can also make it react by heating. From the viewpoint that the reaction is fast and generally a material having high heat resistance is easily obtained, a method of heating and reacting is preferable.

  Although various reaction temperatures can be set, a temperature range with a lower limit of 25 ° C. and an upper limit of 300 ° C. is preferred, a lower limit of 50 ° C. and an upper limit of 280 ° C. are more preferred, and a lower limit of 100 ° C. and an upper limit of 260 ° C. are even more preferred. When the reaction temperature is lower than 25 ° C, the reaction time for sufficient reaction tends to be long, and when the reaction temperature is higher than 300 ° C, the product tends to be thermally deteriorated.

  The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. Rather than carrying out the reaction at a constant temperature, the reaction is preferably carried out while raising the temperature in a multistage manner or continuously in that 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.

  The curable composition of this invention can be used as a molded object. The molding method is not particularly limited as long as it is a method used for an existing liquid resin. For example, there are extrusion molding, compression molding, blow molding, vacuum molding, injection molding, liquid injection molding, cast molding, and the like.

  When applying the hardened | cured material formed by hardening | curing the curable composition of this invention for an optical use, it is preferable to have transparency. More specifically, in terms of transparency, the transmittance at 400 nm of a 3 mm thick cured product is preferably 45% or more in the sense that light is sufficiently transmitted in the visible light range. A sufficient field of view cannot be secured unless the transmittance exceeds 45%. Furthermore, in the sense that the color changes, it is preferably 50% or more, and more preferably 60% or more. In addition, when the degree of discoloration or coloring after an environmental test against light or heat is low, the change in transmittance before and after the test is small, indicating that it can withstand long-term use. Specifically, after a light resistance test described later, the transmittance at 400 nm of a cured product having a thickness of 3 mm is preferably 45% or more, and more preferably 60% or more.

  The adhesive strength of the cured product tends to decrease as the resin itself deteriorates due to the application of light and heat over a long period of use. The cured product of the present invention has an adhesive strength of the cured product (thickness of 10 to 40 μm) after irradiation with 50 MJ per square meter (light resistance test) by a metal halide lamp. Force) is preferably 70% or more, more preferably 80% or more. Showing such adhesive strength clearly shows that the adhesive strength does not decrease even when ultraviolet light is applied for a long time, and has excellent adhesiveness that can realize maintaining good adhesiveness over a long period of time. It is shown. The evaluation of the adhesive strength in the present invention is carried out with reference to a method (US MIL STD-883) that presents the difference in adhesive strength between the initial state and those stored under certain conditions as an index of durability. As the adhesive force here, the die shear adhesive strength of the embodiment described later is used.

  The coating material said by this invention shows the material generally used for the purpose of making various functions adhere on the various base materials. For example, various paints, protective films, flattening films, sealants, molding agents and the like can be mentioned.

  Moreover, the optical material said by this invention shows the material in general used for the use which permeate | transmits light, such as visible light, infrared rays, an ultraviolet-ray, an X-ray, a laser.

  Examples thereof include materials used for liquid crystal display devices such as color filter protective films, TFT flattening films, and substrate materials, and materials used for light emitting diodes (LEDs) such as sealants and die bond agents. Furthermore, substrate materials in the field of liquid crystal displays, light guide plates, prism sheets, deflecting plates, retardation plates, viewing angle correction films, polarizer protective films, color filters and the like, and various coating agents and adhesives used for them are also included. .

  Moreover, the molding agent of the LED element used for an LED display device, the sealing agent of LED, the protective film of a front glass, a front glass substitute material, various coating agents used for them, an adhesive agent, etc. are mentioned.

  Further, examples thereof include an antireflection film for color PDP (plasma display), an optical correction film, a housing material, a front glass protective film, a front glass substitute material, and various coating agents and adhesives used therefor. Also included are substrate materials, light guide plates, prism sheets, deflector plates, retardation plates, viewing angle correction films, polarizer protective films, and various coating agents and adhesives used in plasma addressed liquid crystal (PALC) displays. . Moreover, the protective film of the front glass in an organic EL (electroluminescence) display, a front glass substitute material, various coating agent adhesives used for them, etc. are mentioned. Moreover, various film substrates in a field emission display (FED), a protective film for a front glass, a front glass substitute material, various coating agents used for them, an adhesive, and the like.

  In addition, in the optical recording field, VD (video disk), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disk), disk substrate for optical cards. Examples include materials, pickup lenses, light receiving sensor portions, protective films, and various coating agents and adhesives used for them.

  In the field of optical equipment, steel camera lens materials, finder prisms, target prisms, finder covers, light receiving sensor parts, and various coating agents and adhesives used for them are also included. In addition, there may be mentioned a photographing lens of a video camera, a viewfinder, various coating agents and adhesives used for them. Moreover, the projection lens of a projection television, a protective film, various coating agents used for them, an adhesive agent, etc. are mentioned. Examples include materials for lenses of optical sensing devices, various films, and various coating agents and adhesives used for them.

  In the field of optical components, fiber materials, lenses, waveguides, elements around optical switches in optical communication systems, various coating agents used for them, adhesives, and the like are also included. Examples also include optical fiber materials around the optical connector, ferrules, various coating agents used for them, and adhesives. Examples of optical passive components and optical circuit components include lenses, waveguides, and various coating agents and adhesives used therefor. Examples include substrate materials around the optoelectronic integrated circuit (OEIC), fiber materials, and various coating agents and adhesives used for them.

  In the field of other optical fibers, illumination sensors and light guides for decorative displays, sensors for industrial use, displays and signs, etc., optical fibers for communication infrastructure and home use, and various coating agents and adhesives used for them. An agent etc. are also mentioned.

  Examples of peripheral materials for semiconductor integrated circuits include resist materials for microlithography for LSI and VLSI materials.

  In the field of automobiles and transport equipment, lamp materials such as automotive headlamps, tail lamps, and interior lamps, lamp reflectors, lamp lenses, exterior and interior products such as exterior panels and interior panels, glass substitutes, and various coating agents used for them And adhesives. Moreover, exterior parts for railway vehicles, glass substitutes, and various coating agents and adhesives used for them are also included. Moreover, aircraft exterior parts, glass substitutes, and various coating agents and adhesives used for them are also included.

  In the construction field, examples include glass interlayers and glass substitutes.

  For agriculture, a house covering film is also included.

  Next-generation optical / electronic functional organic materials include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, elements Sealing agents and various coating agents and adhesives used for them.

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

The SiH group value after the reaction was determined by the following method.
(NMR)
A 300 MHz NMR apparatus manufactured by Varian Technologies Japan Limited was used. (B) The reaction rate of the allyl group in the component synthesis was measured by adding the reaction solution diluted to about 1% with deuterated chloroform to the NMR tube, the peak of the methylene group derived from the unreacted allyl group, and the reaction. It calculated | required from the peak of the methylene group derived from an allyl group. As the functional group value of the SiH group-containing compound as the reaction product, the SiH group value (mmol / g) and the remaining allyl group value (mmol / g) in terms of dibromoethane were determined.
(viscosity)
An E-type viscometer manufactured by Tokyo Keiki Co., Ltd. was used. Measurement was performed at a measurement temperature of 23 ° C. using an EHD type 48φ cone.
Example 1
To a 300 ml four-necked eggplant flask, 62 g of toluene, 42 g of 1,3,5,7-tetramethylcyclotetrasiloxane were added and heated so that the internal temperature became 100 ° C. Thereto was added 0.03 g of a platinum vinylsiloxane complex xylene solution (containing 3 wt% as platinum) diluted with 49 g of monoallyl diglycidyl isocyanurate and 50 g of toluene, and the mixture was heated and stirred for 6 hours. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane, toluene and xylene were distilled off under reduced pressure. ^{According to 1} H-NMR, this was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with monoallyl diglycidyl isocyanurate (referred to as partial reactant A1, SiH value: 4 0.5 mmol / g, allyl number: 0.1 mmol / g, viscosity 385 Pa · s). Although a product is a mixture, it contains the following as a main component which is a hardening | curing agent (A) component of this invention. Moreover, the platinum vinylsiloxane complex which is (C) component of this invention is contained.

（実施例２）
３００ｍｌ四口ナスフラスコに１，４−ジオキサン４２ｇ、１、３、５、７−テトラメチルシクロテトラシロキサン６１．９ｇを加えて、内温が１００℃になるように加熱した。そこに、モノアリルジグリシジルイソシアヌレート４８．８ｇ、白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０．０６ｇ、１，４−ジオキサン５０ｇの混合物を滴下し、１８時間加熱撹拌させた。未反応の１、３、５、７−テトラメチルシクロテトラシロキサンおよびキシレン、１，４−ジオキサンを減圧留去した。¹Ｈ−ＮＭＲによりこのものは１、３、５、７−テトラメチルシクロテトラシロキサンのＳｉＨ基の一部がモノアリルジグリシジルイソシアヌレートと反応したもの（部分反応物Ａ２と称す、ＳｉＨ価：４．７ｍｍｏｌ／ｇ、アリル価：０．２ｍｍｏｌ／ｇ、粘度３８５Ｐａ・ｓ）であることがわかった。生成物は混合物であるが、本発明の硬化剤（Ａ）成分である上記のものを主成分として含有している。また、本発明の（Ｃ）成分である白金ビニルシロキサン錯体を含有している。

(Example 2)
To a 300 ml four-necked eggplant flask, 42 g of 1,4-dioxane, 61.9 g of 1,3,5,7-tetramethylcyclotetrasiloxane was added and heated to an internal temperature of 100 ° C. Thereto was added dropwise a mixture of 48.8 g of monoallyl diglycidyl isocyanurate, 0.06 g of a platinum vinylsiloxane complex xylene solution (containing 3 wt% as platinum) and 50 g of 1,4-dioxane, and the mixture was heated and stirred for 18 hours. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane, xylene and 1,4-dioxane were distilled off under reduced pressure. ^{According to 1} H-NMR, this was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with monoallyl diglycidyl isocyanurate (referred to as partial reactant A2, SiH value: 4 0.7 mmol / g, allyl number: 0.2 mmol / g, viscosity 385 Pa · s). Although the product is a mixture, it contains the above-mentioned components which are the curing agent (A) component of the present invention as a main component. Moreover, the platinum vinylsiloxane complex which is (C) component of this invention is contained.

Next, a synthesis example of a compound containing at least two SiH groups in one molecule as component (D) will be described.
(Synthesis Example 1)
To a 2 L autoclave, 696 g of toluene, 556 g of 1,3,5,7-tetramethylcyclotetrasiloxane were added and heated so that the internal temperature became 104 ° C. A mixture of 80 g of triallyl isocyanurate, 0.05 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) and 60 g of toluene was added dropwise and stirred for 7 hours. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. ^{According to 1} H-NMR, this was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with triallyl isocyanurate (referred to as partial reaction product D1, SiH value: 9.4 mmol) / G). Although the product is a mixture, it contains as a main component the following (D) component of the present invention. Moreover, the platinum vinylsiloxane complex which is (C) component of this invention is contained.

（合成例２）
２Ｌオートクレーブにトルエン５２５ｇ、１、３、５、７−テトラメチルシクロテトラシロキサン５７０ｇを加えて、内温が１０５℃になるように加熱した。そこに、ジアリルモノグリシジルイソシアヌレート１２０ｇ、白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０．０５ｇ、トルエン１２０ｇの混合物を滴下した。滴下中、内温が１０９℃まで上昇した。未反応の１、３、５、７−テトラメチルシクロテトラシロキサンおよびトルエンを減圧留去した。¹Ｈ−ＮＭＲによりこのものは１、３、５、７−テトラメチルシクロテトラシロキサンのＳｉＨ基の一部がジアリルモノグリシジルイソシアヌレートと反応したもの（部分反応物Ｄ２と称す、ＳｉＨ価：７．７ｍｍｏｌ／ｇ）であることがわかった。
本発明の（Ｄ）成分である下記のものを主成分として含有している。また、本発明の（Ｃ）成分である白金ビニルシロキサン錯体を含有している。

(Synthesis Example 2)
To a 2 L autoclave, 525 g of toluene, 570 g of 1,3,5,7-tetramethylcyclotetrasiloxane were added and heated so that the internal temperature became 105 ° C. A mixture of 120 g of diallyl monoglycidyl isocyanurate, 0.05 g of a platinum vinylsiloxane complex xylene solution (containing 3 wt% as platinum) and 120 g of toluene was added dropwise. During the dropping, the internal temperature rose to 109 ° C. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. ^{According to 1} H-NMR, this was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with diallyl monoglycidyl isocyanurate (referred to as partial reaction product D2, SiH value: 7. 7 mmol / g).
It contains the following components as the main component (D) of the present invention. Moreover, the platinum vinylsiloxane complex which is (C) component of this invention is contained.

（比較例１）
３００ｍｌ四口ナスフラスコに１，４−ジオキサン４２ｇ、１、３、５、７−テトラメチルシクロテトラシロキサン２３．３ｇを加えて、内温が８５℃になるように加熱した。そこに、モノアリルジグリシジルイソシアヌレート４８．８ｇ、白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０．０５ｇ、１，４−ジオキサン４９ｇの混合物を滴下し、１０時間加熱撹拌させた。未反応の１、３、５、７−テトラメチルシクロテトラシロキサンおよびトルエン、１，４−ジオキサンを減圧留去した。¹Ｈ−ＮＭＲによりこのものは１、３、５、７−テトラメチルシクロテトラシロキサンのＳｉＨ基の一部がモノアリルジグリシジルイソシアヌレートと反応したもの（部分反応物Ａ３と称す、ＳｉＨ価：３．５ｍｍｏｌ／ｇ、アリル価：０．２ｍｍｏｌ／ｇ、粘度＞１０００Ｐａ・ｓ）であることがわかった。生成物は混合物である。
（実施例３〜７および比較例〜３）
（Ａ）成分として実施例１，２の合成物を用い、（Ｂ）成分として、トリアリルイソシアヌレート、ジアリルモノグリシジルイソシアヌレートを用い、（Ｃ）成分として白金−ジビニルテトラメチルジシロキサン錯体のキシレン溶液（白金３重量％含有）を用い、（Ｄ）成分として合成例１，２の合成物を用い、（Ｅ）成分としてγ―グリシドキシプロピルトリメトキシシラン（東レダウコーニング製、Ａ−１８７）とほう酸メチルを用いて、表１、表２に示した配合で硬化性組成物を作製した。配合方法は、（Ｂ）成分と（Ｃ）成分とホウ酸メチルと必要に応じて老化防止剤（ＩＲＧＡＮＯＸ１０１０：ペンタエリスリチルテトラキス（３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート）を混合し、攪拌、脱泡したものに、（Ａ）成分および／又は（Ｄ）成分と１−エチニルシクロヘキサノールとγ―グリシドキシプロピルトリメトキシシランを加えて、さらに攪拌、脱泡したものを硬化性組成物とした。この硬化性組成物を、２枚のガラス板に３ｍｍ厚みのシリコーンゴムシートをスペーサーとして挟み込んで作製したセルに流し込み、６０℃６時間、７０℃１時間、８０℃１時間、１００℃１時間、１２０℃１時間、１５０℃１時間、１８０℃３０分間加熱し硬化物を得た。
得られた各硬化性組成物および各硬化物について、粘度・硬化物の外観・接着性・強度・耐光性・耐熱性を以下に述べる試験方法（粘度に関しては前述の測定方法）により測定した。
（硬化物の外観）
得られた３ｍｍ厚の硬化物の外観を目視により評価した。無色透明に見える硬化物は、４００ｎｍの透過率が８０％以上であることが多い。
（ダイシェア接着性試験）
得られた硬化性組成物を５０μｍのブレードで塗布し、その塗膜に、２×２×０．２ｍｍのガラス板のダイを２×２ｍｍの面を下方にしてスタンプし、硬化性組成物をダイにつけた。このダイを、硬化性組成物が付着した面を下方にしてガラス繊維強化エポキシ（ＦＲ４）基材に乗せ、１５０℃１時間、１８０℃３０分間加熱により硬化して試験片を作製した。このとき、得られる硬化物（ダイと基材との間の硬化物層）は厚み約３０μｍ（厚みが１０〜４０μｍの範囲内）になる。得られた試験片について、デイジ社製、シリーズ４０００ボンドテスター試験機、ＤＳ１００ＫＧロードセルを用いて接着強度（単位；ｋｇＦ）を測定した。各硬化性組成物につきサンプル（試験片）５個を測定し、最高値と最低値を除く３点の平均を接着強度とした。
得られた硬化物より、３ｍｍ×５ｍｍ×５０ｍｍの試験片を切り出し、当該試験片を用いて２３℃の環境下、ＪＩＳＫ６９１１に準じた方法で、曲げ強度を測定した。測定には、島津製作所製オートグラフＡＧ−１０ＴＢを使用した。
（光線透過率）
得られた硬化物について、４７０ｎｍの光線透過率を分光光度計（Ｕ−３３００、日立）を用いて測定し、得られた値を耐光性・耐熱性試験前の光線透過率とした。
（耐光性試験）
得られた硬化物に対してスガ試験機Ｍ６Ｔ型メタリングウェザーメーター（照射量：５０ＭＪ／ｍ^２）を用いて耐光性試験を行った。耐光性試験後の硬化物について、４７０ｎｍの光線透過率を分光光度計（Ｕ−３３００、日立）を用いて測定した。また、上記記載のダイシェア試験片に対して同様の耐光性試験を行い、上記ダイシェア接着性試験と同様にして測定した値をダイシェア耐光性試験値とした。
（耐熱性試験）
得られた硬化物に対して２００℃の熱風オーブンで２４時間耐熱性試験を行った。耐熱性試験後の硬化物について、４７０ｎｍの光線透過率を分光光度計（Ｕ−３３００、日立）で測定した。

(Comparative Example 1)
To a 300 ml four-necked eggplant flask, 42 g of 1,4-dioxane, 23.3 g of 1,3,5,7-tetramethylcyclotetrasiloxane was added and heated to an internal temperature of 85 ° C. A mixture of 48.8 g of monoallyl diglycidyl isocyanurate, 0.05 g of a platinum vinylsiloxane complex in xylene solution (containing 3 wt% as platinum) and 49 g of 1,4-dioxane was added dropwise and heated and stirred for 10 hours. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene and 1,4-dioxane were distilled off under reduced pressure. ^{According to 1} H-NMR, this was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with monoallyl diglycidyl isocyanurate (referred to as partial reactant A3, SiH value: 3 0.5 mmol / g, allyl number: 0.2 mmol / g, viscosity> 1000 Pa · s). The product is a mixture.
(Examples 3 to 7 and Comparative Examples 3)
(A) The composition of Examples 1 and 2 was used as component, triallyl isocyanurate and diallyl monoglycidyl isocyanurate were used as component (B), and xylene of platinum-divinyltetramethyldisiloxane complex was used as component (C). Using a solution (containing 3% by weight of platinum), using the composition of Synthesis Examples 1 and 2 as the component (D), and γ-glycidoxypropyltrimethoxysilane (A-187, manufactured by Toray Dow Corning) as the component (E) ) And methyl borate were used to prepare curable compositions with the formulations shown in Tables 1 and 2. The blending method is (B) component, (C) component, methyl borate and anti-aging agent (IRGANOX1010: pentaerythrityltetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) as required. ) Propionate) is mixed, stirred and degassed, and then (A) component and / or (D) component, 1-ethynylcyclohexanol and γ-glycidoxypropyltrimethoxysilane are added, and the mixture is further stirred and degassed. The foamed product was used as a curable composition, which was poured into a cell prepared by sandwiching a 3 mm-thick silicone rubber sheet as a spacer between two glass plates, 60 ° C. for 6 hours, 70 ° C. for 1 hour. 80 ° C. for 1 hour, 100 ° C. for 1 hour, 120 ° C. for 1 hour, 150 ° C. for 1 hour, and 180 ° C. for 30 minutes to obtain a cured product.
About each obtained curable composition and each hardened | cured material, the viscosity, the external appearance of the hardened | cured material, adhesiveness, intensity | strength, light resistance, and heat resistance were measured with the test method (it is the above-mentioned measuring method regarding a viscosity) described below.
(Appearance of cured product)
The appearance of the obtained cured product having a thickness of 3 mm was visually evaluated. The cured product that appears to be colorless and transparent often has a transmittance of 80% or more at 400 nm.
(Die shear adhesion test)
The obtained curable composition was applied with a 50 μm blade, and a 2 × 2 × 0.2 mm glass plate die was stamped onto the coating film with a 2 × 2 mm surface facing downward, and the curable composition was I put it on the die. The die was placed on a glass fiber reinforced epoxy (FR4) substrate with the surface to which the curable composition was attached facing downward, and cured by heating at 150 ° C. for 1 hour and 180 ° C. for 30 minutes to prepare a test piece. At this time, the obtained cured product (cured product layer between the die and the substrate) has a thickness of about 30 μm (within a thickness of 10 to 40 μm). About the obtained test piece, the adhesive strength (unit; kgF) was measured using the Daisy Co., Ltd. series 4000 bond tester tester and DS100KG load cell. Five samples (test pieces) were measured for each curable composition, and the average of three points excluding the highest value and the lowest value was taken as the adhesive strength.
From the obtained cured product, a 3 mm × 5 mm × 50 mm test piece was cut out, and the bending strength was measured by a method according to JISK6911 using the test piece in an environment of 23 ° C. For the measurement, Autograph AG-10TB manufactured by Shimadzu Corporation was used.
(Light transmittance)
About the obtained hardened | cured material, the light transmittance of 470 nm was measured using the spectrophotometer (U-3300, Hitachi), and the obtained value was made into the light transmittance before a light resistance and a heat resistance test.
(Light resistance test)
The cured product thus obtained was subjected to a light resistance test using a Suga Tester M6T type metaling weather meter (irradiation amount: 50 MJ / m ² ). About the hardened | cured material after a light resistance test, the light transmittance of 470 nm was measured using the spectrophotometer (U-3300, Hitachi). Moreover, the same light resistance test was done with respect to the said die shear test piece, and the value measured like the said die shear adhesiveness test was made into the die shear light resistance test value.
(Heat resistance test)
The obtained cured product was subjected to a heat resistance test in a hot air oven at 200 ° C. for 24 hours. About the hardened | cured material after a heat resistance test, the light transmittance of 470 nm was measured with the spectrophotometer (U-3300, Hitachi).

本発明による硬化剤を用いた硬化物は、光学的透明性、接着性試験より接着性能、曲げ試験より強度を有することが示された。したがって、本発明の硬化剤を使用した硬化性組成物を用いた製品は、その寿命を延長させられることが容易に理解できる。

The cured product using the curing agent according to the present invention was shown to have optical transparency, adhesion performance from the adhesion test, and strength from the bending test. Therefore, it can be easily understood that the product using the curable composition using the curing agent of the present invention can extend its life.

Claims (15)

A curing agent having at least two SiH groups in one molecule, which is a reaction product of the following components and has a viscosity at 23 ° C. of 1000 Pa · s or less.
(Α1) silicon compound having at least 3 SiH groups in one molecule (α2) containing one carbon-carbon double bond reactive with SiH groups in one molecule and at least one polarity Organic compounds having a heterocyclic skeleton containing groups   The curing agent according to claim 1, wherein the heterocyclic skeleton of the component (α2) is isocyanurate.   The curing agent according to claim 1 or 2, wherein at least one of the polar groups of the component (α2) is an epoxy group.   The hardening | curing agent as described in any one of Claims 1-3 whose said ((alpha) 1) component is cyclic polyorganosiloxane.   The mixing ratio of the (α1) component and the (α2) component is (number of moles of SiH groups contained in α1) / (number of moles of carbon-carbon double bond groups having reactivity with SiH groups contained in α2). The hardening | curing agent as described in any one of Claims 1-4 which is 3 or more.   The hardening | curing agent as described in any one of Claims 1-5 whose said ((alpha) 2) component is monoallyl diglycidyl isocyanurate.   The hardening | curing agent as described in any one of Claims 1-6 whose said ((alpha) 1) component is 1,3,5,7- tetramethyltetracyclosiloxane. (A) The curing agent according to any one of claims 1 to 7,
(B) An adhesive curable composition comprising, as essential components, an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule, and (C) a hydrosilylation catalyst.   The adhesive curable composition according to claim 8, further comprising (D) a silicon compound having at least two SiH groups in one molecule.   Furthermore, the adhesive curable composition of Claim 8 or 9 containing (E) adhesiveness imparting agent.   The adhesive curable composition in any one of Claims 8-10 whose transmittance | permeability in wavelength 400nm of the hardened | cured material of 3 mm thickness is 60% or more.   After irradiation of 50 MJ per square meter with a metal halide lamp, the transmittance at 400 nm of a cured product having a thickness of 3 mm is 45% or more, and the adhesive strength of the cured product is 70 compared with the adhesive strength of the cured product before the irradiation. The adhesive curable composition according to any one of claims 8 to 11, which is at least%.   Hardened | cured material formed by hardening | curing the adhesive curable composition as described in any one of Claims 8-12.   A coating material using the adhesive curable composition according to claim 8.   An optical material using the adhesive curable composition according to claim 8.