JP2003327838A - Curing composition and rapid-curing adhesive given by using the curing composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curing composition rapidly cured and capable of giving such a low elastic cured resin as to absorb deformation caused by stress, and to provide a rapid-curing adhesive by using the curing composition. <P>SOLUTION: This curing composition contains (A) an organic compound which has a carbon-carbon double bond having reactivity with a SiH group, (B) a silicon compound which has at least two SiH groups in its molecule, (C) a hydrosilylation catalyst, and (D) an adhesion-improving agent as essential ingredients, wherein the cured product therefrom has a storage elastic modulus in tension of ≤2,000 MPa at 0°C. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition and a fast-curing adhesive using the curable composition. More specifically, the present invention relates to an adhesive for assembling electric products, electronic parts, precision instruments and the like. As a curable composition.

[0002]

2. Description of the Related Art Electrical equipment, precision equipment, and parts used therefor are often assembled by a bonding process. Most of the assembly process is automated, so the adhesive is easy to handle, such as viscosity.
Production efficiency such as bonding time is emphasized. Further, the basic performance required for the adhesive includes retention of adhesiveness when used in a place subject to vibration or in an environment where it is repeatedly exposed to low temperature and high temperature, absorption of strain by the adhesive layer, and the like. . In order to develop such performance, a low elastic adhesive that reduces stress is required, and silicone resin-based or epoxy resin-based low elastic adhesives are known.
However, the existing silicone resin adhesive has a problem in that volatile components are generated, which contaminates products and assembly equipment. Further, epoxy resin adhesives generally have a slow curing speed and have a drawback that it takes a long time to bond them.

[0003]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a curable composition and a curable composition thereof which are fast-curing and which can obtain a low elastic cured product which can absorb strain generated by stress. It is to provide a fast-curing adhesive used.

[0004]

In order to solve the above problems, the present inventors have earnestly studied, and as a result, (A) an organic compound containing a carbon-carbon double bond reactive with a SiH group, (B) a silicon compound containing at least two SiH groups in one molecule, (C) a hydrosilylation catalyst,
A curable composition comprising (D) an adhesion improver as an essential component and having a tensile storage elastic modulus at 0 ° C. of 2
It was found that the above problems can be solved by using a curable composition characterized by having a pressure of 000 MPa or less,
The present invention has been completed.

That is, the present invention provides (A) an organic compound containing a carbon-carbon double bond reactive with a SiH group, (B) a silicon compound containing at least two SiH groups in one molecule, (C) hydrosilylation catalyst, (D)
A curable composition comprising an adhesiveness improver as an essential component and having a tensile storage elastic modulus at 0 ° C. of 2000.
A curable composition (claim 1) characterized by having a pressure of at most MPa, wherein the content of component (A) is at least 0.5% by weight.
Is a monomer component containing a carbon-carbon double bond having reactivity with a SiH group, which is the curable composition (claim 2) according to claim 1, and in the component (A). In addition, 1 carbon-carbon double bond reactive with SiH group
The curable composition (Claim 3) according to claim 1 or 2, which contains at least one polybutadiene in the molecule, and has a viscosity of 10 Pa · s or less at 23 ° C. The curable composition according to any one of claims 1 to 3 (claim 4),
The curable composition (claim 5) according to any one of claims 1 to 4, wherein the gelling time on a hot plate at 120 ° C is 300 seconds or less, and the curable composition according to claim 5 A fast-curing adhesive using a curable composition (claim 6).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

First, the component (A) in the present invention will be described.

The component (A) is an organic compound containing a carbon-carbon double bond reactive with a SiH group.
The organic skeleton constituting the component (A) is not particularly limited as to the organic skeleton constituting the organic skeleton, and examples thereof include polyether-based, polyester-based, polyarylate-based, polycarbonate-based, saturated hydrocarbon-based, polyacrylic acid ester-based, Polyamide-based, phenol-formaldehyde-based (phenol resin-based), polyimide-based organic polymer skeletons, phenol-based, bisphenol-based, aromatic hydrocarbon-based such as benzene and naphthalene, aliphatic hydrocarbon-based, aliphatic alcohol-based, etc. And an organic monomer skeleton composed of two or more of these. The organic compound as the component (A) includes the organic skeleton portion and a group having a carbon-carbon double bond that is reactive with the SiH group that is covalently bonded to the organic skeleton portion. When represented in this way, the group having a carbon-carbon double bond reactive with the SiH group may be covalently bonded to any part of the organic skeleton.

The carbon-carbon double bond reactive with the SiH group of the component (A) is not particularly limited as long as it has reactivity with the SiH group.

The following general formula (I)

[0011]

[Chemical 1] An alkenyl group represented by the formula (R ¹ represents a hydrogen atom or a methyl group) is preferable from the viewpoint of reactivity.

From the ease of obtaining the raw materials,

[0013]

[Chemical 2] Is particularly preferable.

The alkenyl group of the component (A) is represented by the following general formula (II)

[0015]

[Chemical 3] An alkenyl group represented by the formula (R ¹ represents a hydrogen atom or a methyl group) is preferable from the viewpoint of high heat resistance of the cured product.

Further, from the viewpoint of easy availability of raw materials,

[0017]

[Chemical 4] Is particularly preferable.

The alkenyl group may be covalently bonded to the organic skeleton portion of the component (A) via a divalent or higher valent substituent.

The divalent or higher valent substituent has 0 to 10 carbon atoms.
There is no particular limitation as long as it is a substituent of Examples of such substituents include:

[0020]

[Chemical 5]

[0021]

[Chemical 6] Etc.

Further, two or more of these substituents may be connected by a covalent bond to form one divalent or higher valent substituent.

Examples of the group covalently bonded to the organic skeleton as described above include vinyl group, allyl group, methallyl group,
Acrylic group, methacrylic group, 2-hydroxy-3- (allyloxy) propyl group, 2-allylphenyl group, 3-
Allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group, 2,2-bis (allyloxy) Methyl)
Butyl group, 3-allyloxy-2,2-bis (allyloxymethyl) propyl group,

[0024]

[Chemical 7] Etc.

As the organic compound as the component (A), the above organic skeleton portion and S which is covalently bonded to the organic skeleton portion.
It is also possible to use a low molecular weight compound that is difficult to express by being divided into an iH group and a group having a reactive carbon-carbon double bond. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene, cyclopentadiene,
Examples thereof include aliphatic cyclic polyene compound systems such as cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene, and substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.

As the component (A), from the viewpoint that the heat resistance can be further improved, a carbon-carbon double bond reactive with a SiH group is added in an amount of 0.001 m per 1 g of the component (A).
ol or more is preferable, and 0.001 g is included.
Those containing 5 mol or more are more preferable, and those containing 0.008 mol or more per 1 g are particularly preferable.
Specific examples include butadiene, isoprene, vinylcyclohexene, cyclopentadiene, dicyclopentadiene, cyclohexadiene, decadiene, diallylphthalate, trimethylolpropane diallyl ether,
Pentaerythritol triallyl ether, divinylbenzenes (purity 50 to 100%, preferably 80 to 100%), 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and those Oligomer,

[0027]

[Chemical 8] And so on. In the present invention, these may be used alone or in combination of two or more.

The component (A) is preferably one which has fluidity at a temperature of 100 ° C. or lower in order to obtain uniform mixing with other components and good workability, and may be linear or branched. . The lower limit of the molecular weight is 50 and the upper limit is 10.
Although any value of 10,000 can be used, a preferred lower limit is 54, a preferred upper limit is 70,000, a more preferred lower limit is 68, and a more preferred upper limit is 50,000. When the molecular weight is less than 50, the volatility is large, and when the molecular weight exceeds 100,000, the raw material generally has a high viscosity and the workability is poor, and the alkenyl group and Si
The effect of cross-linking due to the reaction with the H group is difficult to be exhibited.

Further, when a monomer component containing a carbon-carbon double bond reactive with a SiH group is used as the component (A), the viscosity of the curable composition is lowered and the workability in the automatic assembly process is reduced. In the present invention, the monomer component containing the carbon-carbon double bond reactive with the SiH group is used in the range of the lower limit of 0.5% by weight and the upper limit of 100% by weight in the component (A). Is preferred, and it is more preferred that the lower limit is 1% by weight and the upper limit is 99.5% by weight.
If it is less than 0.5% by weight, the viscosity of the curable composition tends to increase.

From the same viewpoint, the viscosity of the above-mentioned curable composition is 10 Pa as measured by a rotational viscometer at 23 ° C.
· S or less is preferable, and 5 Pa · s or less is more preferable.

Next, the polybutadiene having at least one carbon-carbon double bond reactive with the SiH group, which is one example of the component (A), will be described.

When polybutadiene is used, it exhibits rubber-like properties and promotes imparting flexibility to the cured product and lowering the elasticity.
The polybutadiene is produced by radical polymerization, anionic polymerization or cation polymerization, and has 1,2-bond as a repeating unit, or has 1,4-bond as a repeating unit, and both are repeated in one molecule. There are those that have units. The double bond of the 1,4-bond may be either cis type or trans type, or may be a mixed type of both. Those having both a 1,2-bond and a 1,4-bond as a repeating unit in one molecule may have regularity or random. In addition, a partially modified alcoholic compound, a carboxylic oxide, an acid anhydride, an esterified compound, a half-esterified compound, an acrylated compound, an imidized compound, an epoxidized compound, an aminated compound, a phenolic compound, or a hydrogenated compound is used. It may be.

In the present invention, the polybutadiene having at least one carbon-carbon double bond reactive with the SiH group in one molecule is not particularly limited, but from the viewpoint of reactivity, 1,2- Polybutadiene with a bond is preferred.

The molecular weight of the above polybutadiene is
The number average molecular weight is preferably in the range of lower limit 110 and upper limit 100,000, more preferably lower limit 165 and upper limit 10,
The range is 000. When it is higher than 100,000, the fluidity tends to be poor.

The content of the 1,2-conjugate is 0.1
It is preferably at least mol%, more preferably at least 1 mol%. If it is less than 0.1 mol%, curing tends to be insufficient.

In the present invention, the above polybutadiene may be used alone or as a mixture of two or more kinds having different molecular weights and / or 1,2-bond contents, in an arbitrary ratio. The above polybutadiene is preferably used in the range of the lower limit of 0% by weight and the upper limit of 99.5% by weight in the component (A), more preferably the lower limit of 0.5% by weight and the upper limit of 99% by weight. If it is used in an amount of more than 99.5% by weight, the viscosity of the curable composition tends to increase.

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

The compound having a SiH group that can be used in the present invention is not particularly limited, and for example, International Publication WO96.
/ 15194, compounds having at least two SiH groups in one molecule, and the like can be used.

Among these, from the viewpoint of availability, a chain-like and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule is preferable, and the compatibility with the component (A) is good. From the viewpoint, further, the following general formula (III)

[0040]

[Chemical 9] (In the formula, R ² represents an organic group having 1 to 6 carbon atoms, and n is 3 to
Represents the number 10. A cyclic polyorganosiloxane having at least two SiH groups in one molecule represented by the formula (1) is preferable. In addition, the substituent R ² in the compound represented by the general formula (III) is preferably composed of C, H and O, and more preferably a hydrocarbon group.

Further, a reaction product of a chain and / or cyclic polyorganosiloxane and one or more compounds selected from organic compounds having a carbon-carbon double bond (hereinafter referred to as component (E)) Is also preferable. The component (E) is an organic compound having an organic skeleton containing at least one carbon-carbon double bond reactive with a SiH group in one molecule, and the same explanation as the component (A) is also available. Can be used.

Preferred examples of the component (E) include allyl ether of novolac phenol and diallyl ether of bisphenol A, diallyl ether of hydrogenated bisphenol A, 2,2'-diallyl bisphenol A, diallyl phthalate and bis (2) of phthalic acid. -Allyloxyethyl) ester, styrene, α-methylstyrene, allyl-terminated polypropylene oxide, polyethylene oxide and the like. The organic compounds as the component (E) can be used alone or in combination of two or more.

The various components (B) described above can be used alone or in admixture of two or more.

The ratio of the component (A) to the component (B) in the curable composition is [the number of moles of the alkenyl group of the component (A) in the curable composition / (B in the curable composition The number of moles of the SiH group of the component) is preferably in a range of lower limit 0.5 and upper limit 30 and more preferably in a range of lower limit 0.75 and upper limit 20. If the above value is less than 0.5, the effect of crosslinking due to the reaction between the alkenyl group and the SiH group tends to be insufficient.
If it is greater than 0, the unreacted component (A) tends to bleed out from the cured product.

The above component (E) and at least 2 in one molecule.
The reaction of the chain and / or cyclic polyorganosiloxane having one SiH group can be carried out using the hydrosilylation catalyst which is the component (C) of the present invention. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-
A vinyl siloxane complex and the like are preferable. Further, these catalysts may be used alone or in combination of two or more kinds. The amount of the catalyst added is not particularly limited, but in order to have sufficient reactivity and to keep the cost relatively low, SiH
The lower limit is preferably 10 ^-8 mol and the upper limit is 10 ^-1 mol, and more preferably the lower limit is 10 ^-6 mol and the upper limit is 10 ^-2 mol, relative to 1 mol of the group. The solvent that can be used in the reaction is not particularly limited, and specific examples thereof include hydrocarbon solvents such as benzene, toluene, hexane and heptane, ether solvents such as tetrahydrofuran, 1,4-dioxane and diethyl ether. A ketone-based solvent such as acetone, methyl ethyl ketone or the like, or a halogen-based solvent such as chloroform, methylene chloride or 1,2-dichloroethane can be preferably used. The solvent may be used as a mixed solvent of two or more kinds. As a solvent,
Toluene, tetrahydrofuran and chloroform are preferred. The amount of the solvent used is such that the reactivity [(E) + (a chain having at least two SiH groups in one molecule, and / or
Alternatively, it is preferable to use the lower limit of 0 mL and the upper limit of 10 mL, more preferably the lower limit of 0.5 mL and the upper limit of 5 mL, more preferably the lower limit of 1 mL and the upper limit of 3 mL with respect to 1 g of the cyclic polyorganosiloxane) component. It is particularly preferable to use. The molar ratio of the component (E) to at least two SiH groups in one molecule and / or the cyclic polyorganosiloxane (E / 1 to at least two SiH groups in one molecule, And / or cyclic polyorganosiloxane) has a lower limit of 5 and an upper limit of 1 from the viewpoint of yield.
It is preferably 00, the lower limit is 7 and the upper limit is 50, and the lower limit is 8 and the upper limit is particularly preferably 20.

Next, the hydrosilylation catalyst which is the component (C) will be described. The hydrosilylation catalyst is not particularly limited as long as it has a catalytic activity for the hydrosilylation reaction, for example, simple substance of platinum, alumina, silica, carbon black or the like on which solid platinum is supported, 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 = C
H ₂ ) ₂ Cl ₂ ), platinum-vinylsiloxane complex (for example, Pt (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt
[(MeViSiO) ₄ ] _m ), platinum-phosphine complex (eg Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phosphite complex (eg Pt [P (OP (OP
h) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ ) (In the formula, Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent integers. .), Dicarbonyldichloroplatinum, Karstedt
Catalysts and Ashby US Patent No. 3
159601 and 3159662, the platinum-hydrocarbon composites, and Lamorrow (La).
and the platinum alcoholate catalysts described in US Pat. No. 3,209,972 to Moreaux. In addition, Modic US Pat. No. 3,516
The platinum chloride-olefin composites described in 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 , PdC
l ₂ .2H ₂ O, NiCl ₂ , TiCl ₄ , and the like.

Among these, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex and the like are preferable from the viewpoint of catalytic activity. Further, these catalysts may be used alone or in combination of two or more kinds.

The amount of the catalyst added is not particularly limited, but in order to have sufficient curability and to keep the cost of the curable composition relatively low, the lower limit is 10 ^{-8 with} respect to 1 mol of SiH groups.
The molar range is preferably in the upper limit of 10 ^-1 mol, and more preferably in the lower limit of 10 ^-6 mol and the upper limit is 10 ^-2 mol.

The sufficient curability described herein means that the curing speed is fast and the bonding time is suitable for the processing speed of the automatic assembly process. Specifically, the curable composition is 12
It can be represented by the gelling time when heated on a hot plate at 0 ° C., and the gelling time is preferably 300 seconds or less,
It is more preferably 200 seconds or less. A curable composition having a gelation time of more than 300 seconds on a hot plate at 120 ° C. requires a long curing time at a high temperature, which may lead to thermal deterioration of the product.

It should be noted that the catalyst amount is not necessarily added when the remaining amount used during the synthesis of the component (B) shows sufficient curability, but it is in the above range for adjusting the curability. It is also possible to newly add.

A co-catalyst can be used in combination with the above catalyst, and examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl maleate, and 2-hydroxy-2-. Examples thereof include acetylene alcohol compounds such as methyl-1-butyne, sulfur compounds such as sulfur alone, and amine compounds such as triethylamine. The amount of the co-catalyst added 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 catalyst, and a lower limit of 10 is more preferable.
^-1 mol and the upper limit is 10 mol.

Further, a curing retarder can be used for the purpose of improving the storage stability of the composition of the present invention or for adjusting the reactivity of the hydrosilylation reaction in the production process. Examples of the curing retarder include compounds containing an aliphatic unsaturated bond, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds and organic peroxides, and these may be used in combination. As a compound containing an aliphatic unsaturated bond, propargyl alcohols,
Examples thereof include en-yne compounds and maleic acid esters. Examples of the organic phosphorus compound include triorganophosphines, diorganophosphines, organophosphines, triorganophosphites and the like. Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, 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 the tin-based compound include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, t-butyl perbenzoate and the like.

Among these curing retarders, benzothiazole, thiazole, dimethylmalate and 3-hydroxy-3-methyl-1-butyne are preferable from the viewpoint of good delay activity and good availability of raw materials.

The addition amount of the storage stability improver is preferably in the range of the lower limit of 10 ^-1 mol and the upper limit of 10 ³ mol, more preferably the lower limit of 1 to 1 mol of the hydrosilylation catalyst used.
Mol, and the upper limit is 50 mol.

Next, the adhesiveness improving agent which is the component (D) will be described. As the adhesiveness improver, in addition to the commonly used adhesives, for example, various coupling agents, epoxy compounds, phenol resins, coumarone-indene resins,
Rosin ester resin, terpene-phenol resin, α-
Examples thereof include methylstyrene-vinyltoluene copolymer, polyethylmethylstyrene, and aromatic polyisocyanate.

Examples of the coupling agent include silane coupling agents. 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 at least one hydrolyzable silicon group in the molecule. As a group reactive with an organic group,
At least one functional group selected from an epoxy group, a methacrylic group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group is preferable from the viewpoint of handleability, and an epoxy group, from the viewpoint of curability and adhesiveness, A methacrylic group and an acrylic group are particularly preferable. The hydrolyzable silicon group is preferably an alkoxysilyl group from the viewpoint of handleability, a methoxysilyl group from the viewpoint of reactivity,
Ethoxysilyl groups are particularly preferred.

Preferred silane coupling agents are:
3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4
-Alkoxysilanes having an epoxy functional group such as -epoxycyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxy Silane, 3-acryloxypropyltrimethoxysilane, 3
-Alkoxysilanes having a methacrylic group or an acryl group such as acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane can be exemplified. .

The addition amount of the silane coupling agent can be variously set, but the lower limit of the addition amount is preferably 0.1 part by weight, relative to 100 parts by weight of [component (A) + component (B)].
It is more preferably 0.5 part by weight, and the preferable upper limit of the added amount is 50 parts by weight, and more preferably 25 parts by weight.
If the added amount is too small, the effect of improving the adhesiveness is not sufficient, and if the added amount is too large, it may have an adverse effect such as bleeding from the cured product.

Examples of the epoxy compound include novolac 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-glycidyl). Oxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, vinylcyclohexene dioxide, 2
-(3,4-Epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid Bisglycidyl ester, triglycidyl isocyanurate,
Examples thereof include monoallyl diglycidyl isocyanurate and diallyl monoglycidyl isocyanurate.

The addition amount of the epoxy compound can be variously set, but the lower limit of the addition amount is preferably 1 part by weight, more preferably 3 parts by weight, relative to 100 parts by weight of the [(A) component + (B) component]. Therefore, the upper limit of the preferable addition amount is 50 parts by weight, and more preferably 25 parts by weight. If the added amount is small, the effect of improving the adhesiveness is not sufficient, and if the added amount is large, the compatibility in the cured product is lowered, and the physical properties may be adversely affected.

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

Further, in the present invention, a silanol condensation catalyst can be further used in order to enhance the effect of the coupling agent or the epoxy compound, and the adhesiveness can be improved and / or stabilized. The silanol condensation catalyst is not particularly limited, but an aluminum compound and / or a titanium compound is preferable. Examples of the aluminum compound serving as a silanol condensation catalyst include aluminum triisopropoxide, sec-butoxyaluminum diisopropoxide, aluminum alkoxides such as aluminum trisec-butoxide, ethyl acetoacetate aluminum diisopropoxide, and aluminum tris (ethyl Examples include aluminum chelates such as acetoacetate), aluminum chelate M (Kawaken Fine Chemicals, alkyl acetoacetate aluminum diisopropoxide), aluminum tris (acetylacetonate), and aluminum monoacetylacetonate bis (ethylacetoacetate). Aluminum chelate is more preferable from the viewpoint of easy handling. As a titanium compound that serves as a silanol condensation catalyst, tetraisopropoxy titanium, tetraalkoxy titaniums such as tetrabutoxy titanium, titanium chelates such as titanium tetraacetylacetonate, ordinarily having a residue such as oxyacetic acid or ethylene glycol. Examples of such titanate coupling agents include:

The amount of the silanol condensation catalyst to be used can be variously set, but the lower limit of the addition amount is preferably 0.1 parts by weight, more preferably 1 part by weight, based on 100 parts by weight of the coupling agent and / or the epoxy compound. Parts, and the preferable upper limit of the addition amount is 50 parts by weight, and more preferably 30 parts by weight. If the addition amount is small, the effect of improving the adhesiveness is not sufficient, and if the addition amount is large, the compatibility in the cured product decreases,
It may adversely affect the physical properties.

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

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

The amount of the silanol source compound used can be variously set, but the preferred lower limit of the amount added is 100 parts by weight, more preferably 1 part by weight, based on 100 parts by weight of the coupling agent and / or the epoxy compound. Parts, and the preferable upper limit of the addition amount is 50 parts by weight, and more preferably 30 parts by weight. If the added amount is small, the effect of improving the adhesiveness is not sufficient, and if the added amount is large, the compatibility in the cured product decreases,
It may adversely affect the physical properties.

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

Next, the tensile storage elastic modulus in the present invention will be described. When the curable composition is heated to cure and then cooled, the cured product tends to shrink. However,
Since it is adhered at the interface with the adherend, it cannot shrink freely and internal stress occurs. Generally, internal stress occurs at a temperature lower than the glass transition temperature (Tg) of the cured product,
Along with this, distortion occurs. On page 177 of "Introduction Epoxy Resin" (1988) published by Kobunshi Shuppankai Co., Ltd., the calculation formula of the internal stress is explained by the one-dimensional elastic model. When the internal stress when cooled is mathematically expressed, [internal stress (MPa)] = ([Tg
(° C)]-[T (° C)]) x ([cured product linear expansion coefficient]
-[Linear expansion coefficient of adherend] x [Tensile elastic modulus (MPa) of cured product at T (° C)] (Equation 1) From Equation 1, it can be seen that it is effective to reduce the tensile elastic modulus in order to reduce the internal stress of the cured product. In the present invention, the tensile storage elastic modulus measured by a dynamic viscoelasticity measuring device was used instead of the tensile elastic modulus, and the internal stress at 0 ° C. was considered. From the viewpoint of reducing internal stress and improving thermal shock resistance, the tensile storage elastic modulus is 2000.
It is preferably MPa or less, and particularly preferably 1500 MPa or less.

Next, various resins that can be added for the purpose of modifying the characteristics of the composition of the present invention will be described. As the resin, polycarbonate resin, polyether sulfone resin, polyarylate resin, epoxy resin,
Examples thereof include cyanate resin, phenol resin, acrylic resin, polyimide resin, polyvinyl acetal resin, urethane resin, and polyester resin, but are not limited thereto.

The composition of the present invention can be directly molded into a film or the like, but it is also possible to dissolve the composition in an organic solvent to form a varnish. The solvent that can be used is not particularly limited, and if specifically illustrated,
Hydrocarbon solvent such as benzene, toluene, hexane, heptane, ether solvent such as tetrahydrofuran, 1,4-dioxane, diethyl ether, ketone solvent such as acetone and methyl ethyl ketone, chloroform, methylene chloride, 1,2-dichloroethane, etc. The halogen-based solvent can be preferably used. The solvent is 2
It can also be used as a mixed solvent of more than one kind. As the solvent, toluene, tetrahydrofuran and chloroform are preferable. The amount of the solvent used is preferably in the range of lower limit 0 mL and upper limit 10 mL, more preferably in the range of lower limit 0.5 mL and upper limit 5 mL, and lower limit 1 mL, with respect to the reactive (B) component 1 g used. Upper limit 3 mL
It is particularly preferable to use the above range. If the usage is low,
It is difficult to obtain the effect of using a solvent such as lowering the viscosity, and if the amount used is large, the solvent remains in the material and problems such as thermal cracks easily occur, and it is also disadvantageous in cost and industrial use Value decreases.

In the composition of the present invention, in addition, an antiaging agent, a radical inhibitor, an ultraviolet absorber, a flame retardant, a surfactant, a storage stability improver, an ozone deterioration inhibitor, a light stabilizer, a thickener, Plasticizer, antioxidant, heat stabilizer, conductivity imparting agent,
An antistatic agent, a radiation blocking agent, a nucleating agent, a phosphorus-based peroxide decomposing agent, a lubricant, a pigment, a metal deactivator, a physical property adjusting agent and the like can be added within a range that does not impair the object and effects of the present invention. .

If necessary, an inorganic filler may be added to the composition of the present invention. Addition of an inorganic filler is effective in increasing the strength of the material. 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 alkoxysilane, acyloxysilane and halogenated silane, and alkoxides, acyloxides and halides of metals such as titanium and aluminum. The method of adding to the composition of the invention and reacting in the composition or a partial reaction product of the composition to form an inorganic filler in the composition can also be mentioned.

Further, various thermosetting resins may be added for the purpose of modifying the characteristics of the composition of the present invention. Examples of the thermosetting resin include epoxy resin, cyanate resin, phenol resin, polyimide resin, urethane resin and the like, but are not limited thereto.

Further, the composition of the present invention may contain additives for improving the properties of the adhesive. Examples of the additives include inorganic fillers such as titanium oxide, aluminum oxide, silica, quartz glass, talc and calcium carbonate, and metal nitride heat conductive fillers such as aluminum nitride and boron nitride.

The adhesive of the present invention is applied to the liquid crystal display field, optical recording field, optical equipment field, optical part field, optical fiber field, semiconductor integrated circuit peripheral material field, automobile / transport machine field, construction field, next-generation optical / field field. Used in the field of electronically functional organic materials.

The curable composition of the present invention is mixed in advance and a carbon-carbon double bond reactive with the SiH group in the composition is reacted with a part or all of the SiH group to form a metal atom and / or It is possible to obtain a material that is cured by subjecting a hydrolyzable group bonded to a semimetal atom to a hydrolytic condensation reaction.

Various methods can be used for mixing the components (A), (B), and (C).
A method of mixing the component (A) with the component (C) and the component (B) is preferable. When the method of mixing the component (C) with the mixture of the components (A) and (B) is difficult to control the reaction. When the method of mixing the component (A) with the mixture of the component (B) with the component (B) is used, the component (B) is reactive with moisture in the environment in the presence of the component (C). It may deteriorate during storage.

When the composition is reacted and cured, the necessary amounts of the respective components (A), (B) and (C) may be mixed at once and reacted, but a part of them may be mixed and reacted. After the reaction, a part of the functional groups in the composition is reacted (B stage) by using the method of mixing the remaining amount and further reacting, or controlling the reaction conditions after mixing and utilizing the difference in reactivity of the substituents. It is also possible to adopt a method in which the adhesive is treated and then cured to further cure.

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

The reaction temperature can be variously set, but a lower limit of 25 ° C. and an upper limit of 300 ° C. are preferable, and a lower limit of 50.
C, the upper limit of 250 ° C is more preferable, and the lower limit of 100 ° C and the upper limit of 200 ° C are more preferable. If the reaction temperature is low, the reaction time for a sufficient reaction will be long, and if the reaction temperature is high, the product may be thermally deteriorated.

The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously if necessary. It is preferable to carry out the reaction while raising the temperature in multiple stages or continuously rather than to carry out at a constant temperature, because a uniform cured product free from distortion can be easily obtained.

The pressure during the reaction can be set variously as necessary,
The reaction can be carried out under normal pressure, high pressure, or reduced pressure.

[0085]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. (Synthesis Example 1) 1, by triallyl isocyanurate
Synthesis of 3,5,7-tetramethylcyclotetrasiloxane modified product (1) In a 1 L four-necked flask equipped with a cooling tube, a stirrer, and a thermometer, 1,3,5,7-tetramethylcyclo manufactured by Shin-Etsu Chemical Co., Ltd. 288 g of tetrasiloxane was added, 360 g of toluene was added and dissolved, and then the temperature was maintained at 110 ° C. Separately, dissolve 40 g of triallyl isocyanurate in 40 g of toluene,
A solution was prepared by adding 0.3 g of a xylene solution of a platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum), and this was added dropwise to the solution in the four-neck flask over 10 minutes, and then stirred. The reaction was carried out for 6 hours. After the reaction, 1
After adding and dissolving 0.6 g of -ethynyl-1-cyclohexanol, the mixture was allowed to cool to 25 ° C. After that, add 1 reaction mixture
The mixture was transferred to a L eggplant flask and volatile matter was distilled off at 60 ° C. under reduced pressure to obtain 130 g of modified product (1).
The hydrosilyl group content of modified product (1) was determined by proton NMR.
As a result of analysis, it was 8.04 mmol / g. As a result of the same analysis, the residual amount of allyl group was 0.10 mmol / g. The content of the hydrosilyl group and the residual amount of the allyl group were 1,2-dibromoethane as an internal standard, and the chemical shift (3.65 ppm) of the proton of this standard substance and the chemical shift of the proton of the hydrosilyl group (4.7 pp) were used.
m) Area or chemical shift of allyl protons (4.
5 ppm) area was determined by comparison. (Synthesis Example 2) Synthesis of 1,3,5,7-tetramethylcyclotetrasiloxane modified product (2) with 2,2-bis (4-allyloxyphenyl) propane 1L equipped with a cooling pipe, a stirrer, and a thermometer Put 1,3,5,7-tetramethylcyclotetrasiloxane (400 g) manufactured by Shin-Etsu Chemical Co., Ltd. into a four-necked flask, and dissolve it by adding 120 g of toluene and then heating to 70 ° C. to obtain platinum-divinyltetramethyldisiloxane. 0.025 g of a xylene solution of the complex (containing 3% by weight of platinum) was added. Separately, a solution prepared by dissolving 103 g of 2,2-bis (4-allyloxyphenyl) propane in 60 g of toluene was prepared, and this was added dropwise to the solution in the four-necked flask over 10 minutes, followed by stirring for 2 hours. It was made to react. After the reaction, the mixture was allowed to cool to 25 ° C., then a solution of 8 mg of benzothiazole in 0.2 g of toluene was added and stirred. Then, the reaction solution was transferred to a 1 L eggplant flask, and the volatile matter was distilled off at 60 ° C. under reduced pressure to obtain 250 g of modified product (2). Modified form (2)
The hydrosilyl group content of the
It was 7.51 mmol / g. No allyl residue was detected. Example 1 Triallyl isocyanurate 5.091
g, Nippon Soda polybutadiene B-1000 (number average molecular weight: 1000) 10.831 g, Kawaken Fine Chemicals aluminum tris (ethyl acetoacetate)
(Commercial name: ALCH-TR) 0.250 g and 0.075 g of a xylene solution of platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum) were mixed, dissolved with stirring, and defoamed to obtain a solution A. In addition, 9.079 g of the modified product (1) prepared in Synthesis Example 1, 0.075 g of 1-ethynyl-1-cyclohexanol and Nippon Unicar 3-
Glycidoxypropyltrimethoxysilane (trade name: A
(187) 1.250 g was mixed, dissolved with stirring, and degassed to obtain a liquid B. After that, mix liquid A and liquid B, stir,
Defoamed. As a result of measuring the viscosity of the mixed liquid at 23 ° C. with an E-type viscometer, it was 1.5 Pa · s. The gelling time on a hot plate at 120 ° C. was measured and found to be 35 seconds. Next, add 10 g of this mixed solution to a 66.5 mmφ ointment can.
Was poured and heated in air at 180 ° C. for 10 minutes to obtain a void-free transparent cured product. Separately, the mixed solution was applied to a glass plate and heated under the same conditions as above to prepare a cured coating film. The cured product produced by the above operation was analyzed and evaluated as follows. First, the tensile storage elastic modulus of a cured product produced from an ointment can was measured at a temperature rising rate of 5 ° C./min by a dynamic viscoelasticity measuring device DVA-200 manufactured by IT measurement control. The tensile storage elastic modulus at 0 ° C. was 1490 MPa. In addition, the adhesiveness of the coating film formed on the glass plate is measured according to JIS K 5400.
It was evaluated by the cross-cut method. As a result of observing the coating film, no peeling was observed and good adhesion was exhibited. Next, another coating film formed on the glass plate was kept in dry ice at -70 ° C for 1 minute and then kept in a hot air oven at 100 ° C for 1 minute. After repeating this thermal shock test three times, cool to 25 ° C,
As a result of similarly evaluating the adhesiveness of the coating film, no peeling was observed,
It showed good adhesion. Example 2 Triallyl isocyanurate 3.001
g, Nippon Soda polybutadiene B-1000 (number average molecular weight: 1000) 15.502 g, Kawaken Fine Chemicals aluminum tris (ethyl acetoacetate)
(Commercial name: ALCH-TR) 0.250 g and 0.113 g of a xylene solution of platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum) were mixed, stirred and dissolved, and defoamed to obtain solution A. In addition, 6.497 g of the modified product (1) prepared in Synthesis Example 1, 0.075 g of 1-ethynyl-1-cyclohexanol, and 3-
Glycidoxypropyltrimethoxysilane (trade name: A
(187) 1.250 g was mixed, dissolved with stirring, and degassed to obtain a liquid B. After that, mix liquid A and liquid B, stir,
Defoamed. As a result of measuring the viscosity of the mixed liquid at 23 ° C. with an E-type viscometer, it was 2.1 Pa · s. The gelling time on a hot plate at 120 ° C. was measured and found to be 39 seconds. Next, add 10 g of this mixed solution to a 66.5 mmφ ointment can.
Was poured and heated in air at 180 ° C. for 10 minutes to obtain a void-free transparent cured product. Separately, the mixed solution was applied to a glass plate and heated under the same conditions as above to prepare a cured coating film. The cured product produced by the above operation was analyzed and evaluated as follows. First, the tensile storage elastic modulus of a cured product produced from an ointment can was measured at a temperature rising rate of 5 ° C./min by a dynamic viscoelasticity measuring device DVA-200 manufactured by IT measurement control. The tensile storage elastic modulus at 0 ° C. was 187 MPa. Further, the adhesiveness of the coating film prepared on the glass plate was evaluated by the cross-cutting method of JIS K5400. As a result of observing the coating film, no peeling was observed and good adhesion was exhibited. Next, another coating film formed on the glass plate was kept in dry ice at -70 ° C for 1 minute and then kept in a hot air oven at 100 ° C for 1 minute. After repeating this thermal shock test 3 times, it was cooled to 25 ° C., and the adhesion of the coating film was evaluated in the same manner. As a result, no peeling was observed and good adhesion was exhibited. (Example 3) 2,2-bis (4-allyloxyphenyl) propane 7.906 g, Nippon Soda's polybutadiene B-1000 (number average molecular weight: 1000) 9.063
Aluminum tris (ethyl acetoacetate) manufactured by Kawaken Fine Chemicals (trade name: ALCH-TR)
250 g and xylene solution of platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum) 0.075 g
Was mixed, stirred, dissolved, and defoamed to obtain a solution A. Further, 8.032 g of modified product (2) prepared in Synthesis Example 2
-Ethynyl-1-cyclohexanol (0.075 g) and Nippon Unicar 3-glycidoxypropyltrimethoxysilane (trade name: A-187) 1.250 g were mixed,
What was stirred, dissolved and defoamed was designated as solution B. Then, the liquid A and the liquid B were mixed, stirred, and defoamed. The viscosity of the mixed solution is 23 ° C.
Below, it was 0.6 Pa.s as a result of measurement with an E-type viscometer. The gelling time on a hot plate at 120 ° C. was measured and found to be 41 seconds. Next, 10 g of this mixed solution was poured into a 66.5 mmφ ointment can, and the mixture was heated at 180 ° C. for 10 minutes.
It was heated in air to obtain a void-free transparent cured product. Separately, the mixed solution was applied to a glass plate and heated under the same conditions as above to prepare a cured coating film. The cured product produced by the above operation was analyzed and evaluated as follows. First, the tensile storage elastic modulus of a cured product produced from an ointment can was measured at a temperature rising rate of 5 ° C./min by a dynamic viscoelasticity measuring device DVA-200 manufactured by IT measurement control. Tensile storage modulus at 0 ° C is 778 MPa
Met. Further, the adhesiveness of the coating film prepared on the glass plate was evaluated by the cross-cutting method of JIS K5400. As a result of observing the coating film, no peeling was observed and good adhesion was exhibited. Next, another coating film formed on the glass plate was kept in dry ice at -70 ° C for 1 minute and then kept in a hot air oven at 100 ° C for 1 minute. After repeating this thermal shock test 3 times, it was cooled to 25 ° C., and the adhesion of the coating film was evaluated in the same manner. As a result, no peeling was observed and good adhesion was exhibited. (Example 4) 2,2-bis (4-allyloxyphenyl) propane 4.983 g, Nippon Soda polybutadiene B-1000 (number average molecular weight: 1000) 13.871
Aluminum tris (ethyl acetoacetate) manufactured by Kawaken Fine Chemicals (trade name: ALCH-TR)
250 g and xylene solution of platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum) 0.113 g
Was mixed, stirred, dissolved, and defoamed to obtain a solution A. In addition, 6.146 g of modified product (2) prepared in Synthesis Example 2
-Ethynyl-1-cyclohexanol (0.075 g) and Nippon Unicar 3-glycidoxypropyltrimethoxysilane (trade name: A-187) 1.250 g were mixed,
What was stirred, dissolved and defoamed was designated as solution B. Then, the liquid A and the liquid B were mixed, stirred, and defoamed. The viscosity of the mixed solution is 23 ° C.
Below, it was 1.0 Pa.s as a result of measurement with an E-type viscometer. The gelling time on a hot plate at 120 ° C. was measured and found to be 41 seconds. Next, 10 g of this mixed solution was poured into a 66.5 mmφ ointment can, and the mixture was heated at 180 ° C. for 10 minutes.
It was heated in air to obtain a void-free transparent cured product. Separately, the mixed solution was applied to a glass plate and heated under the same conditions as above to prepare a cured coating film. The cured product produced by the above operation was analyzed and evaluated as follows. First, the tensile storage elastic modulus of a cured product produced from an ointment can was measured at a temperature rising rate of 5 ° C./min by a dynamic viscoelasticity measuring device DVA-200 manufactured by IT measurement control. The tensile storage elastic modulus at 0 ° C. was 67 MPa. In addition, the adhesiveness of the coating film prepared on the glass plate is
It was evaluated by the cross-cutting method of IS K 5400. As a result of observing the coating film, no peeling was observed and good adhesion was exhibited.
Next, another coating film formed on the glass plate was kept in dry ice at -70 ° C for 1 minute and then kept in a hot air oven at 100 ° C for 1 minute. After repeating this thermal shock test 3 times, 2
As a result of cooling to 5 ° C. and similarly evaluating the adhesiveness of the coating film,
No peeling was observed and good adhesion was exhibited. (Comparative Example 1) 9.937 g of triallyl isocyanurate
And 0.075 g of a xylene solution of platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum) are mixed,
What was stirred, dissolved and defoamed was designated as solution A. In addition, Synthesis Example 1
15.063 g of the modified product (1) prepared in 1. and 0.075 g of 1-ethynyl-1-cyclohexanol were mixed, stirred and dissolved, and defoamed to obtain a liquid B. Then, the liquid A and the liquid B were mixed, stirred, and defoamed. When the viscosity of the mixed solution is 23 ° C., E
As a result of measurement with a Brookfield viscometer, it was 0.7 Pa · s. In addition, as a result of measuring the gelation time on a hot plate at 120 ° C,
It was 33 seconds. Next, 10 g of this mixed solution was poured into a 66.5 mmφ ointment can and heated in air at 180 ° C. for 10 minutes, and as a result, a cracked transparent cured product was obtained. Separately, the mixed solution was applied to a glass plate and heated under the same conditions as above to prepare a cured coating film. The cured product produced by the above operation was analyzed and evaluated as follows. First, the tensile storage elastic modulus of a cured product produced from an ointment can was measured at a temperature rising rate of 5 ° C./min by a dynamic viscoelasticity measuring device DVA-200 manufactured by IT measurement control. Tensile storage modulus at 0 ° C is 2100MP
It was a. Further, the adhesiveness of the coating film prepared on the glass plate was evaluated by the cross-cutting method of JIS K5400. As a result of observing the coating film, some peeling was observed, but it showed adhesiveness. Next, another coating film formed on the glass plate was kept in dry ice at -70 ° C for 1 minute and then kept in a hot air oven at 100 ° C for 1 minute. After repeating this thermal shock test three times, it was cooled to 25 ° C. and the adhesion of the coating film was evaluated in the same manner. As a result, 80% or more of the coating film was peeled off.

[0086]

Industrial Applicability Since the material produced from the composition of the present invention is a low elastic cured product which can be obtained by rapid curing and can absorb strain generated by stress, it is industrially very useful.

Continued front page    F-term (reference) 4J002 AC031 AC061 AF023 BC011                       BC083 BC093 BE041 BF051                       BG041 BK001 BK003 CC031                       CC033 CC042 CD023 CD053                       CD063 CD103 CD143 CE003                       CF001 CF161 CG001 CH051                       CH052 CL001 CM041 DA117                       DD007 DD077 DE097 EC077                       EE017 EE027 ER008 EU198                       EW017 EW067 EX036 EX058                       EX068 EZ007 FB297 FD010                       FD142 FD146 FD157 FD200                       FD203 FD208 GJ01 GN00                       GQ00                 4J040 DF041 EB051 ED001 EE001                       EG001 EH031 EL021 GA01                       GA31 KA14

Claims (6)

[Claims] 1. An organic compound containing (A) a carbon-carbon double bond reactive with a SiH group, (B) a silicon compound containing at least two SiH groups in one molecule,
A curable composition comprising (C) a hydrosilylation catalyst and (D) an adhesion improver as essential components, wherein the cured product has a tensile storage elastic modulus at 0 ° C. of 2000 MPa or less. Composition. 2. At least 0.5% by weight in the component (A)
Is a monomer component containing a carbon-carbon double bond reactive with a SiH group, The curable composition according to claim 1. 3. The component (A) contains polybutadiene having at least one carbon-carbon double bond reactive with a SiH group in one molecule.
Alternatively, the curable composition according to claim 2. 4. The curable composition according to claim 1, which has a viscosity at 23 ° C. of 10 Pa · s or less. 5. A gelation time of 300 on a hot plate at 120 ° C.
The curable composition according to any one of claims 1 to 4, which is not more than a second. 6. A fast-curing adhesive using the curable composition according to claim 5.