JPH10147713A - Thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin compsn. excellent in the storability in the form of a soln. thereof and capable of forming a cured product excellent in adhesion to various bases, thermal resistance, moist heat resistance and electrical insulating properties without causing cracks in the course of the curing. SOLUTION: This compsn. comprises (A) a hydrolyzate of a hydrolyzable organosilane compd. and/or partial condensate thereof, (B) a polyamic acid having a hydrolyzable silyl group and/or a polyimide having a hydrolyzable silyl group and (C) a chelating compd. or an alkoxide compd. of a metal selected from among zirconium, titanium and aluminum.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hydrolyzable organosilane compound and / or a partial condensate thereof and a polyamic acid and / or a polyimide having a hydrolyzable silyl group, and has a storage stability. The present invention relates to a novel thermosetting resin composition having excellent crack resistance, adhesion, heat resistance, moisture and heat resistance, electrical insulation and the like.

[0002]

BACKGROUND OF THE INVENTION It is well known that alkoxysilane compounds form polysiloxane resins by hydrolysis and subsequent dehydration condensation reactions. This polysiloxane resin has thermosetting properties, and although the cured product is excellent in heat resistance and electrical insulation, when an alkoxysilane compound is used as a starting material, the volume shrinkage during curing is large,
There is a problem that cracks are easily generated in the cured product.
Then, the hydrolyzate of the alkoxysilane compound and / or
Or, an attempt is made to mix an acrylic resin or the like with the partial condensate thereof to prevent the occurrence of cracks during curing. For example, a partial condensate of an organosilane, a dispersion of colloidal silica, and a silicone-modified acrylic resin (See, for example, JP-A-60-135465), a composition comprising a condensate of an organosilane, a chelate compound of a zirconium alkoxide and a vinyl resin having a hydrolyzable silyl group (for example, JP-A-64-1).
No. 769), a composition comprising a partial condensate of an organosilane, a hydrolyzable silyl group-containing vinyl resin, a metal chelate compound, and β-diketones and / or β-ketoesters (see, for example, JP-A No. 5882
4 gazettes) have been proposed. However, all of the cured products obtained from these compositions have the disadvantage that the inherent heat resistance of the polysiloxane resin is impaired.
Further, generally a polyimide resin obtained from a tetracarboxylic dianhydride and a diamine compound via a polyamic acid,
Used for alignment films for liquid crystals, insulating films for semiconductors, protective films, adhesives, etc.Aromatic polyimide resins have excellent heat resistance and high strength. It is used. However, since polyimide resins generally have lower electric insulation and lower moisture resistance than polysiloxane resins, it has been proposed to modify polyimide resins with polysiloxane resins. For example, JP-A-58-7437 and JP-A-58-13
No. 631 and the like, as a diamine compound constituting a polyimide resin, H ₂ N- (CH ₂ ) _3- (Si (CH ₃ ) ₂ O) _m -Si (CH ₃ ) _2- (CH ₂ ) _3- A method using a dimethyl silicone oligomer represented by NH ₂ (where m is an integer of 1 to 100) has been proposed,
Such a composition has a disadvantage that heat resistance is reduced. Also, JP-A-63-99236, JP-A-63-99236
No. 536 and the like disclose a method of mixing a hydrolysis / condensate of alkoxysilane and a polyamic acid (ie, polyamic acid) solution.
There is a disadvantage that the dispersibility of the polysiloxane component in the polyimide resin in the coating film is poor, and the smoothness of the coating film is poor. Further, JP-A-6-207024 discloses a solution obtained by hydrolyzing and condensing an alkoxysilane in a polyamic acid solution having a specific silyl group. On the other hand, when the content of the polysiloxane component increases, the heat resistance of the coating film decreases, and the storage stability of the mixed solution of the polyamic acid and the hydrolysis / condensation product of the alkoxysilane is poor.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems in the prior art, and its object is to provide a solution which is excellent in storage stability and has no cracks during curing. Another object of the present invention is to provide a thermosetting resin composition capable of forming a cured product excellent in adhesion to various substrates, heat resistance, heat and humidity resistance, electrical insulation and the like.

[0004]

The gist of the present invention is that (A)
A hydrolyzate of a hydrolyzable organosilane compound and / or
Or a partial condensate thereof, (B) a polyamic acid having a hydrolyzable silyl group and / or a polyimide having a hydrolyzable silyl group, and (C) a chelate compound of a metal selected from the group consisting of zirconium, titanium and aluminum, and / or Or a thermosetting resin composition containing an alkoxide compound.

Hereinafter, the present invention will be described in detail. (A) Component The (A) component in the present invention comprises a hydrolyzate of a hydrolyzable organosilane compound and / or a partial condensate thereof. As the hydrolyzable organosilane compound, the following general formula (1) (R ¹ ) _n Si (OR ² ) _4-n (1) [In the general formula (1), R ¹ has 1 to ¹ carbon atoms. 8 organic groups,
R ² represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 2. (Hereinafter, referred to as “silane compound (I)”). In the general formula (1), examples of the organic group having 1 to 8 carbon atoms for R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
i-butyl group, sec-butyl group, t-butyl group, n-
In addition to linear or branched alkyl groups such as pentyl, n-hexyl, n-heptyl and n-octyl,
3-chloropropyl group, 3-bromopropyl group, 3,
3,3-trifluoropropyl group, 3-glycidoxypropyl group, 3- (meth) acryloxypropyl group, 3-
Examples thereof include a mercaptopropyl group, a 3-aminopropyl group, a 3-dimethylaminopropyl group, a 2- (3,4-epoxycyclohexyl) ethyl group, a vinyl group, and a phenyl group. In the general formula (1), when two R ¹ are present, each R ¹ may be mutually the same or different. Further, as the alkyl group having 1 to 5 carbon atoms of R ² , for example,
Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group,
Examples thereof include straight-chain or branched-chain groups such as a t-butyl group and an n-pentyl group. Examples of the acyl group having 1 to 4 carbon atoms include an acetyl group, a propionyl group, and a butyryl group. it can. In the general formula (1), R ²
When two to four are present, each R ² may be mutually the same or different.

Specific examples of such a silane compound (I) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane and tetra-silane.
tetraalkoxysilanes such as i-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane,
alkyltrialkoxysilanes such as i-propyltriethoxysilane, n-butyltrimethoxysilane and i-butyltrimethoxysilane; 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3- Haloalkyl trialkoxysilanes such as trifluoropropyltrimethoxysilane and 3,3,3-trifluoropropyltriethoxysilane; glycides such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane (Meth) acryloxyalkyl trialkoxysilanes such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropyltriethoxysilane; 3-mercaptopropyltrimethoate Mercaptoalkyl trialkoxysilanes such as silane and 3-mercaptopropyltriethoxysilane; aminoalkyltrialkoxysilanes such as 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane; vinyltrimethoxysilane and vinyltriethoxy Vinyltrialkoxysilanes such as silane; phenyltrialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane; and 3,4-epoxycyclohexylethyltrimethoxysilane and 3,4-epoxycyclohexylethyltriethoxysilane. , 4-epoxycyclohexylalkyl trialkoxysilanes; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane Di -n- propyl dimethoxysilane, di -n- propyl diethoxy silane, di -i- propyl dimethoxysilane, di -i- propyl diethoxy silane, diphenyl dimethoxy silane,
Dialkoxysilanes such as diphenyldiethoxysilane; and acyloxysilanes such as tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, dimethyldiacetoxysilane, and diethyldiacetoxysilane. Among these silane compounds (I), tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane and the like are preferable. In the present invention, the silane compound (I) can be used alone or in combination of two or more. In the present invention, the component (A)
The silane compound (I) can be used after being hydrolyzed and partially condensed in advance. Usually, when the silane compound (I) and the component (B) described below are blended, an appropriate amount of water is added. During the preparation of the composition, the silane compound (I) is hydrolyzed and partially condensed to obtain the component (A). The amount of water added during the hydrolysis and partial condensation of the silane compound (I) is usually per equivalent of the alkoxysilyl group and / or the acyloxysilyl group in the silane compound (I).
It is about 0.3-1 mol, preferably about 0.3-0.8 mol. The weight average molecular weight in terms of polystyrene (hereinafter, referred to as “Mw”) of the component (A) determined by gel permeation chromatography (GPC) is preferably from 2,000 to 100,000.

Component (B) The component (B) in the present invention comprises a polyamic acid having a hydrolyzable silyl group and / or a polyimide having a hydrolyzable silyl group. As the component (B), a hydrolyzable silyl group represented by the following general formula (2) (hereinafter, referred to as the component (B))
It is referred to as “hydrolyzable silyl group (2)”. ) Is a repeating unit represented by the following general formula (3) in a polyamic acid (hereinafter, referred to as “repeating unit (3)”) or a repeating unit represented by the following general formula (4) in a polyimide (hereinafter, referred to as “repeating unit”). With respect to 1 mol of the repeating unit (4) ”).
Polyamic acids or polyimides containing from 02 to 0.8 mol, particularly preferably from 0.02 to 0.5 mol, are preferred. However, when the thermosetting resin composition of the present invention contains both a polyamic acid and a polyimide, the average content of the hydrolyzable silyl group (2) is equal to that of the repeating unit (3) and the repeating unit (4). It is within the above range for a total of 1 mole.

[0008]

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[In the general formula (2), R ¹ has 1 to ¹ carbon atoms.
An organic group of 8 and R ² represent an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, and m is an integer of 0 to 2. ]

[0010]

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[0011]

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[In the general formulas (3) and (4), R ³ represents a tetravalent organic group, and R ⁴ represents a divalent organic group. In the general formula (2), examples of the organic group having 1 to 8 carbon atoms for R ¹ and the alkyl group having 1 to 5 carbon atoms or the acyl group having 1 to 4 carbon atoms for R ² include, for example, the general formula (1) Each of R ¹
It can be mentioned the groups exemplified for and R ^2. In the general formula (2), when two R ¹ are present, each R ¹ may be the same or different from each other. When two or three R ² are present, each R ² may be the same or different from each other. Is also good. Further, R ¹ and R ² in the general formula (2) are each represented by the general formula (1)
May be the same as or different from R ¹ and R ² . In the general formulas (3) and (4), the tetravalent organic group for R ³ may be any of an aliphatic organic group, an alicyclic organic group and an aromatic organic group, and particularly preferably has 6 to 6 carbon atoms. 120 aromatic organic groups are preferred. Examples of the tetravalent aromatic organic group include:

[0013]

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[Wherein, R ^{5 to} R ¹⁰ may be the same or different from each other, and include a hydrogen atom, an alkyl group (for example, a methyl group,
Ethyl group), a fluoroalkyl group (eg, a trifluoromethyl group) or a phenyl group. And the like. The divalent organic group for R ⁴ may be any of an aliphatic organic group, an alicyclic organic group, and an aromatic organic group, and is preferably an aromatic organic group having 6 to 120 carbon atoms. As the divalent aromatic organic group, for example,

[0015]

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[In the formula, R ^{11 to} R ¹⁶ may be the same or different from each other, and represent a hydrogen atom, an alkyl group (eg, methyl group, ethyl group, etc.), a fluoroalkyl group (eg, trifluoromethyl group, etc.) Or a phenyl group. And the like. Repeating unit in polyamic acid (3) and repeating unit in polyimide (4)
May each be present in one or more types. Also,
In the present invention, the polyamic acid may be partially imidized, and the imidation ratio in this case is less than 50%, while the polyimide may not be partially imidized, and The imidation ratio is 50% or more, preferably 90% or more. As the method for synthesizing the component (B) in the present invention, various methods can be adopted,
Although not particularly limited, for example, (a) a repeating unit (3)
And a diamine compound corresponding to the repeating unit (3) are polycondensed in an organic solvent to obtain a solution of a polyamic acid, and then a carboxylic acid anhydride group and a hydrolyzable group And / or a silane compound having a functional group capable of reacting with a carboxyl group and a hydrolyzable group (hereinafter, these silane compounds are collectively referred to as “functional silane compound”). A method for obtaining a solution of a polyamic acid having a hydrolyzable silyl group, (b) in the presence of a functional silane compound, corresponding to the tetracarboxylic dianhydride corresponding to the repeating unit (3) and the repeating unit (3) A method of polycondensing a diamine compound with an organic solvent to obtain a solution of a polyamic acid having a hydrolyzable silyl group, (c) a method of the above (a) or (b); A polyamic acid obtained by the above method is subjected to a thermal or chemical dehydration ring-closing reaction in an organic solvent to obtain a solution of a polyimide having a hydrolyzable silyl group, corresponding to (d) the repeating unit (3) And a diamine compound corresponding to the repeating unit (3) are polycondensed in an organic solvent to obtain a solution of a polyamic acid, and then the polyamic acid is subjected to a thermal or chemical method in the solution. A polyimide solution by a dehydration ring-closing reaction by a conventional method, and then a functional silane compound to obtain a solution of a polyimide having a hydrolyzable silyl group, (e) corresponding to the repeating unit (3) Tetracarboxylic dianhydride, a silane compound having two amino groups and a hydrolyzable group, for example, the following general formula

[0017]

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[0018] [where, R ^1, R ² and m have the same meanings as R ^1, R ² and m, respectively, in formula (2), R ⁵ is a divalent organic group (preferably 1 number phenylene group or a C ~ 1
0 alkylene group). And a compound represented by the formula:
A method of obtaining a solution of a polyamic acid having a hydrolyzable silyl group by polycondensation in an organic solvent together with a diamine compound corresponding to the general formula (3), if necessary. A method of obtaining a polyimide solution by subjecting the obtained polyamic acid to a dehydration ring-closing reaction in an organic solvent by a thermal method or a chemical method to obtain a polyimide solution. Among these methods, the method (a), (d) or (e) is preferable, and the method (a) or (d) is particularly preferable.

Examples of the functional silane compound include a carboxylic acid anhydride group such as an acid anhydride of 3,4-dicarboxyphenyltrimethoxysilane and an acid anhydride of 3,4-dicarboxybenzyltrimethoxysilane. Silanes; Mercaptosilanes such as mercaptomethyltrimethoxysilane, 2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane; 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane,
3-aminopropyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane, (2-aminoethylamino) methyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3-
(2-aminoethylamino) propyldimethoxymethylsilane, 3- [2- (2-aminoethylamino) ethylamino] propyltrimethoxysilane, N- (3-trimethoxysilylpropyl) urea, N- (3-tri Ethoxysilylpropyl) urea, 2- (2-aminoethylthio) ethyltrimethoxysilane, 2- (2-aminoethylthio) ethyltriethoxysilane, 2- (2-aminoethylthio) ethyldimethoxymethylsilane, 2-
Aminosilanes such as (2-aminoethylthio) ethyldiethoxymethylsilane; bis (3-trimethoxysilylpropyl) amine, bis (3-triethoxysilylpropyl) amine, 3-cyclohexylaminopropyltrimethoxysilane, Cyclohexylaminopropyldimethoxymethylsilane, 3-phenylaminopropyltrimethoxysilane, 3-phenylaminopropyldimethoxymethylsilane, 3-benzylaminopropyltrimethoxysilane, 3-benzylaminopropyldimethoxymethylsilane, 3- (p-vinylbenzyl) Amino) propyltrimethoxysilane, 3- (p-vinylbenzylamino) propyldimethoxymethylsilane, 3-allylaminopropyltrimethoxysilane, 3-allylaminopropyldimethoxy Iminosilanes such as tylsilane, 3-piperazinopropyltrimethoxysilane, 3-piperazinopropyldimethoxymethylsilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycid Epoxy silanes such as xypropyldimethoxymethylsilane, 3-glycidoxypropyldiethoxymethylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane And isocyanate groups such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyldimethoxymethylsilane, and 3-isocyanatopropyldiethoxymethylsilane. Mention may be made of the emissions, and the like. These functional silane compounds can be used alone or in combination of two or more.

The organic solvent used in the above-mentioned methods (a) to (f) is not particularly limited as long as it is inert to the reaction raw materials and the component (B) obtained and can dissolve them. It is not limited, and examples thereof include amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; aprotic polar solvents such as dimethylsulfoxide; phenol solvents such as phenol and cresol. These organic solvents can be used alone or in combination of two or more. When synthesizing the polyamic acid in each of the above methods, the total amount of the tetracarboxylic dianhydride and the diamine compound is usually 1 to 50% by weight, preferably 2 to 30% by weight based on the total solution weight, Usually, the reaction is carried out at 150 ° C or lower, preferably at 0 to 120 ° C. In the method (c), (d) or (f), the temperature of the thermal imidization reaction when synthesizing the polyimide is usually
50 to 400 ° C, preferably 100 to 350 ° C;
The temperature of the chemical imidization reaction is usually from 0 to 200 ° C.

The content of the hydrolyzable silyl group (2) in the component (B) in the present invention is usually 0.1 to 70% by weight, preferably 0.5 to 60% by weight, particularly preferably 1 to 60% by weight.
５０50% by weight. In this case, when the content of the hydrolyzable silyl group (2) is less than 0.1% by weight, the transparency and homogeneity of the obtained cured product tend to decrease. In addition,
70% by weight of the hydrolyzable silyl group (2) in the component (B)
It is practically impossible to contain more than. The logarithmic viscosity [η] (in N-methylpyrrolidone, 30 ° C., 0.5 g / dl) of the component (B) in the present invention is usually 0.1.
It is 0.5-5 dl / g, preferably 0.1-3 dl / g. In the present invention, the component (B) can be used alone or in combination of two or more. The mixing ratio of the component (B) in the present invention is usually 5 to 1 based on 100 parts by weight of the component (A) after the condensation reaction of the thermosetting resin composition.
000 parts by weight, preferably 10 to 800 parts by weight, more preferably 15 to 600 parts by weight. in this case,
When the blending ratio of the component (B) is less than 5 parts by weight, cracks may be generated when the obtained thermosetting resin composition is cured, and when it exceeds 1000 parts by weight, the moisture resistance of the cured product tends to decrease. There is.

Component (C) The component (C) in the present invention comprises a chelate compound and / or alkoxide compound of a metal selected from the group consisting of zirconium, titanium and aluminum. These compounds are considered to promote the condensation reaction between the component (A) and the component (B), and to promote the formation of a co-condensate of both components. As such a component (C),
For example, the following general formula: Zr (OR ¹⁷ ) _p (R ¹⁸ COCHCOR ¹⁹ ) _4-p , Ti (OR ¹⁷ ) _q (R ¹⁸ COCHCOR ¹⁹ ) _4-q or Al (OR ¹⁷ ) _r (R ¹⁸ COCHCOR ¹⁹ ) ₃ Compounds represented by _-r or partial hydrolysates of these compounds can be mentioned. In each of the above formulas, R ¹⁷
And R ¹⁸ may be the same or different from each other, and include an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
sec-butyl group, t-butyl group, n-pentyl group, n
-Represents a linear or branched alkyl group having 1 to 6 carbon atoms such as a hexyl group, and R ¹⁹ represents an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, A butyl group, a linear or branched alkyl group having 1 to 5 carbon atoms such as an n-pentyl group, or a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-
Butoxy group, i-butoxy group, sec-butoxy group, t
-Represents a straight-chain or branched-chain alkoxyl group having 1 to 16 carbon atoms such as a butoxy group, a lauryloxy group and a stearyloxy group. When two or more of R ¹⁷ , R ¹⁸ or R ¹⁹ are present in each of the above formulas, the respective groups may be the same or different from each other. P and q are integers of 0 to 3;
整数 2.

Specific examples of the component (C) include tri-n-
Butoxy ethyl acetoacetate zirconium, di-
n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, etc. Zirconium chelate compounds of the following formulas: di-i-propoxybis (ethylacetoacetate) titanium, di-i-propoxybis (acetylacetate) titanium, di-i-propoxybis (acetylacetate) titanium, tri-n-butoxy・ Ethyl acetoacetate titanium, tri-i-propoxy ・ ethyl acetoacetate titanium, tri-n-butoxy ・ acetoacetate titanium, tri-i-propoxy ・ acetoacetate titanium, di n-butoxybis (ethylacetoacetate) titanium, di-n-butoxybis (acetoacetate) titanium, n-butoxytris (ethylacetoacetate) titanium, n-butoxytris (acetoacetate) titanium, tetrakis ( Titanium chelate compounds such as ethyl acetoacetate) titanium and tetrakis (acetoacetate) titanium; di-i-propoxy ethyl acetoacetate aluminum, di-i-propoxy acetyl acetate aluminum, i-propoxy bis (ethyl acetoacetate) aluminum , I-
Propoxy bis (acetylacetate) aluminum, tris (ethylacetoacetate) aluminum,
Aluminum chelate compounds such as tris (acetylacetate) aluminum and monoacetylacetatebis (ethylacetoacetate) aluminum; tetra-i
-Zirconium alkoxide compounds such as propoxy zirconium and tetra-n-butoxy zirconium; titanium alkoxide compounds such as tetra-i-propoxy titanium and tetra-n-butoxy titanium; tetra-i-propoxy aluminum and tetra-n-butoxy aluminum Aluminum alkoxide compounds and the like can be mentioned. Among these compounds, tri-n-butoxyethylacetoacetate zirconium, di-i-propoxybis (acetylacetate) titanium, di-i-
Propoxy ethyl acetoacetate aluminum and tris (ethyl acetoacetate) aluminum are preferred. In the present invention, the component (C) can be used alone or in combination of two or more. The compounding ratio of the component (C) is as follows.
Usually, 0.01 to 50 parts by weight, based on 100 parts by weight,
Preferably 0.1 to 50 parts by weight, more preferably 0.1 to 50 parts by weight.
It is 5 to 10 parts by weight. In this case, when the mixing ratio of the component (C) is outside the above range, the heat resistance of the obtained cured product tends to decrease.

Further, in the present invention, it is preferable to use the following component (D) in addition to the components (A), (B) and (C). Component (D) Component (D) has the general formula R ¹⁸ COCH ₂ COR ¹⁹ (where, R ¹⁸ and R ^19, R ¹⁸ and R in the general formula representing the metal chelate compound of each component (C)
^It is synonymous with ¹⁹ , but both R ¹⁸ and R ¹⁹ may be the same or different from each other. ) Represented by β-diketones and / or β-ketoesters,
It has an effect of further improving the storage stability of the thermosetting resin composition of the present invention. That is, the component (D) is
By coordinating to a metal atom in the metal chelate compound constituting the component (C), the metal chelate compound (A)
It is considered that by appropriately suppressing the promotion of the condensation reaction between the component and (B), the storage stability of the resulting thermosetting resin composition is improved. Specific examples of such component (D) include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, and n-acetoacetate.
-Butyl, i-butyl acetoacetate, acetoacetate sec-
Butyl, t-butyl acetoacetate, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3 , 5-nonandione, 5
-Methyl-2,4-hexanedione. Among these compounds, acetylacetone and ethyl acetoacetate are preferred, and acetylacetone is particularly preferred. In the present invention, the component (D) can be used alone or in combination of two or more. The mixing ratio of the component (D) is usually 2 mol or more per 1 mol of the component (C),
Preferably it is 3 to 20 mol, more preferably 4 to 15 mol. In this case, if the blending ratio of the component (D) is less than 2 mol, the effect of improving the storage stability of the obtained thermosetting resin composition tends to decrease.

Other Additives Depending on the curing conditions of the thermosetting resin composition of the present invention, at least one curing accelerator (hereinafter, referred to as “component (E)”) may be blended, and relatively low. For curing at a temperature, the combination use of the component (E) is effective. Examples of the component (E) include: alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid; alkaline compounds such as sodium hydroxide and potassium hydroxide; alkyltitanic acid, phosphorus Acidic compounds such as acid, p-toluenesulfonic acid and phthalic acid; 1,2-ethylenediamine, 1,6-hexylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, m-phenylenediamine, p -Phenylenediamine, ethanolamine,
Amines such as triethylamine and N-methylmorpholine, and various modified amines used as curing agents for epoxy resins; 3-aminopropyltriethoxysilane;
Amino group-containing silane compounds such as (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane, and 3-anilinopropyltrimethoxysilane; (C ₄ H ₉ ) ₂ Sn (OCOC _{11
H 23) 2, (C 4} H 9) 2 Sn (OCOCH = CHCOOCH 3) 2, (C 4 H 9) 2 Sn (OCOC
H = CHCOOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn
(OCOCH = CHCOOCH ₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOC ₄ H ₉ ) ₂ ,
(C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOC ₈ H ₁₇ ) ₂ , carboxylic acid type organotin compounds such as Sn (OCOC ₈ H ₁₇ ) ₂ ; (C ₄ H ₉ ) ₂ Sn (SCH ₂ COO) ₂ ,
(C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COO) ₂ , (C
₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COO) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOCH ₂ CH ₂ OC
OCH ₂ S) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOCH ₂ CH ₂ CH ₂ CH ₂ OCOCH
₂ S) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂
COOC ₁₂ H ₂₅ ) ₂ ,

[0026]

Embedded image

A mercaptide-type organotin compound such as (C ₄ H ₉ )
₂ Sn = S, (C ₈ H ₁₇ ) ₂ Sn = S,

[0028]

Embedded image

(C ₄ H ₉ ) ₂ S
n = O, reaction product of oxide type organic tin oxide such as (C ₈ H ₁₇ ) ₂ Sn = O and an ester compound such as ethyl silicate, dimethyl maleate, diethyl maleate, dioctyl phthalate, etc. Organic tin compounds and the like can be mentioned. (E)
The mixing ratio of the components is usually 15% by weight or less, preferably 10% by weight or less, based on the total solid content of the components (A) to (E). The component (C) also functions as a curing accelerator. The method of adding the component (E) is not particularly limited, and can be added at the time of preparing the thermosetting resin composition of the present invention and / or at an appropriate stage after the preparation. Further, for example, fillers such as clay, zeolite, talc, mica, silica, carbon black, graphite, alumina, calcium carbonate, wollastonite, glass, carbon, alumina, potassium titanate, aluminum borate, silicon carbide, nitrided Fibers such as silicon, aromatic polyamide, polyamide imide, polyimide, wholly aromatic polyester, ultrahigh molecular weight polyethylene, high-strength polyacrylonitrile, and high-strength polyvinyl alcohol, or reinforcing materials such as whiskers can be blended. The reinforcing material is used in the form of a fabric such as a woven fabric, a nonwoven fabric, or a knitted fabric, and can be used by impregnating the fabric with the thermosetting resin composition of the present invention. These fillers and reinforcing materials can be used alone or in combination of two or more. In addition to the above additives, if necessary, antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers,
Antistatic agent, flame retardant, lubricant, antifogging agent, antifungal agent, pigment,
Dyes, dispersants, thickeners, leveling agents, silane coupling agents, titanium coupling agents, methyl orthoformate,
A dehydrating agent such as methyl orthoacetate and tetraethoxysilane can also be blended.

Preparation and Use of Thermosetting Resin Composition The thermosetting resin composition of the present invention is preferably prepared by preparing a composition containing the components (A), (B) and (C). It can be prepared by adding the above-mentioned component (D) as needed. Preferred methods for preparing the thermosetting resin composition are the following methods, and particularly preferable are the other methods. The mixture of the silane compound (1), the component (B), and the component (C) was added to an equivalent of the alkoxysilyl group and / or the acyloxysilyl group in the silane compound (1),
After adding 0.3 to 1 mol of water to hydrolyze and partially condense the silane compound (1) to prepare a composition comprising the components (A) to (C), if necessary, (D) How to add components. Silane compound (1) with respect to silane compound (1)
The silane compound (1) is hydrolyzed and partially condensed by adding 0.3 to 1 mol of water per equivalent of the alkoxysilyl group and / or the acyloxysilyl group therein, and then the components (B) and (C) Are added simultaneously or stepwise, and a condensation reaction is further performed to prepare a composition comprising the components (A) to (C), and then the component (D) is added as necessary. To a mixture of the silane compound (1) and the component (C), 0.3 to 1 mol of water is added per equivalent of the alkoxysilyl group and / or the acyloxysilyl group in the silane compound (1), and the silane compound (1) is added. ) Is hydrolyzed and partially condensed, then the component (B) is added, and a condensation reaction is further carried out to prepare a composition comprising the components (A) to (C). How to add components. In the methods (1) to (4), the component (E) and the other additives can be blended at an appropriate stage. In the present invention, at least two or more of the components (A), (B) and (C) constituting the thermosetting resin composition are chemically bonded partially or entirely. Is also good.

In the present invention, an organic solvent can be used to adjust the total solid content of the thermosetting resin composition and also adjust the viscosity. Such an organic solvent is not particularly limited as long as it is inert to the thermosetting resin composition of the present invention and can dissolve the same. Examples of the organic solvent include n
Aliphatic hydrocarbons such as pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane and methylcyclohexane System solvent: benzene, toluene, xylene, ethylbenzene,
Trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i
Aromatic hydrocarbon solvents such as -propylbenzene, n-amylnaphthalene and the like; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol- 3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, monoalcohol solvents such as cresol; ethylene glycol, 1, 2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,
4, hexanediol-2,5, heptanediol-
Polyhydric alcohol solvents such as 2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl- n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethyl nonanone, cyclohexanone, methyl cyclohexanone, 2, Ketone solvents such as 4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, fenchone; ethyl ether;
i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolan, 4-methyldioxolan, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , Ethylene glycol diethyl ether, ethylene glycol mono-n-
Butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether , Diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n
-Butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether,
Ether solvents such as tripropylene glycol monomethyl ether, tetrahydrofuran and 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate ,
I-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate,
Methylpentyl acetate, 2-ethylbutyl acetate, 2-acetic acid
Ethylhexyl, benzyl acetate, cyclohexyl acetate,
Methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate,
Diethylene glycol mono-n-butyl ether acetate,
Glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-lactic acid n Ester solvents such as amyl, diethyl malonate, dimethyl phthalate and diethyl phthalate; N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N- Nitrogen-containing solvents such as dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone; Can be mentioned.

The thermosetting resin composition of the present invention has excellent storage stability as a solution, does not generate cracks during curing, and has a cured product having good adhesion to various substrates, heat resistance, heat and moisture resistance, and the like. Excellent electrical insulation and the like.
Therefore, the thermosetting resin composition of the present invention is, in particular, an interlayer insulating film or a flattening film between multilayer wiring of a semiconductor element,
It can be very suitably used as a protective film or an electric insulating film of various electric devices and electronic parts, and is also useful as an adhesive or a paint requiring heat resistance. Further, the thermosetting resin composition of the present invention is applied to an appropriate substrate which has been subjected to a release treatment in advance, a thermosetting thin film is formed, and the thin film is forcibly peeled off from the substrate before curing, whereby the thermosetting film is formed. A curable film can be obtained, and the thermosetting film is useful as a heat-resistant adhesive film for electric equipment, electronic parts, and the like. Alternatively, the thermosetting thin film which is forcibly peeled off from the substrate is cured, or the thermosetting thin film formed on an appropriate substrate which has been previously subjected to a mold release treatment is heated and cured, and then the obtained cured thin film is obtained. Can be obtained by forcibly peeling off from the substrate. Further, a solution of the thermosetting resin composition of the present invention was impregnated into a suitable cloth such as a glass cloth, and then dried, or prepreg dried, or the resin composition without solvent was impregnated into a suitable cloth such as a glass cloth. The prepreg is also useful as a laminated material such as a copper-clad laminate. Further, the thermosetting resin composition of the present invention is also useful as a thermosetting molding material in the form of, for example, a powder or a pellet. The substrate used when forming a thermosetting film or a cured film from the thermosetting resin composition of the present invention is not particularly limited, for example, iron, nickel, stainless steel, titanium, aluminum, copper, Metals such as various alloys; ceramics such as silicon nitride, silicon carbide, sialon, aluminum nitride, boron nitride, boron carbide, zirconium oxide, titanium oxide, alumina, silica, and mixtures thereof; Si, Ge, SiC, SiGe And semiconductors such as GaAs; ceramic materials such as glass and ceramics; and heat-resistant resins such as aromatic polyamides, polyamideimides, polyimides and wholly aromatic polyesters. The substrate may be subjected to a release treatment in advance, if desired, and a chemical treatment with a silane coupling agent, a titanium coupling agent, or the like, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, or the like. Appropriate pretreatment such as vacuum deposition can also be performed. When applying the thermosetting resin composition of the present invention to the substrate, a spin coating method, a roll coating method,
Appropriate coating means such as a casting coating method, a dip coating method, and a spray coating method can be employed. Further, the coating thickness can be appropriately controlled by selecting the coating means and adjusting the solid content concentration and the viscosity of the composition solution.

[0033]

Embodiments of the present invention will be described below more specifically with reference to examples. However, the present invention
The present invention is not limited to these embodiments. Parts and percentages in the examples and comparative examples are based on weight unless otherwise specified. Each evaluation in Examples and Comparative Examples was performed in the following manner. The composition sample to which the storage stability (E) component was not added was sealed and stored in a polyethylene bottle at room temperature for one month, and the presence or absence of gelation was visually determined. Further, for those which did not cause gelation, the viscosity was measured by a BM type viscometer (manufactured by Tokyo Keiki Co., Ltd.). A composition sample was applied on a crack-resistant glass plate using an applicator having a slit width of 254 μm, dried at 350 ° C. for 60 minutes, and the appearance of the coating film was visually observed and evaluated according to the following criteria. ：: no cracks were observed, ×: cracks were observed. Adhesion No. A sample of the composition was applied using a 6 bar coater and dried at 350 ° C. for 60 minutes.
The tape peeling test was performed three times by a grid test based on SK5400, and the evaluation was made based on the average number (n) of the 100 grids in which the coating film was in close contact with the substrate. Add the composition sample to a heat-resistant aluminum pan,
After drying for 0 minutes, SSC manufactured by Seiko Electronic Industry Co., Ltd.
5200 thermogravimetric analyzer (TGA)
The 5% weight loss temperature was measured at a heating rate of ° C./min. On a substrate of moist heat resistance various, No. A composition sample was applied using a 6 bar coater, dried at 350 ° C. for 60 minutes,
After performing a moist heat resistance test (PCT) for 250 hours under the conditions of ° C, 100% humidity and 2 atm, the adhesion test was performed to evaluate the moist heat resistance. A composition sample was applied on a dielectric stainless steel plate using a spinner and dried at 350 ° C. for 60 minutes. Then, using a Yokogawa-Hewlett-Packard Co., Ltd. HP16451B electrode and HP4284A Precision LCR meter,
The dielectric constant at 1 MHz was measured.

[0034]

【Example】

Production Example 1 (Synthesis of Component (B)) 25.0 parts of bis (3,4-dicarboxyphenyl) sulfone dianhydride and 2,2-bis [4- (4-aminophenoxy) phenyl] propane 24.6 parts Were reacted in 450 parts of N-methylpyrrolidone at 25 ° C. for 2 hours, and further reacted at 180 ° C. for 3 hours. Next, water in the reaction solution was azeotropically distilled off while adding toluene dropwise. Thereafter, 3.59 parts of 3-aminopropyltrimethoxysilane was added to the obtained reaction solution, and the mixture was reacted at 25 ° C. for 2 hours. Then, 4.10 parts of 3-isocyanatopropyltrimethoxysilane was added, and the mixture was added at 120 ° C. The reaction was carried out for 2 hours to obtain a 10% solution of the component (B). The component (B) is referred to as a component (B-1).

Example 1 Methyltrimethoxysilane 1 was used as the silane compound (1).
00 parts (solids equivalent: 49 parts) obtained in Production Example 1 (B-1)
100 parts of a 10% solution of the components, di-i- as component (C)
Propoxy ethyl acetoacetate aluminum 5
Parts, 14 parts of ion-exchanged water and N-methylpyrrolidone 8
After reacting 0 parts at 60 ° C. for 4 hours, 5 parts of acetylacetone is added as the component (D), and the mixture is reacted at 60 ° C. for 1 hour to obtain a thermosetting resin composition (I) having a solid concentration of 20%.
Was prepared. Evaluation results of the thermosetting resin composition (I)
The results are shown in Tables 1 and 2.

Examples 2 to 3 Thermosetting resin compositions (II) and (III) were prepared in the same manner as in Example 1, except that the composition was as shown in Table 1. Evaluation results of these thermosetting resin compositions,
The results are shown in Tables 1 and 2.

Comparative Examples 1 to 3 Thermosetting resin compositions (i) to (iii) were prepared in the same manner as in Example 1 except that the composition was as shown in Table 1. Table 1 shows the evaluation results of these thermosetting resin compositions.
And Table 2.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

The thermosetting resin composition of the present invention is excellent in storage stability as a solution, does not generate cracks during curing, and has good adhesion to various substrates, heat resistance, heat and humidity resistance, A cured product excellent in electric insulation and the like can be formed. Therefore, the thermosetting resin composition of the present invention is very suitable particularly as an interlayer insulating film or a flattening film between multilayer wirings of a semiconductor element, a protective film or an electrical insulating film of various electric devices and electronic components, and the like. Besides being usable, it is also useful as an adhesive, a paint, a thermosetting film, a cured film, a prepreg, a cured molded product, and the like.

Continuing on the front page (72) Inventor Minoru Matsubara 2--11-24 Tsukiji, Chuo-ku, Tokyo Nippon Gosei Rubber Co., Ltd. (72) Inventor Yasutake Inoue 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Go Inside Rubber Co., Ltd. (72) Inventor Kohei Goto 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside Japan Rubber Co., Ltd.

Claims (1)

[Claims] (A) a hydrolyzate of a hydrolyzable organosilane compound and / or a partial condensate thereof; (B) a polyamic acid having a hydrolyzable silyl group and / or a polyimide having a hydrolyzable silyl group; And (C) a thermosetting resin composition containing a chelate compound and / or an alkoxide compound of a metal selected from the group consisting of zirconium, titanium and aluminum.