JPH10204292A - Thermosetting resin composition and cured article of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition excellent in storage stability as a solution, free from cracks in curing process, and capable of forming a cured article excellent in adhesive properties to various substrates, heat resistance, resistance to moist heat, electrical insulating properties, etc. SOLUTION: This resin composition consists of (A) a hydrolysate of a hydrolyzable organosilane compound and/or its partial condensate, (B) a polyamic acid having a carboxylic acid anhydride group and/or a polyimide having a carboxylic acid anhydride group, and (C) a chelate compound of a metal selected from a group of zirconium, titanium and aluminum and/or an alkoxide compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hydrolyzate of a hydrolyzable organosilane compound and / or a partial condensate thereof, and a polyamic acid and / or a polyimide having a carboxylic acid anhydride 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.
In addition, a polyimide resin obtained from a tetracarboxylic dianhydride and a diamine compound via a polyamic acid is generally used for an alignment film for liquid crystal, an insulating film for a semiconductor, a protective film, an adhesive, and particularly an aromatic resin. Polyimide resins have excellent heat resistance and high strength, and are therefore used for applications requiring these properties. 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, Japanese Patent Application Laid-Open Nos.
No. 13631 discloses a diamine compound constituting a polyimide resin as H ₂ N— (CH ₂ ) ₃ — (Si (CH ₃ ) ₂ O) _m —Si (CH ₃ ) ₂ —NH ₂ (however, m is an integer of 1 to 100), and a method using a dimethyl silicone oligomer represented by
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. When the content of the polysiloxane component is increased, the heat resistance of the coating film is reduced, and the storage stability of a mixed solution of a polyamic acid and a hydrolyzed / condensed product of an 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 present invention relates to (A) a hydrolyzate of a hydrolyzable organosilane compound and / or a partial condensate thereof, and (B) a polyamic acid and / or carboxylic acid having a carboxylic anhydride group. It comprises a polyimide having an acid anhydride 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.

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 general formula (1), R ¹ has 1 to ¹ carbon atoms. 8 represents an organic group, 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)”) is preferable. 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, and an n-type organic group.
Linear or branched alkyl groups such as -butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, etc. , 3-chloropropyl group, 3-bromopropyl group, 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 3- (meth) acryloxypropyl group, 3-mercaptopropyl group, 3- (Substituted) aminopropyl group, 2- (3,4-epoxycyclohexyl)
Examples include an ethyl group, a vinyl group, and a phenyl group. In the general formula (1), when two R ¹ are present,
R ¹ may be the same or different from each other. Examples of the alkyl group having 1 to 5 carbon atoms for R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group and a t- A butyl group,
Examples thereof include straight-chain or branched-chain groups such as an n-pentyl group. Examples of the acyl group having 1 to 4 carbon atoms include, for example,
Examples include an acetyl group, a propionyl group, and a butyryl group. In the general formula (1), when ² to 4 R ² are present, each R ² may be the same or different from each other.

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, 3-mercaptopropyltriethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-dimethylaminopropyltrimethoxysilane, 3-dimethylaminopropyltriethoxy Aminoalkyl trialkoxysilanes such as silane; 3,4-epoxycyclohexylalkyltrialkoxysilanes such as 3,4-epoxycyclohexylethyltrimethoxysilane and 3,4-epoxycyclohexylethyltriethoxysilane;
Vinyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; phenyltrialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane; dimethyldimethoxysilane;
Dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, diphenyldimethoxy Dialkoxysilanes such as silane and 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) can be used by previously hydrolyzing and partially condensing the silane compound (I). However, usually, the silane compound (I) and the components (B) and (C) described later are used. Is added, an appropriate amount of water is added, so that the silane compound (I) is hydrolyzed and partially condensed during the preparation of the composition to obtain the component (A). The amount of water added during the hydrolysis and partial condensation of the silane compound (I) is usually 0.3 to 1.2 mol per equivalent of the alkoxysilyl group and / or the acyloxysilyl group in the silane compound (I). , Preferably 0.3 to 1
It is about a mole. 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 carboxylic acid anhydride group and / or a polyimide having a carboxylic acid anhydride group. Such a component (B) is specifically, a carboxylic acid anhydride group represented by the following general formula (2) (hereinafter referred to as a “carboxylic acid anhydride group ( 2) "and a repeating unit represented by the following general formula (3) (hereinafter referred to as" repeating unit (3) ") or a repeating unit represented by the following general formula (4) ( Hereinafter, referred to as “repeating unit (4)”).

[0008]

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[0009]

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[0010]

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[In the general formulas (2), (3) and (4), R ³ represents a tetravalent organic group, and R ⁴ represents a divalent organic group. In the general formulas (2), (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. However, an aromatic organic group having 6 to 120 carbon atoms is particularly preferable. Examples of the tetravalent aromatic organic group include:

[0012]

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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 (eg, methyl group, ethyl group, etc.), a fluoroalkyl group (eg, trifluoromethyl group, etc.) or phenyl Which represents a group). 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,

[0014]

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(Wherein R ^{11 to} R ¹⁶ may be the same or different from each other, and include a hydrogen atom, an alkyl group (eg, a methyl group,
Ethyl group), a fluoroalkyl group (for example, a trifluoromethyl group) or a phenyl group). One or more kinds of the repeating unit (3) in the polyamic acid and the repeating unit (4) in the polyimide can be present. In the present invention, the polyamic acid may be partially imidized,
In this case, the imidation ratio is less than 50%, and the polyimide may not be partially imidized, and the imidation ratio of the polyimide is 50% or more, preferably 90% or more. Here, the imidation ratio represents a ratio of the repeating unit (4) to the total of the repeating unit (3) and the repeating unit (4).

Various methods can be used for synthesizing the component (B) in the present invention, and are not particularly limited. For example, (a) tetracarboxylic dianhydride corresponding to the repeating unit (3) And a diamine compound corresponding to the repeating unit (3) are subjected to polycondensation in an organic solvent under the presence of an excess amount of tetracarboxylic dianhydride to obtain a polyamic acid solution. The polyamic acid obtained by the method (a) may be subjected to a dehydration ring-closing reaction by a thermal method or a chemical method in an organic solvent to obtain a solution of a polyimide having a carboxylic acid anhydride group. . Of these methods, in particular (b)
Is preferred.

Specific examples of the tetracarboxylic dianhydride used in the above method (a) include 2,3,2 ', 3'
-Biphenyltetracarboxylic dianhydride, 2,3
3 ′, 4′-biphenyltetracarboxylic dianhydride,
3,4,3 ', 4'-biphenyltetracarboxylic dianhydride, 9,9-bis (2,3-dicarboxyphenyl)
Fluorene dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,
3,3-hexafluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,1
3,3,3-hexafluoropropane dianhydride, 9,9
-Bis [4- (2,3-dicarboxyphenoxy) phenyl] fluorene dianhydride, 9,9-bis [4- (3
4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane dianhydride Object, 2,2-bis [4-
(3,4-dicarboxyphenoxy) phenyl] -1,
Examples thereof include 1,1,3,3,3-hexafluoropropane dianhydride.

Further, specific examples of the diamine compound used in the method (a) include 9,9-bis (2-aminophenyl) fluorene, 9,9-bis (3-aminophenyl) fluorene, , 9-bis (4-aminophenyl) fluorene, 9,9-bis [4- (2-aminophenoxy) phenyl] fluorene, 9,9-bis [4-
(3-aminophenoxy) phenyl] fluorene, 9,
9-bis [4- (4-aminophenoxy) phenyl] fluorene, 2,2-bis (2-aminophenyl) -1,
1,1,3,3,3-hexafluoropropane, 2,2
-Bis (3-aminophenyl) -1,1,1,3,3
3-hexafluoropropane, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2′-diaminodiphenyl ether, 2,3′-diaminodiphenyl ether, 2 ,
4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether,
2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 2,4'-diaminobiphenyl, 3,3'-
Diaminobiphenyl, 3,4′-diaminobiphenyl,
4,4'-diaminobiphenyl, 4,4'-diamino-
2,2′-bis (trifluoromethyl) biphenyl,
2,2'-diamino-4,4'-bis (trifluoromethyl) biphenyl, 2- (3-aminophenyl) -3 '
-Aminobiphenyl, 2,2'-bis (3-aminophenyl) biphenyl 9,9-bis [3-phenyl-4- (4-amino-2-
Trifluoromethylphenoxy) phenyl] fluorene.

The organic solvent used in the above methods (a) and (b) is not particularly limited as long as it is inert to the reaction raw materials and the obtained component (B) 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. In synthesizing the polyamic acid according to the method (a), the total concentration of the tetracarboxylic dianhydride and the diamine compound is usually 1 to 1 with respect to the total solution weight.
50% by weight, preferably 2 to 30% by weight;
The reaction is carried out at 50 ° C or lower, preferably at 0 to 120 ° C. In the method (b), the temperature of the thermal imidization reaction when synthesizing the polyimide is usually 50 to 400.
° C, preferably 100 to 350 ° C, and the temperature of the chemical imidization reaction is usually 0 to 200 ° C.

The carboxylic acid anhydride group (2) in the component (B) in the present invention is usually present at both ends of the molecular chain of polyacic acid or polyimide, but is present only at one of the molecular chain ends. Is also good. In the present invention, (B)
The content of the carboxylic acid anhydride group (2) in the component is usually
It is 0.01 to 30% by weight, preferably 0.05 to 25% by weight, particularly preferably 0.1 to 20% by weight.

The component (B) in the present invention may further have a hydrolyzable silyl group, if necessary. Examples of the method for synthesizing the component (B) having the hydrolyzable silyl group include: (c) a carboxylic acid anhydride group in the polycondensation of a tetracarboxylic dianhydride and a diamine compound in the method (a). And / or a silane compound having a hydrolyzable group and / or a silane compound having a hydrolyzable group and a functional group capable of reacting with a carboxyl group (hereinafter, these silane compounds are collectively referred to as “functional silane compound”). (D) following the polycondensation of the tetracarboxylic dianhydride and the diamine compound in the method (a), a functional silane compound is added;
Reacting the functional silane compound with a polyamic acid, (e) subjecting the polyamic acid having a hydrolyzable silyl group obtained by the method (c) or (d) to a thermal method in an organic solvent, or A method of performing a dehydration ring-closing reaction by a chemical method, (f) a method of adding a functional silane compound and reacting the functional silane compound with polyimide following the method of (b), )), A silane compound having two amino groups and a hydrolyzable group as a part of the diamine compound, for example, the following general formula:

[0022]

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Wherein R ¹ represents an organic group having 1 to 8 carbon atoms, R ² represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, and X represents a divalent organic group (preferably Represents a phenylene group or an alkylene group having 1 to 10 carbon atoms;
It is an integer of 2. A) using a compound represented by
(H) A method of subjecting the polyamic acid having a hydrolyzable silyl group obtained by the method (g) to a dehydration ring closure reaction by a thermal method or a chemical method in an organic solvent, and the like. The use ratio of the silane compound having two amino groups and the hydrolyzable group in the method (g) is usually 50 mol% with respect to all diamine compounds.
Or less, preferably 30 mol% or less. (C) ~
Among the methods (H), the methods (D), (F) and (G) are preferable, and the methods (D) and (F) are particularly preferable.

The functional silane compound used in the method (c), (d) or (f) includes, for example,
Carboxylic acid anhydride group-containing silanes such as acid anhydride of 3,4-dicarboxyphenyltrimethoxysilane and acid anhydride of 3,4-dicarboxybenzyltrimethoxysilane;
Mercaptosilanes such as mercaptomethyltrimethoxysilane, 2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , 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-triethoxysilylpropyl ) Urea, 2- (2-aminoethylthio) ethyltrimethoxysilane, 2- (2-aminoethylthio) ethyltriethoxysilane, 2- (2-aminoethylthio) ethyldimethoxymethylsilane, 2- (2
-Aminoethylthio) ethyldiethoxymethylsilane,
Aminosilanes such as 2-aminophenyltrimethoxysilane, 2-aminophenyltriethoxysilane, 3-aminophenyltrimethoxysilane, 3-aminophenyltriethoxysilane, 4-aminophenyltrimethoxysilane, and 4-aminophenyltriethoxysilane , Bis (3-trimethoxysilylpropyl) amine, bis (3-triethoxysilylpropyl) amine, 3-cyclohexylaminopropyltrimethoxysilane, 3-cyclohexylaminopropyldimethoxymethylsilane,
3-phenylaminopropyltrimethoxysilane, 3-
Phenylaminopropyldimethoxymethylsilane, 3-
Benzylaminopropyltrimethoxysilane, 3-benzylaminopropyldimethoxymethylsilane, 3- (p
-Vinylbenzylamino) propyltrimethoxysilane, 3- (p-vinylbenzylamino) propyldimethoxymethylsilane, 3-allylaminopropyltrimethoxysilane, 3-allylaminopropyldimethoxymethylsilane, 3-piperazinopropyltrimethoxy Iminosilanes such as silane and 3-piperazinopropyldimethoxymethylsilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycid Epoxy silanes such as xypropyldiethoxymethylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane; 3-isocyanate Trimethoxysilane, 3-isocyanate propyl triethoxysilane,
3-isocyanatopropyldimethoxymethylsilane,
Isocyanate silanes such as 3-isocyanatopropyldiethoxymethylsilane can be exemplified. These functional silane compounds can be used alone or in combination of two or more.

Logarithmic viscosity [η] of component (B) in the present invention (N-methylpyrrolidone, 30 ° C., 0.5 g / d
l) is usually 0.05 to 5 dl / g, preferably 0.1 to 5 dl / g.
1-3 dl / g. In the present invention, the component (B) can be used alone or in combination of two or more. The blending ratio of the component (B) in the present invention is usually based on 100 parts by weight of the component (A) after hydrolysis and condensation.
5 to 1000 parts by weight, preferably 10 to 800 parts by weight,
More preferably, it is 15 to 600 parts by weight. In this case, if the blending ratio of the component (B) is less than 5 parts by weight, cracks may be generated during curing of the obtained thermosetting resin composition. Tends to decrease.

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 may be methyl, ethyl, n-propyl, i-propyl, n-
Butyl group, sec- butyl group, t- butyl group, n- pentyl group, a linear or branched alkyl group having 1 to 6 carbon atoms such as n- hexyl, R ¹⁹ is a methyl group, an ethyl group A methoxy group, a linear or branched alkyl group having 1 to 5 carbon atoms, such as n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group; Ethoxy group, n-propoxy group, i-
Propoxy group, n-butoxy group, i-butoxy group, se
c-butoxy group, t-butoxy group, lauryloxy group,
Straight or branched chain carbon atoms such as a stearyloxy group
Indicate 16 alkoxyl groups. In the above formulas, R ¹⁷ and R ¹⁸
Alternatively, when two or more R ¹⁹ are present, each group may be the same or different from each other. Also, p and q are 0
And r is an integer of 0 to 2.

Specific examples of the component (C) include tri-n-
Butoxy ethyl acetoacetate zirconium, tri-t-butoxy ethyl acetoacetate zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, n-butoxy Tris (ethyl acetoacetate) zirconium, t-butoxy tris (ethyl acetoacetate) zirconium,
Zirconium tetrakis (ethylacetoacetate),
Tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tri-t-butoxy (acetylacetonate)
Zirconium chelate compounds such as zirconium, di-t-butoxybis (acetylacetonato) zirconium, t-butoxytris (acetylacetonato) zirconium, tetrakis (acetylacetonato) zirconium; di-i-propoxybis (ethyl) Acetoacetate) titanium, di-i-propoxybis (acetylacetate) titanium, di-i-propoxybis (acetylacetate) titanium, i-propoxytris (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate) titanium , Tri-n-butoxy ethyl acetoacetate titanium, tri-i-propoxy
Ethyl acetoacetate titanium, tri-n-butoxy
Titanium acetoacetate, tri-i-propoxy acetoacetate titanium, di-n-butoxybis (ethylacetoacetate) titanium, di-n-butoxybis (acetoacetate) titanium, n-butoxytris (ethylacetoacetate) ) Titanium, n-butoxy tris (acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, tetrakis (acetoacetate) titanium, i-propoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate) titanium, etc. Titanium chelate compound; di-i-propoxyethyl acetoacetate aluminum, di-i-
Aluminum propoxy acetyl acetate, i-propoxy bis (ethyl acetoacetate) aluminum, i-propoxy bis (acetyl acetate) aluminum, tris (ethyl aceto acetate) aluminum, tris (acetyl acetate) aluminum, mono acetyl acetate bis ( Aluminum chelate compounds such as ethyl acetoacetate) aluminum; zirconium alkoxides such as tetra-i-propoxy zirconium, tetra-n-butoxy zirconium, tetra-t-butoxy zirconium; tetra-i-propoxy titanium, tetra-n-butoxy titanium Titanium alkoxides, etc .; aluminum alkoxides, such as tri-i-propoxy aluminum and tri-n-butoxy aluminum. Door can be. Among these components (C), tri-n-butoxyethylacetoacetate zirconium, di-i-propoxybis (ethylacetoacetate) titanium, di-i-propoxybis (acetylacetate) titanium, di-i -Propoxy ethyl acetoacetate aluminum, 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) in the present invention is usually 0.1 to 100 parts by weight, preferably 0.3 to 80 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). Particularly preferably, it is 0.5 to 60 parts by weight. In this case, if the compounding ratio of the component (C) is less than 0.1 parts by weight, the heat resistance of the obtained cured product tends to decrease, and if it exceeds 100 parts by weight, the obtained thermosetting resin composition cures. Sometimes cracks may occur.
The component (C) can also be used as a kind of the component (E) described later, and the mixing ratio in that case is the total amount of the mixing ratio and the mixing ratio of the component (E).

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. ), And has an action of further improving the storage stability of the thermosetting resin composition of the present invention. That is, the component (D) coordinates with the metal atom in the metal chelate compound constituting the component (C), thereby accelerating the condensation reaction between the component (A) and the component (B) of the metal chelate compound. It is considered that by appropriately suppressing the action, the action of improving the storage stability of the obtained thermosetting resin composition is exhibited. Specific examples of such component (D) include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, n-butyl acetoacetate, i-butyl acetoacetate, and acetoacetate sec. -Butyl, t-butyl acetoacetate, 2,4-hexanedione,
2,4-heptanedione, 3,5-heptanedione,
2,4-octanedione, 3,5-octanedione,
Examples thereof include 2,4-nonanedione, 3,5-nonanedione, and 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, preferably 3 to 20 mol, and more preferably 4 to 15 mol, per 1 mol of the component (C). 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.

Depending on the curing conditions of the thermosetting resin composition of the present invention, the following curing accelerator (hereinafter referred to as "component (E)")
That. ) May be blended. For curing at a relatively low temperature, the combination use of the component (E) is effective. (E) Component Specific 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; alkyl titanates , Phosphoric acid, p-toluenesulfonic acid, phthalic acid and other acidic compounds; 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 ,

[0030]

Embedded image

(C ₄ H ₉ )
₂ Sn = S, (C ₈ H ₁₇ ) ₂ Sn = S,

[0032]

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, based on the total solid content of the components (A) to (E).
It is as follows. 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.

Other Additives Further, the thermosetting resin composition of the present invention includes, for example, clay, zeolite, talc, mica, silica, carbon black, graphite, alumina, calcium carbonate,
Filler such as wollastonite, glass, carbon, alumina, potassium titanate, aluminum borate, silicon carbide, silicon nitride, aromatic polyamide, polyamide imide, polyimide, wholly aromatic polyester, ultra high molecular weight polyethylene, high strength poly Fibers such as acrylonitrile and high-strength polyvinyl alcohol and 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 reinforcements can be used alone or
A mixture of more than one species can be used. In addition to the above additives, if necessary, antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, antistatic agents, flame retardants, lubricants, antifoggants, antifungal agents, pigments, dyes, dispersions Agents, thickeners, leveling agents, silane coupling agents, titanium coupling agents, and dehydrating agents such as methyl orthoformate, methyl orthoacetate and tetraethoxysilane.

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. Particularly preferred methods for preparing the thermosetting resin composition are the following 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),
A method in which 0.3 to 1 mol of water is added to hydrolyze and partially condense the silane compound (1) to prepare a composition comprising the components (A) to (C). The remaining amount of the silane compound (1) and the component (C) and 1 equivalent of an alkoxysilyl group and / or an acyloxysilyl group in the silane compound (1) are added to a part of the mixture of the component (B) and the component (C). A method of preparing a composition comprising the components (A) to (C) by adding 0.3 to 1 mol of water per unit to hydrolyze and partially condense the silane compound (1). 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) Or a mixture of the component (B) and the component (C) is added at a time or in a stepwise manner, and further subjected to a condensation reaction to prepare a composition comprising the components (A) to (C). how to. A mixture of the silane compound (1) and a part of the component (D) is added in an amount of from 0.3 to 0.3 equivalents per equivalent of the alkoxysilyl group and / or the acyloxysilyl group in the silane compound (1).
One mole of water is added to hydrolyze the silane compound (1).
Partially condensing, then adding the remaining amount of the component (B) and the remaining amount of the component (C) separately, or adding a mixture of the remaining amount of the component (B) and the remaining amount of the component (C) at one time or in steps; A method of preparing a composition comprising the components (A) to (C) by further performing a condensation reaction. In the above-mentioned method,
The component (E) and the other additives can be blended at an appropriate stage.

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. Examples of such an organic solvent include n-pentane, isopentane,
aliphatic hydrocarbon solvents such as n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane and methylcyclohexane; benzene, toluene,
Aromatic hydrocarbon solvents such as xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, amylnaphthalene; 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-
Ethyl butanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol,
sec-octanol, nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-
Undecyl alcohol, trimethyl nonyl alcohol,
Mono-alcohol solvents such as sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl carbinol, diacetone alcohol, cresol Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol,
-Methyl-2,4-pentanediol, pentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol,
Triethylene glycol, tripropylene glycol,
Polyhydric alcohol solvents such as glycerin; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl-n-pentyl ketone, ethyl butyl ketone, methyl hexyl ketone, diisobutyl ketone ,
Ketone solvents such as trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fuenchion;

Ethyl ether, isopropyl ether,
n-butyl ether, hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolan, 4-methyldioxolan,
Dioxane, dimethyl dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl 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 monobutyl ether, diethylene glycol dibutyl ether,
Ether solvents such as diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol dibutyl ether, monopropylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl 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-acetate
Butyl, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, nonyl acetate, Methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate,
Propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-pentyl propionate, methoxypropionic acid Methyl, ethyl ethoxypropionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate,
Ester solvents such as diethyl malonate, dimethyl phthalate and diethyl phthalate; N-methylformamide, N,
N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N
-Solvents based on nitrogen compounds such as -dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone; dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, 1,3
-Solvents based on sulfur compounds such as propane sultone. These organic solvents can be used alone or in combination of two or more.

The thermosetting resin composition of the present invention has excellent storage stability as a solution, has no 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 ceramics such as glass and ceramics; and heat-resistant resins such as aromatic polyamide, polyamide imide, polyimide and wholly aromatic polyester. 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, it is possible to employ an appropriate application means such as a spin coating method, a roll coating method, a casting coating method, a dip coating method, and a spray coating method. it can. Also,
The coating thickness can be appropriately controlled by selecting a coating means and adjusting the solid content concentration and viscosity of the composition solution.

[0039]

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 0 ° C./min. A composition sample was added to a heat-resistant aluminum pan, dried at 450 ° C. for 60 minutes under reduced pressure of 1 Torr or less, and then subjected to SSC5200 thermogravimetric analyzer (T
GA) at a rate of 10 ° C./min.
The% weight loss temperature was measured. 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, dried at 350 ° C. for 60 minutes, and then dried with a Yokogawa-Hewlett-Packard Co., Ltd. HP16451B electrode and HP4284A Precision LCR meter.
The dielectric constant at MHz was measured. A composition sample is applied on a dielectric stainless steel plate using a spinner and dried at 450 ° C. for 60 minutes under a reduced pressure of 1 Torr or less, and then H, manufactured by Yokogawa-Hewlett-Packard Co., Ltd.
The dielectric constant at 1 MHz was measured using a P16451B electrode and an HP4284A precision LCR meter.

[0040]

【Example】

Production Example 1 (Synthesis of Component (B)) 25.0 parts of bis (3,4-dicarboxyphenyl) sulfone dianhydride and 2,4.6-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, while the toluene was added dropwise, water in the reaction solution was azeotropically distilled off to obtain a 10% solution of the component (B).

Production Example 2 (Synthesis of Component (B)) 2,2-bis (3,4-dicarboxyphenyl) -1,
50.2 parts of 1,1,3,3,3-hexafluoropropane dianhydride and 53.5 parts of 9,9-bis [4- (4-aminophenoxy) phenyl] fluorene were added to methyl methoxypropionate 400 After reacting at 23 ° C. for 2 hours in the same part, it was further reacted at 145 ° C. for 3 hours. Then
While toluene was added dropwise, water in the reaction solution was azeotropically distilled off to obtain a 20% solution of the component (B).

Production Example 3 (Synthesis of Component (B)) 25.2 parts of 2,3,2 ', 3'-biphenyltetracarboxylic dianhydride and 9,9-bis (4-aminophenyl)
27.7 parts of fluorene and γ-butyrolactone 450
After reacting at 23 ° C for 2 hours in the part,
For 3 hours. Next, while the toluene was added dropwise, water in the reaction solution was azeotropically distilled off to obtain 10% of the component (B).
% Solution was obtained.

Example 1 A mixture of 500 parts of a 10% solution of the component (B) obtained in Production Example 1 and 10 parts of di-n-butoxybis (ethylacetoacetate) zirconium was reacted at 23 ° C. for 20 minutes. Thereafter, 100 parts of methyltrimethoxysilane (49 parts in terms of solid content), 2 parts of di-n-butoxybis (ethylacetoacetate) zirconium and 14 parts of ion-exchanged water
The resulting mixture was further reacted at 60 ° C. for 4 hours, and then 5 parts of acetylacetone was added and reacted at 60 ° C. for 1 hour to prepare a thermosetting resin composition (I) having a solid concentration of 15%. Table 1 shows the evaluation results of the thermosetting resin composition (I).
And Table 2.

Example 2 A mixture of 100 parts of a 10% solution of the component (B) obtained in Production Example 1 and 2 parts of di-n-butoxybis (ethylacetoacetate) titanium was reacted at 23 ° C. for 20 minutes. After that, 80 parts of methyltrimethoxysilane (solid conversion 3
9.2 parts), 20 parts of dimethyldimethoxysilane (12.8 parts in terms of solid content), 2 parts of di-n-butoxybis (ethylacetoacetate) titanium and 13 parts of ion-exchanged water. After reacting for 4 hours, add 5 parts of acetylacetone and react at 60 ° C. for 1 hour.
A thermosetting resin composition (II) having a solid content of 27% was prepared. Tables 1 and 2 show the evaluation results of the thermosetting resin composition (II).

Example 3 2000 parts of a 10% solution of the component (B) obtained in Production Example 1 and di-n-butoxybis (ethylacetoacetate)
After reacting a mixture of 40 parts of zirconium at 23 ° C. for 20 minutes, 10 parts of tetraethoxysilane (2.9 parts in terms of solids), 70 parts of methyltrimethoxysilane (34.3 parts in terms of solids), and dimethyldimethoxy 20 parts of silane (12.8 parts in terms of solid content) and 13 parts of ion-exchanged water were added, and further reacted at 60 ° C. for 4 hours to prepare a thermosetting resin composition (III) having a solid concentration of 10%. . Tables 1 and 2 show the evaluation results of the thermosetting resin composition (III).

Comparative Example 1 100 parts of methyltrimethoxysilane (49 in terms of solid content)
Part), a mixture of 500 parts of a 10% solution of the component (B) obtained in Production Example 1 and 14 parts of ion-exchanged water were reacted at 60 ° C. for 4 hours to obtain a thermosetting resin composition having a solid concentration of 14%. (I) was prepared. Tables 1 and 2 show the evaluation results of the thermosetting resin composition (i).

Comparative Example 2 100 parts of methyltrimethoxysilane (49 in terms of solid content)
Part), a mixture of 10 parts of di-n-butoxybis (ethylacetoacetate) zirconium and 14 parts of ion-exchanged water was reacted at 60 ° C. for 4 hours, and then reacted with di-n-butoxybis (ethylacetoacetate). Zirconium 2
And 5 parts of acetylacetone were added and reacted at 60 ° C. for 1 hour to prepare a thermosetting resin composition (ii) having a solid content of 35%. Tables 1 and 2 show the evaluation results of the thermosetting resin composition (ii).

Comparative Example 3 A mixture of 500 parts of a 10% solution of the component (B) obtained in Production Example 1 and 10 parts of di-n-butoxybis (ethylacetoacetate) zirconium was reacted at 23 ° C. for 20 minutes. A thermosetting resin composition (iii) having a solid content of 10% was prepared. Tables 1 and 2 show the evaluation results of the thermosetting resin composition (iii).

[0049]

[Table 1]

[0050]

[Table 2]

Example 4 250 parts of a 20% solution of the component (B) obtained in Production Example 2,
21.1 parts of zirconium n-butoxybis (ethylacetoacetate), 296 methyl methoxypropionate
Part of γ-butyrolactone and 394 parts of
After reacting at 20 ° C. for 20 minutes, 100 parts of methyltrimethoxysilane (49 parts in terms of solid content) and 1 part of ion-exchanged water
9.9 parts were added and further reacted at 60 ° C. for 4 hours to prepare a thermosetting resin composition (IV) having a solid content of 10%. Tables 3 and 4 show the evaluation results of the thermosetting resin composition (IV).

Example 5 28.1 parts of a 20% solution of the component (B) obtained in Production Example 2, 16.2 parts of zirconium di-n-butoxybis (ethylacetoacetate), methyl methoxypropionate 42
Part and 259 parts of γ-butyrolactone are
After reacting at 20 ° C for 20 minutes, 92.3 parts (45.5 parts in terms of solid content) of methyltrimethoxysilane and 7.7 parts (5.0 parts in terms of solid content) of phenyltrimethoxysilane were added, and the mixture was heated to 60 ° C. The temperature was raised. Thereafter, ion-exchanged water 15.
Five parts were added over 1 hour, and the mixture was further reacted at 60 ° C. for 3 hours. Then, methanol in the reaction solution was distilled off under reduced pressure to prepare a thermosetting resin composition (V) having a solid content of 13%. Tables 3 and 4 show the evaluation results of the thermosetting resin composition (V).

Example 6 28.1 parts of a 20% solution of the component (B) obtained in Production Example 2, 12.5 parts of di-i-propoxybis (ethylacetoacetate) titanium, 42 parts of methyl methoxypropionate and After reacting a mixture of 259 parts of γ-butyrolactone at 60 ° C. for 1 hour, methyltrimethoxysilane 9
2.3 parts (45.5 parts in terms of solids) and 7.7 parts (5.0 parts in terms of solids) of phenyltrimethoxysilane were added, and the temperature was raised to 60 ° C. Then 15.5 ion-exchanged water
Then, the reaction solution was further reacted at 60 ° C. for 3 hours, and then methanol in the reaction solution was distilled off under reduced pressure to prepare a thermosetting resin composition (VI) having a solid content of 13%. Tables 3 and 4 show the evaluation results of the thermosetting resin composition (VI).

Example 7 92.3 parts of methyltrimethoxysilane (4 in terms of solid content)
5.5 parts), 7.7 parts of phenyltrimethoxysilane (5.0 parts in terms of solid content), 9.4 parts of di-i-propoxybis (ethylacetoacetate) titanium, 209 parts of methyl methoxypropionate and γ 14. A mixture of 69 parts of butyrolactone was kept at 60 ° C., and ion-exchanged water was added to the mixture.
After adding 5 parts over 1 hour, the mixture was further reacted at 60 ° C. for 1 hour. Next, methanol in the reaction solution was distilled off under reduced pressure, and then a 10% solution of the component (B) 5 obtained in Production Example 3 was prepared.
6.1 parts, di-i-propoxybis (ethylacetoacetate) titanium 7.6 parts and γ-butyrolactone 1
52 parts were added and reacted at 60 ° C. for 1 hour. Thereafter, 14.0 parts of di-i-propoxybis (ethylacetoacetate) titanium and 1.9 parts of ion-exchanged water were added, and the mixture was further reacted at 60 ° C. for 1 hour to obtain a thermosetting resin having a solid content of 10%. Composition (VII) was prepared. Tables 3 and 4 show the evaluation results of the thermosetting resin composition (VII).

[0055]

[Table 3]

[0056]

[Table 4]

[0057]

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.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C08K 5:56 5:05) (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 Nippon Gosei Rubber Co., Ltd. (72) Inventor Kohei Goto 2-11-24 Tsukiji, Chuo-ku, Tokyo Nippon Gosei Rubber Co. In company

Claims (2)

[Claims] 1. A hydrolyzate of a hydrolyzable organosilane compound and / or a partial condensate thereof, (B) a polyamic acid having a carboxylic acid anhydride group and / or a polyimide having a carboxylic acid anhydride 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. 2. A cured product obtained by curing the thermosetting resin composition according to claim 1.