JPH10242136A - Insulating film and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insulating film having a low dielectric constant and a high heat resistance, high moisture resistance, etc., and a semiconductor device which has the insulating film on a wiring layer, does not consume much electric power, and has a high-speed operability, high reliability, etc. SOLUTION: An insulating film 4 is composed of the cured material of a curable resin composition containing at least one kind of component selected out of a group composed of (A) the hydrolytic product of a hydrolytic organosilane compound and/or its partial condensate, (B) a hydrolytic silyl group and/or polyamic acid having a carboxylic acid anhydride group, and the hydrolytic silyl group and/or polyimide having the carboxylic acid anhydride group. A semiconductor device has the above-mentioned insulating film on a wiring layer 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulating film and a semiconductor device, and more particularly, to a low dielectric constant insulating film made of a cured product of a polyorganosiloxane and a polyimide, and the insulating film. And a semiconductor device formed on a wiring layer.

[0002]

2. Description of the Related Art Today, semiconductor devices are widely used in various electronic devices.
There is an increasing demand for lower power consumption, higher speed, improved reliability, and the like. As one of means for satisfying the above-mentioned requirements, reduction of the dielectric constant of an insulating film disposed between wiring layers and improvement of heat resistance and the like have been studied. Known materials for the low dielectric constant insulating film include, for example, SiOF and organic SOG (Spin on Glas).
s), fluorocarbon polymer, polyimide, polyparaxylylene, benzocyclobutene polymer and the like. These materials reduce the dielectric constant by containing a fluorine atom and / or an alkyl group in the insulating film molecule to lower the density or lower the polarizability of the molecule itself. The introduction of a siloxane structure, an imide bond or an aromatic ring therein improves the heat resistance. However, the insulating film having a low dielectric constant is not sufficiently reduced in dielectric constant with, for example, SiOF as compared with an insulating film (silicon oxide film) conventionally used in a semiconductor device. Organic materials such as polyimide film fat, polyparaxylylene, and benzocyclobutene polymer were inferior in heat resistance and moisture resistance, and none of them were satisfactory as a low dielectric constant insulating film.

[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 an insulating film having a low dielectric constant and excellent in heat resistance, moisture resistance, and the like. An object of the present invention is to provide a semiconductor device having the insulating film over a wiring layer and having excellent low power consumption, high-speed operation, reliability, and the like.

[0004]

The gist of the present invention is to firstly provide (A) a hydrolyzable organosilane compound hydrolyzate and / or a partial condensate thereof, and (B) a hydrolyzable silyl group and And / or curing of a curable resin composition containing at least one component selected from the group consisting of a polyamic acid having a carboxylic acid anhydride group and a polyimide having a hydrolyzable silyl group and / or a carboxylic acid anhydride group. An insulating film, which is made of a material.

[0005] The gist of the present invention is, secondly, a semiconductor device having a wiring layer and the insulating film formed on the wiring layer;
Consists of

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 represents an organic group, and R ² represents an alkyl group having 1 to 5 carbon atoms or 1 to 5 carbon atoms.
4 represents an acyl group, 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; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ) 3,4-epoxycyclohexylalkyl trialkoxysilanes such as ethyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane,
Diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane Dialkoxysilanes such as silane; tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane,
Examples include acyloxysilanes such as 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) may be used alone or
A mixture of more than one species can be used. In the present invention, the component (A) can be used by previously hydrolyzing and partially condensing the silane compound (I), and when the silane compound (I) and the component (B) described later are blended, By adding an appropriate amount of water, the silane compound (I) can be hydrolyzed and partially condensed to prepare the component (A) during the preparation of the composition. 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). And preferably about 0.3 to 1 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.

(B) Component The component (B) in the present invention has a polyamic acid having a hydrolyzable silyl group and / or a carboxylic anhydride group, and a polyamic acid having a hydrolyzable silyl group and / or a carboxylic anhydride group. It is composed of at least one component selected from the group consisting of polyimide. As such a component (B),
A hydrolyzable silyl group represented by the following general formula (2) (hereinafter, referred to as “hydrolyzable silyl group (2)”) and / or
Alternatively, a carboxylic anhydride group represented by the following general formula (3) (hereinafter, referred to as “carboxylic anhydride group (3)”):
A repeating unit represented by the following general formula (4) in a polyamic acid (hereinafter, referred to as “repeating unit (4)”) or a repeating unit represented by the following general formula (5) in a polyimide (hereinafter, referred to as a “repeating unit ( The components introduced in 5)) are preferred.

[0009]

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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. ]

[0011]

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[0012]

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[0013]

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[In the general formulas (3), (4) and (5), R ³ represents a tetravalent organic group, and R ⁴ represents a divalent organic group. However, R ³ and R ⁴ in each formula may be the same or different from each other. 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), (4) and (5), R ³
The tetravalent organic group 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. Examples of the tetravalent aromatic organic group include:

[0015]

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[In the formula, R ^{5 to} R ¹⁰ may be the same or different from each other, and represent 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,

[0017]

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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, a methyl group, an ethyl group, etc.), a fluoroalkyl group (eg, a trifluoromethyl group, etc.) Or a phenyl group. And the like. Repeating unit (4) in polyamic acid and repeating unit (5) in polyimide
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.

Various methods can be used for synthesizing the component (B) in the present invention, and are not particularly limited. Examples of the polyamic acid or polyimide having a hydrolyzable silyl group (2) include (A) A) A polycarboxylic acid solution is obtained by polycondensing a tetracarboxylic dianhydride corresponding to the repeating unit (4) and a diamine compound corresponding to the repeating unit (4) in an organic solvent, and then obtaining a carboxylic acid anhydride. Silane compound having a functional group capable of reacting with a carboxyl group and / or a silane compound having a hydrolyzable group (hereinafter, these silane compounds are collectively referred to as “functional silane compound”). .)
To obtain a solution of a polyamic acid having a hydrolyzable silyl group, (b) in the presence of a functional silane compound, a tetracarboxylic dianhydride corresponding to the repeating unit (4) and a repeating unit ( 4) a method of polycondensing the diamine compound corresponding to 4) in an organic solvent to obtain a solution of a polyamic acid having a hydrolyzable silyl group, and (c) a method obtained by the method (a) or (b). A dehydration ring-closing reaction of the polyamic acid in an organic solvent by a thermal method or a chemical method to obtain a solution of a polyimide having a hydrolyzable silyl group, (d) tetracarboxylic acid corresponding to the repeating unit (4) An acid dianhydride and a diamine compound corresponding to the repeating unit (4) are polycondensed in an organic solvent to obtain a solution of a polyamic acid. Alternatively, a dehydration ring-closing reaction is performed by a chemical method to obtain a polyimide solution, and then a functional silane compound is reacted to obtain a polyimide solution having a hydrolyzable silyl group. The corresponding tetracarboxylic dianhydride, a silane compound having two amino groups and a hydrolyzable group, for example, the following general formula

[0020]

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[0021] [where, R ^1, R ² and m have the same meanings as R ^1, R ² and m, respectively, in the general formula (2), R ¹⁷ is 2
Organic group (preferably a phenylene group or a group having 1 to 1 carbon atoms)
10 alkylene groups). A polyamic acid solution having a hydrolyzable silyl group by polycondensing the compound represented by the formula (1) together with a diamine compound corresponding to the general formula (4), if necessary, in an organic solvent; F)
The polyamic acid obtained by the method (e) can be produced by a method of obtaining a polyimide solution by subjecting the polyamic acid to a dehydration and ring closure reaction in an organic solvent by a thermal method or a chemical method. The polyamic acid or polyimide having a carboxylic anhydride group (3) is, for example, (G)
The polyamic acid is obtained by polycondensing a tetracarboxylic dianhydride corresponding to the repeating unit (4) with a diamine compound corresponding to the repeating unit (4) in an organic solvent in the presence of an excess amount of the tetracarboxylic dianhydride. How to obtain a solution of the acid,
(H) A method of obtaining a polyimide solution by subjecting the polyamic acid obtained by the method (g) 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 methods for producing a polyamic acid or a polyimide having a hydrolyzable silyl group (2) include (a), (d) and (e).
The method (a) or (d) is particularly preferable, and the method (h) is particularly preferable as a method for producing a polyamic acid or a polyimide having a carboxylic anhydride group (3). Further, a polyamic acid or a polyimide having both a hydrolyzable silyl group (2) and a carboxylic anhydride group (3) is, for example, the above-mentioned (A)
To (f) and any one of the above methods (g) to (h).

Examples of the functional silane compound used for producing a polyamic acid or polyimide having a hydrolyzable silyl group (2) include, for example, acid anhydrides of 3,4-dicarboxyphenyltrimethoxysilane, Carboxylic acid anhydride group-containing silanes such as acid anhydride of 4-dicarboxybenzyltrimethoxysilane; mercaptomethyltrimethoxysilane, 2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane,
Mercaptosilanes such as 3-mercaptopropyldimethoxymethylsilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyl Dimethylmethoxysilane, 3-aminopropyldimethylethoxysilane, (2-aminoethylamino) methyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propyldimethoxymethyl Silane, 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-amino Aminosilanes such as ethylthio) ethyldiethoxymethylsilane; 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-piperazinopropyl Iminosilanes such as trimethoxysilane and 3-piperazinopropyldimethoxymethylsilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3- Epoxysilanes such as glycidoxypropyldiethoxymethylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane; 3-isocyanate Over preparative 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.

The organic solvent used in each of the above methods is not particularly limited as long as it is inert to the reaction raw materials and the component (B) obtained and can dissolve them. For example, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i
Aliphatic hydrocarbon solvents such as heptane, 2,2,2-trimethylpentane, n-octane, i-octane, cyclohexane, methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene,
n-propylbenzene, i-propylbenzene, n-butylbenzene, methylethylbenzene, diethylbenzene, triethylbenzene, di-i-propylbenzene,
aromatic hydrocarbon solvents such as n-amylnaphthalene; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-i-propyl ketone, methyl-n-butyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, Methyl-n-hexyl ketone, diethyl ketone, ethyl-n-propyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, di-i-propyl ketone, di-n-butyl ketone, di-i-butyl ketone, cyclohexanone , 2-methylcyclohexanone,
3-methylcyclohexanone, 4-methylcyclohexanone, 2,4-pentanedione, acetonylacetone,
Ketone solvents such as diacetone alcohol, acetophenone and fenchone; ethyl ether, n-propyl ether, i-propyl ether, n-butyl ether, n
-Hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, Ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol monophenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-propyl ether, Ethylene glycol di-n-butyl ether, diethylene glycol monomethyl ether, Chi glycol monoethyl ether, diethylene glycol mono -n- propyl ether, diethylene glycol mono -n- butyl ether,
Diethylene glycol mono-n-hexyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n
-Propyl ether, diethylene glycol di-n-butyl ether, ethoxytriglycol, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol di-
n-propyl ether, tetraethylene glycol di-
ether solvents such as n-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; diethylene carbonate, γ-butyrolactone, γ-valerolactone, methyl acetate, ethyl acetate , N-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-acetate
Pentyl, sec-pentyl acetate, 3-methoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, 1-methylcyclohexyl acetate, 2-acetic acid
Methylcyclohexyl, 3-methylcyclohexyl acetate, 4-methylcyclohexyl 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 ether acetate, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether , Diethylene glycol mono-n-propyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate,
Glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-propyl propionate, i-propyl propionate, n-butyl propionate, i-butyl propionate, n-amyl propionate, i-amyl propionate, oxalate Diethyl oxalate, di-n-propyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, phthalic acid Diethyl, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, n-butyl pyruvate, methyl α-methoxypropionate, ethyl α-methoxypropionate, n-propyl α-methoxypropionate, α-methoxypropionic acid n-butyl, methyl α-ethoxypropionate, α-ethoxy Ester solvents such as ethyl cypropionate, n-propyl α-ethoxypropionate and n-butyl α-ethoxypropionate; N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N -Nitrogen compound solvents such as -methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone; dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, 1,3-propane sultone And the like. These organic solvents can be used alone or in combination of two or more. In the synthesis of the polyamic acid in each of the above methods, the total amount of tetracarboxylic dianhydride and diamine compound,
The reaction is usually carried out at 1 to 50% by weight, preferably 2 to 30% by weight, based on the total solution weight, and usually at 150 ° C or lower, preferably 0 to 120 ° C. In addition, (c),
In the method (d), (f) or (h), 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 hydrolyzable silyl group (2) and / or carboxylic anhydride group (3) in the component (B) in the present invention are usually present at both ends of the molecular chain of polyamic acid or polyimide. It may be present only at either one end. In the present invention, the content of the hydrolyzable silyl group (2) in the component (B) is usually 0.1 to 7.
0% by weight, preferably 0.5 to 60% by weight, particularly preferably 1 to 50% by weight, and the content of the carboxylic anhydride group (3) in the component (B) is usually 0.1%. -30% by weight, preferably 0.05-25% by weight, particularly preferably 0.1-20% by weight. However, when the component (B) has both the hydrolyzable silyl group (2) and the carboxylic anhydride group (3), the content of each group is appropriately selected within the above range. Logarithmic viscosity [η] of component (B) in the present invention (in N-methylpyrrolidone at 30 ° C,
0.5 g / dl) is usually 0.05 to 5 dl / g, preferably 0.1 to 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 1000 parts by weight, preferably 1 to 100 parts by weight of the component (A) after the hydrolysis / partial condensation reaction.
0 to 800 parts by weight, more preferably 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 curable resin composition, and if it exceeds 1000 parts by weight, the moisture resistance of the obtained cured product decreases. Tend to.

(C) Component In the present invention, a chelate compound of a metal selected from the group consisting of zirconium, titanium and aluminum and / or
Alternatively, it is preferable to further mix at least one compound selected from alkoxide compounds (hereinafter, referred to as “component (C)”). 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 ¹⁸ ) _p (R ¹⁹ COCHCOR ²⁰ ) _4-p , Ti (OR ¹⁸ ) _q (R ¹⁹ COCHCOR ²⁰ ) _4-q or Al (OR ¹⁸ ) Compounds represented by _r (R ¹⁹ COCHCOR ²⁰ ) _3-r or partial hydrolysates of these compounds. In each of the above formulas, R ¹⁸
And R ¹⁹ 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,
i-butyl group, sec-butyl group, t-butyl group, n-
A pentyl group, a linear or branched alkyl group having 1 to 6 carbon atoms such as an n-hexyl group, R ²⁰ represents an ethyl group,
n-propyl group, i-propyl group, n-butyl group, i-
Butyl, sec-butyl, t-butyl, n-pentyl and other linear or branched alkyl groups having 1 to 5 carbon atoms, or methoxy, ethoxy, n-propoxy and i-propoxy groups , N-butoxy group, i-butoxy group, sec-butoxy group, t-butoxy group, lauryloxy group, stearyloxy group and the like. R in each of the above formulas
^18, when R ¹⁹ or the R ²⁰ there are two or more, each group may be the same or different from each other. Further, p and q are integers of 0 to 3, and r is an integer of 0 to 2.

As a specific example of the component (C), 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; tri-i-propoxy aluminum and tri-n-butoxy aluminum Aluminum alkoxide compounds and the like can be mentioned. Among these compounds, zirconium tri-n-butoxyethylacetoacetate, titanium di-i-propoxybis (acetylacetate), aluminum di-i-propoxyethylacetoacetate, and aluminum tris (ethylacetoacetate) 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 usually 0.1 to 100 parts by weight, preferably 0.3 to 80 parts by weight, and particularly preferably 100 parts by weight of the total of the components (A) and (B). Is 0.5 to 60 parts by weight. In this case, if the blending ratio of the component (C) is less than 0.1 part by weight, the heat resistance of the obtained cured product tends to decrease, and if it exceeds 100 parts by weight, cracks may occur during curing of the curable resin composition. May occur.

Further, in the present invention, the following component (D) is preferably blended in addition to the components (A), (B) and (C). Component (D) Component (D) has the general formula R ¹⁹ COCH ₂ COR ²⁰ (where, R ¹⁹ and R ^20, R ¹⁹ and R in the general formula representing the metal chelate compound of each component (C)
^It is synonymous with ²⁰ , but both R ¹⁹ and R ²⁰ 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 curable resin composition. That is, the component (D) is the component (C)
By coordinating to a metal atom in the metal chelate compound constituting the component, the action of accelerating the condensation reaction between the component (A) and the component (B) of the metal chelate compound is appropriately suppressed, whereby the curable resin It is considered that the compound exhibits an effect of improving the storage stability of the composition. 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, 2,4-nonanedione, 3,5-nonanedione and 5-methyl-2,4-hexanedione can be mentioned. Of these compounds, acetylacetone and ethyl acetoacetate are preferred,
In particular, acetylacetone is preferred. These components (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 mixing ratio of the component (D) is less than 2 mol, the effect of improving the storage stability of the curable resin composition tends to decrease.

Other Additives In the present invention, at least one curing accelerator (hereinafter, referred to as “component (E)”) may be blended depending on the curing conditions of the curable resin composition. For curing at a relatively low temperature, the combined 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 Acid, p
-Acidic compounds such as toluenesulfonic acid and phthalic acid;
2-ethylenediamine, 1,6-hexylenediamine,
Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, m-
Amines such as phenylenediamine, p-phenylenediamine, ethanolamine, triethylamine and N-methylmorpholine, and various modified amines used as curing agents for epoxy resins; 3-aminopropyltriethoxysilane, 3- (2-amino Amino group-containing silane compounds such as ethylamino) 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 = CHCOOC
H ₃ ) ₂ , (C ₄ H ₉ ) ₂ Sn (OCOCH = 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 = CHC
Carboxylic acid type organotin compounds such as OOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOC ₈ H ₁₇ ) ₂ , 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 OCOCH 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 ,

[0029]

Embedded image

Mercaptide-type organotin compounds such as (C ₄ H ₉ ) ₂ Sn = S, (C ₈ H ₁₇ ) ₂ Sn = S,

[0031]

Embedded image

Sulfide type organic tin compounds such as (C ₄ H ₉ ) ₂ Sn = O, (C ₈ H ₁₇ ) ₂ Sn = O, etc .; ethyl silicate; dimethyl maleate; Examples include organotin compounds such as reaction products with ester compounds such as diethyl maleate and dioctyl phthalate. These components (E) can be used alone or in combination of two or more. The proportion of the component (E) 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 when the curable resin composition of the present invention is prepared and / or at an appropriate stage after the preparation. Further, if necessary, a dispersant, a thickener, a leveling agent, a silane coupling agent, a titanium coupling agent, and a dehydrating agent such as methyl orthoformate, methyl orthoacetate, and tetraethoxysilane can also be blended. .

Preparation of Curable Resin Composition The curable resin composition of the present invention contains the above components (A) and (B) as essential components, and preferably comprises a composition containing the above component (C). It is desirable to prepare it by a method of adding the component (D) and the like as necessary. Particularly preferred methods for preparing the curable 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),
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. Part of the mixture of the component (B) and the component (C), the remainder of the mixture of the component (1) and the mixture of the component (B) and the component (C) were added to the alkoxysilyl group in the silane compound (1). / Or per equivalent of an acyloxysilyl group,
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 separately or preliminarily mixed, added temporarily or stepwise, and further subjected to a condensation reaction to prepare a composition comprising the components (A) to (C). How to add components. A mixture of the silane compound (1) and a part of the component (C) is added in an amount of 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).
Component (B) and the remainder of component (C) are separately or preliminarily mixed, and then added temporarily or stepwise, and a condensation reaction is further carried out to obtain components (A) to (C). After preparing a composition comprising, if necessary, (D)
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, an organic solvent can be used to adjust the total solid concentration of the curable resin composition and also adjust the viscosity. Such an organic solvent is not particularly limited as long as it is inert to the curable resin composition of the present invention and can dissolve it. Examples of the organic solvent include n-pentane, i-pentane, n-hexane, i-hexane,
aliphatic hydrocarbon solvents such as n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, methylcyclohexane;
Benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene,
aromatic hydrocarbon solvents such as i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec- Butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, s
ec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, s
ec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, n-undecyl alcohol, sec-undecyl Alcohol, trimethylnonyl alcohol, n-tetradecyl alcohol, sec-tetradecyl alcohol, n-heptadecyl alcohol,
sec-heptadecyl alcohol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol , Diacetone alcohol, phenol, cresol and other monoalcohol solvents; ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2-methylpentanediol-2,4, hexane Diol-2,5,
Polyhydric alcohol solvents such as heptanediol-2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin; acetone, methyl ethyl ketone, methyl-n-propyl ketone , Methyl-i-propyl ketone, methyl-n-butyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, methyl-n-hexyl ketone, diethyl ketone, ethyl-n-propyl ketone, ethyl-n-butyl ketone, Di-n-propyl ketone, di-i-propyl ketone, di-n-butyl ketone, di-i-butyl ketone, cyclohexanone, 2-methylcyclohexanone,
3-methylcyclohexanone, 4-methylcyclohexanone, 2,4-pentanedione, acetonylacetone,
Ketone solvents such as diacetone alcohol, acetophenone and fenchone; ethyl ether, n-propyl ether, i-propyl ether, n-butyl ether, n
-Hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, Ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol monophenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-propyl ether, Ethylene glycol di-n-butyl ether, diethylene glycol monomethyl ether, Chi glycol monoethyl ether, diethylene glycol mono -n- propyl ether, diethylene glycol mono -n- butyl ether,
Diethylene glycol mono-n-hexyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n
-Propyl ether, diethylene glycol di-n-butyl ether, ethoxytriglycol, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol di-
n-propyl ether, tetraethylene glycol di-
ether solvents such as n-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; diethylene carbonate, γ-butyrolactone, γ-valerolactone, methyl acetate, ethyl acetate , N-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-acetate
Pentyl, sec-pentyl acetate, 3-methoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, 1-methylcyclohexyl acetate, 2-acetic acid
Methylcyclohexyl, 3-methylcyclohexyl acetate, 4-methylcyclohexyl 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 ether acetate, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether , Diethylene glycol mono-n-propyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate,
Glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-propyl propionate, i-propyl propionate, n-butyl propionate, i-butyl propionate, n-amyl propionate, i-amyl propionate, oxalate Diethyl oxalate, di-n-propyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, phthalic acid Diethyl, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, n-butyl pyruvate, methyl α-methoxypropionate, ethyl α-methoxypropionate, n-propyl α-methoxypropionate, α-methoxypropionic acid n-butyl, methyl α-ethoxypropionate, α-ethoxy Ester solvents such as ethyl cypropionate, n-propyl α-ethoxypropionate and n-butyl α-ethoxypropionate; N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N -Nitrogen compound solvents such as -methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone; dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, 1,3-propane sultone And the like. These organic solvents can be used alone or in combination of two or more.

[0035]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Insulating Film and Semiconductor Device The curable resin composition of the present invention has no cracks when cured, and the cured product has a low dielectric constant, heat resistance, moisture resistance, and various substrates. It has excellent adhesion to water and electrical insulation, and has a low water absorption. Therefore, the cured product formed from the curable resin composition of the present invention can be used for various electronic and
It is useful as an insulating film in electric equipment, and can be particularly suitably used as an insulating film in a semiconductor device having a wiring layer and an insulating film formed on the wiring layer.

Next, a semiconductor device of the present invention having the insulating film and a manufacturing process thereof will be described with reference to FIG. Here, FIG. 1A illustrates a semiconductor component in a stage before reaching the semiconductor device of the present invention, and FIG. 1B illustrates a semiconductor device of the present invention. Referring to FIG. 1A, an appropriate first layer made of SiOF, organic SOG, fluorocarbon polymer, polyimide, polyparaxylylene, benzocyclobutene polymer or the like is formed on a silicon substrate 1 having a transistor formed on its surface. Is formed, and a first wiring layer 3 is formed on the first insulating film 2. Such a semiconductor component can be manufactured, for example, as follows. First, a silicon oxide film is formed on the silicone substrate 1 to a thickness of 500 to 1000 nm by a thermal oxidation method, a CVD (gas phase chemical growth) method, a plasma CVD method, or the like. After that, a metal film made of aluminum or an aluminum alloy is formed to a thickness of 400 to 600 nm by a sputtering method, and then the wiring film 3 is formed by patterning the metal film by a photolithography method and a dry etching method. Next, the curable resin composition of the present invention is applied on the first wiring layer 3 and the other first insulating film 2 of the semiconductor component obtained as described above, for example, by spin coating, for example. Film thickness of 100 to 10
An insulating film 4 made of a cured product of the curable resin composition is formed by applying the composition to a thickness of 00 nm, and curing and drying the composition at, for example, 350 ° C. for 60 minutes. The present invention illustrated in FIG. Semiconductor device is obtained. The semiconductor device of the present invention and the example of the manufacturing process have been described above, but the semiconductor device of the present invention is not limited to the above. For example, the first wiring layer 3 can be made of copper or a copper alloy,
In addition, the metal forming the first wiring layer 3 may be mixed with polycrystalline silicon, polycide, or the like. Also, the first
As the insulating film 2, the insulating film of the present invention can be used. Further, a silicon oxide film or the like may be further formed between the first wiring layer 3 and the insulating film 4 of the present invention by, for example, a CVD method. In addition, the wiring layer may be a multilayer of two or more layers. In this case, the insulating film of the present invention is formed between the wiring layers, and the wiring layers are electrically connected by through holes as necessary. Connect to Further, the upper surface of the insulating film of the present invention located at the outermost layer can be planarized by, for example, mechanochemical polishing. The semiconductor device of the present invention obtained in this manner has an insulating film formed on a wiring layer having a low dielectric constant, and has excellent heat resistance, moisture resistance, adhesion to various substrates, electrical insulation properties, etc. Because of its low performance, it is excellent in low power consumption, high-speed operation, reliability and the like.

[0037]

EXAMPLES Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. 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. A curable resin composition sample was applied on a crack-resistant glass plate using an applicator having a slit width of 254 μm,
After curing and drying for 0 minutes, 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 curable resin composition was applied using a 6-bar coater, cured and dried at 350 ° C. for 60 minutes, and then subjected to a tape peeling test three times by a grid test in accordance with JIS K5400.
The evaluation was made based on the average number (n) of the 0 pieces in which the coating film was in close contact with the substrate. Put the curable resin composition sample in a heat-resistant aluminum pan,
After curing and drying at 50 ° C. for 60 minutes, SSC5200 thermogravimetric analyzer (TGA) manufactured by Seiko Denshi Kogyo KK
Was used to measure the 5% weight loss temperature in air at a heating rate of 10 ° C./min to evaluate heat resistance. On a substrate of moist heat resistance various, No. A curable resin composition sample is applied using a 6 bar coater and cured at 350 ° C. for 60 minutes.
After being dried and subjected to a moisture and heat resistance test (PCT) for 250 hours under the conditions of 121 ° C., 100% humidity and 2 atm, the adhesion test was performed to evaluate the moisture and heat resistance. A curable resin composition sample is applied on a dielectric stainless steel plate using a spinner, cured and dried at 350 ° C. for 60 minutes, and then HP1 manufactured by Yokogawa-Hewlett-Packard Co., Ltd.
6451B electrode and HP4284A Precision LC
The dielectric constant at 1 MHz was measured using an R meter. A curable resin composition sample was applied on a silicon wafer using a spinner, cured and dried at 350 ° C. for 60 minutes, and then left at 85 ° C. and 85% humidity for 24 hours. From the weight change, the water absorption was evaluated.

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. Then, while the toluene was being added dropwise, water in the reaction solution was azeotropically distilled off to obtain a 10% solution of the component (B) composed of a polyimide having a carboxylic anhydride group (3). The component (B) is referred to as a component (B-1).

Production Example 2 (Synthesis of Component (B)) The solution of the component (B-2) obtained in the same manner as in Production Example 1 was added with 3-
3.59 parts of aminopropyltrimethoxysilane were added,
After reacting at 25 ° C. for 2 hours, 4.10 parts of 3-isocyanatopropyltrimethoxysilane was added, and
For 2 hours to obtain a 10% solution of the component (B) comprising a polyimide having a hydrolyzable silyl group (2).
The component (B) is referred to as a component (B-2).

Example 1 100 parts of a 10% solution of the component (B-1) obtained in Production Example 1 and 10 parts of di-n-butoxybis (ethylacetoacetate) zirconium as the component (C) were heated at 23 ° C. 2
After reacting for 0 minutes, 100 parts of methyltrimethoxysilane (49 parts in terms of solid content) as a silane compound (1),
2 parts of di-n-butoxybis (ethylacetoacetate) zirconium and 14 parts of ion-exchanged water are added as an additional component (C), and the mixture is further reacted at 60 ° C. for 4 hours. And add 6
The mixture was reacted at 0 ° C. for 1 hour to prepare a curable resin composition having a solid content of 15%. Table 2 shows the evaluation results of the cured products formed from the curable resin compositions.

Examples 2-3 A curable resin composition was prepared in the same manner as in Example 1 except that the composition was as shown in Table 1. Table 2 shows the evaluation results of the cured products formed from these curable resin compositions.
Shown in

Comparative Examples 1 to 3 Curable resin compositions were prepared in the same manner as in Example 1 except that the composition was as shown in Table 1. Table 2 shows the evaluation results of the cured products formed from these curable resin compositions.
Shown in

Example 4 Methyltrimethoxysilane 1 as the silane compound (1)
00 parts (solid content conversion 49 parts), obtained in Production Example 2 (B-2)
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 0 parts were reacted at 60 ° C. for 4 hours, 5 parts of acetylacetone was added as the component (D) and reacted at 60 ° C. for 1 hour to prepare a curable resin composition having a solid content of 20%. Table 4 shows the evaluation results of the cured products formed from the curable resin compositions.

Examples 5 to 6 Curable resin compositions were prepared in the same manner as in Example 4 except that the composition was as shown in Table 3. Table 4 shows the evaluation results of the cured products formed from these curable resin compositions.
Shown in

Comparative Examples 4 to 6 Curable resin compositions were prepared in the same manner as in Example 4 except that the composition was as shown in Table 3. Table 4 shows the evaluation results of the cured products formed from these curable resin compositions.
Shown in

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

The insulating film of the present invention has a low dielectric constant without causing cracks during curing when forming the same, and has heat resistance, moisture resistance, adhesion to various substrates, and electrical insulation. Excellent and low water absorption. Therefore, the semiconductor device of the present invention having the insulating film has low power consumption, high operation speed, and high reliability.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a semiconductor device of the present invention and a manufacturing process thereof.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Insulating film 3 Wiring layer 4 Insulating film of the present invention

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI H01L 21/768 H01L 21/90 S 21/31 21/95 (72) Inventor Minoru Matsubara 2--24 Tsukiji, Chuo-ku, Tokyo Japan Go Inside Rubber Company (72) Inventor Yasutake Inoue 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Go Rubber Company (72) Inventor Kohei Goto 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] 1. A hydrolyzate of a hydrolyzable organosilane compound and / or a partial condensate thereof, and (B) a polyamic acid having a hydrolyzable silyl group and / or a carboxylic anhydride group, and An insulating film comprising a cured product of a curable resin composition containing at least one component selected from the group consisting of a polyimide having a decomposable silyl group and / or a carboxylic anhydride group. 2. A semiconductor device having a wiring layer and the insulating film according to claim 1, formed on the wiring layer.