JPH10152616A - Thermosetting resin composition for electrical insulation material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sealing resin composition excellent in low stress properties, heat resistance, adhesion to various substrates by mixing a vinylsilyl- terminated reactive silicon polymer with a silicon compound having Si-H groups, a silicon compound having Si-H groups and/or Si-H groups and vinylsilyl groups, a hydrosilylation catalyst, a silane coupling agent, etc. SOLUTION: This composition comprises a vinylsilyl-terminated reactive silicon polymer (A) in which at least 30% of the atoms constituting the main chain are silicon atoms and carbon atoms and which has a molecular weight of 1,000 or above, a silicon compound (B) having at least two Si-H groups in the molecule, at least one member (C) selected among silicon compounds each having at least two vinylsilyl groups in the molecule and having a molecular weight of below 1,000 and silicon compounds each having at least two, in total, Si-H groups and vinylsilyl groups in the molecule and having a molecular weight of below 1,000 and a hydrosilylation catalyst (D) together with a silane coupling agent, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to heat resistance, adhesiveness,
The present invention relates to a thermosetting resin composition having excellent curability, and is suitable for use as a potting material for various electronic components such as drip coating and potting of semiconductor elements, potting materials and coating materials for capacitors, etc. The present invention relates to a curable resin composition.

[0002]

2. Description of the Related Art Curable resins such as epoxy resins, imide resins, amide imide resins, unsaturated polyester resins, phenol resins, and polyorganosiloxane resins have been used as resin compositions for sealing electronic parts such as semiconductors. Used from. Resin encapsulation is economically advantageous compared to hermetic seal systems using glass, metal, and ceramic, and is widely used for TCP, COB, IC cards,
It is practically used for sealing of hybrid ICs and the like.

[0003]

However, in recent years, the use conditions of sealing materials have tended to be severe, and low-stress,
Heat resistance, adhesion to a substrate, and the like are important characteristics. Therefore, in recent years, many resin compositions having excellent characteristics have been proposed. However, the tendency of semiconductor elements (chips) to be larger and more highly integrated has been further increased, and conventional resin compositions have been more than adequate. Is gone. That is, for example, when a semiconductor is liquid-sealed with a conventional epoxy-based encapsulant composition, the semiconductor chip warps, cracks, or seals due to thermal stress based on the difference in thermal expansion coefficient between the semiconductor chip and the sealing resin. Problems such as cracks in the resin stop occur.

Further, polyorganosiloxane is used as a material for electric and electronic parts by utilizing its excellent weather resistance and heat resistance. However, its use is limited because of poor adhesion, high moisture permeability, and deterioration of electrodes, substrates, and the like. Therefore, development of a resin composition for sealing excellent in low stress property, heat resistance and adhesion to various base materials has been desired.

[0005]

The above object of the present invention is as follows.
This has been achieved by the means mentioned. In other words, the main chain skeleton
More than 30% of the atoms formed are silicon and carbon.
And a silicon-based polymer with a molecular weight of 1000 or more
The end is a vinylsilyl group (CH_Two= CR'-Si (R)_Two−)
A reactive silicon-based polymer ((A)
Component), and at least two or more Si—H in one molecule.
A silicon compound having a group (component (B));
As a minute, select one of the ingredients listed as
At least one silicon compound having a molecular weight of less than 1000,
At least two or more molecules having a molecular weight of less than 1,000 in one molecule
Vinylsilyl group (CH _Two= CR'-Si (R)_Two−) To
Silicon compound ((A) component) having one molecule of Si
-H group and vinylsilyl group (CH_Two= CR'-Si (R)_Two
-) Having a molecular weight of at least 2 in total of 100
Silicon compound less than 0 (component (II)) and component (D)
Insulating material containing hydrosilylation catalyst as an essential component
The present invention relates to a thermosetting resin composition for materials.

[0006]

First, the reactive silicon-based polymer (component (A)) in the composition will be described. The main chain skeleton of the reactive silicon-based polymer (component (A)) refers to a portion constituting the skeleton of the polymer, excluding a substituent / atom bonded to the skeleton. The reactive silicon-based polymer (component (A)) accounts for 30% of the atoms constituting the main chain skeleton.
The above-mentioned atoms are silicon-based polymers having a molecular weight of 1000 or more composed of silicon and carbon, and the terminal of the molecule is a vinylsilyl group (C
_{H 2 = CR'-Si (R} ) 2 -) , characterized in that a. (In the formula, R represents a monovalent organic group having 1 to 20 carbon atoms. R ′ represents hydrogen or a monovalent organic group.)
From the viewpoint of mechanical characteristics and the like, the total ratio of silicon and carbon in the main chain skeleton is 40% of the total atoms constituting the main chain skeleton.
Or more, more preferably 60% or more, and 80% or more.
The above is particularly preferred. Furthermore, the ratio of the number of silicon and carbon atoms (silicon / carbon) in the main chain skeleton of the reactive silicon-based polymer (component (A)) of the thermosetting resin composition for an electrical insulating material is 0.6. -0.5 is preferable, 0.5-0.4 is more preferable, and 0.4-0.2 is particularly preferable.

The reactive silicon-based polymer (component (A)) has a vinyl silyl group (CH ₂ =
CR′—Si (R) ₂ —).
R ′ is the same as R described above, and specific examples include H, methyl, ethyl, phenyl, and trimethylsiloxy groups. Of these, H is particularly preferred. The molecular weight of the reactive silicon-based polymer (component (A)) is determined by gel permeation chromatography (GP) from the viewpoint of viscosity and solubility.
The number average molecular weight using a polystyrene standard in C) is preferably from 1,000 to 50,000, and from 1500 to 50,000.
30,000 is more preferred. The molecular weight distribution is preferably 5 or less. 3 or less is more preferred.

The main chain skeleton of the reactive silicon-based polymer (component (A)) is basically linear, but may have a branched structure as long as the solubility is not impaired. Absent.
The reactive silicon-based polymer (A) component in the thermosetting resin composition for an electrical insulating material contains 60% in the thermosetting resin composition for an electrical insulating material from the viewpoint of improving heat resistance and mechanical properties.
% By weight or more, more preferably 70% by weight or more, and particularly preferably 80% by weight or more.

The reactive silicon-based polymer (component (A)) in the thermosetting resin composition for an electrical insulating material is disclosed in JP-A-7-18.
It can be manufactured by the method disclosed in US Pat. For example, the main chain skeleton of the reactive silicon-based polymer (component (A)) in the thermosetting resin composition for an electrical insulating material is:
[Si (R) ₂ -X-Si (R) ₂ -CH ₂ CH ₂ -Si
(R) ₂ -Y-Si (R) ₂ -CH ₂ CH _2- ], [Si
(R) ₂ -X-Si (R) ₂ -CH ₂ CH ₂ -Si (R) ₂
—CH ₂ CH ₂ —] or [Si (R) ₂ —CH ₂ CH ₂
—Si (R) ₂ —CH ₂ CH ₂ —] (where R represents 1 carbon atom)
-20 represents a monovalent organic group. ) Is a repeating unit. The above R is specifically methyl, ethyl,
Examples include n-propyl, i-propyl, n-butyl, t-butyl, isoamyl, n-octyl, n-nonyl, phenyl, chloro, and trimethylsiloxy groups.

The above X and Y may be a divalent organic group having 1 to 50 carbon atoms, a divalent organic silicon group or an oxygen atom, and the organic group may contain a functional group.
Specific examples of X and Y include the following structures.

[0011]

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Of these,

[0013]

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Is preferred. Moreover,

[0015]

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Is particularly preferred. The reactive silicon system of the present invention
To illustrate a preferred structure of the polymer (component (A)), C:
H_Two= CH- [Si (Ph) (Me)-p-C₆H_Four-S
i (Ph) (Me) -CH_TwoCH_Two−]_n-Si (Ph)
(Me)-p-C₆H_Four-Si (Ph) (Me) -CH =
CH_Two, CH_Two= CH- [Si (Ph) (Me) -CH_Two
CH_Two-SiMe _Two−p-C₆H_Four-SiMe_Two-CH_TwoCH
_Two]_n-Si (Ph) (Me) -CH = CH_Two, CH_Two= C
H- [SiMe_Two−m-C₆H_Four-SiMe_Two-CH_TwoCH_Two
-SiMe_Two−p-C₆H_Four-SiMe_Two-CH_TwoCH_Two]_n
-SiMe_Two−m-C₆H_Four-SiMe_Two-CH = CH_Two,
CH_Two= CH- [SiMe_Two−p-C₆H_Four-SiMe_Two−
CH_TwoCH_Two-SiMe_Two−m-C₆H_Four-SiMe_Two-CH
_TwoCH_Two]_n-SiMe_Two−p-C₆H_Four-SiMe_Two-CH
= CH_Two, CH_Two= CH- [SiMe_Two−p-C₆H_Four-S
iMe_Two-CH_TwoCH_Two-Si (Ph) (Me)-m-C₆
H_Four-Si (Ph) (Me) -CH_TwoCH_Two]_n-SiMe
_Two−p-C₆H_Four-SiMe_Two-CH = CH_Two, CH _Two= CH
− [SiMe_Two−m-C₆H_Four-SiMe_Two-CH_TwoCH_Two−
SiMe_Two-CH _TwoCH_Two]_n-SiMe_Two−m-C₆H_Four−
SiMe_Two-CH = CH_TwoAnd the like.

In order to form the structural unit represented by the formula (1) according to the second aspect of the present invention in the polymer, Si-
As the H component, HSi (R ¹ ) (R ² ) -p- C ₆ H ₄ -S
As a silicon compound represented by i (R ¹ ) (R ² ) H or a Si-vinyl component, CH ₂ ＣＨCH—Si (R ¹ )
_{^{(R 2) - p -C 6}} H 4 -Si (R 1) (R 2) -CH = C
Silicon compound represented with H ₂ must be used as one component of the hydrosilylation polymerization of at least one of (R ^1, R ² are the same. As R ^1, R ² in the formula (1) in the above formula) is there.

Further, the structural unit represented by the formula (2) is
In order to form it in the molecule, H
SiMe_Two−p-C₆H_Four-SiMe_TwoH and as a component,
CH _Two= CH-Si (R¹) (R^Two) -CH = CH_TwoIndicated by
HS as a silicon compound or Si-H component
i (R¹) (R^Two) -H and Si-vinyl component as C
H_Two= CH-SiMe_Two−p-C₆H_Four-SiMe_Two-CH
= CH_Two(R in the above formula ¹, R^TwoIs R in the formula (1)¹, R^Two
Same as. ), Hydrosilylation
It must be used as one of the components of the polymerization.

Further, in order to form the structural unit represented by the formula (3) in the polymer, as a Si—H component,
^{HSi (R 1) (R 2} ) - m -C 6 H 4 -Si (R 1)
(R ²⁾ a silicon compound represented by H, or a Si- vinyl _{component, CH 2 = CH-Si (} R 1) (R 2) -
_{m -C 6 H 4 -Si (R} 1) (R 2) -CH = silicon compound represented by CH ₂ (R ^1, R ² in the above formula are the same as R ^1, R ² in the formula (1) ) Must be used as one of the components of the hydrosilylation polymerization.

The silicon compound used as the component (B) in the thermosetting resin composition for an electrical insulating material of the present invention is not particularly limited as long as it is a silicon compound having at least two or more SiH groups in one molecule. be able to. For example,
As the component (B), JP-A-3-95266 and JP-A-3
-200807 is a compound having at least two or more SiH groups in one molecule.

As the component (B) of the present invention, an organohydrogenpolysiloxane can be used. The term "organohydrogenpolysiloxane" as used herein refers to a polysiloxane having a hydrocarbon group or a hydrogen atom on a Si atom.

[0022]

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And the like. In addition, as the component (B) of the present invention, hydrosilane represented by the following formulas (4) to (7) or three or more hydrogen atoms on an aromatic ring are SiR ₂ H, SiRH ₂ , Si
An aromatic ring substituted with H ₃ (R represents a monovalent organic group having 1 to 20 carbon atoms) and a hydrosilane comprising the substituent can also be preferably used. These compounds are 1
One type or two or more types may be used. H _a SiR
_(4-a) (4), H _(a-1) SiR _(4-a) -(X) _m (SiR
H) _n SiR _(4-a) H _(a-1) (5), R ′-(X) _m (Si
RH) _{(n + 2)} -R '(6), [X-SiR
_(4-a) H _(a-2) ] _{(n + 2)} (7) (wherein, R represents 1 to 2 carbon atoms)
0 represents a monovalent organic group, R ′ represents hydrogen or a monovalent organic group, X represents a divalent group, a is an integer of 3 to 4, n is
Represents an integer of 0 to 30, and m represents an integer of 1 to 31. As the monovalent organic group in the formulas (4) to (7), for example,
Methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, isoamyl, n-octyl, n-nonyl, phenyl group, chloro group, trimethylsiloxy group and the like, methyl group, phenyl group preferable. Specific examples of the divalent group X in the formulas (5), (6), and (7) include the following structures.

[0024]

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(Wherein, n represents an integer of 1 to 4).

[0026]

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(Wherein Me represents a methyl group and n is the same as described above). Moreover,

[0028]

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(Wherein, n is the same as described above) is particularly preferred. As preferred specific examples of the component (B),

[0030]

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(Wherein Me is the same as above, Ph is a phenyl group, and n is an integer of 3 to 5). The component (A) which is one of the components (C) in the thermosetting resin composition for an electrical insulating material of the present invention has at least two or more vinylsilyl groups (CH ₂に) in one molecule.
Any silicon compound having a molecular weight of less than 1000 and having CR'-Si (R) _2- ) can be used without limitation.
Specifically, vinyl silane represented by the formulas (8) to (13), or three or more hydrogens on the aromatic ring are replaced by SiR ₂ (CH
_{= CH 2), SiR (CH} = CH 2) 2, Si (CH = C
H ₂ ) ₃ (R represents a monovalent organic group having 1 to 20 carbon atoms.)
A vinyl silane composed of an aromatic ring substituted with and the substituent can also be preferably used. One or two or more of these compounds may be used. (CH = CH ₂ )
_{SiR 2 -X-SiR 2 (CH} = CH 2) (8), (C
_{H 2 = CH) SiR 2 (} CH = CH 2) (9), (CH 2
ＣＨCH) _a SiR _(4-a) (10), (CH ₂ ＣＨCH) _(a-1)
SiR _(4-a) -(X) _m (SiR (CH = CH ₂ )) _n Si
R _{(4-a )} (CH = CH ₂ ) _(a-1) (11), R ′-(X) _{m
(SiR (CH = CH 2)} ) (n + 2) -R '(12), [X
—SiR _(4-a) (CH = CH ₂ ) _(a-2) ] _{(n + 2)} (13)
(Wherein, R represents a monovalent organic group having 1 to 20 carbon atoms,
R ′ represents hydrogen or a monovalent organic group, X represents a divalent group, a is an integer of 3 to 4, n is an integer of 0 to 30, and m is 1
Represents an integer of ~ 31. R and X in the formulas (8) to (13) represent the formulas (4) to (7)
Same as the inside, and preferred structure is also the same.
As preferred specific examples of the (A) component,

[0032]

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(Wherein Me is the same as described above, Ph is a phenyl group, and n is an integer of 3 to 5). The component (B), which is one of the components (C) of the present invention, contains at least 2 of a Si-H group and a vinylsilyl group (CH ₂ ＣＲCR′—Si (R) ₂ —) in one molecule. Any silicon compound having a molecular weight of at least one and having a molecular weight of less than 1,000 can be used without particular limitation. Specific examples include the following compounds.

[0034]

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The ratio of the total of the components (A), (B), and (C) in the thermosetting resin composition for an electrical insulating material of the present invention is preferably 0.5 to 5. Preferably, 0.
8 to 3 are more preferable, and 0.9 to 2 are particularly preferable.
(D) in the thermosetting resin composition for an electrical insulating material of the present invention
As the hydrosilylation catalyst as a component, a generally known hydrosilylation catalyst can be suitably used. For example, a complex of platinum, a substance in which solid platinum is supported on a simple substance such as alumina, silica, or carbon black, a complex of chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone, or the like, a platinum-olefin complex (for example, Pt (CH _Two
ＣＨCH ₂ ) ₂ (PPh ₃ ) ₂ Pt (CH ₂ ＣＨCH ₂ ) ₂ C
l ₂ ); a platinum-vinylsiloxane complex (eg, Pt
_n (ViMe ₂ SiOSiMe ₂ Vi) _m , Pt [(MeV
iSiO) ₄ ] _m ), a platinum-phosphine complex (for example, P
t (PPh ₃ ) ₄ , P (PBu) ₄ ), platinum-phosphite complex (for example, Pt [P (OPh) ₃ ] ₄ )
e is a methyl group, Bu is a butyl group, Vi is a vinyl group, Ph
Represents a phenyl group, m and n represent integers), dicarbonyldichloroplatinum, and a platinum-hydrocarbon complex described in Ashby U.S. Pat. Nos. 3,159,601 and 3,159,662; Also included are the platinum alcoholate catalysts described in Lamoreaux U.S. Pat. No. 3,220,972. Further, Modic, US Patent No. 35
The platinum chloride-olefin composites described in US Pat. No. 16,946 are also useful in the present invention.

Examples of catalysts other than platinum compounds include
RhCl (PPh_Three)_Three, RhCl_Three, RhAl_TwoO_Three, R
uCl_Three, IrCl_Three, FeCl_Three, AlCl_Three, PdCl
_Two・ 2H_TwoO, NiCl_Two, TiCl_Four, Etc.
You. These catalysts may be used alone or in combination of two or more.
You can use it. From the viewpoint of catalytic activity, chloroplatinic acid, white
Gold-olefin complex, platinum-vinylsiloxane complex, white
Gold acetylacetonate is preferred. As the amount of catalyst
Although there is no particular limitation, in the B component, in some cases, the B component
And the total amount of arsenic present in the combined component
10 mol per 1 mol of drosillyl group^{ー 1}-10^-8mol
It is good to use within the range. And 10 ^{ー 3}-10^-6mo
l is preferred. Furthermore, the thermosetting material for the electric insulating material of the present invention
In order to improve the storage stability of the resin composition,
Good agents can be used. Storage stability improvers are
Eye to improve storage stability of thermosetting resin composition for insulating material
To use. As storage stability improvers, aliphatic unsaturated bond
Compounds containing organic compounds, organic phosphorus compounds, organic sulfur compounds
Substances, nitrogen-containing compounds, tin compounds, organic peroxides, etc.
A storage stability improver may be used in combination. Aliphatic boredom
As a compound containing a sum bond, propargyl alcohol
Ene-yne compounds, maleic acid esters, etc.
It is. As organophosphorus compounds, triorganophosph
, Diorganophosphine, organophospho
And triorganophosphite. Organic
Sulfur compounds include organomercaptan, diol
Ganosulfide, hydrogen sulfide, benzothiazole, benzo
Thiazole disulfite and the like are exemplified. Nitrogen content
As the compound, ammonia, primary to tertiary alkylamine,
Examples include arylamine, urea, hydrazine and the like. S
Stannous halide dihydrate,
Stannous rubonate and the like are exemplified. As an organic peroxide
Is di-t-butyl peroxide, dicumyl peroxy
, Benzoyl peroxide, t-butyl perbenzoate, etc.
Is exemplified. The storage stability improver is benzothiazole
, Thiazole and dimethylmalate are preferred, and dimethyl
Lumarate is preferred, but not limited to
No. The storage stability improver is added to 1 mol of the platinum catalyst used.
On the other hand, it is preferable to use in the range of 0 to 1000 mol.
And more preferably used in the range of 10 to 500 mol.
It is particularly preferable to use in the range of 30 to 300 mol.
New

The silane coupling agent as the component (E) of the thermosetting resin composition for an electrical insulating material of the present invention includes:
A silane coupling agent having at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group and a silicon-bonded alkoxy group in a molecule is preferable. Among the above functional groups, an epoxy group, a methacryl group, and an acryl group are particularly preferable in the molecule from the viewpoint of curability and adhesiveness. Specifically,
Examples of the organosilicon compound having an epoxy functional group and a silicon-bonded alkoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl).
Ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane are exemplified. Examples of the organosilicon compound having a methacryl group or an acryl group and a silicon-bonded alkoxy group include 3-methacryloxypropyltrimethoxysilane,
Methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltri Ethoxysilane is mentioned.

As the organoaluminum compound which is the component (F) of the thermosetting resin composition for an electric insulating material of the present invention, a chelate organic compound which is a useful catalyst for a hydrolysis condensation reaction of an alkoxysilyl group is preferable. Specific examples include aluminum acetylacetonate. Further, as the organic titanium compound as the component (F) of the present invention, an organic titanium compound having a Ti—O—C bond, which is a useful catalyst for a hydrolysis-condensation reaction of an alkoxysilyl group, is preferable. Specific examples include tetraalkoxytitanium such as tetraisopropoxytitanium and tetrabutoxytitanium, and general titanate coupling agents such as those having a residue such as oxyacetic acid and ethylene glycol.

The polyvalent alkoxysilane as the component (G) of the thermosetting resin composition for an electrical insulating material of the present invention includes:
Various alkoxysilanes can be used. Specifically, tetramethoxysilane, tetraethoxysilane, tetra (n
Tetraalkoxysilanes and condensates thereof such as -propyl) silane and tetra (n-butyl) silane and trialkoxysilanes and condensates thereof such as methyltriethoxysilane and ethyltriethoxysilane can be used.

Further, for the purpose of improving the storage stability of the thermosetting resin composition for an electric insulating material of the present invention, a storage stability improver can be used. The storage stability improver is used for the purpose of enhancing the storage stability of the curable composition. As the storage stability improver, a storage stability improver such as a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, and an organic peroxide may be used in combination. Absent. Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohol, ene-yne compounds, and maleic esters. Examples of the organic phosphorus compound include triorganophosphine, diorganophosphine, organophosphone, and triorganophosphite. Organic sulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide,
Benzothiazole, benzothiazole disulfite and the like are exemplified. As the nitrogen-containing compound, ammonia,
Examples thereof include primary to tertiary alkylamines, arylamines, urea, and hydrazine. Examples of the tin compound include stannous halide dihydrate, stannous carboxylate, and the like. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, t-butyl perbenzoate and the like. The storage stability improver is preferably benzothiazole, thiazole, or dimethylmalate, and dimethylmalate is preferred, but is not limited thereto. The storage stability improver is preferably used in the range of 0 to 1000 mol, more preferably in the range of 10 to 500 mol, and particularly preferably in the range of 30 to 300 mol, based on 1 mol of the platinum catalyst used.

When an inorganic filler is added to the thermosetting resin composition for an electrical insulating material of the present invention, it is mainly used to alleviate thermal shock such as soldering, prevent the fluidity of the adhesive, and stabilize or improve the adhesive strength. Since it is effective, it can be preferably used. As the inorganic filler, those having excellent electrical insulation and fine particles are preferable, and examples thereof include alumina, aluminum hydroxide, fused silica, crystalline silica, ultrafine amorphous silica, hydrophobic ultrafine silica, talc, and barium sulfate. Can be.

Further, various resins can be added for the purpose of modifying the properties of the thermosetting resin composition for an electrical insulating material of the present invention. As the resin, epoxy resin, cyanate resin, phenol resin, acrylic resin,
Examples thereof include a polyimide resin, a polyvinyl acetal resin, a urethane resin, and a polyester resin, but are not limited thereto.

The thermosetting resin composition for an electrical insulating material of the present invention can be cast or applied to a film as it is. However, the thermosetting resin composition for an electrical insulating material is dissolved in an organic solvent. A coating varnish can also be used.
The solvent that can be used is not particularly limited, and specific examples thereof include hydrocarbon solvents such as benzene, toluene, hexane, and heptane, tetrahydrofuran, and 1,4.
-Ether solvents such as dioxane and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be suitably used. The solvent can be used as a mixed solvent of two or more kinds. As the solvent, tetrahydrofuran and chloroform are preferred. The amount of the solvent used is preferably in the range of 0 to 10 mL, more preferably in the range of 0.5 to 5 mL, based on 1 g of the reactive silicon-based polymer (component (A)) used. It is particularly preferable to use in the range of 3 mL.

When the composition of the present invention is applied as a sealing resin, potting may be carried out in the same manner as a conventional epoxy resin sealing resin. When the composition of the present invention is used for a printed board, the cured product exhibits a small dielectric constant, and a material having excellent heat resistance and weather resistance can be obtained. When the composition of the present invention is used for a solder resist, a solder resist having a low dielectric constant can be obtained.

The present invention can be suitably used as a sealing material for an electric / electronic insulating material, a potting material for various electronic parts such as a capacitor, a coating material, and the like. Are better. The following examples illustrate the invention more specifically, but do not limit the scope of the invention.

[0046]

【Example】

(Production Example 1) Synthesis of reactive silicon-based polymer (component (A)) 50.70 g of 1,4-bis (dimethylsilyl) benzene
(260.8 mmol) was dissolved in 100 mL of toluene, and 50.00 g of methylphenyldivinylsilane (28
6.9 mmol) and 591 m of platinum vinyl siloxane complex
g (9.71 × 10 ⁻⁵ mmol / mg, Si-viny
160 mL of toluene solution of 10 ^-4 equivalents per 1 group)
Over 3.5 hours (charge ratio: Si-vin)
yl group / Si-H group = 1.1). It was confirmed that the internal temperature rose to 44 ° C. during the dropwise addition. After 20 hours, the solvent was distilled off to produce 94.3 g of a highly viscous reactive silicon-based polymer. Yield: 94%. The obtained reactive silicon-based polymer was subjected to gel permeation chromatography (GPC).
The number average molecular weight was 2,230 and the weight average molecular weight was 4,890 using a polystyrene standard. Further, as a result of quantifying the vinylsilyl group (CH ₂定量 CH—Si (Me) (Ph) —) using 1,2-dibromoethane, the vinyl content was 0.7684 mmol / g. (Production Example 2) Synthesis of reactive silicon-based polymer (component (A)) (2) 35.85 g of 1,3-bis (dimethylsilyl) benzene
(184.8 mmol) was dissolved in 100 mL of toluene, and 1,4-bis (dimethylvinylsilyl) benzene 5 was dissolved.
0.00 g (203.3 mmol) and 419 mg of platinum vinylsiloxane complex (9.71 × 10 ⁻⁵ mmol / m)
g, ^10-4 equivalents with respect to the Si-vinyl group) was added dropwise over 160 hours to 160 mL of a toluene solution (charge ratio: Si-vinyl group / Si-H group = 1.1). It was confirmed that the internal temperature rose to 40 ° C. during the dropwise addition. 20
After an hour, the solvent was distilled off to produce 84.3 g of a highly viscous reactive silicon-based polymer. Yield: 98%. The obtained reactive silicon-based polymer had a number average molecular weight of 3330 and a weight average molecular weight of 69 using a polystyrene standard in gel permeation chromatography (GPC).
90. Further, a vinylsilyl group using 1,2-dibromoethane (CH ₂ ＣＨCH—Si (Me)
As a result of quantification of (Ph)-), the vinyl content was 0.512.
It was 6 mmol / g. (Example 1) 1 g of the reactive silicon-based polymer produced in Production Example (1) and 64 mg (0.768 mmol) of 1,3,5-tris (dimethylsilyl) benzene were quantified and mixed.
3.50 g (14.2 mmol) of 1,4-bis (dimethylvinylsilyl) benzene, 1,3,5,7
1.71 g of tetramethylcyclotetrasiloxane
(7.1 mmol) was added. The Pt-vinylsiloxane complex (9.71 × 10 ⁻⁶ mmol / mg) was added thereto for 30 m.
and g mixed (1x10 respect Si- vinyl ^{- 5} eq)
.

A part of the mixture was taken on a gelling tester, and the snap-up time (time until a rubber-like elastic body was formed) was measured at 100 ° C. Snap up
The time was 32 seconds and the composition was found to be fast setting. (Example 2) 1 g of the reactive silicon-based polymer produced in Production Example (2) and 64 mg (0.513 mmol) of 1,3,5-tris (dimethylsilyl) benzene were quantified and mixed.
3.50 g (14.2 mmol) of 1,4-bis (dimethylvinylsilyl) benzene, 1,3,5,7
1.71 g of tetramethylcyclotetrasiloxane
(7.1 mmol) was added. The Pt-vinylsiloxane complex (9.71 × 10 ⁻⁶ mmol / mg) was added thereto for 28 m.
and g mixed (1x10 respect Si- vinyl ^{- 5} eq)
.

The resin solution was cast on a metal frame covered with a Teflon sheet, heated at 50 ° C. for 5 hours, and then cured by heating at 150 ° C. for 20 hours. The electrical properties of the obtained cured product were measured according to JIS
It was measured by the method described in K6911. The dielectric breakdown strength was 18.2 kV / mm, the dielectric constant was 2.5, the dielectric loss tangent was 0.002, and the surface resistance was 5.0 × 10 ¹² Ω · cm. It has been found that the composition has a small dielectric constant and a small dielectric loss tangent and can be used as a high-frequency insulator.

[0049]

As described above, the present invention provides a silicon-based polymer having a molecular weight of 1000 or more consisting of silicon and carbon in which 30% or more of the atoms constituting the main chain skeleton have a vinyl silyl group (CH). ₂ = CR'-Si (R) _2- ), a reactive silicon-based polymer (component (A)),
And a silicon compound having at least two or more Si-H groups in one molecule (component (B)), and as a component (C), at least one component selected from the components shown as A and B components.
Or more silicon compounds having a molecular weight of less than 1000 and at least two or more vinylsilyl groups (CH ₂ ＣC
R′—Si (R) ₂ —) having a molecular weight of less than 1000 (a component (A)), wherein one molecule contains Si—H
Group and vinylsilyl _{(CH 2 = CR'-Si (} R) 2 -)
Have a molecular weight of at least 2
And a thermosetting resin composition for an electrical insulating material containing a hydrosilylation catalyst as an essential component as a component (D). In the formula, R has 1 to 2 carbon atoms.
0 represents a monovalent organic group, and R ′ represents hydrogen or a monovalent organic group. The thermosetting resin composition for an electrical insulating material has fast curing properties and high insulating properties, and can be widely used for semiconductor mounting applications.

Claims (6)

[Claims] 1. A silicon-based polymer having at least 30% of the atoms constituting the main chain skeleton composed of silicon and carbon and having a molecular weight of at least 1,000, and having a vinyl silyl group (CH ₂
= CR'-Si (R) _2- ), and a silicon compound having at least two or more Si-H groups in one molecule (component (A)). (B) component) and (C) at least one silicon compound having a molecular weight of less than 1000 from among the components shown as the former and second components, and at least two vinylsilyl groups (CH) in one molecule.
₂ = CR'-Si (R) _2- ) with a molecular weight of 1000
Less than a silicon compound ((A) component), in one molecule, a Si—H group and a vinylsilyl group (CH ₂ ＣC
R'-Si (R) _2- ) for at least two silicon compounds having a molecular weight of less than 1000 (component (ii)) and an electrically insulating material containing a hydrosilylation catalyst as an essential component as component (D) Thermosetting resin composition. (In the formula, R represents a monovalent organic group having 1 to 20 carbon atoms, and R ′ represents hydrogen or a monovalent organic group.) 2. The main chain skeleton of the component (A) is represented by the following formula (1):
(3): -Si (R¹) (R^Two)-p-C₆H_Four-Si (R¹) (R^Two) -CH_TwoCH_Two-(1) -Si (R¹) (R^Two) -CH_TwoCH_Two-SiMe_Two−p-C₆H_Four-SiMe_Two-CH _Two CH_Two-(2) -Si (R¹) (R^Two)-m-C₆H_Four-Si (R¹)
(R^Two) -CH_TwoCH_Two-Indicated by any of (3)
30% by weight or more of the structural unit
The terminal is a vinylsilyl group (CH_Two= CR'-Si (R)
_Two-), Characterized in that the number average molecular weight is 1000 or less
The above reactive silicon-based polymer, and at least
Silicon compound having two or more Si-H groups ((B) component
Minutes) and (C) as components A and B
At least one of the components has a molecular weight of less than 1000
Silicon compound, at least two or more vinylsilyl groups (CH
_Two= CR'-Si (R)_Two-) Having a molecular weight of 1000
Less than a silicon compound ((A) component), in one molecule, a Si-H group and a vinylsilyl group (CH_Two= C
R'-Si (R)_Two-) Together, at least two
A silicon compound having a molecular weight of less than 1000 ((Otsu)
Min) and a hydrosilylation catalyst as a component (D) are essential
A thermosetting resin composition for an electrical insulating material as a component. (formula
Wherein R represents a monovalent organic group having 1 to 20 carbon atoms, and R ′ represents
Represents hydrogen or a monovalent organic group. ) 3. The thermosetting resin for an electrical insulating material according to claim 2, wherein the component (A) according to claim 2 is at least 60% by weight of the thermosetting resin composition for an electrical insulating material. Resin composition. 4. In addition to using the components (A) to (D) used in claim 1 as essential components, the following (E):
The thermosetting resin composition for an electrical insulating material according to claim 1, wherein the components (F) and (G) are essential components. (E) Silane coupling agent (F) Organoaluminum compound and / or organotitanium compound (G) Polyvalent alkoxysilane and / or condensate thereof 5. In addition to using the components (A) to (D) used in claim 2 as essential components, the following (E):
The thermosetting resin composition for an electrical insulating material according to claim 1, wherein the components (F) and (G) are essential components. (E) Silane coupling agent (F) Organoaluminum compound and / or organotitanium compound (G) Polyvalent alkoxysilane and / or condensate thereof 6. In addition to using the components (A) to (D) used in claim 3 as essential components, the following (E):
The thermosetting resin composition for an electrical insulating material according to claim 1, wherein the components (F) and (G) are essential components. (E) Silane coupling agent (F) Organoaluminum compound and / or organotitanium compound (G) Polyvalent alkoxysilane and / or condensate thereof