JP2012069783A - Thermoconductive silicone composition and mounting substrate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoconductive silicone composition excellent in curability, and a mounting substrate using the same.SOLUTION: The heating curing type thermoconductive silicone composition comprises (A) a silane having at least two Si-bonded alkoxyl groups in one molecule and/or a polysiloxane having at least two Si-bonded alkoxyl groups in one molecule; (B) a zirconium compound; and (C) 100 to 3000 pts.mass of a thermal conductivity filler having a coefficient of thermal conductivity of more than 10 W/mK based on 100 pts.mass of all silicone components, having a viscosity of 10 to 1000 Pas at 25°C, and used for an adhesive agent between an electronic substrate and a semiconductor device, and the mounting substrate is obtained by heating the electronic substrate and the semiconductor device with the thermoconductive silicone composition and by bonding each other.

Description

  The present invention relates to a thermally conductive silicone composition and a mounting substrate using the same.

Conventionally, condensation-curable or addition-type silicone resin compositions having thermal conductivity have been proposed (Patent Documents 1 to 4).
The applicant of the present application has previously proposed a composition used to seal an optical semiconductor (Patent Document 5).

JP 2008-266449 A JP 2008-101081 A JP 2006-274155 A JP 2004-352947 A Japanese Patent No. 4385078

However, when the silicone resin composition is an addition type, platinum as a curing catalyst is deactivated by the solder flux applied on the electronic substrate, thereby inhibiting the curing of the composition, and in the resulting mounting substrate Adhesiveness between the electronic substrate and the semiconductor device may be deteriorated.
In addition, when the condensation curable silicone resin composition is cured under room temperature conditions, it may take a long time to cure or the curing may be insufficient.
Then, an object of this invention is to provide the heat conductive silicone composition excellent in sclerosis | hardenability.

As a result of earnest research to solve the above problems, the present inventor,
(A) component; silane having two or more silicon atom-bonded alkoxy groups in one molecule and / or polysiloxane having two or more silicon atom-bonded alkoxy groups in one molecule, (B) component; zirconium compound, and ( C) component; containing 100 to 3000 parts by mass of a thermally conductive filler having a thermal conductivity of 10 W / m · K or more with respect to 100 parts by mass of all silicone components, and having a viscosity at 25 ° C. of 10 to 1,000 Pa · s, which can be used as an adhesive between an electronic substrate and a semiconductor device, and the heat-curable heat-conductive silicone composition has excellent curability (specifically, it can be sufficiently cured in a short time). And the present invention was completed.

That is, this invention provides the following 1-14.
1. (A) component; silane having two or more silicon atom-bonded alkoxy groups in one molecule and / or polysiloxane having two or more silicon atom-bonded alkoxy groups in one molecule;
(B) component; zirconium compound, and (C) component; containing 100 to 3000 parts by mass of a thermally conductive filler having a thermal conductivity of 10 W / m · K or more with respect to 100 parts by mass of all silicone components,
The viscosity at 25 ° C. is 10 to 1,000 Pa · s,
A heat-curable heat-conductive silicone composition used as an adhesive between an electronic substrate and a semiconductor device.
2. The component (A) is a polydimethylsiloxane having a viscosity at 25 ° C. of 100 to 1,000,000 mPa · s and having both molecular chain ends sealed with trimethoxysiloxy groups,
Polydimethylsiloxane, alkoxysilane having a viscosity at 25 ° C. of 100 to 1,000,000 mPa · s and having both ends of the molecular chain sealed with an alkoxysilane oligomer containing 5 to 50 wt% of silicon-bonded alkoxy groups The thermally conductive silicone composition according to 1 above, which is at least one selected from the group consisting of oligomers of:
3. 3. The thermal conductive silicone composition according to 1 or 2 above, wherein the component (B) is a compound represented by the following formula (1) and / or a compound represented by the following formula (2).
(In the formula, R ¹ is a hydrocarbon group having 1 to 18 carbon atoms.)
(In the formula, R ² is a hydrocarbon group having 1 to 16 carbon atoms, R ³ is a hydrocarbon group having 1 to 18 carbon atoms, and m is an integer of 1 to 3).
4). The (C) thermally conductive filler is selected from the group consisting of metals, alumina, magnesium oxide, zinc oxide, boron nitride, aluminum nitride, silica powder, diamond, aluminum hydroxide, carbon, and those obtained by surface treatment. 4. The heat conductive silicone composition according to any one of 1 to 3, which is at least one kind.
5. The thermally conductive silicone composition according to any one of 1 to 4 above, wherein the amount of the (B) zirconium compound is 0.001 to 1 part by mass with respect to 100 parts by mass of the component (A).
6). Furthermore, (D) component; The polysiloxane which has a 2 or more silanol group in 1 molecule is contained, The quantity of the said (D) component is 1000 mass parts or less with respect to 100 mass parts of said (A) component. The heat conductive silicone composition in any one of 1-5.
7). Further, the component (E) contains a tin compound, and the amount of the component (E) is 100 parts by mass with respect to 100 parts by mass of the component (A) or 100 parts by mass of the component (A) and the component (D). The thermally conductive silicone composition according to any one of 1 to 6 above, which is 0.001 to 1 part by mass.
8). The thermally conductive silicone composition according to any one of 1 to 7 above, wherein the (C) thermally conductive filler is a combination of alumina and aluminum nitride.
9. The heat conduction according to any one of 1 to 8, wherein the heat conductive filler (C) uses a heat conductive filler having an average particle diameter of 10 μm or less and a heat conductive filler having an average particle diameter of more than 10 μm. Silicone composition.
10. 10. The thermally conductive silicone composition according to any one of 1 to 9, wherein the (C) thermally conductive filler is in a powder form.
11. A mounting substrate obtained by heating and bonding an electronic substrate and a semiconductor device using the heat conductive silicone composition according to any one of 1 to 10 above.
12 12. The mounting board according to 11 above, wherein the material of the electronic board is at least one selected from the group consisting of an epoxy resin, a bismaleimide triazine resin and a polyimide resin.
13. 13. The mounting substrate according to 11 or 12 above, wherein the package material of the semiconductor device is at least one selected from the group consisting of an epoxy resin, a phenol resin, a polyimide resin, and a polyamide resin.
14 14. The mounting board according to any one of the above 11 to 13, wherein the heating temperature is 50 to 200 ° C.

  The thermally conductive silicone composition of the present invention is excellent in curability. The mounting board of the present invention is excellent in heat dissipation.

The present invention will be described in detail below.
The thermally conductive silicone composition of the present invention is
(A) component; silane having two or more silicon atom-bonded alkoxy groups in one molecule and / or polysiloxane having two or more silicon atom-bonded alkoxy groups in one molecule;
(B) component; zirconium compound, and (C) component; containing 100 to 3000 parts by mass of a thermally conductive filler having a thermal conductivity of 10 W / m · K or more with respect to 100 parts by mass of all silicone components,
It is a thermosetting heat conductive silicone composition having a viscosity of 10 to 1,000 Pa · s at 25 ° C. and used as an adhesive between an electronic substrate and a semiconductor device.
The heat conductive silicone composition of this invention can be made into a thermosetting type by containing a zirconium compound, and is excellent in sclerosis | hardenability. Moreover, by containing a heat conductive filler, it is excellent in heat conductivity, and the hardened | cured material obtained from the heat conductive silicone composition of this invention is excellent in heat dissipation.
The thermally conductive silicone composition of the present invention may be hereinafter referred to as “the composition of the present invention”.

The component (A) will be described below. The component (A) contained in the composition of the present invention is a silane having two or more silicon atom-bonded alkoxy groups in one molecule and / or a polysiloxane having two or more silicon atom-bonded alkoxy groups in one molecule. is there.
Silane as component (A) has two or more silicon-bonded alkoxy groups in one molecule. For example, a compound having one silicon atom in one molecule and two or more alkoxy groups bonded to the silicon atom (hereinafter, this compound may be referred to as “silane A1”), two or more in one molecule And a compound in which two or more alkoxy groups are bonded to the silicon atom (hereinafter, this compound may be referred to as “silane A2”).

The silane as the component (A) can have one or more organic groups in one molecule.
Examples of the organic group that silane can have include a hydrocarbon group that may contain at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. Specifically, for example, an alkyl group (preferably having 1 to 20 carbon atoms), γ-glycidoxypropyl group, (meth) acryloxyalkyl group, alkenyl group, aryl group; combinations thereof; these or The thing corresponding to bivalence of these combinations is mentioned. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 2-methyl-1-propenyl group, and a 2-methylallyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Of these, a methyl group, a γ-glycidoxypropyl group, and a (meth) acryloxypropyl group are preferable from the viewpoint of excellent heat-resistant coloring stability.

As silane A1, what is represented by following formula (2) is mentioned, for example.
Si (OR ¹ ) _n R ² _4-n (2)
In formula (2), n is 2, 3 or 4, R ¹ is an alkyl group, and R ² is an organic group. An organic group is synonymous with what was described regarding the organic group of silane.

Examples of the silane A1 include dialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane; methyltrimethoxysilane, methyltriethoxysilane, Trialkoxysilanes such as ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane; tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropyloxysilane; silane coupling agents Can be mentioned. The silane coupling agent is not particularly limited. Examples include γ-glycidoxypropyltrimethoxysilane; (meth) acryloxyalkyltrialkoxysilanes such as γ- (meth) acryloxypropyltrimethoxysilane and γ- (meth) acryloxypropyltriethoxysilane.
In the present invention, (meth) acryloxyalkyltrialkoxysilane means acryloxyalkyltrialkoxysilane or methacryloxyalkyltrialkoxysilane. The same applies to the (meth) acryloxyalkyl group.

Silane A2 (a compound having two or more silicon atoms in one molecule and having two or more alkoxy groups bonded to the silicon atom) has a silicon atom and a silicon atom bonded by a hydrocarbon group. It is mentioned as one of the preferable aspects. Moreover, it is mentioned as one of the preferable aspects that silane A2 does not have a siloxane bond between a silicon atom and a silicon atom.
An example of silane A2 is bis (alkoxysilyl) alkane. Examples of the bis (alkoxysilyl) alkane include those represented by the following formula (VII).
In the formula, R ^{7 to} R ⁸ are each an alkyl group, R ⁹ is a divalent alkane (alkylene group) which may have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, and a is Each is an integer of 1 to 3. Examples of the alkyl group include a methyl group and an ethyl group. The divalent alkane as R ⁹ has the same meaning as the above divalent alkane.

  Examples of the bis (alkoxysilyl) alkane include 1,2-bis (triethoxysilyl) ethane, 1,4-bis (trimethoxysilyl) butane, 1-methyldimethoxysilyl-4-trimethoxysilylbutane, 1, 4-bis (methyldimethoxysilyl) butane, 1,5-bis (trimethoxysilyl) pentane, 1,4-bis (trimethoxysilyl) pentane, 1-methyldimethoxysilyl-5-trimethoxysilylpentane, 1,5 -Bis (methyldimethoxysilyl) pentane, 1,6-bis (trimethoxysilyl) hexane, 1,4-bis (trimethoxysilyl) hexane, 1,5-bis (trimethoxysilyl) hexane, 2,5-bis (Trimethoxysilyl) hexane, 1,6-bis (methyldimethoxysilyl) hexane, 1,7-bi (Trimethoxysilyl) heptane, 2,5-bis (trimethoxysilyl) heptane, 2,6-bis (trimethoxysilyl) heptane, 1,8-bis (trimethoxysilyl) octane, 2,5-bis (tri Methoxysilyl) octane, 2,7-bis (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane, 2,7-bis (trimethoxysilyl) nonane, 1,10-bis (trimethoxysilyl) ) Decane, 3,8-bis (trimethoxysilyl) decane; and those in which a divalent alkane such as bis- (3-trimethoxysilylpropyl) amine has a nitrogen atom.

The silane is preferably bis (trialkoxysilyl) alkane from the viewpoint that it is more excellent in curability and adhesiveness, and bis- (3-trimethoxysilylpropyl) amine, 1,2-bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,7-bis (trimethoxysilyl) heptane, 1,8-bis (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane and 1, At least one selected from the group consisting of 10-bis (trimethoxysilyl) decane is more preferable, and 1,6-bis (trimethoxysilyl) hexane and bis- (3-trimethoxysilylpropyl) amine are more preferable.
Silanes can be used alone or in combination of two or more. Bis (alkoxysilyl) alkane used as silane can be used as an adhesion-imparting agent.

The polysiloxane will be described below.
The polysiloxane as the component (A) has two or more silicon-bonded alkoxy groups in one molecule and has a polysiloxane skeleton as a skeleton. The polysiloxane skeleton may be any of a chain (linear, branched), silicone resin, network, cyclic, or a combination thereof.

(A) As a polysiloxane as a component, the compound represented by Formula (3) is mentioned, for example.
R _m Si (OR ′) _n O _{(4-mn) / 2} (3)
In the formula (3), R is an alkyl group having 1 to 6 carbon atoms, an alkenyl group or an aryl group, R ′ is an alkyl group having 1 to 6 carbon atoms, m is 0 <m <2, and n is 0. <N <2, m + n is 0 <m + n ≦ 3.

Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, and an isopropyl group. Of these, a methyl group is preferable from the viewpoint of excellent heat resistance. Examples of the alkenyl group include those having 1 to 6 carbon atoms, and specific examples include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 2-methyl-1-propenyl group, and a 2-methylallyl group. . Examples of the aryl group include a phenyl group and a naphthyl group.
In the compound represented by the formula (3), the alkyl group having 1 to 6 carbon atoms of R ′ may contain a hetero atom such as an oxygen atom. R ′ may be, for example, an acyl group. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, and a valeryl group.

Further, as the polysiloxane as the component (A), for example, a compound having at least one alkoxysilyl group at one end and having two or more alkoxy groups (derived from an alkoxysilyl group) in one molecule (hereinafter referred to as “ Polysiloxane A1 ")) is a preferred form. Examples of the polysiloxane A1 include a polydiorganosiloxane in which both ends of a molecular chain are sealed with a trimethoxysiloxy group, and both ends of a molecular chain are bonded to a silicon atom-bonded alkoxy group (a silicon atom-bonded alkoxy group is bonded to a silicon atom. Examples thereof include C1-C6 alkoxy groups, specifically, for example, methoxy groups), and polydiorganosiloxanes sealed with alkoxysilane oligomers containing 5 to 50% by weight. The polysiloxane A1 can be obtained, for example, as a reaction product obtained by dealcoholization condensation of 1 mol or more of a silane or alkoxysilane oligomer having an alkoxylyl group with respect to 1 mol of a polysiloxane having both terminal silanol groups.
Examples of the silane having an alkoxy group used for producing the polysiloxane A1 include compounds represented by the above formula (2): Si (OR ¹ ) _n R ² _4-n . Moreover, as an alkoxysilane oligomer containing 5 to 50% by weight of a silicon atom-bonded alkoxy group used for producing polysiloxane A1, for example, the above formula (3): R _m Si (OR ′) _n O _{( 4-mn) / 2} , a methylmethoxy oligomer represented by the following formula (4), and the like. In the present invention, the alkoxysilane oligomer containing 5 to 50% by weight of a silicon atom-bonded alkoxy group is an amount of 5 to 50% by weight with one silicon-bonded alkoxy group as an alkoxy group (for example, methoxy group) in one molecule of the alkoxysilane oligomer. Contains.
As polysiloxane which has a both-ends silanol group used in order to manufacture polysiloxane A1, what is represented by Formula (1) as (D) component: polysiloxane mentioned later is mentioned, for example.
Examples of the polysiloxane A1 include polydimethylsiloxane represented by the following formula (IV) and having both molecular chain ends sealed with a trimethoxysiloxy group.
In formula, n can be made into the numerical value corresponding to the molecular weight of the polysiloxane which has the both-ends silanol group used as a raw material.
The compound represented by the formula (IV) corresponds to, for example, a compound represented by the formula (2) exemplified above as a polymethoxysilane having a silanol group at both ends as a tetramethoxysilane [silane having an alkoxy group]. ] Can be produced by modification.

Examples of the polysiloxane A1 include polydimethylsiloxane in which both molecular chain ends represented by the following formula are sealed with an alkoxysilane oligomer containing 5 to 50% by weight of silicon-bonded alkoxy groups.
In the formula, R ″ is an alkyl group having 1 to 6 carbon atoms (for example, a methyl group), a is an integer of 1 to 100, b is an integer of 0 to 100, and n is a raw material. It can be a numerical value corresponding to the molecular weight of the polysiloxane having a terminal silanol group.

In addition, an oligomer of alkoxysilane can be used as the polysiloxane in the component (A). The oligomer is not particularly limited as long as it is a polysiloxane having an alkoxysilyl group. The oligomer of alkoxysilane is sometimes referred to as “polysiloxane A2” hereinafter. Polysiloxane A2 can have an epoxy group such as a glycidoxy group. As polysiloxane A2, for example, a hydrolytic condensate of alkoxysilane can be used. The hydrolysis condensate of silane that can be contained as the component (A) in the composition of the present invention is a compound having two or more silicon atom-bonded alkoxy groups in one molecule and having a siloxane bond.
The alkoxysilane used when producing the hydrolysis condensate is not particularly limited as long as it is a silane having two or more silicon atom-bonded alkoxy groups in one molecule. A silane having two or more silicon-bonded alkoxy groups in one molecule has the same meaning as described above.
The hydrolysis condensate of alkoxysilane is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.
The viscosity of the hydrolysis-condensation product of alkoxysilane is preferably 5 to 1000 mPa · s, and more preferably 50 to 500 mPa · s. The viscosity of the hydrolysis-condensation product of alkoxysilane can be less than 100 mPa · s.

Examples of the hydrolysis condensate include silicone alkoxy oligomers such as methyl methoxy oligomers; and alkoxysilane oligomers having a 3-glycidoxypropyl group. The silicone alkoxy oligomer can be a silicone resin having a main chain of polyorganosiloxane and a molecular terminal blocked with an alkoxysilyl group. Specific examples of the methylmethoxy oligomer include those represented by the following formula (4).
In formula (4), R ″ is a methyl group, a is an integer of 1 to 100, and b is an integer of 0 to 100.
A commercial item can be used for a hydrolysis-condensation product. Commercially available hydrolysis condensates include, for example, trade names x-40-9246 (weight average molecular weight 6,000, manufactured by Shin-Etsu Chemical Co., Ltd.) as methylmethoxy oligomers, alkoxysilane oligomers having a 3-glycidoxypropyl group As trade name X-40-1053 (manufactured by Shin-Etsu Chemical Co., Ltd.).
The hydrolyzed condensate is preferably an alkoxysilane oligomer having a 3-glycidoxypropyl group, X-40-1053, from the viewpoint of excellent curability and adhesiveness.
The polysiloxane as the component (A) is preferably used in combination with the polysiloxane A1 and the polysiloxane A2 from the viewpoint of excellent curability and excellent adhesiveness.

From the viewpoint that the component (A) is more excellent in curability and excellent in adhesiveness,
A polydimethylsiloxane having a viscosity of 100 to 1,000,000 mPa · s at 25 ° C. and having both molecular chain ends sealed with trimethoxysiloxy groups,
Polydimethylsiloxane, alkoxysilane having a viscosity at 25 ° C. of 100 to 1,000,000 mPa · s and having both ends of the molecular chain sealed with an alkoxysilane oligomer containing 5 to 50 wt% of silicon-bonded alkoxy groups And at least one selected from the group consisting of silanes and silanes.

The viscosity of the polysiloxane as the component (A) is 100 to 1,000,000 mPa · s from the viewpoint of being excellent in curability, having an appropriate length of curing time and pot life, and excellent compatibility. Preferably, it is 500 to 20,000 mPa · s.
When the polysiloxane as the component (A) is polysiloxane A1, the viscosity is more excellent in curability, the curing time and the pot life are appropriate lengths, and from the viewpoint of excellent compatibility, 100 to 1,000, 000 mPa · s is preferable, and 500 to 20,000 mPa · s is more preferable.
When the polysiloxane as the component (A) is polysiloxane A2 (an oligomer of alkoxysilane), the viscosity is more excellent in curability, the curing time, the pot life is an appropriate length, and the compatibility is excellent. It is preferably 5 to 1000 mPa · s, and more preferably 50 to 500 mPa · s. The viscosity of polysiloxane A2 can be less than 100 mPa · s.
In the present invention, the viscosity of the component (A) (polysiloxane) was measured using a B-type viscometer at 25 ° C.

The molecular weight of the component (A) is preferably 5,000 to 1,000,000 from the viewpoint that the curability is excellent, the curing time and the pot life are appropriate lengths, and the compatibility is excellent. More preferably, it is from 1,000 to 100,000.
In the present invention, when the component (A) is polysiloxane, the molecular weight thereof is a polystyrene-reduced weight average molecular weight by gel permeation chromatography (GPC) using chloroform as a solvent.
The component (A) is not particularly limited for its production, and examples thereof include conventionally known ones. (A) A component can be used individually or in combination of 2 or more types, respectively.

  (A) It is preferable to use silane and polysiloxane together from the viewpoint that the component (A) is superior in curability, has an appropriate length of curing time and pot life, and is excellent in compatibility.

When the silane is a bis (alkoxysilyl) alkane, the amount of the bis (alkoxysilyl) alkane is 0.1 to 5% by mass in the total silicone component from the viewpoint of excellent curability and adhesiveness. Is preferred.
In the present invention, the total silicone component means the sum of components capable of forming a silicone resin, and the silicone component can be used as the component (A) and (D) poly (described later). Siloxane is included. Accordingly, when the silicone component is only the component (A), 100 parts by mass of the total silicone component is 100 parts by mass of the component (A), and when the silicone component contains the component (A) and (D) polysiloxane, Is the sum of component (A) and component (D).

  The zirconium compound as component (B) will be described below. The zirconium compound is not particularly limited as long as it is a compound containing zirconium. The zirconium compound can have an organic group. The organic group can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. A zirconium atom may be bonded to an organic group via a heteroatom as described above. The zirconium compound may be a zirconyl compound or an organic carboxylate. Zirconium compounds are represented by the following formula (1) and / or the following formula (2) from the viewpoints of better curability, heat curability, and excellent viscosity stability of the composition at room temperature. Preferably it is a compound.

(In the formula, R ¹ is a hydrocarbon group having 1 to 18 carbon atoms.)
(In the formula, R ² is a hydrocarbon group having 1 to 16 carbon atoms, R ³ is a hydrocarbon group having 1 to 18 carbon atoms, and m is an integer of 1 to 3).

Zirconium compounds [particularly compounds represented by the formula (1) and / or compounds represented by the following formula (2)] are hydrolytic condensations of alkoxysilyl groups around room temperature, between alkoxy groups, silanol groups and silanol groups. Condensation reaction hardly occurs (that is, activity at low temperature is low). In this respect, the inventors of the present invention consider that the reaction mechanism of the zirconium compound is different from that of the tin compound having a rapid hydrolysis condensation at room temperature.
The zirconium compound contained in the composition of the present invention can be activated by heating to condense silicon-bonded alkoxy groups (and / or silanol groups). As a result, the zirconium compound can cure the composition containing at least a silicon-bonded alkoxy group or silanol group compound uniformly by heating.
Thus, the zirconium compound can be used as a heat-latent condensation catalyst having excellent curability. The amount of zirconium compound used can be small.

The compound represented by Formula (1) is demonstrated below. The compound represented by Formula (1) is a zirconyl compound.
In formula (1), R ¹ is a hydrocarbon group having 1 to 18 carbon atoms. Examples of the hydrocarbon group having 1 to 18 carbon atoms include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof. The hydrocarbon group may be linear or branched. The hydrocarbon group can have an unsaturated bond. The hydrocarbon group can have, for example, a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.

Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a heptadecyl group, and an octadecyl group.
Examples of the alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; a naphthene ring (a cycloparaffin ring derived from naphthenic acid); Examples thereof include condensed ring hydrocarbon groups such as an adamantyl group and a norbornyl group.
Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and azulene.
Of these, aliphatic hydrocarbon groups and / or alicyclic hydrocarbon groups are more preferable from the viewpoint of excellent curability, solubility in silicone, and excellent viscosity stability at room temperature of the composition. More preferably, it is a cyclic hydrocarbon group.

  Examples of the compound represented by the formula (1) include aliphatic carboxylates such as zirconyl dioctylate and zirconyl dineodecanoate; alicyclic carboxylates such as zirconyl naphthenate and zirconyl cyclohexane; zirconyl benzoate And aromatic carboxylates.

The compound represented by Formula (2) is demonstrated below. The compound represented by the formula (2) is a zirconium metal salt having an alkoxy group.
In formula (2), R < ² > is a C1-C16 hydrocarbon group, R < ³ > is a C1-C18 hydrocarbon group, respectively, and m is an integer of 1-3.
In the formula (2), when m is 2 or more, the plurality of R ² may be the same or different. Moreover, when m is 1-2, several R < ³ > may be the same or different.

The hydrocarbon group as R ² has 1 to 16 carbon atoms. In R ² , the number of carbon atoms is preferably 3 to 16 and more preferably 4 to 16 from the viewpoint of excellent curability and excellent adhesion and compatibility [for example, compatibility with the component (A)]. More preferred.
Examples of the hydrocarbon group for R ² include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof. The hydrocarbon group may be linear or branched. The hydrocarbon group can have an unsaturated bond. The hydrocarbon group can have, for example, a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. The hydrocarbon group in R ¹ is preferably an alicyclic hydrocarbon group or an aliphatic hydrocarbon group from the viewpoint of excellent curability and excellent adhesion and compatibility.

R ² preferably has a cyclic structure from the viewpoints of excellent curability and excellent compatibility.
Examples of the cyclic structure that R ² can have include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. R ² can have, for example, an aliphatic hydrocarbon group in addition to the cyclic structure.

Examples of the alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; a naphthene ring (a cycloparaffin ring derived from naphthenic acid); Examples thereof include condensed ring hydrocarbon groups such as an adamantyl group and a norbornyl group.
Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and azulene.
Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, and an undecyl group. Is mentioned.
Among these, from the viewpoint of excellent curability and compatibility, an alicyclic hydrocarbon group and an aromatic hydrocarbon group are preferable, and a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a naphthene ring (R ¹ COO— And a phenyl group, more preferably a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a naphthene ring.

In the present invention, the hydrocarbon group as R ³ has 1 to 18 carbon atoms. In R ³ , the number of carbon atoms is preferably 3 to 8 from the viewpoint of excellent curability and excellent compatibility.
Examples of the hydrocarbon group for R ³ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof. The hydrocarbon group may be linear or branched. The hydrocarbon group can have an unsaturated bond. The hydrocarbon group can have, for example, a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. The hydrocarbon group in R ³ is preferably an aliphatic hydrocarbon group from the viewpoint of being excellent in curability and excellent in adhesion and compatibility.

Examples of R ³ O— (alkoxy group) having an aliphatic hydrocarbon group include methoxy group, ethoxy group, propoxy group (n-propoxy group, isopropoxy group), butoxy group, pentyloxy group, hexyloxy group, An octyloxy group is mentioned.
Of these, a methoxy group, an ethoxy group, a propoxy group (n-propoxy group, isopropoxy group), a butoxy group, and a pentyloxy group are preferable from the viewpoint of superior curability and compatibility.

Examples of the zirconium metal salt having an alicyclic hydrocarbon group as a cyclic structure include zirconium alkoxy such as zirconium trialkoxy monocyclopropane carboxylate, zirconium dialkoxydicyclopropane carboxylate, and zirconium monoalkoxy tricyclopropane carboxylate. Cyclopropanecarboxylate;
Zirconium alkoxycyclopentane carboxylates such as zirconium trialkoxy monocyclopentane carboxylates, zirconium dialkoxy dicyclopentane carboxylates, zirconium monoalkoxy tricyclopentane carboxylates;
Such as zirconium tributoxy monocyclohexane carboxylate, zirconium dibutoxy dicyclohexane carboxylate, zirconium monobutoxy tricyclohexane carboxylate, zirconium tripropoxy monocyclohexane carboxylate, zirconium dipropoxy dicyclohexane carboxylate, zirconium monopropoxy tricyclohexane carboxylate Zirconium alkoxycyclohexanecarboxylate;
Zirconium alkoxyadamantane carboxylates such as zirconium trialkoxy monoadamantane carboxylates, zirconium dialkoxydiadamantane carboxylates, zirconium monoalkoxytriadamantane carboxylates;
Zirconium alkoxy naphthates such as zirconium tributoxy mononaphthate, zirconium dibutoxy dinaphthate, zirconium monobutoxy trinaphthate, zirconium tripropoxy mononaphthate, zirconium dipropoxy dinaphthate, zirconium monopropoxy trinaphthate It is done.

As a zirconium metal salt having an aromatic hydrocarbon group as a cyclic structure, for example,
Such as zirconium tributoxy monobenzene carboxylate, zirconium dibutoxy dibenzene carboxylate, zirconium monobutoxy tribenzene carboxylate, zirconium tripropoxy monobenzene carboxylate, zirconium dipropoxy dibenzene carboxylate, zirconium monopropoxy tribenzene carboxylate Zirconium alkoxybenzene carboxylate is mentioned.

Examples of the zirconium metal salt having an aliphatic hydrocarbon group include:
Zirconium alkoxy such as zirconium tributoxy monoisobutyrate, zirconium dibutoxy diisobutyrate, zirconium monobutoxy triisobutyrate, zirconium tripropoxy monoisobutyrate, zirconium dipropoxy diisobutyrate, zirconium monopropoxytriisobutyrate Butyrate;
Zirconium tributoxy mono-2-ethylhexanoate, zirconium dibutoxydi-2-ethylhexanoate, zirconium monobutoxytri-2-ethylhexanoate, zirconium tripropoxymono-2-ethylhexanoate, zirconium dipropoxydi-2-ethylhexanoate, Zirconium alkoxy 2-ethyl hexanoate, such as zirconium monopropoxy tri-ethyl hexanoate;
Such as zirconium tributoxy mononeodecanate, zirconium dibutoxy dineodecanate, zirconium monobutoxy trineodecanate, zirconium tripropoxy mononeodecanate, zirconium dipropoxy dineodecanate, zirconium monopropoxytrineodecanate Zirconium alkoxy neodecanate is mentioned.

  Among these, from the viewpoints of excellent curability and excellent adhesion and compatibility, a zirconium metal salt having an alicyclic hydrocarbon group as a cyclic structure and a zirconium metal salt having an aromatic hydrocarbon group as a cyclic structure are preferable. For the same reason, zirconium trialkoxy mononaphthate, zirconium trialkoxy monoisobutyrate, zirconium trialkoxy mono-2-ethylhexanoate, zirconium trialkoxy monocyclopropanecarboxylate, zirconium trialkoxycyclobutanecarboxylate, zirconium trialkoxy mono Cyclopentanecarboxylate, zirconium trialkoxymonocyclohexanecarboxylate, zirconium trialkoxymonoadamantane carboxylate, zirconium trialkoxymonobenzenecarboxylate, zirconium dialkoxydinaphthate are preferred, zirconium tributoxymononaphthate, zirconium tributoxymonoiso Butyrate, zirconium trib Xymono-2-ethylhexanoate, zirconium tributoxymonocyclopropanecarboxylate, zirconium tributoxymonocyclopentanecarboxylate, zirconium tributoxymonocyclohexanecarboxylate, zirconium trialkoxymonobenzenecarboxylate, zirconium tributoxymonoadamantanecarboxylate, zirconium Dibutoxy dinaphthate and zirconium tripropoxy mononaphthate are more preferable.

The zirconium compound is preferably an alkoxy group-containing zirconium metal salt having 1 to 3 acyl groups (ester bonds) from the viewpoint of excellent curability and excellent thermal potential of catalytic activity.
A zirconium compound can be used individually or in combination of 2 or more types, respectively.

The zirconium compound is not particularly limited for its production. Here, taking the compound represented by the formula (2) as an example, the production method thereof will be described below. As a method for producing a zirconium compound, for example, Zr (OR ³ ) ₄ [zirconium tetraalkoxide. R ³ is a hydrocarbon group having 1 to 18 carbon atoms. R ³ has the same meaning as R ³ in Formula (2). The carboxylic acid represented by R ² —COOH [R ² is a hydrocarbon group having 1 to 16 carbon atoms, respectively] R ² has the same meaning as R ² in formula (2). ] 1 mol or more and less than 4 mol can be produced by stirring under a condition of 20 to 80 ° C. in a nitrogen atmosphere.
Regarding the reaction between Zr alcoholate and carboxylic acid, see D.C. C. Reference can be made to Bradley's “Metal alcoholide” Academic Press (1978).

Examples of Zr (OR ³ ) ₄ that can be used to produce a zirconium compound include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetranormal propoxide, zirconium tetrapropoxide, and zirconium tetranormal butoxide. It is done.

  Carboxylic acids that can be used to produce zirconium compounds include, for example, aliphatic carboxylic acids such as acetic acid, propionic acid, isobutanoic acid, octylic acid, 2-ethylhexanoic acid, nonanoic acid, lauric acid; Examples thereof include alicyclic carboxylic acids such as acid, cyclopropane carboxylic acid, cyclopentane carboxylic acid, cyclohexyl carboxylic acid (cyclohexane carboxylic acid), adamantane carboxylic acid and norbornane carboxylic acid; and aromatic carboxylic acids such as benzoic acid.

  The amount of the (B) zirconium compound is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the component (A), from the viewpoint of being excellent in curability and excellent in thermal potential of catalytic activity. More preferably, the amount is 0.001 to 0.1 parts by mass.

  When the composition of the present invention further contains (D) polysiloxane described later, the amount of (B) zirconium compound is more excellent in curability and excellent in thermal potential of catalytic activity, (D) It is preferable that it is 0.001-1 mass part with respect to a total of 100 mass parts of polysiloxane, and it is more preferable that it is 0.001-0.1 mass part.

The thermally conductive filler as component (C) will be described below. The thermally conductive filler contained in the composition of the present invention has a thermal conductivity of 10 W / m · K or more.
Examples of the material constituting the thermally conductive filler include metal, alumina (aluminum oxide), magnesium oxide, zinc oxide, boron nitride, aluminum nitride, silica powder, diamond, aluminum hydroxide, and carbon. The thermally conductive filler may have a surface treated with a surface treatment agent. Examples of the surface treating agent include alkoxysilane, alkylalkoxysilane, fatty acid, and fatty acid ester.

  The heat conductive filler is preferably a combination of alumina and aluminum nitride from the viewpoint of being superior to curability and excellent in heat conductivity.

The thermal conductive filler preferably has an average particle size of 0.1 μm to 50 μm from the viewpoint of being superior to curability and excellent in thermal conductivity.
In addition, the thermally conductive filler is superior to curability, and is excellent in thermal conductivity and adhesiveness, and a thermally conductive filler having an average particle diameter of 10 μm or less and a thermally conductive filler exceeding the average particle diameter of 10 μm; Are preferably used in combination, and it is more preferable to use a heat conductive filler having an average particle size of 20 μm to 40 μm and a heat conductive filler having an average particle size of 0.1 μm to 5 μm in combination.
The average particle size of the thermally conductive filler was measured using a laser diffraction method or a Coulter counter method according to JIS Z 8901.
When the thermally conductive filler is used in combination with alumina and aluminum nitride, the average particle diameter of aluminum nitride is 10 μm or less, and the average particle diameter of alumina is less than 10 μm from the viewpoint of being superior to curability and excellent in thermal conductivity and adhesiveness. The average particle diameter of aluminum nitride is preferably 0.1 μm to 5 μm, and the average particle diameter of alumina is more preferably 20 μm to 40 μm.
In the present invention, the average particle size of alumina was measured using a Coulter counter method. The average particle size of aluminum nitride was measured using a laser diffraction method.

The heat conductive filler is preferably in the form of powder from the viewpoint that it is superior to curability, heat conductivity, and adhesiveness.
The heat conductive fillers can be used alone or in combination of two or more.

  In this invention, the quantity of a heat conductive filler is 100-3000 mass parts with respect to 100 mass parts of all the silicone components. In such a range, it is excellent in sclerosis | hardenability, heat conductivity, and adhesiveness. In the present invention, the total silicone component means the sum of components capable of forming a silicone resin, and the silicone component can be used as the component (A) and (D) poly (described later). Siloxane is included. Accordingly, when the silicone component is only the component (A), 100 parts by mass of the total silicone component is 100 parts by mass of the component (A), and when the silicone component contains the component (A) and (D) polysiloxane, Is the sum of component (A) and component (D). The amount of the thermally conductive filler is preferably 100 to 2000 parts by mass, and 200 to 1500 parts by mass with respect to 100 parts by mass of the total silicone component, from the viewpoint of excellent curability, thermal conductivity, and adhesiveness. More preferably, it is part.

  The composition of the present invention can further contain a polysiloxane having two or more silanol groups in one molecule as the component (D). It is preferable that the composition of this invention further contains (D) component from a viewpoint that it is excellent by sclerosis | hardenability, and is excellent in heat conductivity and adhesiveness.

The polysiloxane that can be further contained in the composition of the present invention is a polysiloxane having two or more silanol groups in one molecule. One preferred embodiment of the polysiloxane is an organopolysiloxane.
The hydrocarbon group that the organopolysiloxane has is not particularly limited. Examples thereof include an aromatic group such as a phenyl group; an alkyl group; and an alkenyl group. The main chain of the polysiloxane as the component (D) may be linear or branched. Examples of the polysiloxane as the component (D) include organopolydialkylsiloxanes in which two or more silanol groups are bonded to the terminal.
The polysiloxane as the component (D) is preferably an organopolydimethylsiloxane in which two silanol groups are bonded to both ends from the viewpoint of excellent curability and adhesiveness. It is more preferable to use a linear organopolydimethylsiloxane having a group bonded to both ends (linear organopolydimethylsiloxane-α, ω-diol). Examples of the polysiloxane as the component (D) include those represented by the following formula (1).

In the formula (1), m can be a numerical value corresponding to the weight average molecular weight of the polysiloxane. m is preferably an integer of 10 to 15,000 from the viewpoint of excellent workability and crack resistance.

The production of the polysiloxane as the component (D) is not particularly limited. For example, a conventionally well-known thing is mentioned.
The viscosity of the polysiloxane as the component (D) is more excellent in curability, and from the viewpoint that the curing time and the pot life are appropriate lengths, the curability is excellent, and the cured product properties are excellent, 100 to 1,000,000 mPa * It is preferable that it is s, and it is more preferable that it is 500-20,000 mPa * s. In the present invention, the viscosity of (D) polysiloxane was measured using a B-type viscometer at 25 ° C.
The molecular weight of the polysiloxane as the component (D) is 5,000 to 1,000 from the viewpoint of being excellent in curability, having an appropriate length of curing time and pot life, excellent in curability, and excellent in physical properties of the cured product. , 000 is preferable, and 20,000 to 100,000 is more preferable.
In the present invention, the molecular weight of the polysiloxane as the component (D) is a weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) using chloroform as a solvent.
(D) The polysiloxane as a component can be used individually or in combination of 2 types or more, respectively.

  The amount of the polysiloxane as the component (D) is preferably 1000 parts by mass or less with respect to 100 parts by mass of the component (A), and is preferably 50 to 900 parts by mass from the viewpoint that the curability is excellent and the adhesiveness is excellent. It is more preferable that

  The composition of the present invention can further contain a tin compound as the component (E). It is preferable that the composition of the present invention further contains a component (E) from the viewpoint of excellent curability and excellent adhesiveness.

The tin compound that can be further contained in the composition of the present invention is preferably a tetravalent tin compound from the viewpoint of excellent curability and excellent adhesiveness. As the tetravalent tin compound, for example, a tetravalent tin compound having at least one alkyl group and at least one acyl group is preferable.
In the present invention, the tin compound can have an acyl group as an ester bond.

Examples of the tetravalent tin compound having at least one alkyl group and at least one acyl group include those represented by the formula (II), those represented by the formula (II), and the polymer type. Is mentioned.
_{^{R 3 a -Sn- [O-CO}} -R 4] 4-a (II)
In the formula, R ³ is an alkyl group, R ⁴ is a hydrocarbon group, and a is an integer of 1 to 3.

Examples of the alkyl group include those having 1 or more carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and an octyl group.
The hydrocarbon group is not particularly limited. Examples thereof include an aliphatic hydrocarbon group such as a methyl group and an ethyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. The hydrocarbon group may be linear or branched. The hydrocarbon group can have an unsaturated bond. The hydrocarbon group can have, for example, a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.

As a bis | screw type | mold of what is represented by Formula (II), what is represented by following formula (III) is mentioned, for example.
In the formula, R ³ and R ⁴ have the same meaning as in formula (II), and a is 1 or 2.

Examples of the tin compound include dialkyltin compounds such as dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dioctyltin diacetate, and dioctyltin maleate [wherein a is 2 represented by the above formula (II) Dibutyltin oxyacetate dibutytin oxyoctylate, dibutyltin oxylaurate dibutyltin bismethylmalate, dialkyltin dimer such as dibutyltin oxyoleate; or dibutyltin malate polymer, dioctyltin malate polymer; monobutyltin And tris (2-ethylhexanoate) [wherein a is 1 represented by the above formula (II)].
Of these, dibutyltin diacetate, dibutyltin dioleate, dibutyltin dilaurate, dibutyltin oxyacetate dibutyltin oxyoctylate, and dibutyltin oxylaurate are preferable from the viewpoints of excellent curability and adhesiveness.
Tin compounds can be used alone or in combination of two or more. The tin compound is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.

  (E) Component: The amount of the tin compound is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the component (A) from the viewpoint that the curability is excellent and the adhesiveness is excellent, and 0.001 More preferably, it is -0.1 mass part.

  When the composition of the present invention further contains (D) polysiloxane, the component (E): the amount of tin compound is more excellent in curability and adhesiveness, from the viewpoint of excellent adhesiveness (A) component and (D) polysiloxane It is preferable that it is 0.001-1 mass part with respect to a total of 100 mass parts of siloxane, and it is more preferable that it is 0.001-0.1 mass part.

  Further, the amount of the tin compound is preferably 0.1 mol or more and less than 4 mol with respect to 1 mol of the zirconium compound, from the viewpoint of excellent curability and excellent adhesiveness, and 0.5 to 1.5 mol More preferably, it is a mole.

  The composition of this invention can contain an additive further as needed in the range which does not impair the objective and effect of this invention other than (A)-(E) component. Examples of additives include curing catalysts other than zirconium compounds and tin compounds, fillers such as inorganic fillers, antioxidants, lubricants, ultraviolet absorbers, thermal light stabilizers, dispersants, antistatic agents, polymerization inhibitors, Antifoaming agent, curing accelerator, solvent, phosphor (for example, inorganic phosphor), anti-aging agent, radical inhibitor, adhesion improver, flame retardant, surfactant, storage stability improver, ozone anti-aging agent, A thickener, a plasticizer, a radiation blocking agent, a nucleating agent, a coupling agent, a conductivity imparting agent, a phosphorus peroxide decomposing agent, a pigment, a metal deactivator, a physical property modifier, and an adhesion imparting agent can be mentioned. Various additives are not particularly limited. For example, a conventionally well-known thing is mentioned.

From the viewpoint that the composition of the present invention is excellent in storage stability, it is mentioned as one of preferred embodiments that substantially does not contain water. In the present invention, “substantially free of water” means that the amount of water in the composition of the present invention is 0.1% by mass or less.
In addition, the composition of the present invention can be mentioned as one of preferred embodiments that substantially does not contain a solvent from the viewpoint of excellent work environment properties. The phrase “substantially free of solvent” in the present invention means that the amount of the solvent in the composition of the present invention is 1% by mass or less.

The composition of the present invention is not particularly limited for its production. For example, it can manufacture by mixing (A)-(C) component and (D) component, (E) component, and an additive which can be used as needed.
When the composition of the present invention further contains (E) a tin compound, it can be used as a mixture obtained by previously mixing (B) a zirconium compound and (E) a tin compound, or (B) Zirconium compounds and (E) tin compounds can be used separately and added to the system.

  The composition of the present invention can be produced as a one-pack type or a two-pack type. When the composition of the present invention is a two-component type, (B) a zirconium compound, (D) a polysiloxane, (E) a first liquid containing a tin compound, which can be used as needed, and (A) It is mentioned as one of the preferable aspects to have the 2nd liquid containing a component. The additive can be added to one or both of the first liquid and the second liquid.

  The composition of the present invention has a viscosity at 25 ° C. of 10 to 1,000 Pa · s. In such a range, the moldability and adhesiveness are excellent. Further, the viscosity of the composition at 25 ° C. is preferably 50 to 500 Pa · s, and more preferably 100 to 400 Pa · s, from the viewpoint of excellent moldability and adhesiveness. In the present invention, the viscosity of the composition was measured using a B-type viscometer at 25 ° C.

The composition of the present invention can be used as an adhesive between an electronic substrate and a semiconductor device.
The optical semiconductor device to which the composition of the present invention can be applied is not particularly limited as long as it is a mounted component. For example, an IC chip in which a semiconductor element such as a diode (LED), an organic electric field element (organic EL), a laser diode, or an LED array is packaged can be used. Examples of the material constituting the IC chip package include resins, ceramics, glasses, metals such as aluminum, and the like.
The electronic substrate to which the composition of the present invention can be applied is not particularly limited. For example, an electronic circuit board such as a printed board can be used. Examples of the material constituting the electronic substrate include resins, ceramics, glasses, metals such as aluminum, and the like. For example, the electronic substrate may include a die pad and a bonding pad. Examples of the die pad include a film pattern made of Au. The same applies to the bonding pad. For example, solder or solder flux may be applied to the electronic substrate.
As a method of using the composition of the present invention, the composition of the present invention is applied to a component and / or a substrate (for example, an optical semiconductor device and / or an electronic substrate), and the component and the substrate are combined (an optical semiconductor device). For example, by mounting at least a portion to which the composition of the present invention is applied to cure the composition of the present invention and bonding the component and the substrate.
The method for applying the composition of the present invention is not particularly limited. Examples thereof include a method using a dispenser, a potting method, screen printing, transfer molding, and injection molding.
In addition to the adhesive between the electronic substrate and the semiconductor device, the composition of the present invention can be used as, for example, an adhesive between a semiconductor laser and its circuit board and a heat sink.

The composition of the present invention is a thermosetting type and can be cured by heating.
The heating temperature is preferably 50 to 200 ° C. from the viewpoint of excellent curability, curing time and pot life can be set to appropriate lengths, and excellent smoothness, moldability, and physical properties of the cured product. 80 ° C to 150 ° C is more preferable, and around 150 ° C is more preferable.
The heating can be performed under substantially anhydrous conditions from the viewpoint of excellent curability and transparency. In the present invention, “heating under substantially anhydrous conditions” means that the atmospheric humidity of the environment during heating is 10% RH or less.

  A cured product (silicone resin) obtained by heating and curing the composition of the present invention has thermal conductivity. The thermal conductivity of the obtained cured product is preferably 0.5 W / m · K or more, and more preferably 2.0 W / m · K or more, from the viewpoint of excellent heat dissipation. The heat conductivity of the cured product was measured using a hot wire method thermal conductivity measuring device in accordance with JIS R 2616 at 25 ° C. The cured product used for the evaluation of the thermal conductivity of the cured product was obtained by curing about 450 g of the composition of the present invention in a size of 30 mm × 50 mm × 100 mm or more and placing it at 80 ° C. for 24 hours. It was used.

The mounting substrate of the present invention will be described below.
The mounting substrate of the present invention is a mounting substrate obtained by heating and bonding an electronic substrate and a semiconductor device using the thermally conductive silicone composition of the present invention.

The composition used as the adhesive for the mounting substrate of the present invention is not particularly limited as long as it is the composition of the present invention.
The electronic board used for the mounting board of the present invention is not particularly limited. The thing similar to the above is mentioned. The material of the electronic substrate is an epoxy resin (for example, glass epoxy), a bismaleimide triazine resin (for example, BT resin manufactured by Mitsubishi Gas Chemical Company), and a polyimide resin from the viewpoint that the adhesiveness by the composition is high and versatility is high. It is preferably at least one selected from the group consisting of

  The semiconductor device used for the mounting substrate of the present invention is not particularly limited. The thing similar to the above is mentioned. The material for the package of the semiconductor device is preferably at least one selected from the group consisting of an epoxy resin, a phenol resin, a polyimide resin, and a polyamide resin from the viewpoint that the adhesiveness by the composition is high and the versatility is high. .

As a method for producing a mounting substrate of the present invention, for example, a composition is applied to an optical semiconductor device and / or an electronic substrate, the optical semiconductor device is mounted on an electronic substrate, and at least a portion to which the composition is applied is heated. Is cured to bond the optical semiconductor device and the electronic substrate.
The method for applying the composition to the optical semiconductor device and / or the electronic substrate is not particularly limited. Examples thereof include a method using a dispenser, a potting method, screen printing, transfer molding, and injection molding. The heating temperature is the same as above.

  By using the composition of the present invention, the mounting substrate of the present invention can be heated without being inhibited by solder flux or the like, and has excellent curability. In addition, the mounting substrate of the present invention has excellent thermal conductivity and excellent adhesion between the optical semiconductor device and the electronic substrate.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the examples.

<Manufacture of zirconium compounds>
Zirconium tributoxy mononaphthate [(B) zirconium compound 1]
17.5 g (0.026 mol) of zirconium tetrabutoxide having a concentration of 87.5% by mass (manufactured by Kanto Chemical Co., Inc.) and naphthenic acid (manufactured by Tokyo Chemical Industry Co., Ltd., average number of carbon atoms of hydrocarbon groups bonded to carboxy groups: 15, 6.6 g (0.026 mol) of neutralization value 220 mg, the same applies hereinafter) was put into a three-necked flask and stirred at room temperature for about 2 hours in a nitrogen atmosphere to obtain a target compound.
The neutralization value of naphthenic acid is the amount of KOH required to neutralize 1 g of naphthenic acid.
The qualitative properties of the synthesized product were analyzed using a Fourier transform infrared spectrophotometer (FT-IR). As a result, absorption near 1700 cm ⁻¹ attributed to COOH derived from carboxylic acid disappeared after the reaction, and a peak derived from COOZr near 1450 to 1560 cm ⁻¹ was confirmed.
The resultant composite is referred to as (B) zirconium compound 1. (B) The average number of carbon atoms of R ^{1 in} the naphthate group (R ¹ COO—) of the zirconium compound 1 is 15.

<Evaluation>
Using the silicone composition obtained as described below, viscosity, adhesion, thermal conductivity, volume resistance, curing time, and curing inhibition due to flux were evaluated by the following methods. The results are shown in Table 1.
[viscosity]
The viscosity of the silicone composition was measured using a B-type viscometer at 25 ° C.
[Adhesiveness]
As the adherend, an aluminum (A1050) adherend or a glass adherend was used. A silicone composition was applied to each adherend in an area of about 20 mm × 20 mm so as to have a thickness of 1 mm, and each was cured at 150 ° C. for 30 minutes to obtain a laminate. In the obtained laminate, a cut of about 2 mm was made at the interface between the cured product of the silicone composition and the adherend, and the cured product was peeled off from the adherend. After peeling, the case where the cured product remained on the adherend was CF, and the case where the cured product did not remain was AF.
[Thermal conductivity]
A silicone composition having a size of 30 mm × 50 mm × 100 mm or more and cured under a condition of 80 ° C. for 24 hours was measured with Model QTM-500 manufactured by Kyoto Electronics Industry Co., Ltd.
[Volume resistance]
Measured with a super high resistance / microammeter manufactured by Advantest Co., Ltd. using a silicone composition that is 30 mm × 50 mm × 100 mm or larger and cured under a condition of 80 ° C. for 24 hours. Went.
[Curing time]
50 g of the silicone composition was measured at 150 ° C. until the surface of the silicone composition was cured and the tack disappeared.
[Inhibition of curing by flux]
As a flux, a solution in which 10% by mass of abietic acid was dissolved in toluene was prepared. This is applied to a glass substrate, and then the silicone composition is applied and cured thereon (curing is performed for 1 hour at 150 ° C.), and after curing, the silicone composition is completely cured at the interface with the glass. In the case, ○, uncured or sticky was marked with ×.

<Manufacture of silicone composition>
The components shown in Table 1 below were uniformly mixed in the amounts shown in the same table (unit: parts by mass) using a vacuum stirrer to produce a silicone composition.
In the examples, a zirconium compound and a tin compound were added to produce a composition.

The details of each component shown in Table 1 are as follows.
(A) Polysiloxane 1: Trimethoxysiloxy-capped dimethylpolysiloxane at both ends (A) Polysiloxane 1 was produced as follows.
A 500 mL three-necked flask equipped with a stirrer and a reflux condenser and a polysiloxane having silanol groups at both ends (polydimethylsiloxane-α, ω-diol, weight average molecular weight 49,000, trade name ss10, manufactured by Shin-Etsu Chemical Co., Ltd.) 100 parts by mass, 10 parts by mass of tetramethoxysilane, and 0.1 part by mass of acetic acid were added and reacted under a nitrogen atmosphere at 100 ° C. for 6 hours. The disappearance of the silanol group possessed by ss10 was confirmed by ¹ H-NMR analysis. The obtained organosiloxane was designated as (A) polysiloxane 1. (A) Polysiloxane 1 is dimethylpolysiloxane represented by the following formula and having both ends blocked with trimethoxysiloxy groups. (A) The weight average molecular weight of the polysiloxane 1 was 55,000. The weight average molecular weight of polysiloxane is expressed in terms of polystyrene by gel permeation chromatography (GPC) analysis using chloroform as a solvent.
The viscosity of (A) polysiloxane 1 at 25 ° C. was 1,500 mPa · s.

-(D) Polysiloxane 1: Silanol dimethyl polysiloxane at both ends, trade name RF 20000, manufactured by Shin-Etsu Chemical Co., Ltd., viscosity 20,000 mPa · s at 25 ° C
(B) Zirconium compound 1: zirconium tributoxynaphthenate produced as described above.
(B) Zirconium compound 2: Zirconyl naphthenate, manufactured by Nippon Chemical Industry Co., Ltd. (E) Tin compound 1: Dibutyltin diacetate, manufactured by Nitto Kasei Co., Ltd. Addition silicone 1: Trade name KE-106, manufactured by Shin-Etsu Chemical Co., Ltd. -(C) Thermally conductive filler 1: Alumina, trade name CB-A25BC, Showa Denko KK, no surface treatment, average particle size 28 μm (measured value by call counter method)
(C) Thermally conductive filler 2: Aluminum nitride powder (AlN), trade name high-purity aluminum nitride powder H, manufactured by Tokuyama, no surface treatment, average particle size 1.13 μm (measured by laser diffraction method)
(A) Silane 1: 1,6-bis (trimethoxysilyl) hexane, trade name KBM3066, manufactured by Shin-Etsu Chemical Co., Ltd. (A) polysiloxane 2: 3-glycidoxypropyltrimethoxysilane oligomer, X-40 -1053, manufactured by Shin-Etsu Chemical Co., Ltd., viscosity at 25 ° C .: 12 mPa · s

As is clear from the results shown in Table 1, Comparative Example 1 containing no thermally conductive filler had low thermal conductivity. In Comparative Example 2 containing the addition type silicone resin, the adhesiveness was low and the curing was inhibited by the flux. Component (B): Comparative Example 3 containing no zirconium compound had a long curing time and a poor curability.
On the other hand, Examples 1 to 4 can be sufficiently cured in a short curing time, are not subject to curing inhibition by the solder flux, and are excellent in curability. In Examples 1 to 4, the viscosity is appropriate, the adhesiveness and thermal conductivity are high, the heat dissipation is excellent, the volume resistance is high, and the insulation is excellent.
As described above, the composition of the present invention can be cured sufficiently in a short curing time, is not subject to curing inhibition by the solder flux, and has excellent curability. When the composition of the present invention is excellent in the above-described curability, the mounting substrate of the present invention using the composition can eliminate the curing inhibition with respect to the flux, and can improve the adhesiveness between the electronic substrate and the semiconductor device. Short time and excellent productivity.
In addition, the mounting substrate of the present invention obtained using the composition of the present invention is excellent in heat dissipation.

Claims (14)

(A) component; silane having two or more silicon atom-bonded alkoxy groups in one molecule and / or polysiloxane having two or more silicon atom-bonded alkoxy groups in one molecule;
(B) component; zirconium compound, and (C) component; containing 100 to 3000 parts by mass of a thermally conductive filler having a thermal conductivity of 10 W / m · K or more with respect to 100 parts by mass of all silicone components,
The viscosity at 25 ° C. is 10 to 1,000 Pa · s,
A heat-curable heat-conductive silicone composition used as an adhesive between an electronic substrate and a semiconductor device. The component (A) is a polydimethylsiloxane having a viscosity at 25 ° C. of 100 to 1,000,000 mPa · s and having both molecular chain ends sealed with trimethoxysiloxy groups,
A polydimethylsiloxane having a viscosity at 25 ° C. of 100 to 1,000,000 mPa · s and having both ends of the molecular chain sealed with an alkoxysilane oligomer containing 5 to 50% by weight of silicon-bonded alkoxy groups,
The thermally conductive silicone composition according to claim 1, which is at least one selected from the group consisting of an oligomer of alkoxysilane and the silane. The thermally conductive silicone composition according to claim 1 or 2, wherein the component (B) is a compound represented by the following formula (1) and / or a compound represented by the following formula (2).
(In the formula, R ¹ is a hydrocarbon group having 1 to 18 carbon atoms.)
(In the formula, R ² is a hydrocarbon group having 1 to 16 carbon atoms, R ³ is a hydrocarbon group having 1 to 18 carbon atoms, and m is an integer of 1 to 3).   The (C) thermally conductive filler is selected from the group consisting of metals, alumina, magnesium oxide, zinc oxide, boron nitride, aluminum nitride, silica powder, diamond, aluminum hydroxide, carbon, and those obtained by surface treatment. The thermally conductive silicone composition according to any one of claims 1 to 3, which is at least one kind.   The amount of said (B) zirconium compound is 0.001-1 mass part with respect to 100 mass parts of said (A) component, The heat conductive silicone composition in any one of Claims 1-4.   Furthermore, (D) component; The polysiloxane which has a 2 or more silanol group in 1 molecule is contained, The quantity of the said (D) component is 1000 mass parts or less with respect to 100 mass parts of said (A) component, Item 6. The thermally conductive silicone composition according to any one of Items 1 to 5.   Further, the component (E) contains a tin compound, and the amount of the component (E) is 100 parts by mass with respect to 100 parts by mass of the component (A) or 100 parts by mass of the component (A) and the component (D). The heat conductive silicone composition according to claim 1, wherein the heat conductive silicone composition is 0.001 to 1 part by mass.   The thermally conductive silicone composition according to any one of claims 1 to 7, wherein the (C) thermally conductive filler is a combination of alumina and aluminum nitride.   The heat according to any one of claims 1 to 8, wherein the heat conductive filler (C) uses a heat conductive filler having an average particle diameter of 10 µm or less and a heat conductive filler having an average particle diameter of more than 10 µm. Conductive silicone composition.   The thermally conductive silicone composition according to claim 1, wherein the (C) thermally conductive filler is in a powder form.   A mounting substrate obtained by heating and bonding an electronic substrate and a semiconductor device using the thermally conductive silicone composition according to claim 1.   The mounting substrate according to claim 11, wherein a material of the electronic substrate is at least one selected from the group consisting of an epoxy resin, a bismaleimide triazine resin, and a polyimide resin.   The mounting substrate according to claim 11 or 12, wherein a material of the package of the semiconductor device is at least one selected from the group consisting of an epoxy resin, a phenol resin, a polyimide resin, and a polyamide resin.   The mounting substrate according to any one of claims 11 to 13, wherein the heating temperature is 50 to 200 ° C.