JP2012021118A - Silanol condensation catalyst, thermosetting silicone resin composition for optical semiconductor sealing use, and sealing body using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting silicone resin composition for optical semiconductor sealing use having excellent heat resistance and thin film curability.SOLUTION: A silanol condensation catalyst contains at least an organohafnium compound represented by formula (1) and/or formula (2) in (C). The thermosetting silicone resin composition for optical semiconductor sealing use contains: (A) 100 pts.mass of an organopolysiloxane having two or more silanol groups per molecule; (B) 0.1-2000 pts.mass of a silane compound having two or more alkoxy groups per molecule; and (C) the organohafnium compound. A sealing body using the thermosetting silicone resin composition is also provided. In the formula (1), n is an integer of 1-4, Ris a hydrocarbon group, and Ris a 1-18C alkyl group. In the formula (2), m is an integer of 1-4, Ris a 1-18C alkyl group, and Rand Rare each a 1-18C hydrocarbon group or alkoxy group and are the same as or different from each other.

Description

  The present invention relates to a silanol condensation catalyst, a thermosetting silicone resin composition for sealing an optical semiconductor, and a sealing body using the same.

  As for the condensation catalyst used in the silicone resin composition, many techniques related to moisture curing have been observed so far (see, for example, Patent Documents 1 and 2), but there is no example that discloses a catalyst having thermal potential related to hafnium. . Further, for example, a silicone resin composition containing a condensation catalyst such as an aluminum catalyst (see, for example, Patent Document 3) has a problem that its heat loss is large and its heat resistance is poor.

JP 2005-120371 A JP 2007-270004 A Japanese Patent Laid-Open No. 2-196860

Further, the inventors of the present invention have found a problem that when a silicone resin composition containing a catalyst having thermal potential is thin-cured, the composition becomes uncured.
Then, an object of this invention is to provide the thermosetting silicone resin composition for optical semiconductor sealing excellent in heat resistance and thin film curability.

  As a result of earnest research to solve the above problems, the present inventor has (A) 100 parts by mass of organopolysiloxane having two or more silanol groups in one molecule, and (B) two or more in one molecule. Thermosetting for optical semiconductor sealing, wherein the composition containing 0.1 to 2000 parts by mass of a silane compound having an alkoxy group and (C) an organic hafnium compound having a specific structure is excellent in heat resistance and thin film curability. It discovered that it could become a silicone resin composition, and completed this invention.

That is, this invention provides the following 1-13.
1. (A) 100 parts by mass of an organopolysiloxane having two or more silanol groups in one molecule;
(B) 0.1 to 2000 parts by mass of a silane compound having two or more alkoxy groups in one molecule;
(C) A thermosetting silicone resin composition for sealing an optical semiconductor, comprising an organic hafnium compound represented by the following formula (1) and / or the following formula (2).
Wherein (1), n is an integer from 1 to 4, R ¹ is a hydrocarbon group, R ² is an alkyl group having 1 to 18 carbon atoms. ]
[In formula (2), m is an integer of 1 to 4, R ² is an alkyl group having 1 to 18 carbon atoms, R ^3, R ⁴ are identical or different, hydrocarbon having 1 to 18 carbon atoms Group or alkoxy group. ]
2. 2. The thermosetting silicone resin composition for optical semiconductor encapsulation according to 1 above, wherein R ¹ has a cyclic structure.
3. R ¹ is at least one selected from the group consisting of cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, naphthene ring, adamantyl group, norbornyl group, phenyl group, naphthyl group and azulene. 3. The thermosetting silicone resin composition for optical semiconductor encapsulation according to 1 or 2, which is a seed.
4). The amount of the (C) organic hafnium compound is 0.001 to 5 parts by mass with respect to 100 parts by mass in total of the (A) organopolysiloxane and the (B) silane compound. The thermosetting silicone resin composition for optical semiconductor sealing of description.
5. Further, (D) a tetravalent tin compound is contained, and the amount of the tetravalent tin compound is 0.01 to 10 mol relative to 1 mol of the (C) organic hafnium compound. Thermosetting silicone resin composition for optical semiconductor encapsulation.
6). Any of (1) to (5) above, wherein the (A) organopolysiloxane is a diorganopolysiloxane having a weight average molecular weight of 1,000 to 1,000,000, which is represented by the following formula (3) and has silanol groups at both ends. A thermosetting silicone resin composition for optical semiconductor encapsulation according to claim 1.
(Wherein R ⁵ are the same or different hydrocarbon groups.)
7). The (B) silane compound is a silane compound represented by the following formula (4), a silane compound represented by the following formula (5), a diorganopolysiloxane represented by the following formula (3), and the following formula (4). The thermosetting for optical semiconductor encapsulation according to any one of 1 to 6 above, which is at least one selected from the group consisting of a silane compound and / or a condensate with a silane compound represented by the following formula (5): Silicone resin composition.
Wherein (4), m is an integer from 1 to 4, R ⁶ is an organic group having 1 to 18 carbon atoms, R ⁷ is a hydrocarbon group having 1 to 6 carbon atoms. ]
R ⁸ _k Si (OR ⁹ ) _l O _{(4-kl) / 2} (5)
[In the formula (5), R ⁸ is an alkyl group having 1 to 6 carbon atoms and / or an aryl group, R ⁹ is an alkyl group having 1 to 6 carbon atoms, and 0 <k <2, 0 <l < 2, 0 <(k + l) ≦ 3. ]
(Wherein R ⁵ are the same or different hydrocarbon groups.)
8). The amount of the (D) tetravalent tin compound is 0.001 to 1 part by mass with respect to a total of 100 parts by mass of the (A) organopolysiloxane and the (B) silane compound. The thermosetting silicone resin composition for optical semiconductor sealing of description.
9. The sealing body which heats and hardens the thermosetting silicone resin composition for optical semiconductor sealing in any one of said 1-8, and seals an optical semiconductor.
10. (C) A silanol condensation catalyst containing at least an organic hafnium compound represented by the following formula (1) and / or the following formula (2).
Wherein (1), n is an integer from 1 to 4, R ¹ is a hydrocarbon group, R ² is an alkyl group having 1 to 18 carbon atoms. ]
[In formula (2), m is an integer of 1 to 4, R ² is an alkyl group having 1 to 18 carbon atoms, R ^3, R ⁴ are identical or different, hydrocarbon having 1 to 18 carbon atoms Group or alkoxy group. ]
11. 11. The silanol condensation catalyst as described in 10 above, wherein R ¹ has a cyclic structure.
12 R ¹ is at least one selected from the group consisting of cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, naphthene ring, adamantyl group, norbornyl group, phenyl group, naphthyl group and azulene. The silanol condensation catalyst according to the above 10 or 11, which is a seed.
13. Furthermore, it contains (D) a tetravalent tin compound, and the amount of the tetravalent tin compound is 0.01 to 10 mol per 1 mol of the (C) organic hafnium compound. Silanol condensation catalyst.

The thermosetting silicone resin composition for optical semiconductor encapsulation of the present invention is excellent in heat resistance and thin film curability. The sealing body of the present invention is excellent in heat resistance and thin film curability.
According to the silanol condensation catalyst of the present invention, the heat resistance and thin film curability of the thermosetting silicone resin composition can be made excellent.

FIG. 1 is a cross-sectional view schematically showing an example of the sealing body of the present invention. FIG. 2 is a cross-sectional view schematically showing another example of the sealing body of the present invention. FIG. 3 is a diagram schematically showing an example of an LED display using the sealing body of the present invention. FIG. 4 is a cross-sectional view schematically showing a cross section of a mold used for curing the composition of the present invention in Examples.

The present invention will be described in detail below.
The silanol condensation catalyst of the present invention is (C) a silanol condensation catalyst containing at least an organic hafnium compound represented by the following formula (1) and / or the following formula (2).
Wherein (1), n is an integer from 1 to 4, R ¹ is a hydrocarbon group, R ² is an alkyl group having 1 to 18 carbon atoms. ]
[In formula (2), m is an integer of 1 to 4, R ² is an alkyl group having 1 to 18 carbon atoms, R ^3, R ⁴ are identical or different, hydrocarbon having 1 to 18 carbon atoms Group or alkoxy group. ]

  The organic hafnium compound will be described below. The (C) organic hafnium compound contained in the silanol condensation catalyst of the present invention is represented by the following formula (1) and / or the following formula (2). The silanol condensation catalyst of the present invention may contain at least one represented by the formula (1) and / or one represented by the formula (2).

The organic hafnium compound represented by the formula (1) will be described below.
Wherein (1), n is an integer from 1 to 4, R ¹ is a hydrocarbon group, R ² is an alkyl group having 1 to 18 carbon atoms. ]

Examples of the hydrocarbon group in R ¹ include an aliphatic hydrocarbon group having 1 to 18 carbon atoms (an alkyl group; including an unsaturated aliphatic hydrocarbon group such as an allyl group), an alicyclic hydrocarbon group, and an aryl group. (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 preferably has a cyclic structure from the viewpoints of excellent heat resistance (for example, heat-resistant coloring stability), excellent thin film curability, and excellent thermosetting and compatibility, and alicyclic carbonization. A hydrogen group, an aromatic hydrocarbon group, or a combination thereof is more preferable. R ¹ 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.
Of these, alicyclic hydrocarbon groups and aromatic hydrocarbon groups are preferred from the viewpoint of excellent heat resistance (for example, heat-resistant coloring stability), excellent thin film curability, thermosetting properties, and compatibility, and cyclopropyl groups. , Cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, naphthene ring, adamantyl group, norbornyl group, phenyl group, naphthyl group, and azulene, more preferably, A propyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a naphthene ring (naphthate group as R ¹ COO—) and a phenyl group are more preferable, and a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group and a naphthene ring are particularly preferable.

In the formula (1), R ² is an alkyl group having 1 to 18 carbon atoms. In R ² , the number of carbon atoms is preferably 3 to 8 from the viewpoint of excellent heat resistance (for example, heat-resistant coloring stability), excellent thin film curability, and excellent thermosetting and compatibility.

Examples of R ² include a methyl group, an ethyl group, a propyl group (n-propyl group, isopropyl group), a butyl group, a pentyl group, a hexyl group, and an octyl group.
Among them, from the viewpoint of excellent heat resistance (for example, heat-resistant coloring stability), excellent thin film curability, thermosetting property, and compatibility, a methyl group, an ethyl group, a propyl group (n-propyl group, isopropyl group), A butyl group and a pentyl group are preferred.

As an organic hafnium compound having an alicyclic hydrocarbon group as a cyclic structure, for example,
Hafnium alkoxy (mono-tri) cyclopropanecarboxylate, hafnium tetracyclopropanecarboxylate,
Hafnium alkoxy (mono-tri) cyclopentanecarboxylate, hafnium tetracyclopentanecarboxylate,
Hafnium alkoxy (mono-tri) cyclohexanecarboxylate, hafnium tetracyclohexanecarboxylate,
Hafnium alkoxy (mono-tri) adamantane carboxylate, hafnium tetraadamantane carboxylate,
Hafnium alkoxy (mono-tri) naphthate and hafnium tetranaphthate can be mentioned.

As an organic hafnium compound having an aromatic hydrocarbon group as a cyclic structure, for example,
Examples include hafnium alkoxy (mono-tri) benzene carboxylate and hafnium tetrabenzenecarboxylate.

As the organic hafnium compound having an aliphatic hydrocarbon group, for example,
Hafnium alkoxy (mono-tri) butyrate, hafnium tetrabutyrate,
Hafnium alkoxy (mono-tri) 2 ethyl hexanoate, hafnium tetra 2 ethyl hexanoate,
Examples include hafnium alkoxy (mono-tri) neodecanate and hafnium tetraneodecanate.
In the present specification, “(mono to tri)” means any one of mono, di and tri.

  Among these, hafnium trialkoxy mono is more preferable from the viewpoints of excellent thin film curability, excellent heat resistance (for example, excellent heat-resistant coloring stability and more capable of suppressing loss on heating), and excellent thermosetting and compatibility. Naphthate, hafnium trialkoxy monoisobutyrate, hafnium trialkoxy mono 2-ethyl hexanoate, hafnium trialkoxy monocyclopropane carboxylate, hafnium trialkoxy cyclobutane carboxylate, hafnium trialkoxy monocyclopentane carboxylate, hafnium trialkoxy mono Cyclohexanecarboxylate, hafnium trialkoxymonoadamantanecarboxylate, hafnium trialkoxymonobenzenecarboxylate, hafnium dialkoxydinaphth Preferred are hafnium tributoxy mononaphthate, hafnium tributoxy monoisobutyrate, hafnium tributoxy mono 2-ethylhexanoate, hafnium tributoxy monocyclopropanecarboxylate, hafnium tributoxy monocyclopentane carboxylate, hafnium tri Butoxy monocyclohexane carboxylate, hafnium trialkoxy monobenzene carboxylate, hafnium tributoxy monoadamantane carboxylate, hafnium dibutoxy dinaphthate, and hafnium tripropoxy mononaphthate are more preferable.

  The organic hafnium compound represented by the formula (2) will be described below.

[In formula (2), m is an integer of 1 to 4, R ² is an alkyl group having 1 to 18 carbon atoms, R ^3, R ⁴ are identical or different, hydrocarbon having 1 to 18 carbon atoms Group or alkoxy group. ]
Alkyl group having 1 to 18 carbon atoms has the same meaning as R ² (alkyl group having 1 to 18 carbon atoms) in the formula (1).
The hydrocarbon group having 1 to 18 carbon atoms is the same as that in which R ¹ (hydrocarbon group) in formula (1) has 1 to 18 carbon atoms.
Examples of the alkoxy group include those having 1 to 18 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group.
R ³ and R ⁴ may have a halogen such as a chlorine atom, a bromine atom or a fluorine atom.
Note equation (2) in the present invention can exhibit the _{^{(R 3 COHCOR 4) m Hf-}} (OR 2) 4-m.

Examples of the organic hafnium compound represented by the formula (2) include:
Examples include hafnium alkoxide (mono-tri) 2,4-pentadionate, hafnium-2,4-pentadionate, hafnium alkylpentadionate, and hafnium fluoropentadionate.
Among these, hafnium di-n is preferred from the viewpoints of excellent thin film curability, excellent heat resistance (for example, excellent heat-resistant coloration stability and more capable of suppressing loss on heating), and excellent thermosetting and compatibility. -Butoxide (bis-2,4-pentadionate), hafnium-2,4-pentadionate, hafnium tetramethylpentadionate, hafnium trifluoropentadionate are preferred.

  The organic hafnium compound is not particularly limited for its production. The organic hafnium compounds can be used alone or in combination of two or more.

The silanol condensation catalyst of the present invention can further contain a tin compound.
The silanol condensation catalyst of the present invention is more excellent in thin film curability, more excellent in heat resistance (for example, excellent in heat-resistant coloring stability and more capable of suppressing heat loss), and further from the viewpoint of excellent thermosetting. It is preferable to contain a compound.
The tin compound that can be further contained in the silanol condensation catalyst of the present invention is excellent in thin film curability, excellent in heat resistance (for example, excellent in heat-resistant coloring stability and more capable of suppressing heat loss), and heat. From the viewpoint of excellent curability, a tetravalent tin compound is preferable.
Examples of the tetravalent tin compound include those represented by the formula (II), bis type and polymer type represented by the formula (II).
_{^{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 meanings 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 oxy from the viewpoints of excellent heat resistance (for example, excellent heat-resistant coloration stability), excellent thin film curability, and excellent thermosetting properties. Acetate dibutyltin oxyoctylate and dibutyltin oxylaurate are preferred.
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.

  The amount of the tin compound is more excellent in thin film curability, more excellent in heat resistance (for example, excellent in heat-resistant coloring stability and more capable of suppressing loss on heating), and from the viewpoint of being excellent in thermosetting (C). It is preferable that it is 0.01-10 mol with respect to 1 mol of organic hafnium compounds, and it is more preferable that it is 0.1-5 mol.

  The silanol condensation catalyst of the present invention can further contain an additive as necessary in addition to the organic hafnium compound and the tin compound as long as the object and effect of the present invention are not impaired. Examples of the additive include adhesives such as bisalkoxysilylalkanes and coupling agents, fillers, phosphors, and the same additives as those which can be further contained in the composition of the present invention described later. It is done.

The silanol condensation catalyst of the present invention is not particularly limited for its production.
For example, when the silanol condensation catalyst of the present invention is composed only of an organic hafnium compound, the organic hafnium compound may be used as the silanol condensation catalyst.
When the silanol condensation catalyst of the present invention further contains a tin compound, it can be produced by mixing an organic hafnium compound and a tin compound.
Moreover, when the silanol condensation catalyst of this invention contains a tin compound further, an organic hafnium compound and a tin compound can be prepared separately, and these can be used.

  The silanol condensation catalyst of the present invention can be used as a catalyst for condensing at least a compound having a silanol group (for example, a hydrocarbon polymer having a silanol group or a polysiloxane having a silanol group) in the silanol group. Examples of the condensation of a compound having a silanol group include condensation of a compound having a silanol group and a compound having a silanol group, and condensation of a compound having a silanol group and a compound having an alkoxy group or an alkoxysilyl group.

Examples of the composition containing at least a compound having a silanol group to which the silanol condensation catalyst of the present invention can be applied include, for example, (A) a polysiloxane having two or more silanol groups in one molecule and (B) The composition containing the silane compound which has a 2 or more alkoxy group in 1 molecule is mentioned.
Examples of the compound having a silanol group contained in the composition to which the silanol condensation catalyst of the present invention can be applied include, for example, the thermosetting silicone resin composition for sealing an optical semiconductor of the present invention. (A) Polysiloxane having two or more silanol groups in one molecule.

Examples of the compound having an alkoxy group or an alkoxysilyl group contained in the composition to which the silanol condensation catalyst of the present invention can be applied include, for example, the thermosetting silicone resin composition for optical semiconductor encapsulation of the present invention. (B) a silane compound having two or more alkoxy groups in one molecule, and an alkoxy oligomer obtained by partially hydrolyzing the silane compound.
By containing the organic hafnium compound, the silanol condensation catalyst of the present invention has excellent thin film curability, excellent heat resistance (for example, excellent heat-resistant coloring stability, and can suppress heat loss), and thermosetting. , Excellent stability at room temperature (inhibition of thickening) and excellent adhesion of silanol compounds.
By further containing a tin compound, the silanol condensation catalyst of the present invention is excellent in thin film curability, excellent in heat resistance (for example, excellent in heat-resistant coloring stability and capable of suppressing heat loss), and thermosetting. , Excellent stability at room temperature (inhibition of thickening) and excellent adhesion of silanol compounds.

As a composition that can contain the silanol condensation catalyst of the present invention, for example,
(A) 100 parts by mass of polysiloxane having two or more silanol groups in one molecule;
(B) 0.1 to 2000 parts by mass of a silane compound having two or more alkoxy groups in one molecule;
(D) The thermosetting silicone resin composition containing the silanol condensation catalyst of this invention is mentioned.
A polysiloxane and a silane compound are synonymous with those contained in the thermosetting silicone resin composition for optical semiconductor encapsulation of the present invention described below.

  The organic hafnium compound contained in the silanol condensation catalyst of the present invention corresponds to the organic hafnium compound contained in the following thermosetting silicone resin composition for optical semiconductor encapsulation of the present invention. Moreover, the tin compound which the silanol condensation catalyst of this invention can further contain corresponds to the tin compound which the following thermosetting silicone resin composition for optical semiconductor sealing of this invention can contain.

The thermosetting silicone resin composition for optical semiconductor encapsulation of the present invention will be described below.
The thermosetting silicone resin composition for optical semiconductor encapsulation of the present invention is
(A) 100 parts by mass of an organopolysiloxane having two or more silanol groups in one molecule;
(B) 0.1 to 2000 parts by mass of a silane compound having two or more alkoxy groups in one molecule;
(C) A thermosetting silicone resin composition for encapsulating an optical semiconductor, comprising an organic hafnium compound represented by the following formula (1) and / or the following formula (2).
Wherein (1), n is an integer from 1 to 4, R ¹ is a hydrocarbon group, R ² is an alkyl group having 1 to 18 carbon atoms. ]
[In formula (2), m is an integer of 1 to 4, R ² is an alkyl group having 1 to 18 carbon atoms, R ^3, R ⁴ are identical or different, hydrocarbon having 1 to 18 carbon atoms Group or alkoxy group. ]
The thermosetting silicone resin composition for sealing an optical semiconductor of the present invention is hereinafter referred to as “the composition of the present invention”.

The organopolysiloxane will be described below. The organopolysiloxane (A) contained in the composition of the present invention is an organopolysiloxane having two or more silanol groups in one molecule.
The main chain of the organopolysiloxane may be linear or branched (for example, silicone resin).
The hydrocarbon group that the organopolysiloxane has is not particularly limited. The hydrocarbon group can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the hydrocarbon group include alkyl groups such as methyl and ethyl groups (chain aliphatic hydrocarbon groups); alicyclic hydrocarbon groups such as cyclohexyl groups; aromatic groups such as phenyl groups; vinyl groups , An alkenyl group such as (meth) acryloyloxy group; an alkoxy group such as methoxy group and ethoxy group; and a phenoxy group. Alkyl such as methyl group and ethyl group from the viewpoint of better thin film curability, better heat resistance (for example, better heat-resistant coloration stability, more effective in reducing heat loss), and better thermosetting. Group; a hydrocarbon group including an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group is preferable.
Silanol groups can be attached to the ends of the organopolysiloxane.
Organopolysiloxane is excellent in thin film curability, excellent in heat resistance (for example, excellent in heat-resistant coloring stability and more capable of suppressing loss on heating), and from the viewpoint of excellent in thermosetting, two or more. An organopolysiloxane having a silanol group bonded to the terminal (or both terminals) and having a hydrocarbon group can be obtained.
Examples of the organopolysiloxane include those having two or more silanol groups bonded to the terminal.
The organopolysiloxane is superior in thin film curability, excellent in heat resistance (for example, excellent in heat-resistant coloring stability and more capable of suppressing loss on heating), and from the viewpoint of excellent thermosetting properties, diorganopolysiloxane. Is preferred.
Examples of the organopolysiloxane include those represented by the following formula (3).
(Wherein R ⁵ are the same or different hydrocarbon groups.)

In formula (3), the hydrocarbon group is not particularly limited. The hydrocarbon group can be, for example, at least one selected from the group consisting of an alkyl group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The hydrocarbon group may be a combination of two or more of an alkyl group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The hydrocarbon group can have, for example, a divalent organic group (for example, an alkylene group) in addition to the alicyclic hydrocarbon group and / or the aromatic hydrocarbon group. The hydrocarbon group can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the hydrocarbon group include alkyl groups (chain aliphatic hydrocarbon groups) such as a methyl group and an ethyl group; alicyclic hydrocarbon groups such as a cyclohexyl group; and aromatic groups such as a phenyl group. . From the viewpoints of better thin film curability, better heat resistance (for example, better heat-resistant coloring stability, more effective in reducing heat loss), and better thermosetting properties, alkyl groups and fats directly bonded to silicon. A cyclic hydrocarbon group and a phenyl group are preferred. When R ⁵ is a different hydrocarbon group, the combination includes, for example, a methyl group, an alkyl group such as an ethyl group (chain aliphatic hydrocarbon group), an alicyclic hydrocarbon group such as a cyclohexyl group, and the like. The combination with at least 1 sort (s) chosen from the group which consists of aromatic groups like a phenyl group is mentioned.
Organopolysiloxane is excellent in thin film curability, heat resistance (for example, excellent in heat-resistant coloring stability and more capable of suppressing heat loss), and two silanols from the viewpoint of excellent thermosetting. It is preferably a polydialkylsiloxane having groups bonded to both ends (which may be linear or branched), and polydimethyl having two silanol groups bonded to both ends. More preferred is siloxane (organopolydimethylsiloxane-α, ω-diol, which may be linear or branched).
Moreover, in Formula (3), n can be made into the numerical value corresponding to the weight average molecular weight of organopolysiloxane. n is preferably an integer of 10 to 15,000 from the viewpoint of excellent workability and crack resistance.
The molecular weight of the organopolysiloxane is excellent in heat resistance (for example, excellent in heat-resistant coloration stability), excellent in thin film curability, excellent in thermosetting, curing time and pot life are appropriately lengthened and cured. From the viewpoint of being excellent and excellent in cured product properties, it is preferably 1,000 to 1,000,000, and more preferably 6,000 to 100,000. In the present invention, the molecular weight of the organopolysiloxane is a weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) using chloroform as a solvent.
The organopolysiloxane is not particularly limited for its production. For example, a conventionally well-known thing is mentioned. The organopolysiloxanes can be used alone or in combination of two or more.

(B) A silane compound is demonstrated below.
The (B) silane compound contained in the composition of the present invention is a silane compound having two or more alkoxy groups in one molecule. The alkoxy group can be bonded to a silicon atom.
Examples of the silane compound include a compound having one silicon atom in one molecule, and a compound having two or more silicon atoms in one molecule and a skeleton being a polysiloxane skeleton.

  The silane compound can have an organic group in addition to the alkoxy group. Examples of the organic group that the silane compound 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. For example, an alkyl group (preferably having 1 to 6 carbon atoms), an alicyclic hydrocarbon group such as a cyclohexyl group, a (meth) acrylate group, an alkenyl group, an aromatic hydrocarbon group (aryl group), these Combinations are 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 (meth) acrylate group, and a (meth) acryloxyalkyl group are preferable from the viewpoint of superior heat-resistant coloring stability.

  Silane compounds are superior in thin film curability, excellent in heat resistance (for example, excellent in heat-resistant coloration stability), excellent in thermosetting, curing time and pot life are appropriate lengths, and are excellent in curability. From the viewpoint of excellent solubility, the silane compound represented by the following formula (4), the silane compound represented by the following formula (5), and the diorganopolysiloxane represented by the following formula (3) and the following formula (4) It is preferably at least one selected from the group consisting of a silane compound and / or a condensate with a silane compound represented by the following formula (5).

The silane compound represented by the formula (4) will be described below.
Wherein (4), m is an integer from 1 to 4, R ⁶ is an organic group having 1 to 18 carbon atoms, R ⁷ is a hydrocarbon group having 1 to 6 carbon atoms. ]
m is superior in thin film curability, superior in heat resistance (for example, excellent in heat-resistant coloration stability), excellent in thermosetting, excellent in thermosetting, curing time and pot life are appropriately long, and is curable. From the viewpoints of excellent compatibility and excellent compatibility, an integer of 2 to 3 is preferable. The organic group having 1 to 18 carbon atoms is the same as the organic group that the silane compound can have. Examples of the hydrocarbon group having 1 to 6 carbon atoms include an alkyl group such as a methyl group and an ethyl group; and an aromatic hydrocarbon group such as a phenyl group.

Examples of the silane compound represented by the formula (4) include dialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane; methyltrimethoxy Trialkoxysilanes such as silane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane; tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetraisopropyloxysilane Silane; trialkoxysilane, hydrolyzate of tetraalkoxysilane; γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropi (Meth) acrylic silanes such as lutriethoxysilane.
In the present invention, (meth) acryl silane means acryl silane or methacryl silane. The same applies to (meth) acrylate groups and (meth) acryloxyalkyl groups.

The silane compound represented by the formula (5) will be described below.
R ⁸ _k Si (OR ⁹ ) _l O _{(4-kl) / 2} (5)
[In the formula (5), R ⁸ is an alkyl group having 1 to 6 carbon atoms and / or an aryl group, R ⁹ is an alkyl group having 1 to 6 carbon atoms, and 0 <k <2, 0 <l < 2, 0 <(k + l) ≦ 3. ]
Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group and an ethyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. Of these, a methyl group is preferred from the viewpoints of better heat resistance and better heat-resistant coloring stability.
Examples of the silane compound represented by the formula (5) include alkylalkoxypolysiloxanes such as methylmethoxypolysiloxane.

The compound represented by Formula (3) used when manufacturing a silane compound is demonstrated below.
(Wherein R ⁵ are the same or different hydrocarbon groups.)
The compound represented by the formula (3) used when producing the silane compound is the same as that represented by the formula (3) as the (A) organopolysiloxane.

  The production of the condensate of the diorganopolysiloxane represented by the formula (3) and the silane compound represented by the formula (4) and / or the silane compound represented by the formula (5) is not particularly limited. For example, it can be produced by subjecting a diorganopolysiloxane represented by the formula (3) to a silane compound represented by the formula (4) and / or a silane compound represented by the formula (5).

  As a combination of the diorganopolysiloxane represented by the formula (3) and the silane compound represented by the formula (4) and / or the silane compound represented by the formula (5) used in the production of the condensate, For example, both end silanol type polydimethylsiloxane and tetraalkoxysilane such as tetramethoxysilane and tetraethoxysilane; (meth) acrylsilane such as γ- (meth) acryloxypropyltrimethoxysilane; methylmethoxypolysiloxane The combination with such an alkyl alkoxy polysiloxane is mentioned.

  The silane compound is excellent in thin film curability, excellent in heat resistance (for example, excellent in heat-resistant coloring stability), and in view of excellent in thermosetting, tetraalkoxysilane such as tetramethoxysilane and tetraethoxysilane; γ A trialkoxy (meth) acryl silane such as (meth) acryloxypropyltrimethoxysilane; an alkylalkoxy polysiloxane such as methylmethoxypolysiloxane; a condensate of these with a diorganopolysiloxane represented by formula (3) Is preferred.

The molecular weight of the silane compound is excellent in thin film curability, superior in heat resistance (for example, excellent in heat-resistant coloring stability), excellent in thermosetting, curing time and pot life are appropriate length, and excellent in curability. From the viewpoint of excellent compatibility, it is preferably 100 to 1,000,000, and more preferably 1,000 to 100,000. In the present invention, when the silane compound is an oligomer or a polymer, the molecular weight is a weight-average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) using chloroform as a solvent.
The production of the silane compound is not particularly limited, and examples thereof include conventionally known compounds. The silane compounds can be used alone or in combination of two or more.

  The amount of the silane compound is superior in heat resistance (for example, excellent in heat-resistant coloring stability), more excellent in thin film curability, excellent in thermosetting, crack resistance, and compatibility. It is 0.1-2000 mass parts with respect to a mass part, It is preferable that it is 0.1-1000 mass parts, It is more preferable that it is 0.1-100 mass parts, 0.5-50 mass parts It is more preferable that the amount is 10 parts by mass or less.

  The organic hafnium compound will be described below. The (C) organic hafnium compound contained in the composition of the present invention is represented by the following formula (1) and / or the following formula (2). The composition of this invention should just contain what is shown by Formula (1) and / or what is shown by Formula (2) at least.

Wherein (1), n is an integer from 1 to 4, R ¹ is a hydrocarbon group, R ² is an alkyl group having 1 to 18 carbon atoms. ]
[In formula (2), m is an integer of 1 to 4, R ² is an alkyl group having 1 to 18 carbon atoms, R ^3, R ⁴ are identical or different, hydrocarbon having 1 to 18 carbon atoms Group or alkoxy group. ]
In the present specification, the organic hafnium compound contained in the composition of the present invention is synonymous with the organic hafnium compound contained in the silanol condensation catalyst of the present invention.

(C) The amount of the organic hafnium compound is excellent in thin film curability, excellent in heat resistance (for example, excellent in heat-resistant coloring stability and more capable of suppressing loss on heating), excellent in thermosetting, and compatible. From the standpoint of superiority, it is preferably 0.001 to 5 parts by mass, and 0.01 to 0.5 parts by mass with respect to 100 parts by mass in total of (A) organopolysiloxane and (B) silane compound. Is more preferable.
By containing the organic hafnium compound, the composition of the present invention is excellent in adhesiveness and can suppress heat loss.

The composition of the present invention may further contain a tin compound.
The composition of the present invention is more excellent in thin film curability, more excellent in heat resistance (for example, excellent in heat-resistant coloring stability and more capable of suppressing loss on heating), and from the viewpoint of excellent thermosetting, further tin. It is preferable to contain a compound.
In this specification, the tin compound contained in the composition of the present invention has the same meaning as the tin compound that the silanol condensation catalyst of the present invention can further contain.

The amount of the tin compound is more excellent in thin film curability, more excellent in heat resistance (for example, excellent in heat-resistant coloring stability and more capable of suppressing loss on heating), and from the viewpoint of being excellent in thermosetting (A). It is preferable that it is 0.001-1 mass part with respect to a total of 100 mass parts of organopolysiloxane and (B) silane compound, and it is more preferable that it is 0.001-0.1 mass part.
In addition, the amount of the tin compound is more excellent in thin film curability, more excellent in heat resistance (for example, excellent in heat-resistant coloring stability and more capable of suppressing loss on heating), and from the viewpoint of excellent thermosetting properties ( C) It is preferable that it is 0.01-10 mol with respect to 1 mol of organic hafnium compounds, and it is more preferable that it is 0.1-5 mol.

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 organopolysiloxane, a silane compound, an organic hafnium compound, and a tin compound.
Examples of the additives include fillers such as inorganic fillers, antioxidants, lubricants, ultraviolet absorbers, thermal light stabilizers, dispersants, antistatic agents, polymerization inhibitors, antifoaming agents, curing accelerators, solvents, Phosphor (for example, inorganic phosphor), anti-aging agent, radical inhibitor, adhesion improver, flame retardant, surfactant, storage stability improver, ozone anti-aging agent, thickener, plasticizer, radiation blocker , Nucleating agents, coupling agents, conductivity imparting agents, phosphorus peroxide decomposing agents, pigments, metal deactivators, physical property modifiers, adhesion imparting agents such as bisalkoxysilylalkanes and coupling agents. . Various additives are not particularly limited. For example, a conventionally well-known thing is mentioned.

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 which may have a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom, and a is 1 to 3 respectively. Is an integer. 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, 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- Sus (trimethoxysilyl) heptane, 2,5-bis (trimethoxysilyl) heptane, 2,6-bis (trimethoxysilyl) heptane, 1,8-bis (trimethoxysilyl) octane, 2,5-bis ( Trimethoxysilyl) octane, 2,7-bis (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane, 2,7-bis (trimethoxysilyl) nonane, 1,10-bis (trimethoxy) Silyl) decane, 3,8-bis (trimethoxysilyl) decane; divalent alkanes such as bis- (3-trimethoxysilylpropyl) amine having a nitrogen atom.

Bis (alkoxysilyl) alkanes are superior in heat resistance (for example, excellent in heat-resistant coloration stability), excellent in thin film curability, excellent in thermosetting, and are hardened, bonded, and transparent in a closed system. From the viewpoint of excellent balance with strength and excellent wet heat resistance, those represented by the formula (II) are preferred, bis (trialkoxysilyl) alkanes are more preferred, 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, At least selected from the group consisting of 1,9-bis (trimethoxysilyl) nonane and 1,10-bis (trimethoxysilyl) decane More preferably seeds, 1,6-bis (trimethoxysilyl) hexane, bis - (3-trimethoxysilyl propyl) amine is more preferred.
Bis (alkoxysilyl) alkanes can be used alone or in combination of two or more.

  The amount of bis (alkoxysilyl) alkane is superior in heat resistance (for example, excellent in heat-resistant coloring stability), excellent in thin film curability, excellent in thermosetting, curable in a closed system, adhesiveness, and transparent From the viewpoints of excellent balance between adhesiveness and adhesive strength and excellent wet heat resistance, it is more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the organopolysiloxane and the silane compound.

Examples of inorganic phosphors include yttrium, aluminum, garnet-based YAG phosphors, ZnS phosphors, Y ₂ O ₂ S phosphors, red-emitting phosphors, and blue-emitting phosphors that are widely used in LEDs. Body and green light emitting phosphor.

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 be produced by mixing an organopolysiloxane, a silane compound, an organic hafnium compound, and a tin compound and additives that can be used as necessary.

  The composition of the present invention can be produced as a one-pack type or a two-pack type. In the case where the composition of the present invention is a two-component type, it is preferable to have a first liquid containing an organopolysiloxane, an organic hafnium compound, and a tin compound, and a second liquid containing a silane compound. As one. The additive can be added to one or both of the first liquid and the second liquid.

The composition of this invention can be used as a composition for optical semiconductor sealing.
The optical semiconductor (light emitting device) to which the composition of the present invention can be applied is not particularly limited. For example, a light emitting diode (LED), an organic electroluminescent element (organic EL), a laser diode, and an LED array are mentioned.
As a method for using the composition of the present invention, for example, the composition of the present invention is applied to an optical semiconductor, and the optical semiconductor to which the composition of the present invention is applied is heated to cure the composition of the present invention. Can be mentioned. The method for applying the composition of the present invention to an optical semiconductor is not particularly limited. Examples thereof include a method using a dispenser, a potting method, screen printing, transfer molding, and injection molding.

The composition of the present invention can be cured by heating.
The heating temperature is excellent in thin film curability, excellent in heat resistance (for example, more capable of suppressing loss on heating), excellent in thermosetting, and can be set to an appropriate length of curing time and pot life. From the viewpoint of suppressing the foaming of alcohol as a by-product due to the condensation reaction, suppressing cracks in the cured product, and being excellent in the smoothness, moldability and physical properties of the cured product, it is cured at around 80 ° C to 150 ° C. It is preferable that the temperature is about 150 ° C.
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.

  The cured product (silicone resin) obtained by heating and curing the composition of the present invention can maintain high transparency with respect to long-term use by a light-emitting element (especially a white LED). Excellent curability, heat resistance, heat-resistant coloring stability, thin film curability, adhesiveness, heat crack resistance, and thermosetting properties, and low heat loss. The cured product obtained is superior in heat-resistant coloring stability than conventional silicone resins because the crosslinked part and skeleton are all siloxane bonds.

In the present invention, the weight loss by heating is the initial cured product obtained by heating and curing the composition of the present invention at 150 ° C. for 240 minutes, and the initial cured product is further heated at 200 ° C. for 1,000 hours. Using the cured product obtained after heating, the weights of both cured products are measured, and the obtained weight is set to a value determined by applying the following formula.
Heat loss (mass%)
= 100- (Weight of cured product after heating / Weight of initial cured product) × 100
When the value of heat loss is 20% by mass or less, heat loss can be suppressed, and it can be said that it is practical as a thermosetting silicone resin composition for optical semiconductor encapsulation.
In the present invention, an initial cured product obtained by heating the thermosetting silicone resin composition for optical semiconductor encapsulation of the present invention is heated at 200 ° C. for 1,000 hours, and the 200 ° C. heating is performed. It is preferable that the heat loss of the subsequent cured product is 20% by mass or less of the initial cured product, and more preferably 0 to 10% by mass.

  A cured product obtained by using the composition of the present invention (when the thickness of the cured product is 2 mm) is an ultraviolet / visible absorption spectrum measuring apparatus (manufactured by Shimadzu Corporation, the same applies hereinafter) according to JIS K0115: 2004. The transmittance measured at a wavelength of 400 nm is preferably 80% or more, more preferably 85% or more.

  In addition, the cured product obtained using the composition of the present invention is subjected to a heat resistance test after initial curing (a test in which the cured product after initial curing is placed at 150 ° C. for 10 days), and then the cured product (thickness: 2 mm). ), The transmittance measured at a wavelength of 400 nm using an ultraviolet / visible spectrum measuring device according to JIS K0115: 2004 is preferably 80% or more, more preferably 85% or more.

  The cured product obtained using the composition of the present invention preferably has a permeability retention ratio (transmittance after heat test / transmittance at initial curing × 100) of 70 to 100%, 80 More preferably, it is -100%.

  In addition to optical semiconductors, the composition of the present invention is used for applications such as display materials, optical recording medium materials, optical equipment materials, optical component materials, optical fiber materials, optical / electronic functional organic materials, and semiconductor integrated circuit peripheral materials. Can be used.

Next, the sealing body of this invention is demonstrated below.
The sealing body of the present invention seals the optical semiconductor by heating and curing the composition of the present invention.
The sealing body of the present invention can be obtained by applying the composition of the present invention to an optical semiconductor, heating the optical semiconductor to cure the composition, and sealing the optical semiconductor.

If the composition used for the sealing body of this invention is a composition of this invention, it will not restrict | limit in particular.
By using the composition of the present invention as a composition in the encapsulant of the present invention, the encapsulant of the present invention is resistant to heat generated from, for example, an optical semiconductor or heating during the production of the encapsulant. (For example, it is excellent in heat-resistant coloring stability and can suppress heat loss), and is excellent in thin film curability and thermosetting.

If the optical semiconductor used for the sealing body of this invention is a light emitting element, it will not restrict | limit in particular. For example, the electronic circuit (LED chip) which has a light emitting diode is mentioned.
The optical semiconductor used for the encapsulant of the present invention is not particularly limited with respect to the emission color. For example, white, blue, red, and green are mentioned. The sealing body of the present invention is applied to a white LED from the viewpoint of being excellent in heat-resistant coloring stability and capable of suppressing heat loss even when exposed to a high temperature due to heat generated from an optical semiconductor for a long time. be able to. The white LED is not particularly limited. For example, a conventionally well-known thing is mentioned.
The size and shape of the optical semiconductor are not particularly limited. Moreover, the kind in particular of an optical semiconductor is not restrict | limited, For example, high power LED, high-intensity LED, general purpose luminance LED is mentioned.
The sealing body of the present invention has at least one optical semiconductor inside one sealing body and can have two or more optical semiconductors.

  As a manufacturing method of the sealing body of the present invention, for example, an application step of applying the composition of the present invention to an optical semiconductor, and heating the optical semiconductor to which the composition has been applied to cure the composition to light What has the heat-hardening process of sealing a semiconductor is mentioned.

  In the applying step, a composition is applied to the optical semiconductor to obtain an optical semiconductor to which the composition is applied. The optical semiconductor used in the application step has the same meaning as described above. The composition used in the application step is not particularly limited as long as it is the composition of the present invention. The method of giving is not particularly limited.

  Next, in the heat curing step, the sealed body of the present invention can be obtained by heating the photosemiconductor to which the composition is applied to cure the composition and encapsulating the photosemiconductor. The heating temperature in the heat curing step is as defined above.

  Examples of the shape of the sealing body of the present invention include, for example, a cured product that directly seals an optical semiconductor, a shell type, a surface mount type, a plurality of optical semiconductors or between and / or the surface of a sealing body. What is sealed is mentioned.

The sealing body of the present invention will be described below with reference to the accompanying drawings. The sealing body of the present invention is not limited to the attached drawings.
FIG. 1 is a cross-sectional view schematically showing an example of the sealing body of the present invention. FIG. 2 is a cross-sectional view schematically showing another example of the sealing body of the present invention.

In FIG. 1, the sealing body 200 has a package 204 on a substrate 210.
The package 204 is provided with a cavity 202 therein. An optical semiconductor 203 and a cured product 202 are disposed in the cavity 202. The cured product 202 is obtained by curing the composition of the present invention. The cured product 202 can contain a fluorescent material or the like in order to cause the sealing body 200 to emit light in a specific color (for example, white).
The cavity 202 may be filled with the composition of the present invention up to the shaded portion 206. The cavity 202 can be filled with another composition, and the hatched portion 206 can be filled with the composition of the present invention.
The optical semiconductor 203 is fixed on the substrate 210 with a mount member 201. Each electrode (not shown) of the optical semiconductor 203 and the external electrode 209 are wire bonded by a conductive wire 207.

In FIG. 2, a sealing body 300 of the present invention includes a substrate 310, an optical semiconductor 303, and inner leads 305 inside a resin 306 having a lamp function.
A cavity (not shown) is provided in the head of the substrate 310. An optical semiconductor 303 and a cured product 302 are arranged in the cavity. The cured product 302 is obtained by curing the composition of the present invention. The cured product 302 can contain a fluorescent material or the like for causing the sealing body 300 to emit light in a specific color. Resin 306 can be formed using the composition of the present invention.
The optical semiconductor 303 is fixed on the substrate 310 with a mount member 301. Each electrode (not shown) of the optical semiconductor 303 is bonded to the substrate 310 and the inner lead 305 by a conductive wire 307.

  The case where the sealing body of the present invention is used for an LED display will be described with reference to the accompanying drawings. FIG. 3 is a diagram schematically showing an example of an LED display using the sealing body of the present invention. In addition, the LED display in which the sealing body of this invention is used is not limited to attached drawing.

  In FIG. 3, an LED display 400 includes an optical semiconductor 401 arranged in a matrix form inside a housing 404, the optical semiconductor 401 is sealed with a cured product 406, and a light shielding member 405 is arranged on a part of the housing 404. Configured. The composition of the present invention can be used for the cured product 406. Further, the sealing body of the present invention can be used as the optical semiconductor 401.

  Applications of the sealing body of the present invention include, for example, automotive lamps (head lamps, tail lamps, directional lamps, etc.), household lighting fixtures, industrial lighting fixtures, stage lighting fixtures, displays, signals, and projectors. .

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

<Manufacture of organic hafnium compounds>
Tributoxyhafnium 2-ethylhexanoate (hafnium compound 1) 45% by weight of hafnium tetrabutoxide (Gelest) 4.7 g (0.01 mol) and 2-ethylhexanoic acid (Kanto Chemical Co.) 1.44 g (0.01 mol) was charged into a three-necked flask and stirred for about 2 hours at room temperature under a nitrogen atmosphere to obtain the target compound.
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 COOHf near 1,450 to 1,560 cm ⁻¹ was confirmed.
The resultant composite is referred to as hafnium compound 1.

・ Tributoxy hafnium naphthate (hafnium compound 2)
1.44 g of 2-ethylhexanoic acid was converted to naphthenic acid (produced by Tokyo Chemical Industry Co., Ltd., average number of carbon atoms of the hydrocarbon group bonded to the carboxy group: 15, neutralization value of 220 mg. The neutralization value of naphthenic acid is naphthenic acid. This is the amount of KOH required to neutralize 1 g.) Experiments and qualifications were performed in the same manner as hafnium compound 1 except that it was changed to 2.55 g (0.01 mol). The resultant composite is referred to as hafnium compound 2. The average number of carbon atoms of R ^{1 in} the naphthate group (R ¹ COO—) of the hafnium compound 2 is 15.

・ Tributoxy hafnium benzene carboxylate (hafnium compound 3)
Experiments and qualifications were performed in the same manner as hafnium compound 1 except that 1.44 g of 2-ethylhexanoic acid was replaced with 1.22 g (0.01 mol) of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.). The resultant composite is referred to as hafnium compound 3.

<Evaluation>
As shown below, the initial cured state, transmittance, heat-resistant coloring stability, thickening after mixing, loss on heating, adhesion, and thin film curability were evaluated. The results are shown in Tables 1 and 2.

-Initial curing state 2 g of the composition obtained as described below was placed in a container so as to have a depth of 1 mm, placed under a condition of 150 ° C. for 12 hours, and the presence or absence of curing after 12 hours was confirmed.
The case where the composition was cured was “◯”, and the case where it was not cured was “x”.

Transmittance evaluation test In the transmittance evaluation test, an initial cured product obtained by curing the composition obtained as described below at 150 ° C. for 4 hours, and a heat resistance test (an initial cured product is further added to 150 Test for heating for 10 days under the condition of ° C.) For each of the cured products (both having a thickness of 2 mm), using an ultraviolet / visible absorption spectrum measuring apparatus (manufactured by Shimadzu Corporation) according to JIS K0115: 2004, respectively. The transmittance at a wavelength of 400 nm was measured. Moreover, the retention with respect to the initial transmittance of the transmittance after the heat test was obtained by the following calculation formula.
Transmittance retention rate (%) = (Transmittance after heat resistance test) / (Initial transmittance) × 100

Heat-resistant coloring stability evaluation test An initial cured product obtained by curing the composition obtained as described below at 150 ° C. for 4 hours, and a heat test (initial cured product at 150 ° C. Test for heating for 10 days.) Regarding the cured product after that, it was visually observed whether the cured product after the heat resistance test was yellow compared with the initial cured product.

・ Thickening after mixing (Evaluation of pot life)
The viscosity (initial viscosity) of the composition under the condition of 25 ° C. immediately after the production shown in Table 1 was mixed and the obtained composition was placed under the condition of 25 ° C., and 24 hours had passed since the production. The viscosity of the later composition (viscosity after 24 hours) was measured using an E-type viscometer under the conditions of RH 50% and 25 ° C., and an increase in viscosity 24 hours after mixing was confirmed.
When the viscosity after 24 hours from the mixing was within 2 times that immediately after the mixing, it was evaluated as “no thickening”. When the composition gelled 24 hours after mixing, it was evaluated as “gelation”. If the viscosity after 24 hours from mixing is within twice that immediately after mixing, the pot life can be considered sufficient.

Heat Loss Evaluation Test In the heat loss evaluation test, an initial cured product obtained by curing 1.0 g of the composition obtained as described below at 150 ° C. for 4 hours was further 1,000 at 200 ° C. Heated for hours. The weight of the cured product was measured using a weigh scale for the initial cured product and the cured product after the heat loss evaluation test. The loss on heating was determined by the following formula. When the heating loss value is 20% by mass or less, it is practical as a thermosetting silicone resin composition for optical semiconductor encapsulation.
Heat loss (mass%) = 100− (weight of cured product after heat loss evaluation test / weight of initial cured product) × 100

-Adhesiveness Using a silicone resin spacer having a length of 25 mm, a width of 10 mm, and a thickness of 1 mm, the composition obtained as described below was poured into an adherend: an alumina plate and heated at 150 ° C for 4 hours. The obtained laminate was placed under conditions of 121 ° C. and 100% RH for 24 hours using a pressure cooker tester. A hand peel test was performed using the cured product after the pressure cooker test (PCT), and the adhesiveness after the test was evaluated based on the fracture form of the cured product after the test.
The evaluation criteria for adhesiveness were “CF” when the fracture mode was cohesive failure and “AF” when the fracture mode was interface fracture.

-Thin film initial cured state A thin film initial cured product (thickness) obtained by potting the composition obtained as described below to a thickness of 0.3 mm or less on glass and cured at 150 ° C. The initial cured state was confirmed with a finger.
The evaluation criteria for the initial thin film curing state are “◎” when cured by heating for less than 4 hours, “◯” when cured by heating for 4 hours to 8 hours, and cured by heating for more than 8 hours. The case was set as “x”.

<Preparation of sample (for evaluation of transmittance and heat-resistant coloring stability)>
The production of the sample will be described below with reference to the accompanying drawings.
FIG. 4 is a cross-sectional view schematically showing a mold used for curing the thermosetting silicone resin composition for optical semiconductor encapsulation of the present invention in Examples.
In FIG. 4, a mold 8 has a PET film 5 disposed on a glass 3 (the size of the glass 3 is 10 cm long, 10 cm wide, 4 mm thick), and a silicon mold spacer 1 ( 5 cm in length, 5 cm in width, and 2 mm in height) are arranged.
The composition 6 was poured into the interior 6 of the spacer 1 using the mold 8, and the sample was cured as follows.

  The mold 8 filled with the composition 6 was placed in an electric oven and heated under the above-described evaluation conditions to cure the composition 6 to produce a cured product 6 (initial cured product) having a thickness of 2 mm. The obtained cured product 6 was used as a sample for evaluating transmittance and heat-resistant coloring stability.

<Manufacture of thermosetting silicone resin composition for optical semiconductor sealing>
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 composition.

Each component shown in Table 1 is as follows.
(A) Polysiloxane 1: Polydimethylsiloxane-α, ω-diol (weight average molecular weight 1,000), trade name x-21-5841, manufactured by Shin-Etsu Chemical Co., Ltd. (A) Polysiloxane 2: polydimethylsiloxane -Α, ω-diol (weight average molecular weight 4,000), trade name PRX-413 (Toray Dow Corning Co., Ltd.)
(A) Polysiloxane 3: polydimethylsiloxane-α, ω-diol, trade name x--21-5848 (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 110,000)
Epoxy silicone: Epoxy-modified polysiloxane (trade name: KF101, manufactured by Shin-Etsu Chemical Co., Ltd.)
· (B) a silane compound 1: silicone alkoxy oligomer _{[R m Si (OR ')} n O (4-mn) / 2, wherein, R is an alkyl group, an alkenyl group or an aryl group having 1 to 6 carbon atoms , R ′ is an alkyl group having 1 to 6 carbon atoms, m is 0 <m <2, n is 0 <n <2, and m + n is 0 <m + n ≦ 3. Weight average molecular weight 6,000. Product name x-40-9246, manufactured by Shin-Etsu Chemical Co., Ltd. Same below)
(B) Silane compound 2: Tetramethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name) with respect to 100 parts by mass of both-end silanol-type polydimethylsiloxane (trade name ss70, Shin-Etsu Chemical Co., Ltd., Mw = 18,000) (KBM-04) 20 parts by mass, 0.01 parts by mass of 2-ethylhexane tin (manufactured by Kanto Chemical Co., Inc.) was added and stirred while reducing the pressure at 60 ° C. for 8 hours, and then the residual tetramethoxysilane at 130 ° C. for 8 hours under reduced pressure. A polydimethylsiloxane having both ends modified with a trimethoxysilyloxy group was obtained. The disappearance of the silanol peak was confirmed by proton NMR. The resulting condensate is referred to as silane compound 2. The weight average molecular weight of the silane compound 2 was 35,000 in terms of polystyrene (hereinafter the same) by gel permeation chromatography (GPC) using chloroform as a solvent.
-(B) Silane compound 3: produced in the same manner as silane compound 2 except that 20 parts by mass of tetramethoxysilane was replaced with 20 parts by mass of a condensate of methyltrimethoxysilane (trade name KC-89, manufactured by Shin-Etsu Chemical Co., Ltd.) To obtain the silane compound 3. The disappearance of the silanol peak was confirmed by proton NMR. The weight average molecular weight of the silane compound 3 was 40,000 in terms of polystyrene by gel permeation chromatography (GPC) using chloroform as a solvent (hereinafter the same).
-(C) Hafnium compounds 1-3: those prepared as described above-(C) Hafnium compound 4: hafnium di-n-butoxide (bis-2,4-pentadionate) (manufactured by Gelest)
· (C) hafnium compound 5: hafnium 2,4 penta dionate _{[Hf (C 5 H 7 O} 2) 4] (Gelest Inc.)
(C) Hafnium compound 6: Hafnium tetramethylheptanedionate (manufactured by Gelest)
(C) Hafnium compound 7: hafnium trifluoropentadiate [C ₂₀ H ₁₆ O ₈ F ₁₂ Hf] (manufactured by Gelest)
・ (D) Tin compound: Dibutyltin diacetate, manufactured by Nitto Kasei Co., Ltd. ・ Tetraalkoxide hafnium: Hafnium tetra n-butoxide, manufactured by Gelest ・ Aluminum compound: Al (acac) ₃ , manufactured by Matsumoto Trading Co. ・ Titanium compound: Titanium tetranormal Butoxide, manufactured by Matsumoto Trading Co., Ltd. Cationic polymerization catalyst: BF ₃ · Et ₂ O (BF ₃ ethyl etherate complex, manufactured by Tokyo Chemical Industry Co., Ltd.)

As is clear from the results shown in Table 1, Comparative Example 6 containing epoxy silicone had low heat-resistant coloring stability and a short pot life. In Comparative Examples 2, 4, and 5 containing an aluminum compound without containing an organic hafnium compound, the heat loss was large and the heat resistance was low. In Comparative Examples 1 and 3 containing only the tin compound without containing the organic hafnium compound, the pot life was short. The comparative example 7 which does not contain an organic hafnium compound but contains a titanium compound is uncured and inferior in curability. The comparative example 8 which does not contain an organic hafnium compound but contains tetraalkoxide hafnium was uncured and inferior in curability.
On the other hand, Examples I and II are excellent in heat resistance because heat loss is suppressed, and excellent in heat-resistant coloring stability and thin film curability. Further, Example II containing a tin compound was more excellent in thin film curability.
In Examples I and II, the result of the fracture test after the PCT test showed cohesive fracture, high adhesion (adhesion under conditions of high temperature, water, and high pressure), excellent transparency, transmittance, and transmission. The rate retention is high, the viscosity after mixing is low, and the pot life can be set to an appropriate length.
As described above, the composition of the present invention is excellent in heat resistance and thin film curability because the loss on heating is suppressed and the heat resistant coloring stability is excellent. In addition, the composition of the present invention is thermosetting [when the composition is used (for example, after mixing two liquids in the case of a two-component type, after opening a container containing the composition in the case of a one-component type), After the composition is placed at room temperature (25 ° C.) for 24 hours, the composition has little gelation or thickening and can be rapidly cured by heating the composition. ] Adhesive (adhesiveness under conditions of high temperature, water, and high pressure), excellent transparency, high transmittance and transmittance retention, low viscosity after mixing, and proper use time Can be.

DESCRIPTION OF SYMBOLS 1 Spacer 3 Glass 5 PET film 6 Composition of this invention (it becomes the inside and the hardened | cured material 6 after hardening)
Type 8
200, 300 Sealed body 201, 301 Mount member 202 Cavity, cured product 203, 303 Optical semiconductor 302 Cured product 204 Package 206 Shaded portion 306 Resin 207, 307 Conductive wire 209 External electrode 210, 310 Substrate 305 Inner Lead 400, 501 LED display 401 Optical semiconductor 404 Case 405 Light shielding member 406 Cured product

Claims (13)

(A) 100 parts by mass of an organopolysiloxane having two or more silanol groups in one molecule;
(B) 0.1 to 2000 parts by mass of a silane compound having two or more alkoxy groups in one molecule;
(C) A thermosetting silicone resin composition for sealing an optical semiconductor, comprising an organic hafnium compound represented by the following formula (1) and / or the following formula (2).
Wherein (1), n is an integer from 1 to 4, R ¹ is a hydrocarbon group, R ² is an alkyl group having 1 to 18 carbon atoms. ]
[In formula (2), m is an integer of 1 to 4, R ² is an alkyl group having 1 to 18 carbon atoms, R ^3, R ⁴ are identical or different, hydrocarbon having 1 to 18 carbon atoms Group or alkoxy group. ] The thermosetting silicone resin composition for optical semiconductor encapsulation according to claim 1, wherein R ¹ has a cyclic structure. R ¹ is at least one selected from the group consisting of cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, naphthene ring, adamantyl group, norbornyl group, phenyl group, naphthyl group and azulene. The thermosetting silicone resin composition for optical semiconductor encapsulation according to claim 1 or 2, which is a seed.   The amount of the (C) organic hafnium compound is 0.001 to 5 parts by mass with respect to 100 parts by mass in total of the (A) organopolysiloxane and the (B) silane compound. The thermosetting silicone resin composition for optical semiconductor sealing as described in 2.   Further, (D) a tetravalent tin compound is contained, and the amount of the tetravalent tin compound is 0.01 to 10 mol per 1 mol of the (C) organic hafnium compound. The thermosetting silicone resin composition for optical semiconductor sealing of description. The (A) organopolysiloxane is a diorganopolysiloxane represented by the following formula (3), having silanol groups at both ends and having a weight average molecular weight of 1,000 to 1,000,000. The thermosetting silicone resin composition for optical semiconductor sealing in any one.
(Wherein R ⁵ are the same or different hydrocarbon groups.) The (B) silane compound is a silane compound represented by the following formula (4), a silane compound represented by the following formula (5), a diorganopolysiloxane represented by the following formula (3), and the following formula (4). It is at least 1 sort (s) chosen from the group which consists of a silane compound shown and / or the condensate with the silane compound shown by following formula (5), Thermosetting for optical semiconductor sealing in any one of Claims 1-6 Silicone resin composition.
Wherein (4), m is an integer from 1 to 4, R ⁶ is an organic group having 1 to 18 carbon atoms, R ⁷ is a hydrocarbon group having 1 to 6 carbon atoms. ]
R ⁸ _k Si (OR ⁹ ) _l O _{(4-kl) / 2} (5)
[In the formula (5), R ⁸ is an alkyl group having 1 to 6 carbon atoms and / or an aryl group, R ⁹ is an alkyl group having 1 to 6 carbon atoms, and 0 <k <2, 0 <l < 2, 0 <(k + l) ≦ 3. ]
(Wherein R ⁵ are the same or different hydrocarbon groups.)   The amount of the (D) tetravalent tin compound is 0.001 to 1 part by mass with respect to a total of 100 parts by mass of the (A) organopolysiloxane and the (B) silane compound. The thermosetting silicone resin composition for optical semiconductor sealing as described in 2.   The sealing body which seals the optical semiconductor by heating and hardening the thermosetting silicone resin composition for optical semiconductor sealing in any one of Claims 1-8. (C) A silanol condensation catalyst containing at least an organic hafnium compound represented by the following formula (1) and / or the following formula (2).
Wherein (1), n is an integer from 1 to 4, R ¹ is a hydrocarbon group, R ² is an alkyl group having 1 to 18 carbon atoms. ]
[In formula (2), m is an integer of 1 to 4, R ² is an alkyl group having 1 to 18 carbon atoms, R ^3, R ⁴ are identical or different, hydrocarbon having 1 to 18 carbon atoms Group or alkoxy group. ] The silanol condensation catalyst according to claim 10, wherein R ¹ has a cyclic structure. R ¹ is at least one selected from the group consisting of cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, naphthene ring, adamantyl group, norbornyl group, phenyl group, naphthyl group and azulene. The silanol condensation catalyst according to claim 10 or 11, which is a seed.   Furthermore, (D) tetravalent tin compound is included, The quantity of the said tetravalent tin compound is 0.01-10 mol with respect to 1 mol of said (C) organic hafnium compounds. Silanol condensation catalyst.