JP5678592B2 - Heat-curable silicone resin composition for optical semiconductor encapsulation and optical semiconductor encapsulant using the same - Google Patents

Description

  The present invention relates to a thermosetting silicone resin composition for optical semiconductor encapsulation and an optical semiconductor encapsulation body using the same.

Conventionally, it has been proposed to use an epoxy resin as a resin for a composition for sealing an optical semiconductor (for example, Patent Document 1). However, the encapsulant obtained from the composition containing the epoxy resin has a problem that the color of the encapsulant is yellowed by heat generated from the white LED element. For this reason, use of the silicone resin which is more excellent in heat resistance and light resistance as a composition for sealing an optical semiconductor is increasing.
For example, a room temperature curable organopolysiloxane containing an organopolysiloxane having two silanol groups, a silane compound having two or more hydrolyzable groups bonded to a silicon atom in one molecule, and an organic zirconium compound. Siloxane compositions have been proposed (for example, Patent Documents 2 and 3).
Further, for example, it has been proposed to mix and heat a condensation catalyst with diorganopolysiloxane having two silanol groups and silane having three or more alkoxy groups (for example, Patent Documents 4 and 5). ).

Japanese Patent Laid-Open No. 10-228249 Japanese Patent Laid-Open No. 2001-200161 Japanese Patent Laid-Open No. 2-196860 JP 2007-224089 A JP 2006-206700 A

  However, in the case of silicone-based resins, gas permeability is high compared to epoxy resins, so air easily passes through, so the silver plating of the optical semiconductor package is likely to change over time due to hydrogen sulfide in the air, and as a result, The brightness tends to decrease.

In addition, in the case of a silicone resin, it is generally performed to harden the resin in order to improve the sulfidation resistance. In that case, however, there is a risk of curing shrinkage, peeling from the LED package, and wire breakage. .
The present inventors have found that by adding a zinc compound to the silicone resin composition, the resistance to silver discoloration can be suppressed by exhibiting resistance to sulfidation with low hardness.
In addition, the inventors of the present application have (A) component: 100 parts by mass of polysiloxane having two or more silanol groups in one molecule and (B) component; an alkoxy group bonded to a silicon atom in one molecule. By using a zinc compound and a zirconium compound having an organic group and / or a hafnium compound having an organic group in combination as a curing catalyst for condensing two or more silane compounds, the composition can be cured by heating. The cured product thus obtained was found to be excellent in permeability and transparency, exhibiting low hardness and sulfidation resistance to suppress discoloration of silver, and completed the present invention.
That is, the present invention provides a thermosetting silicone resin composition for encapsulating an optical semiconductor having a low hardness, maintaining transparency, and excellent in resistance to sulfidation, and an optical semiconductor encapsulant using the same.
The silicone resin composition for heat-curable optical semiconductor encapsulation according to the first aspect of the present invention,
(A) component; 100 mass parts of polysiloxanes having two or more silanol groups in one molecule;
(B) component; 0.1 to 2000 parts by mass of a silane compound having two or more alkoxy groups bonded to a silicon atom in one molecule;
(C) component; a zirconium compound and / or a hafnium compound having an organic group;
Component (D); a zinc compound;
Containing.
In the thermosetting silicone resin composition for optical semiconductor encapsulation, the component (D) may be a complex containing zinc and / or a metal salt.
The said thermosetting silicone resin composition for optical semiconductor sealing WHEREIN: 0.001-1 mass part is contained with respect to a total of 100 mass parts of said (A) component and said (B) component of said (C) component. Can do.
The said thermosetting silicone resin composition for optical semiconductor sealing WHEREIN: 0.001-5 mass parts is contained with respect to a total of 100 mass parts of the said (A) component and the said (B) component of the said (D) component. Can do.
In the thermosetting silicone resin composition for encapsulating an optical semiconductor, the zirconium compound may be a compound represented by the following formula (1) and / or a compound represented by the following formula (2).
... (1)
(In the formula, R ¹ is a hydrocarbon group having 1 to 18 carbon atoms.)
... (2)
(Wherein R ² is the same or different hydrocarbon group having 1 to 16 carbon atoms, R ³ is the same or different hydrocarbon group having 1 to 18 carbon atoms, and m is an integer of 1 to 3). is there.)
In this case, R ² in the formula (2) may have a cyclic structure.
In this case, the R ² in the formula (2) may be at least one selected from the group consisting of a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a naphthene ring.
In the silicone resin composition for encapsulating heat-curable optical semiconductor of the present invention, the hafnium compound is a compound represented by the following formula (I) and / or a compound represented by the following formula (II). Can do.

[In formula (I), 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 the formula (II), m is an integer of 1 to 4, R ² is an alkyl group having 1 to 18 carbon atoms, and R ³ and R ⁴ are the same or different hydrocarbons having 1 to 18 carbon atoms. Group or alkoxy group. ]
In the thermosetting silicone resin composition for optical semiconductor encapsulation, the component (A) is a linear organopolysiloxane having a weight average molecular weight of 1,000 to 1,000,000 represented by the following formula (3): Can be contained.
... (3)
(In the formula, R ⁴ is the same or different and represents an alkyl group or aryl group having 1 to 18 carbon atoms, and n is an integer of 1 or more.)
The optical semiconductor sealing body which concerns on the 2nd aspect of this invention provides the said silicone resin composition for thermosetting optical semiconductor sealing to an LED chip, the said LED chip is heated, and the said thermosetting optical semiconductor sealing It is obtained by curing the silicone resin composition for use and sealing the LED chip.

Since the silicone resin composition for encapsulating heat-curable optical semiconductor of the present invention contains the zinc compound as component (D), by using this composition, even a low-hardness silicone resin cured product can be resistant to sulfidation. It is possible to produce a sealed optical semiconductor that maintains transparency and is excellent in sulfidation resistance.
Since the sealed optical semiconductor of the present invention is formed using the above composition, it has an appropriate hardness that is unlikely to cause cracks, and is excellent in sulfide resistance and transparency.

FIG. 1 is a top view schematically showing an example of a sealed optical semiconductor according to an embodiment of the present invention. 2 is a cross-sectional view schematically showing an AA cross section of the sealed optical semiconductor shown in FIG. FIG. 3 is a cross-sectional view schematically showing an example of a sealed optical semiconductor according to an embodiment of the present invention. FIG. 4 is a cross-sectional view schematically showing an example of a sealed optical semiconductor according to an embodiment of the present invention. FIG. 5 is a diagram schematically illustrating an example of an LED display using the sealed optical semiconductor according to an embodiment of the present invention. FIG. 6 is a block diagram of an LED display device using the LED display shown in FIG. FIG. 7 is a cross-sectional view schematically showing a cross section of a mold used for curing the composition in Examples of the present application. FIG. 8 is a cross-sectional view schematically showing an example of a sealed optical semiconductor according to an embodiment of the present invention.

  Hereinafter, a thermosetting silicone resin composition for encapsulating a photo semiconductor and an encapsulated optical semiconductor using the same according to an embodiment of the present invention will be described in detail.

1. Heat-curable silicone resin composition for encapsulating optical semiconductor The silicone resin composition for encapsulating heat-curable optical semiconductor according to this embodiment is
(A) component; 100 mass parts of polysiloxanes having two or more silanol groups in one molecule;
(B) component; 0.1 to 2000 parts by mass of a silane compound having two or more alkoxy groups bonded to a silicon atom in one molecule;
(C) component; a zirconium compound and / or a hafnium compound having an organic group;
Component (D); a zinc compound;
Containing.
The thermosetting silicone resin composition for encapsulating an optical semiconductor according to the present embodiment may be hereinafter referred to as “the composition according to the present embodiment (first embodiment)”.

1.1. Component (A) The component (A) 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 component (A) may be either linear or branched.
Examples of the component (A) include organopolydialkylsiloxanes in which two or more silanol groups are bonded to the terminal.
From the viewpoint of better heat-resistant coloring stability, the component (A) is preferably an organopolysiloxane or diorganopolysiloxane in which two or more silanol groups are bonded to the terminal, and the two silanol groups are both More preferably, it is an organopolydimethylsiloxane bonded to the end (for example, dimethylpolysiloxane), and a linear organopolydimethylsiloxane having two silanol groups bonded to both ends (linear organopolysiloxane). More preferred is dimethylsiloxane- [alpha], [omega] -diol).
Examples of the component (A) include those represented by the following formula (3) (diorganopolysiloxane).

... (3)
(In the formula, R ⁴ is the same or different and represents an alkyl group or aryl group having 1 to 18 carbon atoms, and n is an integer of 1 or more.)

In formula (3), examples of the alkyl group having 1 to 18 carbon atoms represented by R ⁴ (including chain, branched, cyclic, and combinations thereof) include, for example, a methyl group, an ethyl group, and a propyl group. , A chain or branched alkyl group such as isopropyl group, n-butyl group, isobutyl group or tert-butyl group; a cycloalkane group (cycloalkyl group) such as cyclopentyl group or cyclohexyl group. Examples of the aryl group having 1 to 18 carbon atoms represented by R ⁴ include a phenyl group and a naphthyl group. Among these, the group represented by R ⁴ is preferably a methyl group or a phenyl group, and more preferably a methyl group. R ⁴ may be the same or different.
Moreover, in Formula (3), n can be made into the numerical value corresponding to the weight average molecular weight of (A) component. From the viewpoint of excellent workability and crack resistance, n is preferably an integer of 10 to 15,000.

The component (A) is not particularly limited for its production. For example, a conventionally well-known thing is mentioned. The molecular weight of the component (A) is 1,000 to 1,000,000 from the viewpoint that it is superior in heat-resistant coloration stability, has an appropriate length of curing time and pot life, has excellent curability, and has excellent cured material properties. It is preferable that it is 6,000 to 100,000.
In the present invention, the molecular weight of the polysiloxane is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) using chloroform as a solvent.
(A) A component can be used individually or in combination of 2 types or more, respectively.

1.2. Component (B) The component (B) is not particularly limited as long as it is a compound having two or more alkoxy groups bonded to silicon atoms in one molecule.
As the component (B), for example, a compound having one silicon atom in one molecule and having two or more alkoxy groups bonded to the silicon atom (hereinafter, this compound may be referred to as “silane compound B1”). ) An organopolysiloxane compound having two or more silicon atoms in one molecule, the skeleton being a polysiloxane skeleton, and having two or more alkoxy groups bonded to the silicon atom (hereinafter referred to as “organopolysiloxane compound” Silane compound B2 ").

The component (B) can have one or more organic groups in one molecule.
(B) As an organic group which a component can have, the hydrocarbon group which may contain the at least 1 sort (s) of hetero atom chosen from the group which consists of an oxygen atom, a nitrogen atom, and a sulfur atom is mentioned, for example. Specific examples include alkyl groups (preferably those having 1 to 6 carbon atoms), (meth) acrylate groups, alkenyl groups, aryl groups, and combinations thereof. 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.

As silane compound B1, what is represented by following formula (4) is mentioned, for example.
Si (OR ⁴ ) _n R ⁵ _4-n (4)
(In the formula, n is 2, 3 or 4, R ⁴ is an alkyl group, and R ⁵ is an organic group.)
As the organic group represented by R ^5, include those described as hydrocarbon groups of the component (A).

Examples of the silane compound B1 include dialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane; methyltrimethoxysilane, methyltriethoxysilane Trialkoxysilanes such as ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane; tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetraisopropyloxysilane; trialkoxysilanes, Hydrolyzate of tetraalkoxysilane; γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxy Examples include (meth) acryloxyalkyltrialkoxysilanes such as silane.
In the present invention, (meth) acryloxytrialkoxysilane means acryloxytrialkoxysilane or methacryloxytrialkoxysilane. The same applies to (meth) acrylate groups and (meth) acryloxyalkyl groups.

Examples of the silane compound B2 include a compound represented by the formula (5).
R _m Si (OR ′) _n O _{(4-mn) / 2} (5)
Wherein 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 preferred from the viewpoints of excellent heat resistance and excellent heat-resistant coloring stability. Examples of the alkenyl group include those having 2 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. These may be the same or different.
In the compound represented by the formula (5), the alkyl group having 1 to 6 carbon atoms represented by 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.

Examples of the silane compound B2 include silicone alkoxy oligomers such as methylmethoxy oligomer.
One preferred embodiment of the silicone alkoxy oligomer is a silicone resin having a main chain of polyorganosiloxane and a molecular terminal blocked with an alkoxysilyl group.
The methyl methoxy oligomer corresponds to, for example, a compound represented by the above formula (5), and examples of the methyl methoxy oligomer include those represented by the following formula (6).
... (6)
(Wherein R ″ is a methyl group, a is an integer of 1 to 100, and b is an integer of 0 to 100.)
A commercially available product can be used as the methylmethoxy oligomer. Examples of commercially available methylmethoxy oligomers include x-40-9246 (weight average molecular weight 6,000, manufactured by Shin-Etsu Chemical Co., Ltd.).

Further, as the silane compound B2, for example, a compound having at least one alkoxysilyl group at one end and having three or more alkoxy groups (derived from an alkoxysilyl group) in one molecule (hereinafter referred to as compound B3). ) Is mentioned as a preferred form. Compound B3 is, for example, a reaction product obtained by dealcoholizing 1 mol or more of a silane compound having an alkoxysilyl group and / or an alkoxy group with respect to 1 mol of polysiloxane having both terminal silanol groups; an alkoxy bonded to a silicon atom A diorganopolysiloxane having an oligomer of a silane compound having two or more groups at both ends can be obtained.
Examples of the silane compound having an alkoxy group used for producing the compound B3 include the compound represented by the above formula (4): Si (OR ⁴ ) _n R ⁵ _4-n and the above formula ( _5): such as _{R m Si (OR ') n} O (4-m-n) / 2 represented by compounds.
As polysiloxane which has a both-ends silanol group used in order to manufacture compound B3, what is represented by said Formula (3) is mentioned, for example.
Examples of the silane compound B3 include those represented by the following formula (7).
... (7)

  From the viewpoint of excellent heat-resistant coloring stability and excellent crack resistance, the component (B) is preferably a compound represented by the above formula (4) and / or a compound represented by the above formula (5). It is more preferable that it is a compound represented by the said Formula (6).

  From the viewpoint of better heat-resistant coloring stability, the component (B) is a tetraalkoxysilane such as tetraethoxysilane; a trialkoxy (meth) acryloxyalkylsilane such as γ- (meth) acryloxypropyltrimethoxysilane; Methyl methoxy oligomer is preferred.

The molecular weight of the component (B) is 100 to 1,000,000 from the viewpoint that it is superior in heat-resistant coloration stability, has an appropriate length of curing time and pot life, and is excellent in curability and compatibility. Preferably, it is 100-100,000.
In addition, in this invention, when (B) component is silane compound B2, the molecular weight shall be the weight average molecular weight of polystyrene conversion by the gel permeation chromatography (GPC) which uses chloroform as a solvent.
(B) A component in particular is not restrict | limited about the manufacture, For example, a conventionally well-known thing is mentioned. (B) component can be used individually or in combination of 2 types or more, respectively.

  From the viewpoint of excellent heat-resistant coloring stability, crack resistance, and compatibility, the amount of the component (B) is 0.1 to 2000 parts by mass with respect to 100 parts by mass of the component (A), and 5 to 100 It is preferable that it is a mass part.

1.3. Component (C) The component (C) is a zirconium compound and / or hafnium compound having an organic group. The zirconium compound having an organic group as the component (C) is a zirconium compound containing a zirconium atom and an organic group. The hafnium compound having an organic group as the component (C) is a hafnium compound containing a hafnium atom and an organic group.
The component (C) acts as a Lewis acid during initial heating for curing the composition according to the present embodiment or after initial curing, and promotes a crosslinking reaction between the component (A) and the component (B). I think that. More specifically, the component (C) is activated by heating and can condense silanol groups (for example, by reaction between silanol groups, silanol groups and alkoxysilyl groups). Thereby, (C) component can harden the composition based on this embodiment uniformly uniformly by heating.
Therefore, the composition according to this embodiment containing the component (C) is excellent in heat-resistant coloring stability.
(C) A component can be used individually or in combination of 2 types or more, respectively.

  The component (C) may be any compound having zirconium or hafnium and an organic group. Zirconium or hafnium can be bonded to the organic group via, for example, a heteroatom such as an oxygen atom, nitrogen atom, sulfur atom, and / or via a linking group such as an ester bond. The organic group includes an aliphatic hydrocarbon group (including chain, branched, cyclic, and combinations thereof. The aliphatic hydrocarbon group can have an unsaturated bond), aromatic hydrocarbon groups, and combinations thereof Is mentioned. The organic group can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the organic group include an organic carboxylate (—O—CO—R); an alkoxy group or a phenoxy group in which a hydrocarbon group is bonded to an oxy group (—O—R); a ligand; These combinations are mentioned.

  More specifically, the zirconium compound as the component (C) is a compound (compound C1) represented by the following formula (1) and / or a compound (compound C2) represented by the following formula (2). it can.

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

1.3.1. Compound C1
Compound C1 is a zirconium metal salt containing zirconyl [(Zr = O) ²⁺ ] as a constituent element. The composition according to this embodiment containing the compound C1 is more excellent in curability.
The acid used for producing the zirconium metal salt of compound C1 is not particularly limited. For example, carboxylic acid and carboxylate are mentioned. Examples of the carboxylic acid and carboxylate include aliphatic carboxylic acids such as acetic acid, propionic acid, octylic acid (2-ethylhexanoic acid), nonanoic acid, stearic acid, and lauric acid; naphthenic acid and cyclohexanecarboxylic acid. Alicyclic carboxylic acids; aromatic carboxylic acids such as benzoic acid; and salts thereof.
From the viewpoint of excellent curability, the compound C1 is more preferably an aliphatic carboxylate and / or an alicyclic carboxylate, and even more preferably an alicyclic carboxylate.
In this case, examples of the aliphatic carboxylate include zirconyl dioctylate and zirconyl dineodecanoate, and examples of the alicyclic carboxylate include alicyclic carboxylates such as zirconyl naphthenate and zirconyl cyclohexane. Examples of the aromatic carboxylate include zirconyl benzoate. From the viewpoint of excellent curability, when the compound C1 is used as the component (C), the compound C1 is preferably one or both of zirconyl dioctylate and zirconyl naphthenate.

1.3.2. Compound C2
Compound C2 has 1 to 3 acyl groups (R ² —CO—) as represented by the above formula (2). In the compound C2 represented by the above formula (2), the acyl group is included in the above formula (2) as a carboxylic acid ester. In the above formula (2), when m is 2 or more, the plurality of R ² may be the same or different. Further, when m is 1-2, a plurality of R ² may be the same or different.

From the viewpoint of excellent heat-resistant coloring stability and excellent compatibility (for example, compatibility with a silicone resin), the hydrocarbon group represented by R ² in the above formula (2) has 3 to 16 carbon atoms. Is preferable, and 4 to 16 is more preferable.
Examples of the hydrocarbon group represented by 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. From the viewpoints of excellent curability and heat-resistant coloring stability and excellent compatibility, the hydrocarbon group represented by R ² is preferably an alicyclic hydrocarbon group and / or an aliphatic hydrocarbon group.

From the viewpoint of excellent heat-resistant coloring stability and excellent compatibility, the hydrocarbon group represented by R ² preferably has a cyclic structure. In this case, examples of the cyclic structure 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 heat-resistant coloring stability and excellent compatibility, the hydrocarbon group represented by R ² is preferably an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and is preferably a cyclopropyl group or a cyclopentyl group. Group, cyclohexyl group, adamantyl group, naphthene ring (naphthate group as R ² COO—) and phenyl group are more preferable, and cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group and naphthene ring are more preferable.

Examples of R ² COO— having an alicyclic hydrocarbon group include a cyclopropylcarbonyloxy group, a cyclobutylcarbonyloxy group, a cyclopentylcarbonyloxy group, a cyclohexylcarbonyloxy group (cyclohexyl carbonate group), and a cycloheptylcarbonyloxy group. (Cycloheptyl carbonate group), cycloalkylcarbonyloxy group such as cyclooctylcarbonyloxy group; naphthate group (naphthenic acid ester); condensed ring hydrocarbon group such as adamantylcarbonyloxy group and norbornylcarbonyloxy group Of carbonyloxy group.
Examples of R ² COO— having an aromatic hydrocarbon group include a phenylcarbonyloxy group, a naphthylcarbonyloxy group, and an azulylcarboxy group.
Examples of R ² COO— having an aliphatic hydrocarbon group include acetate, propionate, butyrate, isobutyrate, octylate, 2-ethylhexanoate, nonanoate, and laurate.
Among them, more excellent heat resistant coloration stability, from the viewpoint of excellent compatibility, R ² COO- having an alicyclic hydrocarbon group, R ² COO- having an aromatic hydrocarbon group, 2-ethylhexanoate is preferred , Cyclopropylcarbonyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group, adamantylcarbonyloxy group, naphthate group, phenylcarbonyloxy group are more preferable, cyclopropylcarbonyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group, adamantyl A carbonyloxy group and a naphthate group are more preferable.

Further, more excellent heat resistant coloration stability, from the viewpoint of excellent compatibility, the number of carbon atoms in the hydrocarbon group represented by R ³ is preferably 3-8.
Examples of the hydrocarbon group represented by R ³ include an aliphatic hydrocarbon 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. From the viewpoint of excellent heat-resistant coloring stability and excellent compatibility, the hydrocarbon group represented by R ³ is preferably an aliphatic hydrocarbon group.

Examples of the R ³ O— (alkoxy group) having an aliphatic hydrocarbon group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and an octyloxy group. . Among these, from the viewpoint of excellent heat-resistant coloring stability and excellent compatibility, R ³ O— (alkoxy group) having an aliphatic hydrocarbon group is a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, An isopropoxy group is preferred.

Examples of the compound C2 having an alicyclic hydrocarbon group as a cyclic structure include zirconium alkoxycyclohexane such as zirconium trialkoxymonocyclopropanecarboxylate, zirconium dialkoxydicyclopropanecarboxylate, and zirconium monoalkoxytricyclopropanecarboxylate. Propanecarboxylate;
Zirconium alkoxycyclopentane carboxylates such as zirconium trialkoxy monocyclopentane carboxylates, zirconium dialkoxy dicyclopentane carboxylates, zirconium monoalkoxy tricyclopentane carboxylates;
Zirconium tributoxy monocyclohexane carboxylate, zirconium dibutoxy dicyclohexane carboxylate, zirconium monobutoxy tricyclohexane carboxylate, zirconium triisopropoxy monocyclohexane carboxylate, zirconium diisopropoxy dicyclohexane carboxylate, zirconium monoisopropoxy tricyclohexane carboxylate Zirconium alkoxycyclohexanecarboxylates such as
Zirconium alkoxyadamantane carboxylates such as zirconium trialkoxy monoadamantane carboxylates, zirconium dialkoxydiadamantane carboxylates, zirconium monoalkoxytriadamantane carboxylates;
Zirconium alkoxy naphtha such as zirconium tributoxy mononaphthate, zirconium dibutoxy dinaphthate, zirconium monobutoxy trinaphthate, zirconium triisopropoxy mononaphthate, zirconium diisopropoxy dinaphthate, zirconium monoisopropoxy trinaphthate Tate.

  Examples of the compound C2 having an aromatic hydrocarbon group as a cyclic structure include zirconium tributoxy monobenzene carboxylate, zirconium dibutoxy dibenzene carboxylate, zirconium monobutoxy tribenzene carboxylate, zirconium triisopropoxy monobenzene carboxylate, Zirconium alkoxybenzenecarboxylates such as zirconium diisopropoxydibenzenecarboxylate and zirconium monoisopropoxytribenzenecarboxylate.

Examples of the compound C2 having an aliphatic hydrocarbon group include zirconium tributoxy monoisobutyrate, zirconium dibutoxy diisobutyrate, zirconium monobutoxy triisobutyrate, zirconium triisopropoxy monoisobutyrate, zirconium diisopropoxy. Zirconium alkoxybutyrate such as diisobutyrate, zirconium monoisopropoxytriisobutyrate;
Zirconium tributoxy mono-2-ethylhexanoate, zirconium dibutoxydi-2-ethylhexanoate, zirconium monobutoxytri-2-ethylhexanoate, zirconium triisopropoxymono-2-ethylhexanoate, zirconium diisopropoxydi-2-ethylhexanoate , Zirconium alkoxy 2-ethyl hexanoates such as zirconium monoisopropoxy tri-2-ethyl hexanoate;
Zirconium tributoxymononeodecanate, zirconium dibutoxydineodecanate, zirconium monobutoxytrineodecanate, zirconium triisopropoxymononeodecanate, zirconium diisopropoxydineodecanate, zirconium monoisopropoxytrineodecanate Zirconium alkoxy neodecanate such as

  Among these, from the viewpoint of excellent heat-resistant coloring stability and excellent compatibility, when using the compound C2 as the component (C), the compound C2 having an alicyclic hydrocarbon group as the cyclic structure, and the aromatic hydrocarbon as the cyclic structure Compound C2 having a group is preferred, zirconium trialkoxy mononaphthate, zirconium trialkoxy monoisobutyrate, zirconium trialkoxy mono-2-ethylhexanoate, zirconium trialkoxy monocyclopropanecarboxylate, zirconium trialkoxycyclobutanecarboxylate, zirconium Trialkoxymonocyclopentanecarboxylate, zirconium trialkoxymonocyclohexanecarboxylate, zirconium trialkoxymonoadamantanecarboxylate, zirconi More preferred are trialkoxy mononaphthate, zirconium tributoxy mononaphthate, zirconium tributoxy monoisobutyrate, zirconium tributoxy mono 2-ethylhexanoate, zirconium tributoxy monocyclopropanecarboxylate, zirconium tributoxy monocyclopentanecarboxyl. Further preferred are rate, zirconium tributoxy monocyclohexanecarboxylate, zirconium tributoxy monoadamantane carboxylate, zirconium tributoxy mononaphthate.

The compound C2 is preferably an alkoxy group-containing zirconium metal salt having 1 to 3 acyl groups (ester bonds) from the viewpoint of superior heat-resistant coloring stability.
Examples of the alkoxy group-containing zirconium metal salt having 1 to 3 acyl groups include zirconium tributoxy mononaphthate, zirconium tributoxy monoisobutyrate, zirconium tributoxy mono-2-ethylhexanoate, zirconium tributoxy mononeo. Decanate, zirconium dibutoxy dinaphthate, zirconium dibutoxy diisobutyrate, zirconium dibutoxy di-2-ethylhexanoate, zirconium dibutoxy dineodecanate, zirconium monobutoxy trinaphthate, zirconium monobutoxy triisobutyrate, Zirconium monobutoxytri-2-ethylhexanoate, zirconium monobutoxytrineodecanate.
Among them, from the viewpoint of excellent heat-resistant coloring stability and excellent compatibility, when using the compound C2 as the component (C), the compound C2 is composed of zirconium tributoxy mononaphthate, zirconium tributoxy monoisobutyrate, and zirconium. It is preferably at least one selected from tributoxy mono 2-ethyl hexanoate.

As a manufacturing method of compound C2, for example, Zr (OR ³ ) ₄ [R ³ is the same or different and is a hydrocarbon group having 1 to 18 carbon atoms. R ³ has the same meaning as ^{R 3} in Formula (2). An example is zirconium tetraalkoxide. ] Carboxylic acid represented by R ² —COOH with respect to 1 mol [R ² is the same or different and is a hydrocarbon group having 1 to 16 carbon atoms. 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 the compound C2 include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetranormal propoxide, zirconium tetraisopropoxide, and zirconium tetranormal butoxide. Can be mentioned.

  Carboxylic acids that can be used to produce compound C2 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.

1.3.3. Hafnium Compound The hafnium compound having an organic group that the composition of the present invention can contain as the component (C) is not particularly limited as long as it is a compound having a hafnium atom and an organic group. Among these, the hafnium compound is preferably a compound represented by the following formula (I) and / or a compound represented by the following formula (II) from the viewpoint of being excellent in sulfidation resistance and excellent in curability.

[In formula (I), 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 the formula (II), m is an integer of 1 to 4, R ² is an alkyl group having 1 to 18 carbon atoms, and R ³ and R ⁴ are the same or different hydrocarbons having 1 to 18 carbon atoms. Group or alkoxy group. ]

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

[In formula (I), 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 has a cyclic structure from the viewpoints of being excellent in sulfidation resistance, excellent in heat resistance (for example, heat-resistant coloring stability), excellent in thin film curability, thermosetting, and compatibility. Preferably, it is an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. 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 hydrocarbons are preferred from the viewpoints of superior sulfidation resistance, excellent heat resistance (for example, heat-resistant coloring stability), excellent thin film curability, thermosetting properties, and compatibility. Group is preferred, 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 More preferably, a cyclopropyl 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 A naphthene ring is particularly preferred.

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

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, methyl group, ethyl group, propyl group (n-propyl) are preferred from the viewpoints of excellent curability, heat resistance (for example, heat-resistant coloring stability), thin film curability, thermosetting property, and compatibility. Group, isopropyl group), butyl group and pentyl group are preferred.

As a 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 a 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 a 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.

  Of these, hafnium trialkoxy mononaphthate and hafnium trialkoxy monoisobutyrate are preferred from the viewpoints of excellent thin film curability, excellent heat resistance (for example, excellent heat-resistant coloring stability), thermosetting property, and compatibility. , Hafnium trialkoxy mono-2-ethylhexanoate, hafnium trialkoxy monocyclopropane carboxylate, hafnium trialkoxycyclobutanecarboxylate, hafnium trialkoxy monocyclopentane carboxylate, hafnium trialkoxy monocyclohexane carboxylate, hafnium trialkoxy monoadamantane carboxy Rate, hafnium trialkoxy monobenzenecarboxylate, hafnium dialkoxydinaphthate are preferred, hafnium tributoxy Naphthate, hafnium tributoxy monoisobutyrate, hafnium tributoxy mono 2-ethylhexanoate, hafnium tributoxy monocyclopropane carboxylate, hafnium tributoxy monocyclopentane carboxylate, hafnium tributoxy monocyclohexane carboxylate, hafnium trialkoxy mono Benzene carboxylate, hafnium tributoxy monoadamantane carboxylate, hafnium dibutoxy dinaphthate, and hafnium tripropoxy mononaphthate are more preferred.

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

[In the formula (II), m is an integer of 1 to 4, R ² is an alkyl group having 1 to 18 carbon atoms, and R ³ and R ⁴ are the same or different hydrocarbons 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 (I).
The hydrocarbon group having 1 to 18 carbon atoms is the same as that in which R ¹ (hydrocarbon group) in formula (I) 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.
In formula (II), R ³ and R ⁴ may be interchanged.

As the hafnium compound represented by the formula (II), for example,
Examples include hafnium alkoxide (mono-tri) 2,4-pentadionate, hafnium-2,4-pentadionate, hafnium alkylpentadionate, and hafnium fluoropentadionate.
Of these, hafnium di-n-butoxide (bis-) is preferred from the viewpoints of superior sulfidation resistance, excellent thin film curability, excellent heat resistance (eg, excellent heat-resistant coloring stability), excellent thermosetting properties, and compatibility. 2,4-pentadionate), hafnium-2,4-pentadionate, hafnium tetramethylpentadionate, and hafnium trifluoropentadionate are preferred.

  From the viewpoint of excellent heat-resistant coloring stability and excellent storage stability, the amount of the component (C) is 0.001 to 1 part by mass with respect to 100 parts by mass in total of the component (A) and the component (B). Is preferably 0.01 to 0.5 parts by mass, and more preferably 0.001 to 0.05 parts by mass.

1.4. (D) Component The zinc compound which is (D) component is a compound containing zinc, for example, a complex and / or metal salt containing zinc. When the composition which concerns on this embodiment contains the zinc compound which is (D) component, sulfur resistance can be provided to hardened | cured material because this zinc compound couple | bonds with sulfur. Thereby, corrosion of silver can be prevented and transparency can be maintained. Moreover, the hardened | cured material obtained using the composition which concerns on this embodiment has sufficient sulfidation resistance, without hardening resin. For this reason, the said hardened | cured material can be a silicone resin which does not produce a crack easily and has moderate hardness. For this reason, when hardened | cured material is used as an optical semiconductor sealing body, the disconnection of the wire contained in this sealing body can be prevented.

  The zinc compound is not particularly limited as long as it is a compound containing zinc. For example, zinc salts; zinc complexes; zinc alcoholates; zinc oxides such as zinc white and zinc stannate; binary and / or multimetal oxides containing zinc, salts and / or complexes thereof, and combinations thereof . Of these, zinc salts and / or zinc complexes are preferred from the viewpoint of superior sulfidation resistance and transparency. The zinc salt is not particularly limited as long as it is a salt formed from zinc and an acid (including inorganic acid and organic acid). The zinc complex is not particularly limited as long as it is a chelate compound formed from zinc and a ligand.

Examples of the complex and metal salt containing zinc as component (D) include zinc bisacetylacetonate, zinc bis-2-ethylhexanoate, zinc (meth) acrylate, zinc neodecanate and other carboxylates, zinc white And zinc oxides such as zinc stannate.
For example, when the cured product formed using the composition according to the present embodiment requires transparency, the component (D) is a resin permeation when the component (D) is added to the resin. The ratio is preferably a zinc compound having a light transmittance of 70% or more at a wavelength of 400 nm, for example.

Specific examples of the zinc compound include those represented by the following formulas (1) and (2), a zinc complex of a salicylic acid compound, and a zinc complex of a diamine compound.
The zinc compound represented by the formula (1) is as follows.
Zn (O—CO—R ¹ ) ₂ (1)
In formula (1), R ¹ is an alkyl group having 1 to 18 carbon atoms, an aryl group. The alkyl group and aryl group having 1 to 18 carbon atoms are the same as the alkyl group and aryl group in R ¹ in the above formula (I). CO in the formula is a carbonyl group (C═O).
When the zinc compound represented by the formula (1) is a salt, examples of the zinc salt include the following formula (1 ′).

In the above formula (1 ′), R ¹ is the same as in formula (1).
Examples of the zinc compound represented by the formula (1) include zinc acetate, zinc 2-ethylhexanoate, zinc octoate, zinc neodecanate; zinc acetyl acetate; zinc (meth) acrylate; and carboxylate such as zinc salicylate. Can be mentioned.

The zinc compound represented by Formula (2) is as follows.
Zn (R ² COCHCOR ³ ) ₂ (2)
In formula (2), R ² and R ³ are the same or different monovalent hydrocarbon groups having 1 to 18 carbon atoms and alkoxy groups. CO in the formula is a carbonyl group (C═O).
When the zinc compound represented by the formula (2) is a complex, examples of the zinc complex include the following formula (2 ′).

In the above formula ^{(2 '), R 2,} R 3 is the same as equation ^{(2), R 2, R} 3 , which are in the same (R ² COCHCOR ³⁾ may be interchanged.
Examples of the monovalent hydrocarbon group having 1 to 18 carbon atoms include an alkyl group having 1 to 18 carbon atoms and an aryl group. A C1-C18 alkyl group and an aryl group are synonymous with the above.
Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.
Examples of the zinc compound represented by the formula (2) include bis (acetylacetonato) zinc complex, 2,2,6,6,6 tetramethyl-3,5-heptanedionate zinc complex, and the like.

  The zinc compound is represented by the formula (1) or the formula (2) from the viewpoint that the sulfidation resistance of the metal layer is more excellent and corrosion (for example, discoloration) of the metal layer can be further suppressed. These are preferably used in combination, such as zinc acetate, zinc 2-ethylhexanoate, zinc octoate, zinc neodecanate, zinc acetyl acetate, zinc (meth) acrylate, zinc salicylate, bis (acetylacetonate) zinc complex, 2 2,6,6,6 tetramethyl-3,5-heptanedionate zinc complex is more preferred.

The compound which concerns on this embodiment is 0.001-5 mass with respect to a total of 100 mass parts of (A) component and (B) component from a viewpoint which can express sulfidation resistance reliably. It is preferably contained in an amount of 0.01 to 0.5 parts by mass, more preferably 0.1 to 0.5 parts by mass.
(D) component can be used individually or in combination of 2 or more types, respectively.

  The composition according to the present embodiment is substantially composed of (A) component, (B) component, (C) component, and (D) component from the viewpoint of excellent sulfidation resistance. Product (a composition containing only the above four components). Here, the “composition consisting essentially of” means that components other than the above four components are 5% by mass or less.

1.6. Other Components In addition to the component (A), the component (B), the component (C), and the component (D), the composition according to the present embodiment is necessary as long as the object and effect of the present invention are not impaired. Depending on the case, additives can be further contained.
Examples of additives include inorganic fillers, antioxidants, lubricants, ultraviolet absorbers, thermal light stabilizers, dispersants, antistatic agents, polymerization inhibitors, antifoaming agents, curing accelerators, solvents, inorganic phosphors, Anti-aging agent, radical inhibitor, adhesion improver, flame retardant, surfactant, storage stability improver, ozone anti-aging agent, thickener, plasticizer, radiation blocker, nucleating agent, coupling agent, conductive Property imparting agents, phosphorus peroxide decomposers, pigments, metal deactivators, physical property modifiers, adhesion imparting agents such as bisalkoxysilylalkanes and coupling agents, and isocyanurate compounds (adhesion imparting agents). . Various additives are not particularly limited. For example, a conventionally well-known thing is mentioned.

Bis (alkoxysilyl) alkane as an additive is an adhesion-imparting agent and is a compound having a divalent alkane (alkylene group) and two alkoxysilyls. When the composition of the present invention further contains a bis (alkoxysilyl) alkane, the adhesiveness and adhesion are excellent. The alkoxysilyl group can have, for example, an alkyl group such as a methyl group or an ethyl group in addition to the alkoxy group. The divalent alkane can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Specifically, the divalent alkane can have an imino group (—NH—), for example. The divalent alkane may be one in which two alkylene groups are bonded via a hetero atom [eg, imino group (—NH—)]. 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. Examples of the divalent alkane as R ⁹ include an alkylene group having 1 to 10 carbon atoms. A divalent alkane has the same meaning as described above.

  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 those represented by the formula (VII) from the viewpoints of excellent transparency, excellent curability, smoothness, and storage stability, and the pot life and curing time are appropriately long. Bis (trialkoxysilyl) alkane is more preferable, bis- (3-trimethoxysilylpropyl) amine, 1,2-bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, The group consisting of 1,7-bis (trimethoxysilyl) heptane, 1,8-bis (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane and 1,10-bis (trimethoxysilyl) decane At least one selected from the group consisting of 1,6-bis (trimethoxysilyl) hexane and bis- (3-trimethoxysilylpro Le) amine are more preferred.
Bis (alkoxysilyl) alkanes can be used alone or in combination of two or more.

  The amount of bis (alkoxysilyl) alkane is excellent in transparency, excellent in curability, smoothness and storage stability, and from the viewpoint that the pot life and the curing time are of appropriate length, (A) polysiloxane and ( B) It is preferable that it is 0.1-5 mass parts with respect to a total of 100 mass parts with a silane compound.

The isocyanurate compound as an additive is not particularly limited as long as it is a compound that forms an isocyanurate skeleton by a polyisocyanate trimer. When the composition of the present invention further contains an isocyanurate compound, the adhesiveness and adhesion are excellent. As an isocyanurate compound, the compound represented by following formula (1) is mentioned, for example.

In the formula (1), R is an organic group or a monovalent hydrocarbon group having an aliphatic unsaturated bond. Furthermore, R can include an epoxy group, a glycidoxy group, an alkoxysilyl group, a (meth) acryloyl group, and the like. R represents at least one selected from the group consisting of an epoxy group, a glycidoxy group, an alkoxysilyl group, and a (meth) acryloyl group, and a hydrocarbon group [for example, an aliphatic hydrocarbon group (either chained, branched, or cyclic). And an unsaturated bond may be included.), An aromatic hydrocarbon group, and a combination thereof. ] Can be combined. Examples of the organic group are the same as described above. The alkoxysilyl group can have 1 to 3 alkoxy groups, and the alkoxy group can have 1 or more carbon atoms. The alkoxysilyl group can have a hydrocarbon group in addition to the alkoxy group. The hydrocarbon group is not particularly limited.
Examples of the isocyanurate derivative represented by the above formula include tris- (3-trimethoxysilylpropyl) isocyanurate.
An isocyanurate compound can be used individually or in combination of 2 types or more, respectively.
The amount of the isocyanurate compound is 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of (A) polysiloxane and (B) silane compound from the viewpoint of excellent adhesion, adhesion and transparency. It is preferable that it is 0.1 to 5 parts by mass.

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.

The composition which concerns on this embodiment is mentioned as one of the aspects with preferable water substantially not included from a viewpoint that it is excellent in storage stability. 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 according to the present embodiment can be mentioned as one of preferred embodiments that does not substantially 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.

1.7. Production The composition according to this embodiment is not particularly limited for production. For example, it can be manufactured by mixing the component (A), the component (B), the component (C), the component (D), and an additive that can be used as necessary.

  The composition according to this embodiment can be produced as a one-component type or a two-component type. In the case where the composition according to this embodiment is a two-component type, it has a first liquid containing the component (A), the component (C) and the component (D), and a second liquid containing the component (B). It is mentioned as one of the preferable embodiments. The additive can be added to one or both of the first liquid and the second liquid.

1.8. Applications and methods of use The composition according to this embodiment can be used as a composition for optical semiconductor encapsulation.
The optical semiconductor to which the composition according to this embodiment 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 of using the composition according to this embodiment, for example, the composition according to this embodiment is applied to an optical semiconductor, and the optical semiconductor to which the composition according to this embodiment is applied is heated to this embodiment. Curing such a composition may be mentioned. The method for applying the composition according to this embodiment is not particularly limited. Examples thereof include a method using a dispenser, a potting method, screen printing, transfer molding, and injection molding.

The composition according to this embodiment can be cured by heating.
The heating temperature can set the curing time and pot life to appropriate lengths, can suppress the foaming of alcohol as a by-product due to the condensation reaction, can suppress cracks in the cured product, and smoothness of the cured product From the viewpoint of excellent moldability and physical properties, curing is preferably performed at about 80 ° C. to 150 ° C., more preferably 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 according to the present embodiment can maintain high transparency against long-term use of LEDs (in particular, white LEDs), Excellent sulfidation, heat-resistant coloring stability and crack resistance. 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.

  A cured product (in the case where the thickness of the cured product is 2 mm) obtained using the composition according to the present embodiment is an ultraviolet / visible absorption spectrum measuring apparatus (manufactured by Shimadzu Corporation, hereinafter) according to JIS K0115: 2004. ) Is preferably 80% or more, and more preferably 85% or more.

  In addition, the cured product obtained using the composition according to this embodiment 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 in accordance with JIS K0115: 2004 is preferably 80% or more, more preferably 85% or more.

  The cured product obtained using the composition according to the present embodiment preferably has a permeability retention rate (transmittance after heat resistance test / transmittance upon initial curing × 100) of 70 to 100%. 80 to 100% is more preferable.

  In addition to optical semiconductors, the composition according to the present embodiment includes, for example, display materials, optical recording medium materials, optical equipment materials, optical component materials, optical fiber materials, optical / electronic functional organic materials, semiconductor integrated circuit peripheral materials, and the like. Can be used for applications.

2. Next, a sealed optical semiconductor according to a second embodiment of the present invention will be described below.
The sealed optical semiconductor according to the present embodiment is obtained by sealing an LED chip by using the thermosetting silicone resin composition for sealing an optical semiconductor according to the first embodiment.
The sealed optical semiconductor according to the present embodiment provides the LED chip with the heat-curable silicone resin composition for sealing an optical semiconductor according to the first embodiment, and heats the LED chip to heat and heat-curable optical semiconductor. It can be obtained by curing the silicone resin composition for sealing and sealing the LED chip.

If the composition used for the optical semiconductor sealing body which concerns on this embodiment is a silicone resin composition for thermosetting optical semiconductor sealing which concerns on the said 1st Embodiment, it will not restrict | limit in particular.
In the optical semiconductor sealing body according to the present embodiment, by using the thermosetting silicone resin composition for optical semiconductor sealing according to the first embodiment as a composition, the optical semiconductor sealing body according to the present embodiment. Has an appropriate hardness that is unlikely to cause cracks, is excellent in sulfidation resistance and transparency, and is excellent in heat-resistant coloring stability against heat generation and light emission from an optical semiconductor chip such as an LED.

The LED chip used for the sealed optical semiconductor according to the present embodiment is not particularly limited as long as it is an electronic circuit having a light emitting diode as a light emitting element.
The LED chip used for the sealed optical semiconductor according to the present embodiment is not particularly limited with respect to the emission color. For example, white, blue, red, and green are mentioned. The sealed optical semiconductor according to the present embodiment can be applied to a white LED from the viewpoint of excellent heat-resistant coloring stability even when exposed to a high temperature due to heat generated from the LED chip for a long time.
The white LED is not particularly limited. For example, a conventionally well-known thing is mentioned.
The size and shape of the LED chip are not particularly limited. Moreover, the kind of LED chip is not particularly limited, and examples thereof include a high power LED, a high luminance LED, and a general-purpose luminance LED.
The sealed optical semiconductor according to the present embodiment has at least one LED chip inside one sealed optical semiconductor, and can have two or more LED chips.

  As a manufacturing method of the optical semiconductor sealing body which concerns on this embodiment, the provision process which provides the silicone resin composition for thermosetting optical semiconductor sealing which concerns on this embodiment to an LED chip, and the said thermosetting light, for example What has heat-curing process which heats the LED chip | tip with which the silicone resin composition for semiconductor sealing was provided, hardens the silicone resin composition for thermosetting optical semiconductor sealing, and seals an LED chip is mentioned. It is done.

  In the applying step, the LED chip is provided with the thermosetting silicone resin composition for encapsulating a photo semiconductor, and the LED chip provided with the thermosetting photo semiconductor encapsulating silicone resin composition is obtained. The LED chip 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 a thermosetting silicone resin composition for encapsulating a photo semiconductor according to the first embodiment. The method of giving is not particularly limited.

  Next, in the heat curing step, the LED chip to which the heat curable photonic semiconductor sealing silicone resin composition is applied is heated to cure the heat curable photonic semiconductor sealing silicone resin composition to produce an LED. By sealing the chip, the sealed optical semiconductor according to this embodiment can be obtained. The heating temperature in the heat curing step is as defined above.

  As a form of the optical semiconductor encapsulant according to the present embodiment, for example, a cured product directly encapsulating an LED chip, a shell type, a surface mount type, a plurality of LED chips or an optical semiconductor encapsulant What seals between and / or the surface is mentioned.

The sealed optical semiconductor according to this embodiment will be described below with reference to the accompanying drawings. In addition, the optical semiconductor sealing body which concerns on this embodiment is not limited to attached drawing. FIG. 1 is a top view schematically showing an example of a sealed optical semiconductor according to the present embodiment, and FIG. 2 is a sectional view schematically showing an AA cross section of the sealed optical semiconductor shown in FIG. It is.
In FIG. 1, reference numeral 600 denotes a sealed optical semiconductor according to the present embodiment, and the sealed optical semiconductor 600 includes an LED chip 601 and a cured product 603 that seals the LED chip 601. The composition according to the first embodiment becomes a cured product 603 after heating. Note that the substrate 609 is omitted in FIG.
In FIG. 2, an LED chip 601 is bonded to a substrate 609 by, for example, an adhesive or solder (not shown), or connected in a flip chip structure. In FIG. 2, wires, bumps, electrodes and the like are omitted.
2 indicates the thickness of the cured product 603. That is, T is a value when the thickness of the cured product 603 is measured from an arbitrary point 605 on the surface of the LED chip 601 in a direction perpendicular to the surface 607 to which the point 605 belongs.
The sealed optical semiconductor according to the present embodiment preferably has a thickness (T in FIG. 2) of 0.1 mm or more from the viewpoint of ensuring transparency and excellent sealing properties. More preferably, it is 1 mm.

  A case where a white LED is used as an example of the sealed optical semiconductor according to this embodiment will be described below with reference to the accompanying drawings. FIG. 3 is a cross-sectional view schematically showing an example of a sealed optical semiconductor according to the present embodiment. FIG. 8 is a cross-sectional view schematically showing an example of the sealed optical semiconductor according to the present embodiment. FIG. 4 is a cross-sectional view schematically showing an example of the sealed optical semiconductor according to the present embodiment.

In FIG. 3, the optical semiconductor encapsulant 200 has a package 204 on a substrate 210.
The package 204 is provided with a cavity 202 therein. A blue LED chip 203 and a cured product 202 are disposed in the cavity 202. The cured product 202 is obtained by curing the composition according to the first embodiment. In this case, the composition according to the present embodiment can contain a fluorescent material or the like that can be used for causing the sealed optical semiconductor 200 to emit white light.
The blue LED chip 203 is fixed on the substrate 210 with a mount member 201. Each electrode (not shown) of the blue LED chip 203 and the external electrode 209 are wire-bonded by a conductive wire 207.
In the cavity 202, the hatched portion 206 may be filled with the composition according to the first embodiment.
Alternatively, the cavity 202 can be filled with another composition, and the hatched portion 206 can be filled with the composition according to the first embodiment.

FIG. 8 shows a case where the sealed optical semiconductor 200 shown in FIG. 3 further has a silver plating layer in the package.
In FIG. 8, the optical semiconductor sealing body 800 has a silver plating layer 810 in a package 204. The optical semiconductor sealing body 800 is the same as FIG. 3 except that the package 204 has a silver plating layer 810.
The cured product 202 and / or the hatched portion 206 can be obtained by curing the composition according to the first embodiment.
By sealing the inside of the package (for example, the inside 202 and / or the inside 206 in FIG. 8) with the composition of the present invention, it is possible to increase the resistance to sulfidation and suppress the discoloration of the silver plating layer. Does not reduce brightness or transparency.
Further, when the interior of the package (for example, the interior 202 in FIG. 8 or the interior 202 and the interior 206) is sealed with the composition of the present invention, the optical semiconductor encapsulant has low hardness and small cure shrinkage. Can prevent peeling from the LED package and wire breakage.

4, the sealed optical semiconductor 300 according to the present embodiment includes a substrate 310, a blue LED chip 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. The blue LED chip 303 and the cured product 302 are disposed in the cavity. The cured product 302 is obtained by curing the composition according to the first embodiment. In this case, the composition according to the first embodiment may contain a fluorescent material or the like that can be used to cause the sealed optical semiconductor 300 to emit white light. In addition, the resin 306 can be formed using the composition according to the first embodiment.
The blue LED chip 303 is fixed on the substrate 310 with a mount member 301.
Each electrode (not shown) of the blue LED chip 303 is bonded to the substrate 310 and the inner lead 305 by a conductive wire 307.

  3 and 4, the LED chip has been described as a blue LED chip. However, an LED chip of three colors of red, green and blue is arranged in the cavity, and an LED chip of three colors of red, green and blue is arranged. One or two of these are selected and placed in the cavity, and a phosphor or the like that can be used to make the LED chip emit white light according to the selected LED color is added to the composition. be able to. A sealed optical semiconductor can be formed by filling the cavity with the composition according to the first embodiment by, for example, a potting method and heating.

  A case where the sealed optical semiconductor according to the present embodiment is used for an LED display will be described with reference to the accompanying drawings. FIG. 5 is a diagram schematically illustrating an example of an LED display using the sealed optical semiconductor according to the present embodiment. FIG. 6 is a block diagram of an LED display device using the LED display shown in FIG. Note that the LED display and the LED display device in which the sealed optical semiconductor according to the present embodiment is used are not limited to the attached drawings.

  In FIG. 5, an LED display (encapsulated optical semiconductor according to this embodiment) 400 has white LED chips 401 arranged in a matrix in a housing 404 and the white LED chips 401 are sealed with a cured product 406. In addition, a light shielding member 405 is arranged in a part of the housing 404. The composition according to the first embodiment can be used for the cured product 406. Moreover, the optical semiconductor sealing body which concerns on this embodiment as the white LED chip 401 can be used.

  In FIG. 6, the LED display device 500 includes an LED display 501 that uses white LEDs. The LED display 501 is electrically connected to a lighting circuit that is a drive circuit. A display or the like that can display various images by output pulses from the driving circuit can be provided. The driving circuit includes a RAM (Random, Access, Memory) 504 that temporarily stores input display data, and a gradation for lighting individual white LEDs to a predetermined brightness from the data stored in the RAM 504. A gradation control circuit (CPU) 503 that calculates a signal and a driver 502 that is switched by an output signal of the gradation control circuit (CPU) 503 and turns on a white LED are provided. A gradation control circuit (CPU) 503 calculates the lighting time of the white LED from the data stored in the RAM 504 and outputs a pulse signal. In addition, the optical semiconductor sealing body which concerns on this embodiment can be used for the LED display and LED display apparatus which can perform color display.

  Applications of the sealed optical semiconductor according to the present embodiment include, for example, automotive lamps (head lamps, tail lamps, directional lamps, etc.), household lighting fixtures, industrial lighting fixtures, stage lighting fixtures, displays, signals, Projector.

3. Examples Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited to these.

3.1. Production of component (C) 3.1.1. Manufacture of zirconium tributoxy mononaphthate (zirconium compound 2) 11.4 g (0.026 mol) of zirconium tetrabutoxide (manufactured by Kanto Chemical Co., Inc.) having a concentration of 87.5% by mass and naphthenic acid (manufactured by Tokyo Chemical Industry Co., Ltd., bonded to carboxy group) 6.6 g (0.026 mol) of the average number of carbon atoms of the hydrocarbon group to be produced is 15, and the neutralization value is 220 mg, and the same applies to a three-necked flask and stirred for about 2 hours at room temperature in a nitrogen atmosphere. It was a thing.
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 (zirconium metal salt) is designated as zirconium compound 2. The average number of carbon atoms of R ^{2 in} the naphthate group (R ² COO—) of the zirconium compound 2 is 15.

3.1.2. Manufacture of tributoxyhafnium 2-ethylhexanoate (hafnium compound 1) Hafnium tetrabutoxide (manufactured by Gelest) 0.026 mol and 2-ethylhexanoic acid 0.026 mol were charged into a three-necked flask, and at room temperature for about 2 hours in a nitrogen atmosphere. Stir to give 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 1450 to 1560 cm ⁻¹ was confirmed. The resultant composite is referred to as hafnium compound 1.

3.2. Evaluation As shown below, the transmittance, heat-resistant coloring stability, thickening after mixing, sulfidation resistance, cured state, and hardness were evaluated. The results are shown in Tables 1 and 2.
3.2.1. Transmittance evaluation test In the transmittance evaluation test, an initial cured product obtained by curing the thermosetting silicone resin composition for encapsulating a photosemiconductor for 12 hours under the condition of 150 ° C, and Ultraviolet / visible absorption spectrum measuring apparatus according to JIS K0115: 2004 for each cured product (each having a thickness of 2 mm) after a heat resistance test (a test in which the initial cured product is further heated for 10 days at 150 ° C.) The transmittance at a wavelength of 400 nm was measured using (manufactured by Shimadzu Corporation). 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

3.2.2. Heat-resistant coloring stability evaluation test An initial cured product obtained by curing a thermosetting silicone resin composition for encapsulating a photo-semiconductor for 4 hours under conditions of 150 ° C. and a heat resistance test (initial A test of heating a cured product for 10 days under the condition of 150 ° C.) Whether the cured product after the heat test was yellowed compared to the initial cured product for the cured product after that (both had a thickness of 2 mm) It was observed visually.

3.2.3. Thickening after mixing Viscosity (initial viscosity) of the composition under conditions of 25 ° C. immediately after mixing and producing the components shown in Tables 1 and 2 and the resulting composition under conditions of 25 ° C. The viscosity (composition after 24 hours) of the composition after 24 hours from the production of the stand was measured under the conditions of RH 50% and 25 ° C. using an E-type viscometer. Increase was confirmed.

3.2.4. Sulfide resistance Hardened sample preparation: A silicone resin composition containing components (A) to (D) is applied to silver plating to a thickness of about 1 mm and cured by heating at 150 ° C. for 12 hours to cure. A sample was made.
Test: Place about 10 g of iron sulfide ground in powder form (large excess with respect to 0.5 mmol of hydrochloric acid) on the bottom of a 10 L desiccator, and place an eye plate (not in contact with iron sulfide) above this iron sulfide. (With a through hole) was mounted in a desiccator and the cured sample was placed on the eye plate. Next, 0.25 mmol hydrogen sulfide (concentration: about 500 ppm, theoretical value 560 ppm) was generated by dropping 0.5 mmol hydrochloric acid into a large excess of iron sulfide (reaction formula: FeS + 2HCl → FeCl ₂ + H _2). S). The silver discoloration was confirmed visually every hour. In Table 1, the case where the discoloration was not confirmed by visual observation was “◯”, and the case where the discoloration was confirmed by visual observation was “x”. In the present invention, the concentration of hydrogen sulfide in the sulfidation resistance test is a theoretical value of 560 ppm. In the sulfidation resistance test, 0.5 mmol of hydrochloric acid is added, so that 0.25 mmol (0.25 mmol × 22.4 liters = 5.6 ml) of hydrogen sulfide is generated. Therefore, the concentration of hydrogen sulfide is [5.6 ml / 10 liter (desiccator volume)] × 10 ⁶ = 560 ppm.

3.2.5. Cured state A cured product obtained by curing the silicone resin composition for encapsulating heat-curable optical semiconductor obtained as described below at 150 ° C. for 12 hours was observed with a tentacle. In Table 1, for example, “◯” indicates that the surface tack was not confirmed in the state of the cured product, and “x” indicates that the surface tack, gel, and uncured were confirmed in the state of the cured product.

3.2.6. Hardness The JIS A hardness of a sample (initial cured product obtained by curing a thermosetting silicone resin composition for encapsulating an optical semiconductor for 12 hours under a condition of 150 ° C.) was obtained according to JIS K6523: The measurement was performed according to the provisions of 2006.

3.3. Sample preparation (for evaluation of transmittance, heat-resistant coloring stability, cured state and hardness)
Production of a sample will be described below with reference to the accompanying drawings.
FIG. 7: is sectional drawing which represents typically the type | mold used in order to harden the silicone resin composition for thermosetting optical semiconductor sealing of this invention in an Example.
In FIG. 7, 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, heat-resistant coloring stability, cured state, and hardness.

3.4. Manufacture of silicone resin composition for heat-curable optical semiconductor encapsulation The components shown in Table 1 and Table 2 below are uniformly mixed in the amounts (unit: parts by mass) shown in the same table using a vacuum stirrer. A silicone resin composition for semiconductor encapsulation was produced.
The compositions of Examples 1 to 3 in Table 1 contain the component (D). On the other hand, the compositions of Comparative Examples 1 to 4 and 6 in Table 1 do not contain the component (D). Comparative Examples 1 and 2 contain the same components as in Examples 1 and 2 except that they do not contain the component (D), and Comparative Examples 3 and 4 contain an aluminum compound or a magnesium compound in place of the component (D), respectively. contains. Comparative Example 6 is an example using an epoxy resin.

Each component shown in Table 1 and Table 2 is as follows.
(A) Polysiloxane 1: Polydimethylsiloxane-α, ω-diol (weight average molecular weight 6,000), trade name x-21-5841, manufactured by Shin-Etsu Chemical Co., Ltd. (A) Polysiloxane 2: Polydimethylsiloxane -Α, ω-diol, trade name x--21-5848 (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 110,000)
Epoxy resin: bisphenol A diglycidyl ether epoxy liquid resin (trade name: EP4100, manufactured by Asahi Denka Kogyo)
(B) Silane compound 1: γ-methacryloxypropyltrimethoxysilane (molecular weight 248), trade name KBM503, manufactured by Shin-Etsu Chemical Co., Ltd. (B) Silane compound 2: silicone alkoxy oligomer [R _m Si (OR ′) _n O _{(4-mn) / 2 wherein} 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, and 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 3: 100 parts by weight of dimethylpolysiloxane (ss70, manufactured by Shin-Etsu Chemical Co., Ltd., Mw = 18000) having silanol groups at both ends in a three-necked separable flask, tetramethoxysilane (KBM-04) 20 parts by weight, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.01 parts by weight of 2-ethylhexanoate tin were added and stirred uniformly, and the mixture was stirred and reacted at 80 ° C. for about 8 hours under reduced pressure. Thereafter, the pressure was reduced at 130 ° C. for 4 hours in order to remove excess tetramethoxysilane. The disappearance of silanol peaks was confirmed by proton NMR, and silane compound 3 having trimethoxysilyl at both ends (trimethoxysilane oligomers at both ends, the main chain being diorganopolysiloxane, both ends trimethoxylyl Dimethylpolysiloxane). The weight average molecular weight of silane compound 3 (expressed in terms of polystyrene by gel permeation chromatography (GPC) using chloroform as a solvent) was 35,000.
(C) Zirconium compound 1: Zirconyl naphthenate (trade name: Naphtex zirconium, manufactured by Nippon Chemical Industry Co., Ltd.)
(C) Zirconium compound 2: zirconium compound 2 produced as described above
(C) hafnium compound 1: tributoxy hafnium 2-ethylhexanoate prepared as described above (C) hafnium compound 2: hafnium 2,4 pentadionate, manufactured by Gelest Co. (D) zinc compound 1: zinc bis Acetylacetonate, manufactured by Kanto Chemical Co., Ltd. (D) Zinc compound 2: Zinc bis 2-ethylhexanoate, manufactured by Hope Pharmaceutical Co., Ltd. Aluminum compound: Ethyl acetate aluminum diisopropylate (trade name: AL-CH, manufactured by Kawaken Fine Chemical Co., Ltd.)
Magnesium compound: Magnesium bis (2-ethylhexanoate) (trade name: Nikka Octix Magnesium, manufactured by Nippon Chemical Industry Co., Ltd.)
Cationic polymerization catalyst: BF ₃ · Et ₂ O (BF ₃ ethyl etherate complex, manufactured by Tokyo Chemical Industry Co., Ltd.)

3.5. Results As is apparent from the results shown in Tables 1 and 2, the cured products obtained using the compositions of Comparative Examples 1 to 4 and Comparative Examples 7 to 10 that do not contain the component (D) are inferior in sulfur resistance. It was. Moreover, the hardened | cured material obtained using the composition of the comparative example 5 which does not contain (C) component became gelatinous by heating. Furthermore, the hardened | cured material obtained using the composition of the comparative example 6 containing an epoxy resin gelatinized, and was inferior to the transmittance | permeability.
On the other hand, the cured products obtained using the compositions of Examples 1 to 6 and Reference Example 1 are excellent in sulfidation resistance, and retain transparency because of high transmittance and transmittance retention. It can be understood that the viscosity after mixing is low and the pot life is excellent. As is clear from the results of Example 6, a zirconium compound and a hafnium compound can be used in combination as the component (D).

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, 800 Encapsulated optical semiconductor of the present invention 201, 301 Mount member 202 Cavity, cured product 203, 303 Blue LED chip 302 Cured product 204 Package 206 Diagonal portion 306 Resin 207, 307 Conductive wire 209 External electrode 210 , 310 Substrate 305 Inner lead 400, 501 LED display 401 White LED chip 404 Case 405 Light shielding member 406 Cured material 500 LED display device 502 Driver 501 LED display 503 Gradation control means (CPU)
504 Image data storage means (RAM) 600 Encapsulated optical semiconductor of the present invention 601 LED chip 603 Cured product 605 point 607 Surface to which point 605 belongs 609 Substrate T Thickness of cured product 603 810 Silver plating layer

Claims (7)

(A) component; 100 mass parts of polysiloxanes having two or more silanol groups in one molecule;
(B) component; 0.1 to 2000 parts by mass of a silane compound having two or more alkoxy groups bonded to a silicon atom in one molecule;
(C) component; a zirconium compound and / or a hafnium compound having an organic group;
Component (D); a zinc compound;
Contain,
The zirconium compound is a compound represented by the following formula (1) and / or a compound represented by the following formula (2), and the hafnium compound is a compound represented by the following formula (I):
The silicone resin composition for heat-curable optical semiconductor encapsulation , wherein the component (D) is a complex and / or metal salt containing zinc .
... (1)
(In the formula, R ¹ is a hydrocarbon group having 1 to 18 carbon atoms.)
... (2)
(In the formula, R ² is the same or different, a hydrocarbon group having 3 to 16 carbon atoms having a cyclic structure, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, A 2-ethylhexyl group, a nonyl group, a decyl group or an undecyl group, and the hydrocarbon group having 3 to 16 carbon atoms having the cyclic structure may have an aliphatic hydrocarbon group in addition to the cyclic structure, R ³ is the same or different hydrocarbon group having 1 to 18 carbon atoms, and m is an integer of 1 to 3)
[In the formula (I), n is an integer of 1 to 4, R ¹ is ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, octyl, 2-ethylhexyl, nonyl. Group, a decyl group, an undecyl group, or a hydrocarbon group having a cyclic structure, and the hydrocarbon group having the cyclic structure may have an aliphatic hydrocarbon group in addition to the cyclic structure, and R ² represents carbon It is a C1-C18 alkyl group. ]   The thermosetting silicone for sealing an optical semiconductor according to claim 1, wherein the component (C) is contained in an amount of 0.001 to 1 part by mass with respect to a total of 100 parts by mass of the component (A) and the component (B). Resin composition. Said containing 0.001 to 5 parts by mass relative to (D) wherein the component (A) component and the (B) total 100 parts by mass of the component, heat-curable optical semiconductor encapsulation according to claim 1 or 2 Silicone resin composition. The cyclic structure in the formula (2) or the cyclic structure in the formula (I) is an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. A silicone resin composition for encapsulating heat-curable optical semiconductors as described in 1. The thermosetting silicone resin for encapsulating a thermosetting optical semiconductor according to claim 4 , wherein the alicyclic hydrocarbon group is at least one selected from the group consisting of a cycloalkyl group, a naphthene ring, and a condensed ring hydrocarbon group. Composition. The said (A) component contains the linear organopolysiloxane of the weight average molecular weight 1,000-1,000,000 represented by following formula (3), In any one of Claims 1-5. The thermosetting silicone resin composition for sealing an optical semiconductor.
... (3)
(In the formula, R ⁴ is the same or different and represents an alkyl group or aryl group having 1 to 18 carbon atoms, and n is an integer of 1 or more.) The silicone resin composition for encapsulating heat-curable optical semiconductor according to any one of claims 1 to 6 is applied to an LED chip, and the LED chip is heated to form the silicone resin composition for encapsulating thermosetting optical semiconductor. An optical semiconductor encapsulant obtained by curing an object and encapsulating the LED chip.