JP5407258B2 - Adhesive silicone resin composition for sealing optical semiconductor and optical semiconductor sealing body using the same - Google Patents

Description

  The present invention relates to a silicone resin composition for sealing an adhesive optical semiconductor and an optical semiconductor sealing 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.
A room temperature-curable organopolysiloxane containing an organopolysiloxane having two silanol groups, a compound having two or more hydrolyzable groups bonded to a silicon atom in one molecule, and an organic zirconium compound Compositions have been proposed (for example, Patent Documents 2 and 3).
It has also been proposed to mix and heat a condensation catalyst to diorganopolysiloxane having two silanol groups and silane having three or more alkoxy groups (for example, Patent Documents 4 and 5).
In addition, room temperature moisture-curable silicone rubber compositions containing specific diorganopolysiloxanes, disilaalkane compounds and curing catalysts have been proposed (for example, Patent Documents 6 and 7).

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 JP 2007-119768 A JP 2003-221506 A

However, an organopolysiloxane composition containing a conventional organopolysiloxane having two silanol groups, a compound having two or more hydrolyzable groups bonded to a silicon atom in one molecule, and an organozirconium compound The inventor of the present application has found that although the product is room temperature moisture-curing and thermosetting, the curability is poor, the viscosity is increased during the operation, the transparency is lost, and the workability is poor.
A composition comprising an organopolysiloxane having two silanol groups, a silicon compound having two or more hydrolyzable groups bonded to a silicon atom in one molecule, and an aluminum compound as a condensation catalyst The inventors of the present invention have found that the cured product is fragile and the cured product becomes brittle in the resulting cured product.
In addition, the inventor of the present application also discloses an organopolysiloxane having two silanol groups, a silicon compound having two or more hydrolyzable groups bonded to a silicon atom in one molecule, and a conventional condensation such as an aluminum system. When a composition containing a catalyst is cured at room temperature or by heating to obtain a polysiloxane as a cured product, when the obtained cured product is exposed to a high temperature, the siloxane bond of the polysiloxane is broken. It has been found that the cured product becomes brittle. Further, the cut portion forms a cyclic polysiloxane such as a six-membered ring, and the cyclic polysiloxane bleeds out to the surface of the cured product or outside the system, and the shape stability of the cured product is greatly impaired.
The inventor of the present application also includes a polysiloxane having two or more silanol groups in one molecule and a silicon compound having two or more alkoxy groups and / or hydroxy groups bonded to a silicon atom in one molecule. The present inventors have previously found that a composition containing a zirconium metal salt is excellent in heat-resistant coloring stability, workability, and curability, and can suppress heat loss. However, this composition has a problem of poor adhesion after the pressure cooker test.
Then, this invention aims at providing the adhesive resin semiconductor sealing silicone resin composition which is excellent in the adhesiveness after a pressure cooker test, heat-resistant coloring stability, workability | operativity, and curability, and can suppress a heat loss. To do.

As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that heat loss of the cured product can be suppressed by using a zirconium metal salt.
(A) 100 parts by mass of polysiloxane having two or more silanol groups in one molecule, and (B) two or more alkoxy groups and / or hydroxy groups bonded to silicon atoms in one molecule. A composition containing 0.1 to 100 parts by mass of a silicon compound, (C) 0.001 part by mass or more and less than 0.1 part by mass of a zirconium metal salt, and (D) a bis (alkoxysilyl) alkane is pressure. The present invention has been completed by finding that it can be an adhesive silicone resin composition for encapsulating an optical semiconductor that is excellent in adhesiveness, heat-resistant coloring stability, workability, and curability after the cooker test, and that can suppress heat loss.

That is, this invention provides the following 1-9.
1. (A) 100 parts by mass of polysiloxane having two or more silanol groups in one molecule;
(B) 0.1 to 100 parts by mass of a silicon compound having two or more alkoxy groups and / or hydroxy groups bonded to a silicon atom in one molecule;
(C) zirconium metal salt 0.001 parts by mass or more and less than 0.1 parts by mass;
(D) A silicone resin composition for sealing an adhesive optical semiconductor containing bis (alkoxysilyl) alkane.
2. 2. The silicone resin composition for sealing an adhesive optical semiconductor according to 1 above, wherein the zirconium metal salt is represented by the following formula (I).
(In the formula, R represents a hydrocarbon group.)
3. 3. The silicone resin composition for sealing an adhesive optical semiconductor according to 1 or 2 above, wherein the bis (alkoxysilyl) alkane is represented by the following formula (A).
(R ¹ O) ₃ —Si—R ² —Si— (OR ¹ ) ₃ (A)
[In Formula (A), R ¹ is an alkyl group, R ² is an alkylene group having 2 to 10 carbon atoms, and R ¹ may be the same or different. ]
4). 4. The silicone resin for sealing an adhesive optical semiconductor according to any one of 1 to 3 above, wherein the polysiloxane is a linear organopolydimethylsiloxane-α, ω-diol having a molecular weight of 1,000 to 1,000,000. Composition.
5. 5. The silicone resin composition for sealing an adhesive optical semiconductor according to any one of 1 to 4, wherein the silicon compound is a compound represented by the following formula (2) and / or a compound represented by the formula (3): .
Si (OR ¹ ) _n R ² _4-n (2)
R _m Si (OR ′) _n O _{(4-mn) / 2} (3)
[In Formula (2), n is 2, 3 or 4, R ¹ is a hydrogen atom or an alkyl group, and R ² is an organic group.
In the formula (3), R is an alkyl group having 1 to 6 carbon atoms, an alkenyl group or an aryl group, R ′ is a hydrogen atom and 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 <2 . ]
6). The silicone resin composition for sealing an adhesive optical semiconductor according to any one of 1 to 5 above, wherein the amount of the bis (alkoxysilyl) alkane is 0.1 to 2 parts by mass with respect to 100 parts by mass of the polysiloxane. object.
7). The bis (alkoxysilyl) alkane is 1,2-bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,7-bis (trimethoxysilyl) heptane, 1,8-bis. Any one of the above 1 to 6, which is at least one selected from the group consisting of (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane and 1,10-bis (trimethoxysilyl) decane. Adhesive silicone resin composition for optical semiconductor encapsulation.
8). The silicone resin composition for sealing an adhesive optical semiconductor according to any one of the above 1 to 7, wherein the zirconium metal salt is one or both of zirconyl dioctylate and zirconyl naphthenate.
9. The optical semiconductor sealing body by which the LED chip is sealed with the silicone resin composition for adhesive optical semiconductor sealing in any one of said 1-8.

The silicone resin composition for encapsulating an adhesive optical semiconductor of the present invention is excellent in adhesiveness, heat-resistant coloring stability, workability, and curability after the pressure cooker test, and can suppress heat loss.
The sealed optical semiconductor of the present invention is excellent in adhesiveness, heat-resistant coloring stability and curability after the pressure cooker test, and has low loss on heating.

The present invention will be described in detail below.
The silicone resin composition for sealing an adhesive optical semiconductor of the present invention comprises (A) 100 parts by mass of polysiloxane having two or more silanol groups in one molecule, and (B) a silicon atom bonded in one molecule. 0.1 to 100 parts by mass of a silicon compound having two or more alkoxy groups and / or hydroxy groups, (C) 0.001 part by mass or more and less than 0.1 part by mass of a zirconium metal salt, and (D) bis It is a composition containing (alkoxysilyl) alkane.
In addition, the silicone resin composition for sealing an adhesive optical semiconductor of the present invention may be hereinafter referred to as “the composition of the present invention”.

(A) The polysiloxane will be described below.
The polysiloxane contained in the composition of the present invention is a polysiloxane having two or more silanol groups in one molecule.
One preferred embodiment of the polysiloxane is an organopolysiloxane.
Polysiloxane is a straight-chain organopolydimethylsiloxane (straight-chain organopolydimethylsiloxane) in which two silanol groups are bonded to both ends from the viewpoint of excellent heat-resistant coloring stability and curability and lower heat loss. Polydimethylsiloxane-α, ω-diol) is preferred.
Examples of the polysiloxane include those represented by the following formula (1).

In formula (1), m is preferably an integer of 10 to 15,000 from the viewpoint of excellent workability and crack resistance.

Polysiloxane is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.
The molecular weight of the polysiloxane is preferably 1,000 to 1,000,000 from the viewpoint that the curing time and the pot life are appropriate lengths, the curability is excellent, and the cured product properties are excellent. More preferably, it is ~ 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.
Polysiloxanes can be used alone or in combination of two or more.

(B) A silicon compound is demonstrated below.
The silicon compound contained in the composition of the present invention is not particularly limited as long as it is a compound having two or more alkoxy groups and / or hydroxy groups bonded to a silicon atom in one molecule.
For example, a compound having one silicon atom in one molecule and having two or more alkoxy groups and / or hydroxy groups bonded to the silicon atom (hereinafter, this compound may be referred to as “silicon compound B1”), Organopolysiloxane compound having two or more alkoxy groups and / or hydroxy groups having two or more silicon atoms in one molecule, the main skeleton being a polysiloxane skeleton, and bonded to the silicon atom (hereinafter referred to as this organo The polysiloxane compound may be referred to as “silicon compound B2”).

The silicon compound can have one or more organic groups in one molecule.
As an organic group which a silicon compound can have, the hydrocarbon group which may contain at least 1 sort (s) 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 silicon compound B1, what is represented by following formula (2) is mentioned, for example.
Si (OR ¹ ) _n R ² _4-n (2)
In formula (2), n is 2, 3 or 4, R ¹ is a hydrogen atom or an alkyl group, and R ² is an organic group. An organic group is synonymous with what was described regarding the organic group of a silicon compound.

Examples of the silicon 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, Tetraalkoxysilane hydrolyzate; methyl trihydroxysilane, ethyltrihydroxysilane, phenyltrihydroxysilane Hydroxy silane; tetrahydroxy-silane; .gamma. (meth) acryloxy propyl trimethoxy silane, (meth) acryloxy sialic quilt trialkoxysilane such as .gamma. (meth) acryloxy propyl triethoxy silane.
In the present invention, (meth) acryloxytrialkoxysilane means acryloxytrialkoxysilane or methacryloxytrialkoxysilane. The same applies to (meth) acrylate groups and (meth) acryloxyalkyl groups.

As silicon compound B2, the compound represented by Formula (3) is mentioned, for example.
R _m Si (OR ′) _n O _{(4-mn) / 2} (3)
In the formula (3), R is an alkyl group having 1 to 6 carbon atoms, an alkenyl group or an aryl group, R ′ is a hydrogen atom and 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 <2 .
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 1 to 6 carbon atoms, and specific examples include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 2-methyl-1-propenyl group, and a 2-methylallyl group. . Examples of the aryl group include a phenyl group and a naphthyl group.
In the compound represented by the formula (3), R ′ can contain an acyl group in addition to a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. 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 silicon compound B2 include silicone alkoxy oligomers such as methylmethoxy oligomer.
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 the compound represented by the formula (3), and specific examples of the methyl methoxy oligomer include those represented by the following formula (4).
In formula (4), R ″ is a methyl group, a is an integer of 1 to 1000, and b is an integer of 0 to 1000.
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.).

  From the viewpoint that the silicon compound is excellent in curability and heat cracking resistance, those represented by the formulas (2) and (3) are preferable.

  From the viewpoint of excellent curability and heat-resistant coloring stability, silicon compounds are tetraalkoxysilanes such as tetraethoxysilane; trialkoxy (meth) acryloxyalkyls such as γ- (meth) acryloxypropyltrimethoxysilane. Silane; methyl methoxy oligomer is preferred.

The molecular weight of the silicon compound is preferably from 100 to 1,000,000, preferably from 100 to 10,000, from the viewpoint that curing time and pot life are appropriate lengths, excellent curability, and compatibility. More preferably.
In the present invention, when the silicon compound is silicon compound B2, the molecular weight thereof is a polystyrene-reduced weight average molecular weight by gel permeation chromatography (GPC) using chloroform as a solvent.
The production of the silicon compound is not particularly limited, and examples thereof include conventionally known ones. A silicon compound can be used individually or in combination of 2 types or more, respectively.

  The amount of the silicon compound is 0.1 to 100 parts by mass, preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the polysiloxane, from the viewpoint of excellent crack resistance and compatibility. It is more preferably 1 to 10 parts by mass.

The zirconium metal salt will be described below.
The zirconium metal salt contained in the composition of the present invention is a salt having a zirconium atom as a metal.
The zirconium atom of the zirconium metal salt preferably forms zirconyl [(Zr = O) ²⁺ ] from the viewpoint of being excellent in heat loss and curability.
The acid used for producing the zirconium metal salt is not particularly limited. For example, carboxylate is mentioned. Examples of the carboxylate include aliphatic carboxylic acids such as acetic acid, propionic acid, octylic acid (2-ethylhexanoic acid), nonanoic acid, stearic acid, and lauric acid; alicyclic rings such as naphthenic acid and cyclohexanecarboxylic acid Carboxylic acids of the formula; aromatic carboxylic acids such as benzoic acid.
The zirconium metal salt is preferably a carboxylate salt, more preferably an aliphatic carboxylate salt or an alicyclic carboxylate salt, from the viewpoint that the loss on heating can be further suppressed. More preferably.

Examples of the zirconium metal salt include a zirconyl metal salt represented by the following formula (I) and a zirconium metal salt represented by the formula (II).
In the formula, R represents a carbon hydride group. The hydrocarbon group as R represents a carboxylic acid residue. R may be the same or different.

The zirconyl metal salt is preferably a compound represented by the formula (I) from the viewpoint that the loss on heating can be further suppressed and the curability is excellent.
Since the zirconyl metal salt represented by the formula (I) has a structure of Zr = O, it is more excellent in curability than the zirconium metal salt represented by the formula (II).
Examples of the compound represented by the formula (I) include aliphatic carboxylates such as zirconyl dioctylate and zirconyl dineodecanoate; alicyclic carboxylates such as zirconyl naphthenate and zirconyl cyclohexane; and zirconyl benzoate. And aromatic carboxylates.
Zirconium metal salts can be used alone or in combination of two or more.
The zirconium metal salt is preferably one or both of zirconyl dioctylate and zirconyl naphthenate from the viewpoint that the loss on heating can be further suppressed.

The amount of the zirconium metal salt is 0.001 part by mass or more and less than 0.1 part by mass with respect to 100 parts by mass of the polysiloxane from the viewpoint that the loss on heating can be suppressed, thereby further suppressing the loss on heating. From the viewpoint of being able to do, it is preferably 0.005 to 0.09 parts by mass, and more preferably 0.01 to 0.05 parts by mass.
The zirconium metal salt is considered to act as a Lewis acid during the initial heating for curing the composition and the heating after the initial curing, and promote the crosslinking reaction between the polysiloxane and the silicon compound.

(D) The bis (alkoxysilyl) alkane will be described below.
The bis (alkoxysilyl) alkane contained in the composition of the present invention is an alkane having two silyl groups having at least one alkoxy group.
The composition of this invention is excellent in the adhesiveness after a pressure cooker test by containing bis (alkoxy silyl) alkane.

The bis (alkoxysilyl) alkane preferably has 2 or 3 alkoxy groups bonded to one silyl group from the viewpoint of superior adhesiveness after the pressure cooker test.
Examples of the bis (alkoxysilyl) alkane include compounds represented by the following formula (A).
(R ¹ O) ₃ —Si—R ² —Si— (OR ¹ ) ₃ (A)
[In Formula (A), R ¹ is an alkyl group, R ² is an alkylene group having 2 to 10 carbon atoms, and R ¹ may be the same or different. ]

Examples of the alkyl group include a methyl group and an ethyl group.
Examples of the alkylene group having 2 to 10 carbon atoms include an ethylene group, a group obtained by removing two hydrogen atoms from propane, a group obtained by removing two hydrogen atoms from butane, a group obtained by removing two hydrogen atoms from pentane, and hexane. A group obtained by removing two hydrogen atoms from heptane, a group obtained by removing two hydrogen atoms from octane, a group obtained by removing two hydrogen atoms from octane, a group obtained by removing two hydrogen atoms from nonane, and two hydrogen atoms removed from decane Groups.

From the viewpoint that bis (alkoxysilyl) alkane is superior in adhesion after the pressure cooker test, 1,2-bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,7-bis At least one selected from the group consisting of (trimethoxysilyl) heptane, 1,8-bis (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane and 1,10-bis (trimethoxysilyl) decane The seed is preferred, and 1,6-bis (trimethoxysilyl) hexane is more preferred.
Bis (alkoxysilyl) alkanes can be used alone or in combination of two or more.

  The amount of the bis (alkoxysilyl) alkane is preferably 0.1 to 2 parts by mass, and 0.5 to 1 part by mass with respect to 100 parts by mass of the polysiloxane, from the viewpoint that the adhesiveness after the pressure cooker test is excellent. It is more preferable that

  The composition of the present invention is superior in adhesion after the pressure cooker test, excellent in heat-resistant coloration stability, and can suppress heat loss more, so that polysiloxane, silicon compound, zirconium metal salt, bis (alkoxy) A composition comprising silyl) alkane is preferred.

In addition to polysiloxane, silicon compound, zirconium metal salt, and bis (alkoxysilyl) alkane, the composition of the present invention may further contain additives as necessary within the range not impairing the object and effect of the present invention. Can do.
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 Examples include property-imparting agents, phosphorus peroxide decomposers, pigments, metal deactivators, and physical property modifiers. Various additives are not particularly limited. For example, a conventionally well-known thing is mentioned.

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

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

The composition of the present invention is not particularly limited for its production. For example, it can be produced by mixing polysiloxane, a silicon compound, a zirconium metal salt, a bis (alkoxysilyl) alkane, and an additive that can be used as necessary.
The composition of the present invention can be produced as a one-pack type or a two-pack type. In the case where the composition of the present invention is made into a two-component type, it is mentioned as one of preferred embodiments that it has a first liquid containing polysiloxane and a zirconium metal salt and a second liquid containing a silicon compound. . The additive can be added to one or both of the first liquid and the second liquid. The bis (alkoxysilyl) alkane can be added to one or both of the first liquid and the second liquid.

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

The composition of the present invention can be cured by heating.
The heating temperature is excellent due to loss on heating, excellent curability, the curing time and pot life can be set to appropriate lengths, the by-product alcohol by the condensation reaction can be prevented from foaming, and the cured product From the viewpoint that cracks can be suppressed and the smoothness, moldability, and physical properties of the cured product are excellent, curing is preferably performed at about 80 ° C to about 150 ° C, and more preferably about 150 ° C.
When the heating temperature is as described above, the composition of the present invention can be cured under mild conditions, and foaming of the cured product can be suppressed by alcohol which is a by-product of the condensation reaction.
In the heating, the heating is preferably 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 obtained by heating and curing the composition of the present invention can maintain transparency for long-term use of LEDs (in particular, white LEDs), and adhesion after a pressure cooker test. Excellent heat-resistant coloring stability and heat-cracking resistance, and low heat loss.

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

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

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

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

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

Next, the sealed optical semiconductor of the present invention will be described below.
The encapsulated optical semiconductor of the present invention is an encapsulated optical semiconductor in which LED chips are encapsulated with the silicone resin composition for encapsulating an adhesive optical semiconductor of the present invention.
As a manufacturing method of the optical semiconductor sealing body of this invention, the silicone resin composition for adhesive optical semiconductor sealing of this invention is provided to an LED chip, the said LED chip is heated, and the said adhesive optical semiconductor sealing is carried out, for example. Examples include those for curing the silicone resin composition for sealing the LED chip.

If the composition used for the optical semiconductor sealing body of this invention is a silicone resin composition for adhesive optical semiconductor sealing of this invention, it will not restrict | limit in particular.
By using the adhesive resin semiconductor sealing silicone resin composition of the present invention as a composition in the optical semiconductor encapsulant of the present invention, the optical semiconductor encapsulant of the present invention has adhesiveness after a pressure cooker test, It has excellent heat-resistant coloring stability against heat generation, light emission, and the like from the LED chip, and can suppress heat loss due to heat generation from the LED chip and heating at the time of manufacturing the optical semiconductor sealing body.

The LED chip used for the sealed optical semiconductor of the present invention 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 in the sealed optical semiconductor of the present invention is not particularly limited with respect to the emission color. For example, white, blue, red, and green are mentioned. From the viewpoint that the sealed optical semiconductor of the present invention is excellent in heat-resistant coloring stability and can suppress heat loss even when exposed to a high temperature due to heat generated from the LED chip for a long time. Can be applied.
The kind of LED chip is not particularly limited, and examples thereof include a high power LED, a high luminance LED, and a general luminance LED.

  As a form of the optical semiconductor sealing body of the present invention, for example, a cured product directly sealing an LED chip, a shell type, a surface mounting type, a plurality of LED chips or an optical semiconductor sealing body and / or Or what has sealed the surface is mentioned.

The sealed optical semiconductor of the present invention will be described below with reference to the accompanying drawings. The sealed optical semiconductor of the present invention is not limited to the attached drawings. FIG. 1 is a top view schematically showing an example of the sealed optical semiconductor of the present invention, and FIG. 2 is a sectional view schematically showing an AA cross section of the sealed optical semiconductor shown in FIG.
In FIG. 1, reference numeral 600 denotes a sealed optical semiconductor of the present invention, and the sealed optical semiconductor 600 includes an LED chip 601 and a cured product 603 that seals the LED chip 601. The composition of the present invention 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.
From the viewpoint of ensuring transparency and excellent sealing properties, the sealed optical semiconductor of the present invention preferably has a thickness (T in FIG. 2) of 0.1 mm or more, and is 0.5 to 1 mm. More preferably.

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

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 of the present invention. In this case, the composition of the present invention can contain a fluorescent material or the like that can be used to cause 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 of the present invention.
Alternatively, the cavity 202 can be filled with another composition, and the hatched portion 206 can be filled with the composition of the present invention.

In FIG. 4, the sealed optical semiconductor 300 of the present invention 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 of the present invention. In this case, the composition of the present invention may contain a fluorescent material or the like that can be used to cause the sealed optical semiconductor 300 to emit white light. Further, the resin 306 can be formed using the composition of the present invention.
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 obtained by filling the cavity with the composition of the present invention by, for example, a potting method and heating.

  A case where the sealed optical semiconductor of the present invention is used for an LED display will be described with reference to the accompanying drawings. FIG. 5 is a diagram schematically showing an example of an LED display using the sealed optical semiconductor of the present invention. FIG. 6 is a block diagram of an LED display device using the LED display shown in FIG. In addition, the LED display and LED display apparatus in which the optical semiconductor sealing body of this invention is used are not limited to attached drawing.

  In FIG. 5, an LED display (encapsulated optical semiconductor of the present invention) 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. A light shielding member 405 is arranged in a part of the housing 404. The composition of the present invention can be used for the cured product 406. Further, the sealed optical semiconductor of the present invention can be used as the white LED chip 401.

  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 of this invention can be used for the LED display and LED display apparatus which can perform color display.

  Applications of the sealed optical semiconductor of the present invention include, for example, automotive lamps (head lamps, tail lamps, directional lamps, etc.), household lighting fixtures, industrial lighting fixtures, stage lighting fixtures, displays, signals, and projectors. Can be mentioned.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
1. Evaluation As shown below, initial curing state, transmittance, heat-resistant coloring stability, loss on heating, crack, viscosity, curability, and adhesion after a pressure cooker test were evaluated. The results are shown in Tables 1 and 2.
(1) Initially cured state An initial cured product (thickness is 2 mm) obtained by curing the silicone resin composition for sealing an adhesive optical semiconductor obtained as described below at 150 ° C. for 4 hours. The initial cured state (transparency, coloring state) was visually confirmed.
(2) Transmittance evaluation test In the transmittance evaluation test, an initial cured product obtained by curing the adhesive resin-sealing silicone resin composition obtained as follows for 4 hours at 150 ° C. , And a heat-resistant test (a test in which the initial cured product is further heated at 150 ° C. for 10 days), and a cured product (both having a thickness of 2 mm), respectively, UV / visible absorption spectrum measurement according to JIS K0115: 2004 The transmittance at a wavelength of 400 nm was measured using an apparatus (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.
Retention rate (%) = (transmittance after heat resistance test) / (initial transmittance) × 100

(3) Heat-resistant coloring stability evaluation test An initial cured product obtained by curing the silicone resin composition for sealing an adhesive optical semiconductor obtained as described below at 150 ° C. for 4 hours, and a heat test About the hardened | cured material (all are thickness 2mm) after (the test which heats an initial stage hardened | cured material for 10 days on 150 degreeC conditions) the hardened | cured material after a heat test turned yellow compared with the initial hardened | cured material. It was observed visually.
(4) Heat Loss Evaluation Test In the heat loss evaluation test, an initial cured product obtained by curing the adhesive resin-sealing silicone resin composition for 4 hours under the condition of 150 ° C. is further 1,000 at 200 ° C. Heated for hours. The weight of the cured product was measured using a weigh scale for the initial cured product and the cured product after the heat loss evaluation test.
The loss on heating was determined by the following formula.
Heat loss (%) = 100− (weight of cured product after weight loss evaluation test / weight of initial cured product) × 100
When the heating loss value is 20% or less, it is practical as a silicone resin composition for sealing an adhesive optical semiconductor.
(5) Presence or absence of cracks Initial cured products obtained by curing the silicone resin composition for sealing an adhesive optical semiconductor obtained as described below at 150 ° C. for 4 hours were each visually cured. The presence or absence of cracks was confirmed.

(6) Viscosity Viscosity (initial viscosity) of the composition under the condition of 25 ° C. immediately after production by mixing the components shown in Table 1 and 24 hours after production when the produced composition is placed under the condition of 25 ° C. The viscosity of the composition after the passage of time was measured using an E-type viscometer under the conditions of RH 50% and 25 ° C.
(7) Curability The time required for the adhesive photo-semiconductor sealing silicone resin composition to be cured under the conditions of 150 ° C. for the adhesive photo-semiconductor sealing silicone resin composition obtained as follows. evaluated.
Evaluation criteria for curability were “◯” when cured within 4 hours, “Δ” when cured for more than 4 hours but less than 24 hours, and “X” when not cured after 24 hours.
(8) Adhesiveness after pressure cooker test Using a silicone resin spacer 25 mm long x 10 mm wide x 1 mm thick, the obtained silicone resin composition for sealing an optical semiconductor is poured onto an adherend: alumina plate. And heated at 150 ° C. for 4 hours. The obtained laminate was placed under conditions of 121 ° C. and 100% RH for 24 hours using a pressure cooker tester. A hand peel test was performed using the cured product after the pressure cooker test, and the adhesion after the pressure cooker test was evaluated by the fracture form of the cured product after the test.
The evaluation was “CF” when the fracture mode was cohesive fracture and “AF” when the fracture mode was interfacial fracture.

2. Sample Preparation (1) Sample Preparation Sample preparation 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 adhesive 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.

(2) Manufacture of sample The mold 8 filled with the composition 6 is put in an electric oven and heated under the above-mentioned evaluation conditions to cure the composition 6, and a cured product 6 (initial cured product) having a thickness of 2 mm. Manufactured.
The obtained cured product 6 was used as a sample for evaluation.

3. Production of Silicone Resin Composition for Adhesive Optical Semiconductor Encapsulation The components shown in Tables 1 and 2 below are uniformly mixed in the amounts (unit: parts by mass) shown in the same table using a vacuum agitator. A silicone resin composition for semiconductor encapsulation was produced.

Details of the components shown in Table 1 are as follows.
(A) Polysiloxane 1: Polydimethylsiloxane-α, ω-diol (weight average molecular weight 1,000), m = 11 in formula (1), trade name x-21-5841, manufactured by Shin-Etsu Chemical Co., Ltd. (A) Polysiloxane 2: trade name x-21-9701, manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 3000
(A) Polysiloxane 3: trade name ss-10, manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 40000
(B) silicon compound 1: γ-methacryloxypropyltrimethoxysilane (molecular weight 248), trade name KBM503, manufactured by Shin-Etsu Chemical Co., Ltd. (B) silicon compound 2: silicone alkoxy oligomer (weight average molecular weight 6,000), Trade name x-40-9246, manufactured by Shin-Etsu Chemical Co., Ltd. (B) silicon compound 3: tetraethoxysilane (molecular weight 208), manufactured by Tama Chemical Industry Co., Ltd. (C) zirconium metal salt 1: zirconyl naphthenate (Nippon Chemical Industry) (Made by company)
(D) bis (alkoxysilyl) alkane 1: bis (triethoxysilyl) ethane, manufactured by Shin-Etsu Chemical Co., Ltd. (D) bis (alkoxysilyl) alkane 2: bis (trimethoxysilyl) hexane, Toray Dow Corning・ Methyltrimethoxysilane: MTMS manufactured by Tama Chemical Industry Co., Ltd.

Each component shown in Table 2 is as follows.
(A) Polysiloxane 1: Polydimethylsiloxane-α, ω-diol (weight average molecular weight 1,000), m = 11 in formula (1), trade name x-21-5841, manufactured by Shin-Etsu Chemical Co., Ltd. (A) Polysiloxane 2: trade name x-21-5848, manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 67000
Epoxy silicone: Epoxy-modified polysiloxane (trade name: KF101, manufactured by Shin-Etsu Chemical Co., Ltd.)
(B) silicon compound 1: γ-methacryloxypropyltrimethoxysilane (molecular weight 248), trade name KBM503, manufactured by Shin-Etsu Chemical Co., Ltd. (B) silicon compound 2: silicone alkoxy oligomer (weight average molecular weight 6,000), Trade name x-40-9246, manufactured by Shin-Etsu Chemical Co., Ltd. (B) Silicon compound 3: tetraethoxysilane (molecular weight 208), manufactured by Tama Chemical Industry Co., Ltd. (C) Zirconium metal salt 1: zirconyl octylate (Nippon Chemical Industry) (Made by company)
(C) Zirconium metal salt 2: Zirconyl naphthenate (manufactured by Nippon Chemical Industry Co., Ltd.)
Aluminum catalyst: AL-CH, manufactured by Kawaken Fine Chemical Co. Cationic polymerization catalyst: BF ₃ · Et ₂ O (BF ₃ ethyl etherate complex, manufactured by Tokyo Chemical Industry Co., Ltd.)
Zirconium chelate 1: zirconium tetraacetylacetonate (Matsumoto Fine Chemical Co., Ltd.)
Zirconium chelate 2: zirconium tributoxy monoacetylacetonate (
(Matsumoto Fine Chemical Co., Ltd.)
・ Zirconium alcoholate: Zirconium tetranormal butoxide (manufactured by Kanto Chemical Co., Inc.)
・ Dibutyltin dilaurate: manufactured by Tokyo Chemical Industry ・ Dibutyltin diacetate: manufactured by Nitto Kasei ・ Titanium diisopropoxybis (ethylacetoacetate): manufactured by Matsumoto Fine Chemical

As is apparent from the results shown in Tables 1 and 2, Comparative Example 1 which did not contain a zirconium metal salt but contained an aluminum catalyst had a large loss on heating.
In Comparative Example 1 containing an aluminum catalyst, the loss on heating was large.
In Comparative Example 2 containing 0.1 parts by mass or more of zirconium metal salt with respect to 100 parts by mass of polysiloxane, the loss on heating was large. Comparative Example 3 containing a zirconium metal salt in an amount of 0.1 parts by mass or more with respect to 100 parts by mass of polysiloxane has a large loss on heating, the initial cured state is clouded, and transparency is lost, resulting in poor workability and heat resistance. The coloring stability was poor.
Comparative Example 4 containing epoxy silicone was inferior in heat-resistant coloring stability.
In Comparative Example 5 containing no zirconium metal salt and containing zirconium chelate instead, the initial cured state was yellowed, the workability was poor, the heat-resistant coloring stability was poor, and the heat loss was large.
In Comparative Example 6 containing a zirconium chelate different from Comparative Example 5, gelation occurred in the initial cured state, and the curability and workability were poor.
Comparative Example 7 containing no zirconium metal salt and containing zirconium alcoholate instead was inferior in curability.
In Comparative Examples 8 to 10 which did not contain a zirconium metal salt and contained a tin catalyst instead, gelation occurred at room temperature in the initial stage of mixing, or the curability at high temperature was inferior.
In Comparative Examples 11 to 12 which did not contain a zirconium metal salt and contained a titanium catalyst instead, gelation occurred at room temperature in the initial stage of mixing, or the curability at high temperature was inferior.
Comparative Example 13, which does not contain bis (alkoxysilyl) alkane and instead contains a compound having one alkoxysilyl group in one molecule such as methyltrimethoxysilane, is insufficient in curability and after the pressure cooker test. Adhesiveness was poor.
On the other hand, Examples 1-3 are excellent in adhesiveness after heat cooker test, heat-resistant coloring stability, and workability (increase in viscosity and white turbidity during work are suppressed), and heat loss is 20%. It can suppress below and is excellent in sclerosis | hardenability.
Moreover, Examples 1-3 were excellent in transparency, the transmittance | permeability and the transmittance | permeability retention rate were high, and there was no generation | occurrence | production of a crack.

About the sample after the heat loss evaluation test of the comparative example 1, it analyzed using GC-MS (gas chromatograph mass spectrometer: Hewlett Packard, the product made from JEOL), and brand name DB-5 (made by Agilent Technologies) as a column. . The analysis conditions were an injection temperature of 280 ° C., 50 ° C. × 3 minutes, and 10 ° C./min. The temperature was raised to 320 ° C. at a rate of temperature rise of 320 ° C. and held at 320 ° C. for 15 minutes. The results are shown in FIGS.
FIG. 8 is a GC / MS-TIC spectrum chart of the sample after the heat loss evaluation test of Comparative Example 1. In FIG. 8, the vertical axis represents abundance. In FIG. 8, a prominent peak was confirmed around a retention time (RT) of 4.22 minutes.
FIG. 10 is a mass spectrum chart of hexamethylcyclotrisiloxane by GC-MS. In FIG. 10, the mass to charge ratio (m / z) of hexamethylcyclotrisiloxane was 207.0.
FIG. 9 is a mass spectrum chart by GC-MS of the peak at a retention time of 4.09 minutes in FIG. In FIG. 9, the mass spectrum (m / z) of the peak at a retention time of 4.09 minutes was 207.0, which was consistent with the result of FIG. Therefore, the peak at the retention time of 4.09 minutes in FIG. 8 is considered to be due to hexamethylcyclotrisiloxane.
Further, the peak at a retention time of 1.72 minutes in FIG. 8 is known to be due to trimethylsilanol (m / z: 75.0).
From this, it was found that when an initial cured product obtained from a composition containing an aluminum catalyst was placed under a high temperature condition for a long time, impurities such as hexamethylcyclotrisiloxane and trimethylsilanol were generated.
Since Examples 1 to 3 have less heat loss than Comparative Example 1, Examples 1 to 3 are considered to produce less cyclic siloxane than Comparative Example 1.

FIG. 1 is a top view schematically showing an example of the sealed optical semiconductor 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 the sealed optical semiconductor of the present invention. FIG. 4 is a cross-sectional view schematically showing an example of the sealed optical semiconductor of the present invention. FIG. 5 is a diagram schematically showing an example of an LED display using the sealed optical semiconductor 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 of the present invention in Examples. FIG. 8 is a GC / MS-TIC spectrum chart of the sample after the heat loss evaluation test of Comparative Example 1. FIG. T.A. : Mass spectrum chart by GC-MS of the peak at 4.09 minutes. FIG. 10 is a mass spectrum chart of hexamethylcyclotrisiloxane by GC-MS.

Explanation of symbols

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 Encapsulated optical semiconductor 201, 301 Mount member 202 Cavity, cured product 203, 303 Blue LED chip 302 Cured product 204 Package 206 Shaded portion 306 Resin 207, 307 Conductive wire 209 External electrode 210, 310 Substrate 305 Inner lead 400, 501 LED display 401 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

Claims (10)

(A) 100 parts by mass of polysiloxane having two or more silanol groups in one molecule;
(B) 0.1 to 100 parts by mass of a silicon compound having two or more alkoxy groups and / or hydroxy groups bonded to a silicon atom in one molecule;
(C) zirconium metal salt C 0.001 parts by mass or more and less than 0.1 parts by mass;
(D) bis (alkoxysilyl) alkane,
The silicone resin composition for encapsulating an adhesive optical semiconductor, wherein the zirconium metal salt C is a zirconium metal salt c 1 in which a zirconium atom forms (Zr = O) ²⁺ . The silicone resin composition for sealing an adhesive optical semiconductor according to claim 1, wherein the zirconium metal salt c1 is a compound represented by the following formula (I).
(In the formula, R represents a hydrocarbon group, and R may be the same or different.)   The silicone resin composition for sealing an adhesive optical semiconductor according to claim 1, wherein the zirconium metal salt C is a carboxylate. The silicone resin composition for adhesive optical semiconductor encapsulation according to any one of claims 1 to 3, wherein the bis (alkoxysilyl) alkane is represented by the following formula (A).
(R ¹ O) ₃ —Si—R ² —Si— (OR ¹ ) ₃ (A)
[In Formula (A), R ¹ is an alkyl group, R ² is an alkylene group having 2 to 10 carbon atoms, and R ¹ may be the same or different. ]   The silicone for sealing an adhesive optical semiconductor according to any one of claims 1 to 4, wherein the polysiloxane is a linear organopolydimethylsiloxane-α, ω-diol having a molecular weight of 1,000 to 1,000,000. Resin composition. 6. The compound according to claim 1, wherein the silicon compound is a compound represented by the following formula (2) and / or a compound having two or more silicon atoms and represented by the following formula (3). Silicone resin composition for sealing an adhesive optical semiconductor.
Si (OR ¹ ) _n R ² _4-n (2)
R _m Si (OR ′) _n O _{(4-mn) / 2} (3)
[In Formula (2), n is 2, 3 or 4, R ¹ is a hydrogen atom or an alkyl group, and R ² is an organic group.
In the formula (3), R is an alkyl group having 1 to 6 carbon atoms, an alkenyl group or an aryl group, R ′ is a hydrogen atom and 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 <2 . ]   The amount of the bis (alkoxysilyl) alkane is 0.1 to 2 parts by mass with respect to 100 parts by mass of the polysiloxane. The silicone resin for sealing an adhesive optical semiconductor according to claim 1. Composition.   The bis (alkoxysilyl) alkane is 1,2-bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,7-bis (trimethoxysilyl) heptane, 1,8-bis. It is at least one selected from the group consisting of (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane and 1,10-bis (trimethoxysilyl) decane. The silicone resin composition for adhesive optical semiconductor sealing of description.   The adhesive silicone resin sealing silicone resin composition according to any one of claims 1 to 8, wherein the zirconium metal salt c1 is one or both of zirconyl dioctylate and zirconyl naphthenate.   The optical semiconductor sealing body by which LED chip is sealed with the silicone resin composition for adhesive optical semiconductor sealing in any one of Claims 1-9.