JP2012184353A - Heat-curable silicone resin composition for sealing optical semiconductor and optical semiconductor package using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-curable silicone resin composition for sealing an optical semiconductor excellent in adhesiveness which can be easily cured by heating while suppressing shrinkage due to curing with easy operation.SOLUTION: This heat-curable silicone resin composition for sealing an optical semiconductor includes 100 pts.wt. of a reaction product (I) obtained by condensation reaction of (A) 100 pts.wt. of an organopolysiloxane resin having an RSiOunit (where R is a hydrocarbon group and/or hydroxy group), an SiOunit and a silanol group, and (C) 10-200 pts.wt. of a diorganopolysiloxane whose both terminals of molecular chain are encapsulated with silanol groups and/or alkoxysiloxy groups and having 5-10,000 mPa s viscosity, in the presence of a base; (B) 10-500 pts.wt. of an alkoxysilane oligomer having 5-50 wt.% of an alkoxy group bound to a silicon atom; and (D) a condensation catalyst. The optical semiconductor package uses the silicone resin composition.

Description

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

  Conventionally, it contains a condensation reaction product of an organopolysiloxane and a diorganopolysiloxane whose molecular chain ends are blocked with a functional group-containing silyl group, a (meth) acrylic functional alkoxysilane, etc., and is curable at room temperature and ultraviolet light. An organopolysiloxane composition has been proposed (for example, Patent Document 1).

JP 2008-13719 A

However, organopolysiloxane compositions containing (meth) acryl-functional alkoxysilanes and the like have to be irradiated with ultraviolet rays in order to cure them, resulting in troublesome work and low adhesion to metals and plastics. was there.
Further, the inventors of the present application (A) an organopolysiloxane resin having an R ₃ SiO _0.5 unit (wherein R is a hydrocarbon group and / or a hydroxyl group), an SiO ₂ unit and a silanol group, C) Diorganopolysiloxane having a viscosity of 5 to 10000 mPa · s having both ends of the molecular chain sealed with silanol groups and / or alkoxysiloxy groups, and (B) 5 to 50 weights of silicon atom-bonded alkoxy groups. It has been found that a cured product obtained by heat-curing an alkoxysilane oligomer having a% content with a condensation catalyst has room for improvement in terms of curing shrinkage.
Accordingly, an object of the present invention is to provide a thermosetting silicone resin composition for encapsulating a photo semiconductor that is easy to work, suppresses curing shrinkage, can be easily cured by heating, and has excellent adhesion.

As a result of intensive studies to solve the above problems, the inventors of the present application have found that (A) R ₃ SiO _0.5 unit (wherein R is a hydrocarbon group and / or a hydroxyl group), a SiO ₂ unit, a silanol group, 10 parts by weight of a diorganopolysiloxane having a viscosity of 5 to 10000 mPa · s at 25 ° C. in which 100 parts by weight of an organopolysiloxane resin having a molecular weight and (C) both ends of a molecular chain are sealed with silanol groups and / or alkoxysiloxy groups 100 parts by weight of reaction product (I) obtained by subjecting a part to a condensation reaction in the presence of a base,
(B) 10 to 500 parts by weight of an alkoxysilane oligomer having 5 to 50% by weight of a silicon atom-bonded alkoxy group,
(D) The composition containing a condensation catalyst can be a heat-curable silicone resin composition for encapsulating a photo-semiconductor that is easy to work, suppresses curing shrinkage, can be easily cured by heating, and has excellent adhesion. The present invention was completed.

That is, this invention provides the following 1-8.
1. (A) R ₃ SiO _0.5 unit (wherein R is a hydrocarbon group and / or hydroxyl group), 100 parts by weight of an organopolysiloxane resin having a SiO ₂ unit and a silanol group, and (C) both ends of the molecular chain Obtained by subjecting 10 to 200 parts by weight of a diorganopolysiloxane having a viscosity of 5 to 10,000 mPa · s sealed with silanol groups and / or alkoxysiloxy groups in the presence of a base. 100 parts by weight of product (I),
(B) 10 to 500 parts by weight of an alkoxysilane oligomer having 5 to 50% by weight of a silicon atom-bonded alkoxy group,
(D) A thermosetting silicone resin composition for encapsulating an optical semiconductor, comprising a condensation catalyst.
2. 2. The thermosetting silicone resin composition for encapsulating a photo-semiconductor according to 1 above, wherein the base is ammonia and / or a tertiary amine.
3. 3. The thermosetting silicone resin composition for sealing an optical semiconductor according to 1 or 2 above, wherein the component (D) is at least one selected from the group consisting of a zirconium compound, a tin compound and a zinc compound.
4). 4. The thermosetting silicone resin composition for sealing an optical semiconductor according to any one of 1 to 3 above, wherein the component (C) is polydimethylsiloxane in which both ends of the molecular chain are sealed with silanol groups.
5. Further, (F) an organopolysiloxane resin having _0.5 units of R ₃ SiO (wherein R is a hydrocarbon group and / or a hydroxyl group), an SiO ₂ unit and a silanol group, the organopolysiloxane resin ( The silicone resin composition for thermosetting optical semiconductor encapsulation according to any one of 1 to 4 above, wherein the amount of F) is 10 to 500 parts by weight with respect to 100 parts by weight of the reaction product (I).
6). Further, (E) an oligomer type silane coupling agent having one or more silicon atom-bonded alkoxy groups and one or more epoxy groups in one molecule, and the amount of the component (E) is the component (I) and the component (B) The silicone resin composition for thermosetting optical semiconductor sealing in any one of said 1-4 which is 0.01-10 weight part with respect to a total of 100 weight part of a component.
7). Further, (E) an oligomer type silane coupling agent having one or more silicon atom-bonded alkoxy groups and one or more epoxy groups in one molecule, and the amount of the component (E) is the component (I), 6. The silicone resin composition for heat-curable optical semiconductor encapsulation according to 5 above, which is 0.01 to 10 parts by weight with respect to 100 parts by weight of the total of component (B) and component (F).
8). 8. An optical semiconductor package sealed with the thermosetting silicone resin composition for sealing an optical semiconductor according to any one of 1 to 7 above.

  The heat-curable silicone resin composition for encapsulating an optical semiconductor of the present invention is easy to work, suppresses curing shrinkage, can be easily cured by heating, and is excellent in adhesiveness. The optical semiconductor package of the present invention is cured by heating and is obtained by an easy operation, and cure shrinkage is suppressed and the adhesiveness is excellent.

FIG. 1 is a cross-sectional view schematically showing an example of the optical semiconductor package of the present invention. FIG. 2 is a cross-sectional view schematically showing another example of the optical semiconductor package of the present invention.

The present invention will be described in detail below.
The silicone resin composition for thermosetting optical semiconductor encapsulation of the present invention (the composition of the present invention)
(A) R ₃ SiO _0.5 unit (wherein R is a hydrocarbon group and / or hydroxyl group), 100 parts by weight of an organopolysiloxane resin having a SiO ₂ unit and a silanol group, and (C) both ends of the molecular chain Obtained by subjecting 10 to 200 parts by weight of a diorganopolysiloxane having a viscosity of 5 to 10,000 mPa · s sealed with silanol groups and / or alkoxysiloxy groups in the presence of a base. 100 parts by weight of product (I),
(B) 10 to 500 parts by weight of an alkoxysilane oligomer having 5 to 50% by weight of a silicon atom-bonded alkoxy group,
(D) A thermosetting silicone resin composition for encapsulating an optical semiconductor, containing a condensation catalyst.

The reaction product (I) will be described below. The reaction product (I) contained in the composition of the present invention comprises (A) R ₃ SiO _0.5 unit (wherein R is a hydrocarbon group and / or a hydroxyl group), a SiO ₂ unit, a silanol group, 10 parts by weight of a diorganopolysiloxane having a viscosity of 5 to 10000 mPa · s at 25 ° C. in which 100 parts by weight of an organopolysiloxane resin having a molecular weight and (C) both ends of a molecular chain are sealed with silanol groups and / or alkoxysiloxy groups Part is obtained by a condensation reaction in the presence of a base.
In the present invention, it is considered that the silanol group of the component (A) and the silanol group and / or alkoxysiloxy group at both ends of the molecular chain of the component (C) undergo a dehydration condensation reaction in the presence of a base and are combined. By subjecting the component (C) having a relatively low molecular weight to a condensation reaction with the component (A), volatilization of the component (C) may be suppressed during heat curing as compared to a composition containing the component (C) as it is. There is sex. Such suppression of volatilization of the component (C) is considered to contribute to suppression of volume hardening shrinkage. In addition, the said mechanism is a guess of this inventor, and even if it is mechanisms other than the above, it is in the scope of the present invention.

(A) The organopolysiloxane resin will be described below. The organopolysiloxane resin (A) used in the production of the reaction product (I) includes R ₃ SiO _0.5 units (wherein R is a hydrocarbon group and / or a hydroxyl group), SiO ₂ units, Any organopolysiloxane resin having a silanol group is not particularly limited. One preferred embodiment of the organopolysiloxane resin is that at least a part of the skeleton has a network structure. Among these, MQ resin is preferable from the viewpoint of further suppressing curing shrinkage, being excellent in adhesiveness, becoming a cured product having appropriate hardness, and being excellent in flexibility. The hydrocarbon group as R in the R ₃ SiO _0.5 unit can be monovalent. Examples of the hydrocarbon group (including chain, branched, cyclic, and combinations thereof) include aliphatic hydrocarbon groups (including chain, branched, and cyclic), aromatic hydrocarbon groups, and combinations thereof. . The integer can be an integer of 1 to 6 carbon atoms of the hydrocarbon group, and examples include a methyl group, an ethyl group, and a phenyl group.

The hydroxyl group content of the component (A) can be 0.5 to 5.0 wt% (wt%).
The ratio of the number of R ₃ SiO _0.5 units to the number of SiO ₂ units [(R ₃ SiO _0.5 units) :( SiO ₂ units), molar ratio] is more excellent in adhesiveness by suppressing cure shrinkage and having an appropriate hardness. From the viewpoint of providing a cured product having a flexibility and imparting flexibility, it is preferably 0.4: 1 to 1.2: 1, and more preferably 0.6: 1 to 0.8: 1. preferable.

(A) As organopolysiloxane resin, what is represented by following formula (I) is mentioned, for example.
(R ¹ SiO _3/2 ) a (R ² ₂ SiO _2/2 ) b (R ³ ₃ SiO _1/2 ) c (SiO _4/2 ) d (XO _1/2 ) e (I)
In the formula, c and d are positive numbers, a and b are 0 or positive numbers, e is a positive number, c: d is 0.4: 1 to 1.2: 1, and a / b is a number from 0 to 0.1, a / c is a number from 0 to 2, d / (a + b + c + d) is a number from 0 to 0.8, and e / (a + b + c + d) is from 0 to 0.0. It is a number of 6.
Examples of R ^{1 to} R ³ include a methyl group and a hydroxyl group, and examples of X include a hydrogen group. a and b can be set to 0, d / (a + b + c + d) can be set to 0.6, and e / (a + b + c + d) can be set to 0.07.

  (A) The weight average molecular weight of the organopolysiloxane resin is preferably 2000 to 10,000 from the viewpoint of further suppressing curing shrinkage, being excellent in adhesiveness, becoming a cured product having appropriate hardness, and being excellent in flexibility. More preferably, it is 3000 to 5000. (A) The weight average molecular weight of the organopolysiloxane resin is a weight average molecular weight expressed in terms of polystyrene by gel permeation chromatography (GPC) using toluene as a solvent.

(A) The organopolysiloxane resin is not particularly limited for its production. (A) The organopolysiloxane resins can be used alone or in combination of two or more.
(A) A component is mentioned as one of the aspects with preferable that it does not have an epoxy group.

(C) The diorganopolysiloxane will be described below. The diorganopolysiloxane (C) used in the production of the reaction product (I) has a viscosity at 25 ° C. of 5 to 10,000 mPa · s in which both ends of the molecular chain are sealed with silanol groups and / or alkoxysiloxy groups. s diorganopolysiloxane. (C) The skeleton of the diorganopolysiloxane is preferably linear from the viewpoint of further suppressing curing shrinkage, being excellent in adhesiveness, becoming a cured product having an appropriate hardness, and being excellent in crack resistance.
(C) The silanol group which diorganopolysiloxane has at both molecular chain ends can have a hydrocarbon group in addition to the hydroxy group. The hydrocarbon group has the same meaning as described above, and examples thereof include a methyl group and an ethyl group.
(C) The alkoxy group of the alkoxysiloxy group that the diorganopolysiloxane has at both ends of the molecular chain preferably has 1 to 6 carbon atoms, specifically, for example, alkyl such as methoxy group and ethoxy group Groups. The alkoxysiloxy group may have 1 to 3 alkoxy groups. The alkoxysiloxy group can have, for example, a hydrocarbon group in addition to the alkoxy group. The hydrocarbon group is as defined above. Examples of the alkoxysiloxy group include a trialkoxysiloxy group, and more specific examples include a trimethoxysiloxy group.

As the diorganopolysiloxane having both molecular chain ends sealed with alkoxysiloxy groups, for example, polydimethylsiloxane represented by the following formula (IV) and having both molecular chain ends sealed with trimethoxysiloxy groups is exemplified. Can be mentioned.

In the formula, n can be a numerical value corresponding to the molecular weight and / or viscosity of the polysiloxane.

Component (C) is a polydimethylsiloxane in which both ends of the molecular chain are sealed with silanol groups from the viewpoint that the cured shrinkage is further suppressed, the adhesion is excellent, the cured product has an appropriate hardness, and the crack resistance is excellent. Is preferred.
In this invention, the viscosity in 25 degreeC of (C) component is 5-10000 mPa * s. The viscosity at 25 ° C. of the component (C) is preferably 5 to 10,000 mPa · s from the viewpoint that the curing shrinkage is further suppressed, the adhesiveness is excellent, the cured product has an appropriate hardness, and the crack resistance is excellent. More preferably, the pressure is 20 to 1000 mPa · s. In the present invention, the viscosity of each component was measured using a B-type viscometer at 25 ° C.
(C) The weight average molecular weight of the diorganopolysiloxane is preferably 500 to 60,000 from the viewpoint of further suppressing curing shrinkage, being excellent in adhesion, becoming a cured product having appropriate hardness, and being excellent in crack resistance. More preferably, it is 2000-25000. (C) The weight average molecular weight of diorganopolysiloxane is a weight average molecular weight expressed in terms of polystyrene by gel permeation chromatography (GPC) using toluene as a solvent.
(C) The production of the diorganopolysiloxane is not particularly limited. (C) The diorganopolysiloxane can be used alone or in combination of two or more.

  In the present invention, the amount of (C) diorganopolysiloxane is 10 to 200 parts by weight per 100 parts by weight of (A) organopolysiloxane resin. The amount of (C) diorganopolysiloxane is preferred from the viewpoint that the reaction product (I) obtained in an excessive amount with respect to (A) the organopolysiloxane resin in the condensation reaction is difficult to gel. (C) The amount of diorganopolysiloxane suppresses curing shrinkage and is more excellent in adhesiveness, becomes a cured product having an appropriate hardness, has excellent crack resistance, and has a viewpoint that the reaction product (I) obtained is difficult to gel. From (A) 100 parts by weight of the organopolysiloxane resin, the amount is preferably 10 to 200 parts by weight, and more preferably 50 to 150 parts by weight.

The base will be described below. The base used in producing the reaction product (I) is not particularly limited. Examples of the base include amine compounds such as ethylamine, propylamine, isopropylamine, butylamine, diethylamine, dibutylamine, and triethylamine; ammonia (ammonia can be mentioned as one of the preferred embodiments used as ammonia water). It is done. Among these, tertiary amines such as ammonia (ammonia water) and triethylamine are preferable from the viewpoints that cured shrinkage is further suppressed, the adhesiveness is excellent, the cured product has an appropriate hardness, and excellent removability. .
The bases can be used alone or in combination of two or more.

  From the viewpoint that the amount of the base further suppresses curing shrinkage, is superior in adhesiveness, becomes a cured product having appropriate hardness, and is excellent in reactivity, it is based on 100 parts by weight of the total of the component (A) and the component (C). 0.001 to 3.0 parts by weight is preferable, and 0.005 to 0.1 parts by weight is more preferable.

The condensation reaction is not particularly limited. The condensation reaction temperature can usually be 1 to 120 ° C. The reaction time can be about 0.5 to 12 hours. A condensation reaction catalyst and a solvent can be used for the condensation reaction.
After completion of the condensation reaction, the solvent and / or unreacted organopolysiloxane, diorganopolysiloxane, condensation reaction catalyst and the like can be distilled off as necessary. Furthermore, in order to adjust the viscosity of the condensation reaction product, for example, a low molecular cyclic siloxane such as an organopolysiloxane or octamethylcyclotetrasiloxane whose end is blocked with a trimethylsiloxy group or the like; an aliphatic hydrocarbon compound; an aromatic Hydrocarbon compounds; liquid paraffin; isoparaffin can be added.

Examples of the reaction product (I) include those obtained by the following reaction formula. The reaction product (I) is not limited to the following formula.

The reaction product (I) can be a mixture. When the reaction product (I) is a mixture, examples of the reaction product (I) include a mixture containing two or more condensates of the component (A) and the component (C); the component (A) and the component (C And a condensate with the component (condensates may be two or more), and a mixture containing the component (A) and / or the component (C). As the reaction product (I), for example, a mixture containing at least a condensate of the component (A) and the component (C) (the condensate may be two or more) and the component (C) is preferable. It is mentioned as one of the aspects.
The reaction product (I) is a (meth) acryl functional group [(meth) acryloyloxy group. The same applies below. ] Is preferable from the viewpoint that the number of work steps is small, the workability is excellent, the workability is suppressed, the shrinkage is further suppressed, the adhesiveness is excellent, and the color fastness is excellent.
One preferred embodiment of the reaction product (I) is that it does not have an epoxy group. The reaction products (I) can be used alone or in combination of two or more.

(B) The alkoxysilane oligomer will be described below. The alkoxysilane oligomer contained in the composition of the present invention is an oligomer obtained by using a monomer containing at least alkoxysilane, having 5 to 50% by weight of silicon-bonded alkoxy groups, and having a polysiloxane skeleton. (B) The alkoxysilane oligomer is mentioned as one of preferred embodiments in which at least a part of the skeleton has a network structure. For example, MQ resin, DT resin, and MDT resin are mentioned. Among these, DT resin is preferable from the viewpoint of suppressing curing shrinkage and improving adhesiveness, resulting in a cured product having appropriate hardness and excellent curability, and R ₂ SiO _1.0 unit (wherein R is a hydrocarbon group) And / or a hydroxyl group) and a resin having RSiO _1.5 units (DT resin). The hydrocarbon group can be monovalent. A hydrocarbon group is synonymous with said hydrocarbon group.
(B) The alkoxysilane used when producing the alkoxysilane oligomer is not particularly limited as long as it is a compound having an alkoxy group and 1 to 3 silicon atoms. The alkoxy group which alkoxysilane has can be 1-4. The alkoxy group preferably has 1 to 6 carbon atoms, and examples thereof include a methoxy group and an ethoxy group. The alkoxysilane can have, for example, a hydrocarbon group in addition to the alkoxy group. The hydrocarbon group is as defined above. The alkoxysilane used when manufacturing an alkoxysilane oligomer can be used individually or in combination of 2 types or more, respectively.

The silicon atom-bonded alkoxy group of the alkoxysilane oligomer is the same as the alkoxy group of the alkoxysilane used when producing the alkoxysilane oligomer.
In the present invention, the amount of the silicon atom-bonded alkoxy group possessed by the alkoxysilane oligomer (as the amount of the alkoxy group bonded to the silicon atom. Note that the amount of the silicon atom-bonded alkoxy group does not include the silicon atom). 5 to 50% by weight in the molecule. The amount of the silicon atom-bonded alkoxy group contained in the alkoxysilane oligomer is 5 in one molecule of the alkoxysilane oligomer from the viewpoint of further suppressing curing shrinkage, being excellent in adhesiveness, becoming a cured product having appropriate hardness, and being excellent in curability. It is preferably ˜50% by weight, more preferably 10 to 30% by weight.

(B) The alkoxysilane oligomer is not particularly limited for its production. (B) An alkoxysilane oligomer can be used individually or in combination of 2 types or more, respectively.
Component (B) is a (meth) acryl functional group [(meth) acryloyloxy group. The same applies below. ] Is preferable from the viewpoint that the number of work steps is small, the workability is excellent, the workability is suppressed, the shrinkage is further suppressed, the adhesiveness is excellent, and the color fastness is excellent. The composition of the present invention preferably contains substantially no component (B) having a (meth) acryl functional group for the same reason as described above. The fact that the composition of the present invention does not substantially contain the component (B) having a (meth) acryl functional group has (B) a (meth) acryl functional group with respect to 100 parts by weight of the reaction product (I). The component is less than 1 part by weight.
Moreover, it is mentioned as one of the aspects with preferable (B) component not having an epoxy group.

  In this invention, the quantity of (B) alkoxysilane oligomer is 10-500 weight part with respect to 100 weight part of reaction products (I). (B) The amount of the alkoxysilane oligomer further suppresses curing shrinkage and is superior in adhesiveness, becomes a cured product having an appropriate hardness, and is excellent in curability, with respect to 100 parts by weight of the reaction product (I), The amount is preferably 10 to 500 parts by weight, and more preferably 10 to 200 parts by weight.

  (D) The condensation catalyst will be described below. The (D) condensation catalyst contained in the composition of the present invention is not particularly limited. Among these, at least selected from the group consisting of a zirconium compound, a tin compound and a zinc compound, from the viewpoint of further suppressing curing shrinkage, being excellent in adhesiveness, becoming a cured product having appropriate hardness, and being excellent in heat curability and handleability. One type is preferred.

  (D) It is mentioned as one of the aspects in which the condensation catalyst preferably has an organic group. (D) The condensation catalyst is bonded to an organic group (hydrocarbon group) via a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom and / or via a bonding group such as an ester bond. can do. The organic group (hydrocarbon group) is an aliphatic hydrocarbon group (including chain, branched, cyclic, and combinations thereof. The aliphatic hydrocarbon group can have an unsaturated bond), an aromatic hydrocarbon. Groups and combinations thereof. The organic group (hydrocarbon group) can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the organic group having a bonding group (hydrocarbon group) include organic carboxylates (—O—CO—R); those in which a hydrocarbon group is bonded to an oxy group, such as an alkoxy group and a phenoxy group (— O—R); ligands; combinations thereof.

The zirconium compound contains a compound [zirconyl [(Zr = O) ²⁺ ] represented by the formula (1) as a constituent element from the viewpoint that a cured product that is superior in adhesiveness and hardly discolors can be obtained. And / or a compound represented by formula (2).
(1)
(In the formula, R ¹ is a hydrocarbon group having 1 to 18 carbon atoms.)
(2)
(In the formula, R ² is a hydrocarbon group having 1 to 16 carbon atoms, R ³ is a hydrocarbon group having 1 to 18 carbon atoms, and m is an integer of 1 to 3).
The hydrocarbon group in Formula (1) and Formula (2) has the same meaning as the organic group that (D) the condensation catalyst can have.

  The zirconium compound represented by the formula (1) is preferably an aliphatic carboxylate and / or an alicyclic carboxylate, and more preferably an alicyclic carboxylate. Examples of the zirconium compound represented by the formula (1) include aliphatic carboxylates such as zirconyl dioctylate and zirconyl dineodecanoate; alicyclic carboxylates such as zirconyl naphthenate and zirconyl cyclohexane; zirconyl benzoate; An aromatic carboxylate such as The zirconium compound represented by the formula (1) is preferably one or both of zirconyl dioctylate and zirconyl naphthenate from the viewpoint of obtaining a cured product that is superior in adhesiveness and hardly discolored.

The zirconium compound of formula (2), if it is the formula (2) was m is 2 or more, plural R ² may be the same or different. Moreover, when m is 1-2, several R < ³ > may be the same or different.
From the viewpoint of excellent heat-resistant coloring stability and compatibility (for example, compatibility with a silicone resin), the hydrocarbon group represented by R ² in the above formula (2) preferably has 3 to 16 carbon atoms. More preferably, it is 4-16. The hydrocarbon group represented by R ² has the same meaning as described above.

The hydrocarbon group represented by R ² preferably has a cyclic structure from the viewpoint that a cured product that is superior in adhesiveness and hardly discolors can be obtained. Examples of the cyclic structure include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. R ² can have a cyclic structure in combination with, for example, an aliphatic hydrocarbon group.
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.

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. The hydrocarbon group represented by R ³ has the same meaning as R ² except for the number of carbon atoms. R ³ is preferably an aliphatic hydrocarbon group from the viewpoint of excellent heat-resistant coloring stability and excellent compatibility.
R ³ O-(alkoxy) having an aliphatic hydrocarbon group, among others, from the viewpoint of excellent heat coloration stability, excellent compatibility, R ³ O-(alkoxy) having an aliphatic hydrocarbon group Is preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, or an isopropoxy group.

  Among these, from the viewpoint of excellent heat-resistant coloring stability and compatibility, a compound having an alicyclic hydrocarbon group as a cyclic structure and a compound having an aromatic hydrocarbon group as a cyclic structure are preferable, and a zirconium trialkoxy monoester Zirconium tributoxy mononaphthate, zirconium tributoxy monoisobutyrate, zirconium tributoxy mono 2-ethylhexanoate, zirconium tributoxy monocyclopropane carboxylate, zirconium tributoxy monocyclopentane carboxylate, zirconium tributoxy More preferred are monocyclohexane carboxylate, zirconium tributoxy monoadamantane carboxylate, and zirconium tributoxy mononaphthate.

  The tin compound will be described below. The tin compound that can be contained as the condensation catalyst in the composition of the present invention is more preferably a tetravalent tin compound from the viewpoint of obtaining a cured product that is excellent in adhesiveness and hardly changes in color. The tetravalent tin compound is preferably a tetravalent tin compound having at least one alkyl group and at least one acyl group (ester bond).

Examples of tetravalent tin compounds having at least one alkyl group and at least one acyl group include those represented by the following formula (II), bis type compounds represented by formula (II), and polymers: A type is mentioned.
_{^{R 3 a -Sn- [O-CO}} -R 4] 4-a (II)
In the formula, R ³ is an alkyl group, R ⁴ is a hydrocarbon group, and a is an integer of 1 to 3.
Examples of the alkyl group include those having 1 or more carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and an octyl group.
The hydrocarbon group is not particularly limited. For example, the thing similar to the above is mentioned.

  Among them, dibutyltin diacetate, dibutyltin dioleate, dibutyltin dilaurate, dibutyltin oxyacetate dibutyltin oxyoctylate, and dibutyltin oxylaurate are preferable from the viewpoint of excellent heat-resistant coloring stability and thin film curability.

The zinc compound will be described below. The zinc compound that the composition of the present invention can contain as the (D) condensation catalyst is not particularly limited as long as it is a compound containing zinc. Examples thereof include zinc salts; zinc complexes; zinc alcoholates; zinc oxides such as zinc white and zinc stannate; binary and / or multi-metal oxides containing zinc, salts and / or complexes thereof, and combinations thereof.
Examples of the zinc compound include those represented by the following formulas (1) and (2).
In formula (1), R ¹ is an alkyl group having 1 to 18 carbon atoms, an aryl group.
Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, octyl, 2-ethylhexyl, nonyl, decyl, and undecyl. . Examples of the aryl group include a phenyl group, a naphthyl group, and azulene.

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. In formula (2), R ² and R ³ 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 include zinc acetate, zinc acetyl acetate, zinc 2-ethylhexanoate, zinc octylate, zinc neodecanoate, zinc laurate, zinc stearate, and zinc naphthenate. Carboxylic acid salts such as zinc alicyclic carboxylates, zinc benzoates, zinc p-tert-butylbenzoates, zinc aromatic carboxylates such as zinc salicylates; zinc (meth) acrylates; zinc acetylacetonates [Zn ( II) Zinc chelates such as acetylacetonate, Zn (acac) ₂ ], 2,2,6,6-tetramethyl-3,5-heptanedionate Zn.

  When the composition of this invention contains (D) zinc compound as a condensation catalyst, the composition excellent in transparency and sclerosis | hardenability is obtained. Among these, (D) the zinc compound is excellent in adhesiveness and becomes a cured product having an appropriate hardness, excellent in transparency, curability, smoothness and storage stability, and has a pot life and a curing time having an appropriate length. From the viewpoint of becoming, zinc salts and zinc chelates are preferable, and ethyl acetoacetate aluminum diisopropylate, 2-ethylhexanoic acid aluminum, zinc 2-ethylhexanoate, and zinc acetylacetonate are more preferable.

  When the composition of the present invention contains a zinc compound as a condensation catalyst, the composition of the present invention also has hydrogen sulfide resistance. The composition of the present invention can suppress corrosion of metal (for example, discoloration of silver) due to excellent resistance to sulfidation (for example, resistance to hydrogen sulfide). Therefore, the composition of the present invention contains a zinc compound as a condensation catalyst, thereby suppressing, for example, corrosion of metal in a semiconductor light emitting device such as a metal reflector, and maintaining light reflectivity over time. For example, a reduction in luminance of a semiconductor light emitting device can be suppressed. (D) A zinc compound can be used individually or in combination of 2 types or more, respectively.

  (D) A condensation catalyst can be used individually or in combination of 2 types or more, respectively. (D) As a combination of a condensation catalyst, at least 2 sorts chosen from the group which consists of a zirconium compound, a tin compound, and a zinc compound is mentioned, for example. Among these, a combination of a zirconium compound and a tin compound is preferable from the viewpoint of further suppressing curing shrinkage, being excellent in adhesiveness, becoming a cured product having curability and appropriate hardness, and being excellent in handleability. The amount ratio of the zirconium compound and the tin compound is preferably 0.1: 1 to 2: 1 from the viewpoint of further suppressing the curing shrinkage and being excellent in adhesiveness and excellent in curability and handling properties.

  (D) The amount of the condensation catalyst further suppresses curing shrinkage, is excellent in adhesiveness, becomes a cured product having an appropriate hardness, and is excellent in curability from the viewpoint of the reaction product (I) and the component (B). It is preferably 0.001 to 0.5 parts by weight with respect to 100 parts by weight in total or 100 parts by weight in total of reaction product (I), component (B) and component (F), More preferably, it is 0.1 parts by weight.

The composition of the present invention further contains (F) an organopolysiloxane resin having R ₃ SiO _0.5 units (wherein R is a hydrocarbon group and / or a hydroxyl group), SiO ₂ units and silanol groups. Can do. The composition of the present invention preferably further contains a component (F) from the viewpoint of further suppressing curing shrinkage, being excellent in adhesiveness, and being excellent in flexibility. The component (F) has the same meaning as the component (A).
(F) A component can be used individually or in combination of 2 types or more, respectively.
The amount of the organopolysiloxane resin (F) is 10 to 500 parts by weight with respect to 100 parts by weight of the reaction product (I) from the viewpoint of further suppressing curing shrinkage, being excellent in adhesiveness and excellent in flexibility. It is preferably 10 to 400 parts by weight, more preferably 30 to 200 parts by weight.

  The composition of the present invention may further contain (E) an oligomer type silane coupling agent having one or more silicon atom-bonded alkoxy groups and one or more epoxy groups in one molecule. The composition of the present invention preferably further contains (E) an oligomer type silane coupling agent from the viewpoint of further suppressing curing shrinkage and being excellent in adhesiveness. The oligomer type silane coupling agent (E) that can be further contained in the composition of the present invention is an oligomer type polysiloxane having one or more silicon-bonded alkoxy groups and one or more epoxy groups in one molecule. is there. When the composition of the present invention further contains the component (E), a cured product that is excellent in adhesiveness and hardly discolors can be obtained. When the composition of the present invention is heated and used, the oligomer type silane coupling agent (E) contained in the composition of the present invention is like an epoxy silane (monomer) having one silicon atom depending on its viscosity. It does not volatilize from the composition and can remain in the system, contributing to the development of excellent adhesiveness. Moreover, when epoxy equivalent is 140-1000 g / mol, it is excellent by adhesiveness. Moreover, the cured | curing material obtained does not discolor by heating or light because it is an epoxy group containing the functional group which an oligomer type silane coupling agent (E) has.

The silicon atom-bonded alkoxy group (alkoxy group bonded to the silicon atom) of the oligomer type silane coupling agent (E) is the same as the alkoxy group of the aforementioned alkoxysiloxy group. The silicon atom to which the alkoxy group is bonded can have, for example, a hydrocarbon group in addition to the alkoxy group. The hydrocarbon group is as defined above. Examples of the alkoxysiloxy group include a trialkoxysiloxy group, and more specific examples include a trimethoxysiloxy group. The amount (% by weight) of the alkoxy group contained in one molecule of the oligomer type silane coupling agent (E) is preferably 20 to 50% by weight from the viewpoint of obtaining a cured product that is superior in adhesion and hardly discolored.
The epoxy group possessed by the oligomer type silane coupling agent (E) can be one or two or more from the viewpoint of obtaining a cured product that is superior in adhesion and hardly discolored. The epoxy group can be bonded to the silicon atom via a hydrocarbon group and / or a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. The hydrocarbon group is not particularly limited, and examples thereof include an alkylene group such as a methylene group, an ethylene group, and a trimethylene group; and an alkylene group having an ether bond such as — (CH ₂ ) ₃ —O—CH ₂ —.

The oligomer type silane coupling agent (E) is a polysiloxane and has a siloxane skeleton. One preferred embodiment of the oligomer type silane coupling agent (E) is a silicone alkoxy oligomer. The oligomer type silane coupling agent (E) may have a chain, branched, network, or a combination thereof. The SO ₂ content (% by weight) of one molecule of the oligomer type silane coupling agent (E) is preferably 30 to 50% by weight from the viewpoint of obtaining a cured product that is superior in adhesiveness and hardly discolored.
The epoxy equivalent of the oligomer type silane coupling agent (E) is preferably 140 to 1000 g / mol, and preferably 300 to 900 g / mol from the viewpoint that a cured product that is excellent in adhesiveness and hardly discolors can be obtained. More preferred.
The viscosity at 25 ° C. of the oligomer type silane coupling agent (E) is preferably 10 to 200 mPa · s (mm ² / s) from the viewpoint of obtaining a cured product that is superior in adhesion and hardly discolored. More preferably, it is 10-100 mPa * s.

As a method for producing the oligomer type silane coupling agent (E), for example, at least an epoxy silane such as 3-glycidyloxypropyltrimethoxysilane is included, and if necessary, dialkoxyalkylsilane and trialkoxyalkylsilane are included. It can be obtained by hydrolytic condensation of the resulting alkoxysilane.
Examples of commercially available oligomer-type silane coupling agents (E) include x-41-1053, x-41-1059A, and x-41-1056 (all manufactured by Shin-Etsu Chemical Co., Ltd.). The oligomer type silane coupling agent (E) can be used alone or in combination of two or more.

  The amount of the component (E) is 100 parts by weight of the total of the component (I) and the component (B), or the component (I) and the component (B), from the viewpoint of suppressing the curing shrinkage and improving the adhesiveness. The amount is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total of the component and the component (F).

The composition of this invention can contain an additive further as needed in the range which does not impair the objective and effect of this invention other than said component.
Examples of the additives include fillers such as inorganic fillers, antioxidants, lubricants, ultraviolet absorbers, thermal light stabilizers, dispersants, antistatic agents, polymerization inhibitors, antifoaming agents, curing accelerators, solvents, Phosphor (for example, inorganic phosphor), anti-aging agent, radical inhibitor, adhesion improver, flame retardant, surfactant, storage stability improver, ozone anti-aging agent, thickener, plasticizer, radiation blocker , Nucleating agent, coupling agent, conductivity imparting agent, phosphorus peroxide decomposing agent, pigment, metal deactivator, physical property modifier, bis (alkoxysilyl) alkane, bis (alkoxysilylalkyl) amine, isocyanurate Examples include compounds, silane coupling agents other than the component (E), adhesion promoters, adhesion assistants, photopolymerization initiators, and thermal polymerization initiators. Various additives are not particularly limited. For example, a conventionally well-known thing is mentioned.

As additives, bis (alkoxysilyl) alkane and bis (alkoxysilylalkyl) amine can be used as an adhesion-imparting agent. When the composition of the present invention further contains bis (alkoxysilyl) alkane and bis (alkoxysilylalkyl) amine, the adhesiveness is excellent and the adhesiveness is excellent.
In the bis (alkoxysilyl) alkane or bis (alkoxysilylalkyl) amine, the alkoxysilyl group can have an alkyl group such as a methyl group or an ethyl group in addition to the alkoxy group.
Bis (alkoxysilyl) alkane is a compound having a divalent alkane (alkylene group) and two alkoxysilyls. The divalent alkane may have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
Bis (alkoxysilylalkyl) amine has a divalent alkane having an imino group (—NH—) [that is, a divalent alkane can have two alkylene groups bonded via an imino group (—NH—). . ] A compound having two alkoxysilyls. The divalent alkane of bis (alkoxysilylalkyl) amine may have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
A compound in which the structures of bis (alkoxysilyl) alkane and bis (alkoxysilylalkyl) amine are combined can be represented by, for example, the following formula (VII).

In the formula, each of R ^{7 to} R ⁸ is an alkyl group, and R ⁹ may have a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom, which is a divalent alkane [bis (alkoxysilyl) alkane In the case of bis (alkoxysilylalkyl) amine] in which two alkylene groups are bonded via an imino group (—NH—), and a is an integer of 1 to 3, respectively. 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.

Bis (alkoxysilyl) alkanes or bis (alkoxysilylalkyl) amines are excellent in adhesion and can be cured more easily to discolor, resulting in transparency, adhesion at high temperatures, curability, smoothness, and storage stability. From the viewpoint of excellent, pot life, and curing time having an appropriate length, those represented by the formula (VII) are preferable, bis (trialkoxysilyl) alkane and bis (trialkoxysilylalkyl) amine are more preferable, Bis- (3-trimethoxysilylpropyl) amine, 1,2-bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,7-bis (trimethoxysilyl) heptane, 1, 8-bis (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane and 1,10-bis (trimethyl) More preferably at least one selected from the group consisting of Kishishiriru) decane, 1,6-bis (trimethoxysilyl) hexane, bis - (3-trimethoxysilyl propyl) amine is more preferred.
Bis (alkoxysilyl) alkanes and bis (alkoxysilylalkyl) amines can be used alone or in combination of two or more.

  The amount of bis (alkoxysilyl) alkane and / or bis (alkoxysilylalkyl) amine is excellent in adhesiveness, and a cured product that is not easily discolored is obtained. Transparency, adhesiveness at high temperatures, curability, smoothness, storage (E) component, (F) which can be used as needed from a viewpoint that it is excellent in stability, and pot life and hardening time become suitable length, (I) component, (B) component, and as needed The amount is more preferably 0.1 to 5 parts by weight based on 100 parts by weight of the total components.

  The composition of the present invention is a (meth) acryl functional group [(meth) acryloyloxy group. The same applies hereinafter. Is not substantially contained (for example, the (meth) acryl functional alkoxysilane represented by the general formula (1) contained in the composition described in Patent Document 2). It is preferable from the viewpoint that it is excellent in workability, suppresses curing shrinkage, is superior in adhesiveness, and is excellent in discoloration resistance. The fact that the composition of the present invention does not substantially contain an alkoxysilane having a (meth) acryl functional group means that the alkoxysilane having a (meth) acryl functional group is 1 weight with respect to 100 parts by weight of the reaction product (I). It means less than a part.

The composition of the present invention is not particularly limited for its production. For example, it can manufacture by mixing (I) component, (B) component, (D) component, (E) component which can be used as needed, (F) component, and an additive.
The composition of the present invention can be produced as a one-pack type or a two-pack type.

The composition of the present invention can be used as a thermosetting silicone composition for optical semiconductor encapsulation. 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.
The adherend to which the composition of the present invention can be applied is not limited to an optical semiconductor. For example, semiconductors other than optical semiconductors; rubber; plastics such as polyphthalamide, polyimide, polycarbonate, (meth) acrylic resin; glass; metals such as silver, silver plating, aluminum, aluminum nitride, boron nitride; ceramics Is mentioned.
As a method for using the composition of the present invention, for example, the composition of the present invention is applied to an optical semiconductor, and the optical semiconductor to which the composition of the present invention is applied is heated to cure the composition of the present invention. Can be mentioned. The method for applying the composition of the present invention 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. Heating temperature is better due to adhesion, resulting in a cured product with appropriate hardness, resulting in a cured product that is difficult to discolor, excellent adhesion and thin film curability, and setting the curing time and pot life to an appropriate length. From the viewpoint of being able to suppress the foaming of alcohol as a by-product due to the condensation reaction, suppressing cracks in the cured product, and being excellent in the smoothness, moldability, and physical properties of the cured product, in the vicinity of 80 ° C. to 150 ° C. It is preferable to cure, more preferably around 150 ° C.
The heating can be performed under substantially anhydrous conditions from the viewpoint of excellent curability and excellent transparency. In the present invention, “heating under substantially anhydrous conditions” means that the atmospheric humidity of the environment during heating is 10% RH or less.

  A cured product (silicone resin) obtained by heating and curing the composition of the present invention is excellent in adhesiveness, has an appropriate hardness, and is high for use with long-term LEDs (especially white LEDs). Transparency can be maintained, and heat resistance coloring stability, thin film curability, adhesion, and heat crack resistance are excellent.

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 optical semiconductor package of the present invention will be described below.
The optical semiconductor package of the present invention is an optical semiconductor package encapsulated with the silicone resin composition for encapsulating heat-curable optical semiconductor of the present invention.
The optical semiconductor package of the present invention is obtained by applying the silicone composition for encapsulating heat-curable optical semiconductor of the present invention to an optical semiconductor package (hereinafter sometimes referred to as “LED chip”), and heating the LED chip. It can be obtained by sealing the LED chip by curing the silicone composition for encapsulating heat-curable optical semiconductor.

The composition used for the optical semiconductor package of the present invention is not particularly limited as long as it is the heat-curable silicone composition for encapsulating an optical semiconductor of the present invention.
The optical semiconductor package of the present invention is a cured product having excellent adhesiveness and appropriate hardness by using the thermosetting silicone composition for sealing an optical semiconductor of the present invention as a composition. Difficult to color against light emission, etc., excellent in heat-resistant coloring stability, adhesiveness, transparency, thin film curability, and can prevent the generation of heat from LED chips and the occurrence of cracks and peeling during the production of optical semiconductor packages. .

  The LED chip used in the optical semiconductor package 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 for the optical semiconductor package of the present invention is not particularly limited. For example, white, blue, red, and green are mentioned. The optical semiconductor package of the present invention has excellent adhesiveness, a cured product having an appropriate hardness, and a cured product that is excellent in adhesion and hardly discolored even when exposed to high temperatures due to heat generated from the LED chip for a long time. It can be applied to a white LED from the viewpoint of being obtained and having excellent transparency and heat-resistant coloring stability and excellent adhesiveness at high temperatures.

  Examples of the method for producing the optical semiconductor package of the present invention include an applying step of applying the silicone composition for encapsulating heat-curable optical semiconductor of the present invention to an LED chip, and the silicone composition for encapsulating thermosetting optical semiconductor of the present invention. And a heat curing step of sealing the LED chip by heating the LED chip to which the heat resistance is applied to cure the thermosetting silicone composition for encapsulating an optical semiconductor.

  In the application step, the LED chip is provided with the thermosetting silicone semiconductor sealing resin composition and the thermosetting silicone semiconductor sealing silicone composition. 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 heat-curable silicone composition for encapsulating an optical semiconductor according to the present invention. The method of giving is not particularly limited.

  Next, in the heat curing step, the LED chip to which the silicone composition for encapsulating thermosetting optical semiconductor is applied is heated to cure the silicone composition for encapsulating thermosetting optical semiconductor to form the LED chip. By sealing, the optical semiconductor package of the present invention can be obtained. The heating temperature in the heat curing step is as defined above. The LED chip may be blown in the heat curing step.

  As the form of the optical semiconductor package of the present invention, for example, a cured product directly sealing an LED chip, a shell type, a surface-mount type, a plurality of LED chips or between and / or the surface of an optical semiconductor package What is sealed is mentioned.

The optical semiconductor package of the present invention will be described below with reference to the accompanying drawings. The optical semiconductor package of the present invention is not limited to the attached drawings.
FIG. 1 is a cross-sectional view schematically showing an example of the optical semiconductor package of the present invention.
In FIG. 1, an optical semiconductor package 800 includes a semiconductor light emitting element 803, a frame body 804 having a recess 802, and a sealing material 808, and the semiconductor light emitting element 803 is provided at the bottom (not shown) of the recess 802. The frame body 804 includes a reflector 820 obtained from a Group 11 metal on the side surface and / or bottom surface (not shown) of the recess 802, and the sealing material 808 seals the semiconductor light emitting element 803 and the reflector 820. To do. Examples of the frame material include polyphthalamide.
The sealing material 808 is obtained by curing the composition of the present invention. In the recess 802, the hatched portion 806 may be filled with the silicone resin composition of the present invention. Alternatively, the portion denoted by reference numeral 808 may be another transparent layer, and the hatched portion 806 may be a sealing material included in the optical semiconductor package of the present invention. The sealing material can contain a fluorescent substance or the like.
Each optical semiconductor package can have one or a plurality of semiconductor light emitting elements. The semiconductor light emitting device may be disposed in the frame with the light emitting layer (the surface opposite to the surface in contact with the mount member) facing up.
The semiconductor light emitting element 803 is disposed on the bottom (not shown) of the recess 802 formed by the frame body 804 and the substrate 810, and is fixed by the mount member 801.
When the end portions 812 and 814 included in the frame body 804 are integrally coupled so that the reflector forms a bottom surface, or a side surface and a bottom portion, the semiconductor light emitting element can be disposed on the bottom portion of the reflector.
The reflector 820 may have a tapered opening end (not shown) whose cross-sectional dimension increases as the distance from the bottom (not shown) of the recess 802 increases.
Examples of the mounting member include silver paste and resin. Each electrode (not shown) of the semiconductor light emitting element 803 and the external electrode 809 are wire bonded by a conductive wire 807.
In the optical semiconductor package 800, the recess 802 can be sealed with a sealing material 808, 806, or 802 (a portion in which the portion 808 and the portion 806 are combined).

  FIG. 2 is a cross-sectional view schematically showing another example of the optical semiconductor package of the present invention. In FIG. 2, an optical semiconductor package 900 has a lens 901 on the optical semiconductor package 800 shown in FIG. The lens 901 may be formed using the composition of the present invention.

  Applications of the optical semiconductor package 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. .

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these.
<Production of reaction product (I)>
(I) Reaction product 1
(A) Organopolysiloxane resin 1 (50 g) is dissolved in toluene (25 g), and (C) diorganopolysiloxane 1 (50 g) is added thereto and stirred for 5 minutes. : 26 wt%) and stirred for 24 hours under room temperature conditions.
After the reaction, suction was performed for 1 hour at room temperature under reduced pressure, and then suction was performed for 3 hours at 100 ° C. under reduced pressure to remove toluene in the system to obtain a reaction product (I). The obtained reaction product (I) is referred to as (I) reaction product 1. The obtained (I) reaction product 1 is a mixture of (A) an organopolysiloxane resin 1 and (C) a diorganopolysiloxane 1 and an unreacted (C) diorganopolysiloxane 1. is there.

The details of (A) organopolysiloxane resin 1 are as follows (the same applies hereinafter).
(A) Organopolysiloxane resin 1: MQ resin (weight average molecular weight 4000, trade name: SR1000, manufactured by Momentive Materials Japan GK) SR1000 has a structure represented by the following formula (I).
(R ¹ SiO _3/2 ) a (R ² ₂ SiO _2/2 ) b (R ³ ₃ SiO _1/2 ) c (SiO _4/2 ) d (XO _1/2 ) e (I)
In the formula, a and b are 0, c: d is 0.6: 1 to 0.7: 1, R ^{1 to} R ³ are methyl groups, X is a hydrogen group, and d / (a + b + c + d) is 0. .6, e / (a + b + c + d) is 0.07.
(C) Details of the diorganopolysiloxane 1 are as follows (the same applies hereinafter).
(C) Diorganopolysiloxane 1: linear polydimethylpolysiloxane (weight average molecular weight 3000) having both molecular chain ends blocked with silanol groups, viscosity at 25 ° C., 40 mPa · s, trade name KF9701, Shin-Etsu Chemical Made by company

(I) Reaction product 2
(A) Organopolysiloxane resin 1 (50 g) is dissolved in toluene (25 g), to which (C) diorganopolysiloxane 1 (50 g) is added and stirred for 5 minutes, and 0.05 g of triethylamine is added thereto for 24 hours. Stir at room temperature.
After the reaction, suction was performed for 1 hour at room temperature under reduced pressure, and then suction was performed for 3 hours at 100 ° C. under reduced pressure to remove toluene in the system to obtain a reaction product (I). The obtained reaction product (I) is referred to as (I) reaction product 2. The obtained (I) reaction product 2 is a mixture of (A) an organopolysiloxane resin 1 and (C) a diorganopolysiloxane 1 and an unreacted (C) diorganopolysiloxane 1. is there.

<Evaluation>
The composition obtained as described below was used to evaluate the long-term reliability (adhesiveness) under hardness and high-temperature conditions by the following method. The results are shown in Table 1.
1. Hardness The JIS A hardness of the initial cured product obtained by curing the composition obtained as described below at 150 ° C. for 24 hours was measured in accordance with the provisions of JIS K6523: 2006. When the hardness (JIS A hardness) is in the range of 30 to 90, it can be said that the hardness of the initial cured product is appropriate.
2. Volume curing shrinkage 2 g of the composition of the present invention was placed in an aluminum container and heated at 150 ° C. for 24 hours to obtain a cured product.
Measurement of Shrinkage Ratio Specific gravity was measured using a micromeritics AccuPick 1330 manufactured by Shimadzu Corporation, and the specific gravity of the composition before curing and the specific gravity and weight of the cured product after curing were measured. The volume before curing and the volume after curing are calculated from the obtained specific gravity and weight, and these are applied to the formula: [(volume before curing−volume after curing) / volume before curing] × 100 to reduce the volume shrinkage (% )
The volume shrinkage is preferably 10% or less, and more preferably 5% or less, from the viewpoint that cracks and peelings are less likely to occur in the cured product. If the volume shrinkage rate is greater than 10%, cracks or peeling may occur.

3. Long-term reliability (adhesiveness)
The manufactured composition obtained as described below is used in an LED package (manufactured by Enomoto Co., Ltd. The LED package has a polyphthalamide frame and a silver-plated lead frame / reflector, and so on). Poured and cured at 150 ° C. for 8 hours to obtain a laminate of the cured product and the adherend.
The obtained cured product was placed under conditions of 150 ° C. for 500 hours, and the state after 500 hours was visually confirmed. The presence or absence of cracks and peeling from the LED package (frame, or frame and reflector) was visually confirmed.
As a result of the evaluation, the case where the cured product was excellent in adhesiveness without cracks or peeling from the LED package was indicated as “◯”, and the case where the cured product was cracked or peeled off from the LED package was indicated as “x”.

<Production of composition>
The components shown in Table 1 below were uniformly mixed in the amounts shown in the same table (unit: parts by weight) using a vacuum stirrer to produce a thermosetting silicone resin composition for encapsulating an optical semiconductor. Note that (D) condensation catalyst 1 and (D) condensation catalyst 2 were mixed beforehand.

The details of each component shown in Table 1 are as follows.
-(I) Reaction products 1 and 2: prepared as described above-(F) Organopolysiloxane resin 1: same as above-(C) diorganopolysiloxane 1: same as above-(B) alkoxysilane oligomer 1: DT resin, alkoxysilane oligomer having 14% by weight of silicon-bonded methoxy group in one molecule, weight average molecular weight 20,000, trade name XR31-B2733, manufactured by Momentive Performance Materials, Inc. (D) condensation catalyst 1 : Tributoxyzirconium naphthate Zirconium tetrabutoxide (manufactured by Kanto Chemical Co., Ltd., 0.026 mol) and 6.6 g (0.026 mol) of naphthenic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred and reacted at room temperature for about 2 hours. The target compound was obtained. 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 obtained synthesized product is referred to as (D) condensation catalyst 1. (D) The average number of carbon atoms of R ^{1 in} the naphthate group (R ¹ COO—) of the condensation catalyst 1 is 15.
(D) Condensation catalyst 2: dibutyltin diacetate (manufactured by Nitto Kasei Co., Ltd.)
(D) Condensation catalyst 3: zinc 2-ethylhexanoate (Hope Pharmaceutical Co., Ltd.)
(E) Oligomeric silane coupling agent 1: 3-glycidoxypropyl group-containing methoxysilane oligomer, viscosity 12 mPa · s (mm ² / s), epoxy equivalent 830 g / mol, alkoxy group amount 50 weight per molecule %, 39% by weight of SO ₂ per molecule, trade name X-40-1053 (a silicone oligomer containing an epoxy group and blocked with methoxy / ethoxy at the molecular end), manufactured by Shin-Etsu Chemical Co., Ltd.

As is apparent from the results shown in Table 1, the reaction product (I) is not contained and is similar to the (A) organopolysiloxane resin used in producing the reaction product (I) instead (F In Comparative Example 1 containing an organopolysiloxane resin and (C) a diorganopolysiloxane, the volume cure shrinkage was large. (B) The comparative example 2 which does not contain the alkoxysilane oligomer which has 5 to 50 weight% of silicon-bonded alkoxy groups did not harden | cure and did not adhere | attach.
On the other hand, Examples 1 to 6 do not require ultraviolet irradiation, are easy to work, suppress curing shrinkage, can be easily cured by heating, and are excellent in adhesiveness and long-term reliability. In the present specification, excellent long-term reliability means, for example, that it is difficult to cause peeling or cracking even under high temperature conditions for a long period of time and is excellent in durability. The composition of the present invention is excellent in long-term reliability.

800, 900 Optical semiconductor package 801 Mount member 802 Concavity, silicone resin layer 803 Semiconductor light emitting element 804 Frame body 806 Shaded portion (silicone resin layer)
807 Conductive wire 808 Silicone resin layer (other transparent layers)
809 External electrode 812, 814 End 810 Substrate 820 Reflector 901 Lens

Claims (8)

(A) R ₃ SiO _0.5 unit (wherein R is a hydrocarbon group and / or hydroxyl group), 100 parts by weight of an organopolysiloxane resin having a SiO ₂ unit and a silanol group, and (C) both ends of the molecular chain Obtained by subjecting 10 to 200 parts by weight of a diorganopolysiloxane having a viscosity of 5 to 10,000 mPa · s sealed with silanol groups and / or alkoxysiloxy groups in the presence of a base. 100 parts by weight of product (I),
(B) 10 to 500 parts by weight of an alkoxysilane oligomer having 5 to 50% by weight of a silicon atom-bonded alkoxy group,
(D) A thermosetting silicone resin composition for encapsulating an optical semiconductor, comprising a condensation catalyst.   The silicone resin composition for thermosetting optical semiconductor encapsulation according to claim 1, wherein the base is ammonia and / or a tertiary amine.   The thermosetting silicone resin composition for encapsulating a thermosetting optical semiconductor according to claim 1, wherein the component (D) is at least one selected from the group consisting of a zirconium compound, a tin compound, and a zinc compound.   The silicone resin composition for encapsulating heat-curable optical semiconductor according to any one of claims 1 to 3, wherein the component (C) is polydimethylsiloxane in which both ends of the molecular chain are sealed with silanol groups. Further, (F) an organopolysiloxane resin having _0.5 units of R ₃ SiO (wherein R is a hydrocarbon group and / or a hydroxyl group), an SiO ₂ unit and a silanol group, the organopolysiloxane resin ( The amount of F) is 10 to 500 parts by weight with respect to 100 parts by weight of the reaction product (I). The thermosetting silicone resin composition for encapsulating an optical semiconductor according to any one of claims 1 to 4.   And (E) an oligomer type silane coupling agent having one or more silicon atom-bonded alkoxy groups and one or more epoxy groups in one molecule, wherein the amount of the component (E) is the component (I) and It is 0.01-10 weight part with respect to a total of 100 weight part of said (B) component, The thermosetting silicone resin composition for optical semiconductor sealing in any one of Claims 1-4.   Further, (E) an oligomer type silane coupling agent having one or more silicon atom-bonded alkoxy groups and one or more epoxy groups in one molecule, wherein the amount of the component (E) is the component (I), The thermosetting silicone resin composition for optical semiconductor encapsulation according to claim 5, wherein the amount is 0.01 to 10 parts by weight relative to 100 parts by weight of the total of the component (B) and the component (F).   The optical semiconductor package sealed with the silicone resin composition for thermosetting optical semiconductor sealing in any one of Claims 1-7.