TWI746495B - Thermosetting resin composition, prepreg, cured product, optical semiconductor composition, and optical semiconductor element - Google Patents

Abstract

The subject of the present invention is to provide a thermosetting resin composition excellent in reliability as a sealing material for LEDs, which has both high refractive index, gas barrier properties, and thermal shock resistance. The present invention is a thermosetting resin composition containing the following (A), (B) and (C): (A) as a silsesquioxane having a SiH group and an organopolysiloxane having two alkenyl groups A thermosetting resin containing SiH groups and alkenyl groups; (B) a straight line having an alkenyl group or SiH group at both ends, an aryl group in the main chain, and a silicone chain as the main structure Chain compound; and (C) Pt catalyst.

Description

Thermosetting resin composition, prepreg, cured product, light semi Conductor composition and optical semiconductor element

The present invention provides a thermosetting resin composition, a cured product obtained by curing the thermosetting resin composition, an optical semiconductor composition and an optical semiconductor element using the cured product, the thermosetting resin composition The product contains a thermosetting resin containing silsesquioxane and organopolysiloxane, and it has both high refractive index, gas barrier properties and resistance to cold and heat shock.

Light-emitting diodes (Light Emitting Diodes, LEDs) are used for a wide range of applications such as lighting. With the increase in output of white LEDs, the required characteristics of LED sealing materials have gradually become stricter. Therefore, there is a strong demand for a thermosetting resin composition that is capable of coping with increased output of white LEDs, has a high refractive index, and also has thermal shock resistance.

A silsesquioxane material excellent in heat resistance and ultraviolet (Ultra Violet, UV) resistance has attracted attention, and LED sealing materials using the material have been reported.

Patent Document 1 discloses a sealing material for LEDs that is advantageously used for a thermosetting resin composition of a thermosetting resin having a SiH group introduced into a cage octasesquisiloxane and an organopolysiloxane having an alkenyl group.

Patent Document 2 discloses a thermosetting resin composition using an incomplete cage silsesquioxane commonly called a double-decker type. Silsesqui Oxyane is a structure-controlled compound obtained by hydrolysis and condensation of phenyltrimethoxysilane. The position of Si-Ph group is not random, but is structure-controlled, so it is not only a high refractive index, but also heat resistance And excellent light resistance.

Patent Document 2 discloses a thermosetting resin containing SiH groups and vinyl groups, which is a compound obtained by modifying the SiH group on the silanol group of a silsesquioxane with an incomplete cage structure and a compound having an alkenyl group Obtained by the reaction of organopolysiloxane. It is also shown that the resin obtained by curing the thermosetting resin not only has a high refractive index, but also has high heat resistance, and is further combined with a polyphthalamide resin base material or a silver base material as the LED package material. The adhesion is good.

Patent Literature 3 and Patent Literature 4 describe that by blending a linear polyorganosiloxane having SiH groups at one end into a thermosetting resin composition using a double-layer silsesquioxane, it can be cured against heat. The resin imparts resistance to cold and heat shock.

Patent Document 5 describes a silicone gel composition containing as a component an organopolysiloxane having SiH groups at both ends, which is heated under reduced pressure to remove volatile low-molecular-weight silicones.

Patent Document 6 proposes a corrosive gas-permeable (gas barrier) composition used in a silver-plated surface used in an LED substrate related to a decrease in brightness for LED lighting.

Patent Document 7 and Patent Document 8 describe the use of a linear compound having a specific structure to provide a thermosetting resin composition and a thermosetting resin with features such as heat resistance.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2012-102167

Patent Document 2: International Publication No. 2011/145638

Patent Document 3: International Publication No. 2014/065143

Patent Document 4: International Publication No. 2014/077216

Patent Document 5: Japanese Patent Laid-Open No. 2008-231247

Patent Document 6: Japanese Patent Laid-Open No. 2014-129478

Patent Document 7: Japanese Patent Laid-Open No. 2012-140617

Patent Document 8: Japanese Patent Laid-Open No. 2012-21157

Since the composition of Patent Document 1 is basically composed of -Me ₂ Si-O units, the refractive index is not high. Furthermore, the properties of the composition are solid at room temperature and can be applied to the sealing of LEDs using a molding method, but cannot be applied to the sealing of LEDs of a dispenser method.

The use of a cured product of a thermosetting resin containing SiH groups and a vinyl group described in Patent Document 2 has a problem of poor adhesion performance when the content of the double-layer silsesquioxane is small. The thermosetting resin It is obtained by the reaction of a double-layer silsesquioxane with 4 SiH groups and an organopolysiloxane with 2 vinyl groups.

On the other hand, when the content of silsesquioxane is high, the adhesion performance is improved, but the resin may become too hard. As a result, the stress cannot be relieved, and peeling from the LED package may occur during the thermal shock test. condition. Furthermore, in the wire bonding type packaging method, there is a problem that wire cutting is likely to occur.

Furthermore, with the expansion of LED lighting applications, it is impossible to ignore the decrease in brightness due to the corrosion of the corrosive gas on the silver-plated surface used in the LED substrate.

Although Patent Document 3 and Patent Document 4 show that the thermal shock resistance can be improved, they do not describe the gas barrier properties against corrosive gases.

Although Patent Document 6 describes a composition for improving gas barrier properties, there is no description about thermal shock resistance.

The gas barrier properties and thermal shock resistance are required performances of the sealing material for LEDs, but the two are in an opposite relationship and it has been difficult to achieve both.

Furthermore, in recent years, there has been a demand for higher gas barrier properties, and it is difficult to meet the demand with the existing sealing materials for LEDs.

The present invention provides a thermosetting resin composition that has high refractive index, higher gas barrier properties, and high thermal shock resistance, and is excellent in reliability as a sealing material for LEDs.

The inventors of the present invention made diligent studies in order to solve the above-mentioned problems. As a result, it was discovered that the above problem was solved by including a thermosetting resin containing SiH groups and alkenyl groups, a linear compound having a specific structure, and a Pt catalyst in a thermosetting resin composition, thereby completing the present invention According to the invention, the thermosetting resin is obtained by the reaction of a silsesquioxane having an SiH group and an organopolysiloxane having two alkenyl groups.

That is, the present invention is as described below.

1. A thermosetting resin composition containing the following (A), (B) and (C): (A) as a silsesquioxane having a SiH group and an organopolysiloxane having two alkenyl groups A thermosetting resin containing SiH groups and alkenyl groups; (B) has an alkenyl group or SiH group at both ends, at least one aryl group in the main chain, and a silicone chain as the main structure The linear compound; and (C) Pt catalyst.

2. The thermosetting resin composition according to item 1, wherein (B) is a linear compound having alkenyl groups at both ends, at least one aryl group in the main chain, and a silicone chain as the main structure .

3. The thermosetting resin composition according to item 1, wherein (B) is a linear compound having SiH groups at both ends, at least one aryl group in the main chain, and a silicone chain as the main structure .

4. The thermosetting resin composition according to any one of items 1 to 3, wherein the silsesquioxane in (A) is a double-layer silsesquioxane.

5. The thermosetting resin composition according to any one of items 1 to 4, which further contains the following (D): (D) by making a silsesquioxane having a SiH group, two A compound having an SiH group obtained by reacting an alkenyl organopolysiloxane, an epoxy compound having an alkenyl group, and a silyl compound having an alkenyl group.

6. The thermosetting resin composition according to any one of items 1 to 5, wherein (A) is a compound represented by formula (1):

In formula (1), X is independently a group represented by formula (XI), formula (X-II) or formula (X-III), and the compound represented by formula (1) per molecule [the When the compound is a mixture of the group represented by the formula (XI), the ratio of the group represented by the formula (X-II) and the group represented by the formula (X-III) is different, it is said compound The number of groups represented by formula (XI) of 1 molecule average] is a, the number of groups represented by formula (X-II) is b, and the number of groups represented by formula (X-III) In the case of c, a+2b+c=4, 0<a≦3, 0≦b≦1, 0<c≦3; R ^{1 is} independently an alkyl group with 1 to 4 carbon atoms, or a cyclopentyl group Or cyclohexyl; m is an average value satisfying 1~100; -H (XI)

In formula (X-II), R ² and R ^{3 are} independently alkyl with 1 to 4 carbons, cyclopentyl, cyclohexyl, or phenyl; r is ^{the repeating number of -OSi(R 3} ) ₂ -, which is Meet the average value of 2-20;

In formula (X-III), R ⁴ and R ^{5 are} independently alkyl with 1 to 4 carbons, cyclopentyl, cyclohexyl or phenyl; s is ^{the repeating number of -OSi(R 5} ) ₂ -, which is which the mean value of from 2 to 20; R & lt ⁰ having one double bond unsaturated hydrocarbon group having a carbon number of 2 to 5, R ^{'is 0} carbon atoms and R & lt same saturated hydrocarbon ^0.

7. The thermosetting resin composition according to any one of items 1 to 6, wherein (B) is a compound represented by formula (2):

In formula (2), R ⁶ and R ^{7 are} independently alkyl with 1 to 4 carbons, cyclopentyl, cyclohexyl, or aryl with 6 to 12 carbons; n is -OSi(R ⁷ ) _2- The repetition number is an average value that satisfies 1-50; R ⁰ is hydrogen or an unsaturated hydrocarbon group with 1 double bond with 2-5 carbon atoms.

8. The thermosetting resin composition according to item 7, wherein in the compound represented by formula (2), 50% or more of ^{2n R 7 are aryl groups.}

9. The thermosetting resin composition according to any one of items 1 to 6, wherein (B) is a compound represented by formula (3):

In formula (3), R ⁶ and R ^{7 are} independently alkyl with 1 to 4 carbons, cyclopentyl, cyclohexyl, or aryl with 6 to 12 carbons; j is a number satisfying 1 to 5, and k is an average value of 0 or 1 to 50 satisfied; ⁰ is hydrogen or R & lt carbon atoms having one double bond unsaturated hydrocarbon group having 2 to 5, R ^{0 'is} a saturated hydrocarbon group having a carbon number of 2 to 5; to R & lt hydrogen is not ⁰ In the case of R ^0'and R ⁰ are the same carbon number.

10. The thermosetting resin composition according to item 9, wherein in the compound represented by formula (3), 50% or more of ^{2n R 7 are aryl groups.}

11. The thermosetting resin composition according to any one of items 5 to 10, wherein (D) is a compound represented by formula (D1):

In formula (D1), X'is independently the following formula (a), formula (b), formula (ci), formula (c-ii), formula (c-iii), formula (di), formula (d) -ii) or the group represented by the formula (d-iii), for each molecule of the compound represented by the formula (D1) [the compound is the group represented by the formula (a) and the formula (b), (ci), formula (c-ii), formula (c-iii), formula (di), formula (d-ii) or formula (d-iii) in the case of a mixture of compounds with different ratios of groups represented Below, the number of groups represented by formula (a) of the compound 1 molecule average] is set to A', the number of groups represented by formula (b) is set to B', formula (ci), formula ( c-ii) or the number of groups represented by formula (c-iii) is set to C', and the number of groups represented by formula (di), formula (d-ii) or formula (d-iii) is set to In the case of D', A'+2B'+C'+D'=4, 0.5≦A'≦3.0, 0.5≦2B'≦2.0, 0.1≦C'≦2.0, 0≦D'≦1.0; R ^{1 '} Independently is an alkyl group with 1 to 4 carbons, cyclopentyl or cyclohexyl; m'is an average value satisfying 1 to 100; -H (a)

In the formula (b), R ^{2 'and} R ^3' are independently alkyl carbon atoms, a cyclopentyl group, a cyclohexyl group or a phenyl group having 1 to 4; t is -OSi (R ^{3 ')} ₂ - a number of repetitions, It is an average value that satisfies 1-20;

Formula (di) R ^{4 ',} in Formula (d-ii) R ^{4 "and} of formula ^{(d-iii) R 4'} '' is independently selected from methyl, ethyl, butyl and isobutyl The group in the propyl group; the x in the formula (d-ii) is the ^{repeating number of -OSi(R 4"} ) ₂ -, which is an average value satisfying 1 to 20; the y in the formula (d-iii) is- The number of repetitions of OSi(R ^4''' ) ₂ -is an average value that satisfies 1-10; R ⁰ in formula (d-iii) is an unsaturated hydrocarbon group with 2-5 carbons and one double bond.

12. The thermosetting resin composition according to item 11, wherein in formula (D1) of item 11, R ^1'is a methyl group, m'is an average value that satisfies 1 to 25, and X'is independently formula ( a), the group represented by the formula (b), the formula (ci) or the formula (di).

13. The thermosetting resin composition according to any one of items 1 to 12, wherein the ratio of (A) is 50% to 95% by mass based on the total amount of the thermosetting resin composition, ( The ratio of B) is 2% by mass to 50% by mass.

14. The thermosetting resin composition according to any one of items 1 to 12, wherein the ratio of (A) is 70% to 95% by mass based on the total amount of the thermosetting resin composition, ( The ratio of B) is 2% by mass to 30% by mass, and the hardness is 45 or more.

15. The thermosetting resin composition according to any one of items 5 to 14, wherein the ratio of (D) is 1% by mass to 20% by mass based on the total amount of the thermosetting resin composition.

16. The thermosetting resin composition according to any one of items 1 to 15, wherein an inorganic compound is further dispersed.

17. The thermosetting resin composition according to item 16, wherein the inorganic compound is at least one of a phosphor or a metal oxide.

18. A prepreg obtained by molding the thermosetting resin composition according to any one of items 1 to 17.

19. A hardened product made of any one of items 1 to 17 The thermosetting resin composition or the prepreg described in Item 18 is cured and obtained.

20. A composition for an optical semiconductor containing the thermosetting resin composition according to any one of items 1 to 17, or the prepreg according to item 18.

21. An optical semiconductor element comprising the composition for optical semiconductor according to item 20 as a sealing agent.

22. The cured product according to item 19, which is in the form of a coating film or sheet, and has a thickness of 0.1 μm to 3,000 μm.

The cured product obtained by curing the thermosetting resin composition of the present invention can not only maintain the advantage of high refractive index, but also can reduce the coefficient of elasticity. Therefore, the cured product sealed with the thermosetting resin composition of the present invention has excellent stress relaxation ability, and an optical semiconductor device fabricated using the thermosetting resin composition can form a light that can withstand rigorous reliability tests. Semiconductor device. In addition, since it is a thermosetting resin composition with high gas barrier properties, corrosion of the silver-plated surface used in the LED substrate due to corrosive gas can be suppressed, and the decrease in brightness can be suppressed. Furthermore, it is possible to form an optical semiconductor device that is not only low in hardness, but also low in surface viscosity, dicable, and excellent in formability.

In addition, it is formulated to obtain a hardened product with high hardness, and the obtained hardened product can further improve gas barrier properties, and therefore can further suppress corrosion caused by corrosive gases. It can also be used in applications requiring high gas barrier properties.

The thermosetting resin composition of the present invention can be obtained by using a two-layer silsesquioxane skeleton as a main component of a thermosetting resin (A) and a compound (B) For those exhibiting the above characteristics when used in combination, the thermosetting resin (A) can ensure gas barrier properties, and the compound (B) can ensure gas barrier properties, provide stress relaxation properties, and impart thermal shock resistance.

Since the thermosetting resin composition of the present invention has a two-layer silsesquioxane skeleton as a main component, its cured product is not only excellent in heat resistance, but also excellent in UV resistance.

Hereinafter, the present invention will be described in detail. In addition, in this application, the thermosetting resin defined by (A) may be expressed as thermosetting resin (A) or only (A). In addition, the compound defined by (B) may be expressed as compound (B) or only (B). The same applies to the compounds defined by (D) and (E). (C) Pt catalyst is sometimes expressed as Pt catalyst (C) or only (C).

The thermosetting resin composition of the present invention is characterized by containing the following (A), (B) and (C): (A) as a silsesquioxane having a SiH group and an organopolysilicon having two alkenyl groups A thermosetting resin containing SiH groups and alkenyl groups; (B) has an alkenyl group or SiH group at both ends, at least one aryl group in the main chain, and a silicone chain as the main Structure linear compound; and (C) Pt catalyst.

Hereinafter, each component will be described.

The thermosetting resin defined by (A) is a reaction product of a silsesquioxane having a SiH group and an organopolysiloxane having two alkenyl groups. Examples of silsesquioxanes having SiH groups include double-layer silsesquioxanes and cage silsesquioxanes of T8 structure. The cage silsesquioxane of the T8 structure has 8 functional groups. In contrast, the double-layer silsesquioxane used in the present invention has only 4 functional groups, which makes it easy to control the structure. In addition, unlike the fully condensed cage silsesquioxane, the double-layered silsesquioxane suitably used in the present invention is an incomplete condensed type, has a relatively high degree of molecular freedom, and is excellent in flexibility. From this viewpoint, the double-layer silsesquioxane is preferred.

Examples of the thermosetting resin (A) include a two-layer compound represented by formula (1).

In formula (1), X is independently a group represented by formula (XI), formula (X-II), or formula (X-III). R ^{1 is} independently an alkyl group having 1 to 4 carbons, a cyclopentyl group, or a cyclohexyl group. m is an average value satisfying 1-100. Preferably m is 1.

-H (X-I)

In the formula (X-II), R ² and R ^{3 are} independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, a cyclohexyl group, or a phenyl group. r is the repetition number of -OSi(R ³ ) ₂ -, which is an average value satisfying 2-20. Preferably r is 2-10.

In the formula (X-III), R ⁴ and R ^{5 are} independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, a cyclohexyl group, or a phenyl group. s is the repetition number of -OSi(R ⁵ ) ₂ -, which is an average value satisfying 2-20. The preferable s is 2-10, and the more preferable s is 2-4. R ⁰ is having a double bond in unsaturated hydrocarbon group having a carbon number of 2 to 5, R ^{'is 0} carbon atoms and R & lt same saturated hydrocarbon ^0.

For each molecule of the compound represented by formula (1) [the compound is of formula In the case of a mixture of the group represented by (XI) and the ratio of the group represented by formula (X-II) and the group represented by formula (X-III) in different ratios, it is the average per molecule of the compound ] The number of groups represented by formula (XI) is a, the number of groups represented by formula (X-II) is b, and the number of groups represented by formula (X-III) is c In the case of a+2b+c=4, 0<a≦3, 0≦b≦1, 0<c≦3.

In the present invention, a compound that satisfies the range of a+2b+c=4, 0<a≦3, 0≦b≦1, and 0<c≦3 will be described.

If a>c, the compound represented by formula (1) has more SiH groups than alkenyl groups on average, and can be defined as a so-called SiH-based thermosetting resin.

The alkenyl group is not particularly limited as long as it is a group containing a carbon-carbon double bond, and it is an aliphatic unsaturated hydrocarbon group with 2 to 5 carbon atoms. The alkenyl group may be located in the middle of the molecular chain of the hydrocarbon group or at the end, but in terms of the curing speed of the obtained composition and the physical properties after curing, it is preferably bonded to the end of the molecular chain, especially the end of the molecular chain Of silicon atoms.

As the thermosetting resin (A), it is preferable to use a SiH-based thermosetting resin. From the standpoint of making the excellent properties of the cured product remarkable, a preferable a is 1.0 to 3.0, and a more preferable a is 1.5 to 2.5. The a, b, and c in the compound represented by the formula (1) can be arbitrarily adjusted by, for example, the production method described in International Publication No. 2011/145638.

Based on the total amount of the thermosetting resin composition, the thermosetting resin composition of the present invention preferably contains 50% to 95% by mass of the thermosetting resin (A), more preferably 60% to 90% by mass. quality%. By adding thermosetting resin (A) The blending ratio is set to 60% by mass or more, which can maintain the characteristics of the double-layer silsesquioxane, that is, heat resistance, UV resistance, and high refractive index. Furthermore, by setting it to 80% by mass or more, Further improve heat resistance. In addition, by setting the blending ratio of the thermosetting resin (A) to 95% by mass or less, the viscosity of the thermosetting resin composition can be controlled within a certain range.

The compound defined by (B) is a linear compound having an alkenyl group or SiH group at both ends, at least one aryl group in the main chain, and a siloxane chain as the main structure. For example, the following formula (2 ) Represented by the compound.

In the formula (2), R ⁶ and R ^{7 are} independently an alkyl group having 1 to 4 carbons, a cyclopentyl group, a cyclohexyl group, or an aryl group having 6 to 12 carbons. Preferably R ⁶ or R ⁷ is methyl or phenyl. n is the number of repetitions of -OSi(R ⁷ ) _{2 -.} n is 0 or satisfies the average value of 1 to 150. Preferably, n is an average value satisfying 1-50. R ⁰ is hydrogen or an unsaturated hydrocarbon group with 2 to 5 carbons having one double bond.

In order to provide both gas barrier properties and thermal shock resistance, it is preferable that 50% or more of ^{the 2n pieces of R 7 in the formula (2) are aryl groups.}

The compound represented by formula (2) can be synthesized by a known method. In addition, usually commercially available products can be used. For example, PMV-9925 (R ⁰ = vinyl, ^{50% of R 6} and R ⁷ are methyl groups, and 50% are phenyl groups) manufactured by Gelest Corporation can be cited.

In addition, the compound defined by (B) includes, for example, a compound represented by formula (3).

In formula (3), R ⁶ and R ^{7 are} independently alkyl with 1 to 4 carbons, cyclopentyl, cyclohexyl, or aryl with 6 to 12 carbons, preferably R ⁶ or R ⁷ is methyl Or phenyl. j is a number that satisfies 1 to 5, and k is 0 or an average value that satisfies 1 to 50. R ⁰ is hydrogen or an unsaturated hydrocarbon group with 2 to 5 carbons having one double bond. R ^0'is a saturated hydrocarbon group with 2 to 5 carbons. When R ⁰ is not hydrogen, R ^0'and R ^{0 have} the same carbon number.

In order to provide both gas barrier properties and thermal shock resistance, it is preferable that 50% or more of ^{the 2n pieces of R 7 in the formula (3) are aryl groups.}

The compound represented by formula (3) can be synthesized by the following method.

In the reaction formula, R ⁶ and R ^{7 are} independently alkyl with 1 to 4 carbons, cyclopentyl, cyclohexyl, or aryl with 6 to 12 carbons, j is a number satisfying 1 to 5, and k is 0 or meet the average value of 1-50. The R ⁰ is hydrogen or unsaturated hydrocarbon group having one double bond having 2 to 5 carbon atoms, of formula (3 ') and the formula (3 ") R ^0, or not simultaneously hydrogen having a carbon number of double bonds unsaturated hydrocarbon group of the .R 2 ~ 5 ^{0 'is 0} carbon atoms and R & lt same saturated hydrocarbon group.

The compound represented by formula (3') or formula (3") can be synthesized by a known method. In addition, commercially available products can usually be used. For example, DVDPTS (R ⁰ = vinyl, R ⁶ = methyl, R ⁷ = phenyl, j"=1), DV4P4S (R ⁰ = vinyl, R ⁶ = methyl, R ⁷ = phenyl, j=2), DHDPTS (R ⁰ = hydrogen, R ⁶ = methyl, R ⁷ = phenyl, j = 1). In addition, as long as ^{50% or more of R 8} in the formula (3) is an aryl group, within the above-mentioned range, as the compound represented by the formula (3') or formula (3"), a commonly available one can be selected M ^V DM ^V (R ⁰ = vinyl, R ⁶ = R ⁷ = phenyl, j=1), M'DM' (R ⁰ = hydrogen, R ⁶ = R ⁷ = phenyl, j=1), etc.

The function of the compound (B) is to ensure the gas barrier properties of the thermosetting resin (A) and to lower the coefficient of elasticity, thereby imparting thermal shock resistance to the thermosetting resin composition. The above-mentioned object is achieved by using the thermosetting resin (A) and the compound (B) in combination.

The number average molecular weight of the compound (B) is preferably 208 to 20,000. If the number average molecular weight of the compound (B) is 330 or more, the volatility becomes low, and the volatilization at the stage of preparing and curing the cured composition can be suppressed, which is more preferable. In addition, if the number average molecular weight of the compound (B) is more than 20,000, the gas barrier Since the barrier performance is lowered, it is preferably 20,000 or less. More preferably, it is 330~10000.

In all the thermosetting resin compositions of the present invention, the compounding ratio of the compound (B) is preferably set to 2% by mass to 50% by mass, more preferably set to 5% to 30% by mass. By setting the compounding ratio of the compound (B) to 2% by mass or more, the compounding effect can be expressed. In addition, by setting the compounding ratio of the compound (B) to 50% by mass or less, the compound (B) can be provided while maintaining the heat resistance and UV resistance of the cured product of the thermosetting resin (A). ) The effect of the deployment.

The compound (B) may also use one or two or more of the compounds represented by the formula (2) or (3) in combination. In the case of combined use, if the number average molecular weight of one type is 208 to 20,000, the number average molecular weight of the compound (B) used in combination may be 20,000 or more. Preferably it is 100,000 or less. The total blending ratio in the case of combined use is as described in the above paragraph.

The Pt catalyst in (C) refers to a catalyst containing platinum, and platinum may be unoxidized or oxidized. As the platinum to be oxidized, platinum oxide can be cited, for example. Examples of platinum that is partially oxidized include Adams' catalyst.

Examples of the Pt catalyst (C) include Karsted't catalyst, Speier catalyst, and hexachloroplatinic acid. These Pt catalysts are generally well-known catalysts. Among them, a non-oxidized type Caster catalyst can be preferably used.

The blending ratio of the Pt catalyst (C) is preferably an amount sufficient to promote the curing of the curable resin composition of the present invention, specifically, it is preferably 0.01 ppm to 10 ppm, more preferably 0.05ppm~1ppm. By adding Pt catalyst (C) The blending ratio is set to 0.01 ppm or more, and it can be hardened. By setting the blending ratio of the Pt catalyst (C) to 0.05 ppm or more, curing can proceed quickly. In addition, by setting the blending ratio of the Pt catalyst (C) to 10 ppm or less, the heat resistance of the cured product can be maintained.

The thermosetting resin composition of the present invention may further contain the compound defined by (D) as necessary. The compound (D) is a compound having a SiH group and may or may not have an alkenyl group.

The compound (D) is obtained by reacting a silsesquioxane having an SiH group, an organopolysiloxane having two alkenyl groups, an epoxy compound having an alkenyl group, and a silyl compound having an alkenyl group. As a compound (D), the compound represented by following formula (D1) is mentioned, for example.

In formula (D1), X'is independently the following formula (a), formula (b), formula (ci), formula (c-ii), formula (c-iii), formula (di), formula (d) -ii) or the group represented by the formula (d-iii), for each molecule of the compound represented by the formula (D1) [the compound is of the formula (a) The represented group is related to formula (b), formula (ci), formula (c-ii), formula (c-iii), formula (di), formula (d-ii) or formula (d-iii) In the case of a mixture of compounds having different ratios of groups represented by the compound, the number of groups represented by formula (a) of the compound is set to A', and the group represented by formula (b) The number of groups is set to B',

The number of groups represented by formula (ci), formula (c-ii) or formula (c-iii) is set to C', represented by formula (di), formula (d-ii) or formula (d-iii) When the number of groups is set to D', A'+2B'+C'+D'=4, 0.5≦A'≦3.0, 0.5≦2B'≦2.0, 0.1≦C'≦2.0, 0≦ D'≦1.0.

R ^1'is independently an alkyl group having 1 to 4 carbons, a cyclopentyl group, or a cyclohexyl group, and m'is an average value satisfying 1 to 100.

-H (a)

In the formula (b), R ^{2 'and} R ^3' are independently alkyl having, 1 to 4 cyclopentyl, cyclohexyl or phenyl, t ₂ is -OSi (R ^{3 ')} - number of repetitions, It is an average value that satisfies 1-20.

Formula (di) R ^{4 ',} in Formula (d-ii) R ^{4 "and} of formula ^{(d-iii) R 4'} '' independently methyl, ethyl, butyl or isopropyl The x in formula (d-ii) is the ^{repetition number of -OSi(R 4"} ) ₂ -, which is an average value satisfying 1-20. In formula (d-iii), y is ^{the repetition number of -OSi(R 4'''} ) ₂ -, which is an average value satisfying 1-10. ^{R 0} in the formula (d-iii) is an unsaturated hydrocarbon group having 2 to 5 carbons and having one double bond.

The group represented by the formula (a) is a group derived from a silsesquioxane having a SiH group, and is a compound corresponding to the group represented by the formula (b) and corresponding to the formula (ci) ~ formula (c) -iii) The epoxy derivative of the group represented by the compound corresponding to the group represented by the formula (di) to the formula (d-iii) used as needed is a SiH group residue after the reaction. Therefore, since the group represented by the formula (a) can react with the following thermosetting resin, it has the effect of enhancing the function of the compound of the present invention as an adhesion-imparting material. The thermosetting resin enhances the present invention Compound as a close binding agent The pre-material is used and is the reaction product of silsesquioxane and organopolysiloxane.

The group represented by the formula (b) is a crosslinking component of silsesquioxane and can provide flexibility to the compound of the present invention. Specifically, for example, by crosslinking with formula (D1), a polymer structure like the compound represented by formula (1-1) can be provided.

In formula (1-1), X1 is independently a group represented by formula (a), formula (ci) ~ formula (c-iii), or formula (di) ~ formula (d-iii), and X2 is represented by The formula represented by formula (b). u is the average value satisfying 0-100.

The larger the number of groups represented by the formula (b), that is, the larger the value of B', the greater the number of cross-linking components between the molecules, and the compound of the present invention becomes a high-molecular-weight compound. If B'=0, there is no crosslinking component. If it is in the range of 0<B'≦1, as the value of B'increases, the crosslinking component increases and the molecular weight increases. If it is in the range of B'>1, the cross-linking of molecules is sufficiently advanced, and it becomes a gel form, and therefore cannot be used as a thermosetting resin. By changing the value of B'in the range of 0<B'≦1, the molecular weight of the compound of the present invention can be adjusted.

The groups represented by formulas (ci)~(c-iii) are epoxy groups bonded to SiH residues in the cross-linked body of silsesquioxane and organopolysiloxane, which can improve the compatibility with LEDs. The role of the adhesion of the shell base material. The component (c-i) is a group having a ring skeleton of an isocyanurate group in addition to an epoxy group, and has a function of also improving the adhesion to the metal.

The groups represented by formula (di)~(d-iii) are alkoxysilyl groups or trioxanes bonded to SiH residues in the cross-linked body of silsesquioxane and organopolysiloxane Alkenyl silyl group or alkenyl silyl group.

The group represented by formula (d-i) is a group derived from (D) and is an optional component.

The group represented by the formula (d-i) is used for the purpose of improving the close contact with the metal or the purpose of improving the compatibility with the resin.

In formula (di), R ^4'is independently methyl, ethyl, butyl or isopropyl.

The group represented by formula (d-ii) is a group derived from (D) and is an optional component. The group represented by the formula (d-ii) is used for the purpose of improving the compatibility with the resin, adjusting the viscosity, or adjusting the hardness of the curable resin composition after curing.

In formula (d-ii), R ^{4" is} independently a group selected from methyl, ethyl, butyl and isopropyl, preferably methyl. x is -OSi(R ^4" ) _2- The repetition number of is an average value that satisfies 1-20, and more preferably an average value that satisfies 1-10.

The group represented by formula (d-iii) is a group derived from (D) and is an optional component. The group represented by the formula (d-iii) is used for the purpose of improving the compatibility with the resin, adjusting the viscosity, or adjusting the hardness of the curable resin composition after curing.

In formula (d-iii), R ^{4'" is} independently a group selected from methyl, ethyl, butyl and isopropyl, preferably methyl. y is the repetition number of -OSi(R ^4''' ) ₂ -, and more preferably y is an average value satisfying 1-10. R ⁰ is an unsaturated hydrocarbon group having 1 double bond with 2 to 5 carbon atoms.

A'+2B'+C'+D'=4, 0.5≦A'≦3.0, 0.5≦2B'≦2.0, 0.1≦C'≦2.0, 0≦D'≦1.0. The value of A'to D'can be adjusted according to the compound of the present invention The properties of the thermoplastic resin composition used as the adhesion-imparting material can be adjusted arbitrarily.

The group derived from (D) is further explained. The reaction reagent and reaction method for obtaining the group represented by formula (d-ii) or formula (d-iii) will be described.

First, the reaction reagent for obtaining the group represented by the formula (d-ii) or the group represented by the formula (d-iii) will be described.

As shown in the following reaction formula, make excess moles of divinyl tetramethyl disiloxane (DVDS) and hexamethyl disiloxane (MM) in the presence of an acid catalyst, Perform equilibrium reaction on cyclic octamethyl tetracyclosiloxane (D4) to obtain a balanced mixture of compound a, compound b, and compound c, which is used to obtain the formula (d-ii) The group or the reaction reagent of the group represented by formula (d-iii).

In the reaction formula, a is 1-20, b is 1-20, and c is 1-20.

R ⁰ represents an unsaturated hydrocarbon group having 1 double bond with 2 to 5 carbon atoms.

The molar ratio of the combined reaction of DVDS and MM for D4 is preferably 2 or more. If the molar ratio is 2 or more, the molecular weight of the generated siloxane chain is small, and it becomes a component that can be removed by distillation. In the purification step described later, it becomes easy to remove the excess compound a and compound not participating in the reaction. b and compound c.

The method of the reaction for obtaining the group represented by formula (d-ii) or formula (d-iii) is described.

As the reaction of the compound having an isocyanuryl ring skeleton and epoxy group of the present invention and having a group represented by formula (d-ii) or formula (d-iii), it is derived from (D) The description is given when the group of is a group represented by formula (ci).

As shown in the following reaction formula, in the first stage of the reaction, DD-4H as a two-layer compound having 4 SiH groups and MA-DGIC as (ci) are first subjected to a hydrosilylation reaction. First, A compound having a group represented by formula (ci) is obtained. Furthermore, the compound of formula (c-i) is sold by Shikoku Chemical Co., Ltd. as MA-DGIC. DD-4H can be synthesized according to the method described in International Publication No. 2004/024741.

In the reaction formula, ai is 0.1≦ai≦3.5.

Then, as shown in the following reaction formula, in the second-stage reaction, the number of moles of SiH groups in the first-stage compound is determined by the ethylene of a mixture of compound a, compound b, and compound c. The hydrosilation reaction was carried out so that the molar number of the radical became excessive, and the following product was obtained.

In the reaction formula, ai is 0.1≦ai≦3.5, Xi is 0≦2Xi≦2.0, Yi is 0≦Yi≦3.0, Zi is 0.1≦Zi≦3.5, and Wi is 0≦Wi≦3.0.

R ⁰ is an unsaturated hydrocarbon group having 1 double bond with 2 to 5 carbon atoms.

Although the hydrosilation reaction is carried out in such a way that the molar number of vinyl becomes excessive However, it does not disappear in the high temperature region of 100°C or higher, and furthermore, 120°C or higher, and the remaining SiH groups remain.

The excess compound a, compound b, and compound c not participating in the reaction can be removed by distillation using a thin film evaporator. Or it can also be removed by solvent extraction. Or it can be left as it is arbitrarily by the inventor. The temperature in the case of distilling off excess compound a, compound b, and compound c in the distillation using a thin film evaporator is preferably in the range of 120°C to 180°C, and the operating pressure is preferably 0.13 kPa or less.

The preferred solvent used in the solvent extraction method to remove excess compound a, compound b, and compound c is a solvent with a high dissolving power and a relatively low boiling point. The preferred solvent is lower alcohol. A particularly good solvent is methanol. In order to further improve the degree of purification, it is only necessary to increase the number of repetitions of the solvent extraction operation.

Next, a method for obtaining only the group represented by formula (d-iii) will be described in detail.

As shown in the following reaction formula, in the first stage of the reaction, DD-4H and MA-DGIC are first subjected to hydrosilation reaction to obtain a compound having a group represented by formula (c-i) first.

In the reaction formula, aii is 0.1≦aii≦3.5.

The reactant used in the reaction of the second stage is a compound represented by formula (F).

In formula (F), R'and R" are independently a group selected from alkyl groups having 1 to 4 carbons, cyclopentyl, cyclohexyl, and phenyl, and r is an integer from 0 to 100. R'and R" is preferably methyl. r is preferably 1-100, more preferably 2-20.

R ⁰ is an unsaturated hydrocarbon group having 1 double bond with 2 to 5 carbon atoms.

As shown in the following reaction formula, silicon proceeds so that the molar number of the vinyl group of the compound represented by formula (F) becomes excessive relative to the molar number of the SiH group in the first-stage compound. Hydrogenation reaction obtains the following product.

In the reaction formula, aii is 0.1≦aii≦3.5, Xii is 0≦2Xii≦2.0, Yii is 0≦Yii≦3.0, Zii is 0.1≦Zii≦3.5, and r is 1-20.

R ⁰ is an unsaturated hydrocarbon group having 1 double bond with 2 to 5 carbon atoms.

Although the hydrosilation reaction proceeds in such a way that the molar number of the vinyl group of the compound represented by formula (F) becomes excessive, it does not disappear in the high temperature range of 100°C or higher, and furthermore, 120°C or higher, and the remaining SiH groups remain .

Since the excess organopolysiloxane not participating in the reaction is a compound having a vinyl group, it can remain directly as a resin component capable of having thermosetting properties. Or it can also be removed by solvent extraction etc. suitably. The preferred solvent for removing the excess organopolysiloxane is a solvent with a high dissolving power and a relatively low boiling point. The preferred solvent is lower alcohol. A particularly good solvent is methanol. In order to further improve the degree of purification, it is only necessary to increase the number of repetitions of the solvent extraction operation.

Moreover, as a compound (D), the compound represented by following formula (D2) is mentioned, for example. In formula (D1), R ^1'is a methyl group, m'is an average value satisfying 1-25, and X'is independently formula (a), formula (b), formula (ci), and formula (di) The group represented.

In the formula (D2), h'is an average value satisfying 1-25, preferably 1.

Based on the total amount of the thermosetting resin composition, the thermosetting resin composition of the present invention preferably contains 1% by mass to 20% by mass of the compound (D), and more preferably contains 1% by mass to 15% by mass. By setting the compounding ratio of the compound (D) to 1% by mass or more, the adhesion strength with the LED housing substrate can be improved.

In addition, the epoxy part in the compound (D) can be used arbitrarily, so it is preferably based on the total amount of the thermosetting resin composition, and the total amount of the epoxy part is 0.01% by mass to 10% by mass. The said compound (D) is contained, and it is more preferable to contain the said compound (D) so that the total of an epoxy part becomes 0.05 mass%-5 mass %.

If necessary, the thermosetting resin composition of the present invention may further include an organosiloxane compound (E) having 3 or more alkenyl groups or SiH groups. As such a compound, the compound represented by the following formula is mentioned, for example.

R ⁰ , R ⁶ and R ^{7 are} as described above. v is the average value satisfying 0-10, and w is the average value satisfying 3-5.

Further, it may also be formulated containing ^{_{R 0 R 6 2 SiO 1/2 -}} (M _{^{units), R 7 SiO 3/2 - (}} T units), SiO _4/2 - (Q units) -one as a silicone resin, a partial structure.

In all the thermosetting resin compositions of the present invention, the blending ratio of these compounds is preferably set to 15% by mass or less in total. By setting the blending ratio to 15% by mass or less in total, it is possible to perform viscosity adjustment and hardness adjustment without impairing the characteristics of the thermosetting resin composition provided by the thermosetting resin (A) and the compound (B).

The thermosetting resin composition of the present invention may further contain an alkoxysilane compound if necessary. As such a compound, the compound represented by the following formula is mentioned, for example.

R ⁸ _h Si(OR ⁹ ) _i R ¹⁰ _j (H)

Here, R ⁸ is an alkyl group with a carbon number of 10 or less or a phenyl group having an organic functional group at the end, R ⁹ and R ^{10 are} independently an alkyl group with a carbon number of 5 or less, and h and i are independently 0 to 3 Integer, j is an integer from 0 to 4, h+i+j=4.

As the alkoxysilane compound represented by the above formula, a commercially available compound may be used.

The following components may be further blended in the thermosetting resin composition of the present invention.

<Sclerosis inhibitor>

As the curing inhibitor, a known material used in an addition type curable composition using a hydrosilation catalyst can be used. Specifically, for example, a compound containing two or more alkenyl groups, a compound having an aliphatic unsaturated bond, an organophosphorus compound, a tin-based compound, and an organic peroxide can be cited. These compounds may be used alone or in combination of two or more kinds.

Examples of compounds containing two or more alkenyl groups include disiloxanes, trisiloxanes and 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane containing vinyl groups at both ends Such as vinyl-containing cyclic silicones.

As the compound containing an aliphatic unsaturated bond, for example, 2-methyl-3-butyn-2-ol, 3-methyl-1-dodecyn-3-ol, 3,5-dimethyl 1-hexyn-3-ol, 1-ethynyl-1-cyclohexanol and other propargyl alcohols, ene-yne compounds, maleic anhydride and maleic acid dimethyl maleate, etc. Diesters.

Examples of the organophosphorus compound include triorganophosphines, diorganophosphines, organic phosphines, and triorganophosphites.

Examples of tin-based compounds include stannous halide dihydrate and carboxylic acid Ashok. In addition, examples of organic peroxides include di-tert-butyl peroxide, dicumyl peroxide, benzyl peroxide, and t-butyl perbenzoate.

Among these compounds, 1,3-divinyldisiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, 2-methyl-3-butyne- 2-alcohol or 1-ethynyl-1-cyclohexanol.

By blending a curing inhibitor in the thermosetting resin composition of the present invention, the increase in viscosity at room temperature can be suppressed, and potlife can be ensured. The content of the curing inhibitor in the thermosetting resin composition of the present invention is preferably 0.001% by mass to 5% by mass, and more preferably 0.01% by mass to 3% by mass.

<Inorganic Compound>

The thermosetting resin composition of the present invention can further disperse an inorganic compound for use according to any purpose of imparting thixotropy or imparting optical properties. The inorganic compound used is not limited, and known materials can be used. In addition, the structure of the inorganic compound may be amorphous or crystalline. The combination of inorganic compounds to be dispersed is also not limited. As the inorganic compound, various phosphors or metal oxides can be suitably used. Of course, phosphors or metal oxides can also be used in combination.

First, the case where the inorganic compound is a phosphor will be described. By dispersing a phosphor in the thermosetting resin composition of the present invention, it has a light-emitting function, and it can be used as a composition for LEDs. The content of the phosphor in the thermosetting resin composition of the present invention is preferably 1% by mass to 90% by mass, and more preferably 2% by mass to 50% by mass.

Phosphors that can be used in the thermosetting resin composition of the present invention There is no limit. In addition, the concentration distribution of the phosphor in the composition may be uniform or different. The type of phosphor to be used, the presence or absence of the concentration distribution of the phosphor, and the conditions of the distribution may be determined according to the use environment, use, and purpose of the LED.

The phosphor absorbs the blue light, violet light, and ultraviolet light emitted from the LED chip, converts the wavelength, and emits light with wavelengths in the red, orange, yellow, green, and blue regions that are different from the light of the LED chip. Thereby, part of the light emitted from the LED chip and part of the light emitted from the phosphor are mixed to obtain a multi-color LED including white. Specifically, by optically combining a blue-based LED and a phosphor that emits a yellow-based emission color using light from the LED, a single LED chip can be used to emit white-based light.

Among the aforementioned phosphors, there are a variety of phosphors such as a phosphor that emits green light, a phosphor that emits blue light, a phosphor that emits yellow light, and a phosphor that emits red light. Examples of specific phosphors used in the present invention include known phosphors such as organic phosphors, inorganic phosphors, fluorescent pigments, and fluorescent dyes. As an organic phosphor, allyl sulfonamide can be cited. Melamine-formaldehyde co-condensation dyes, perylene-based phosphors, etc., in terms of long-term use, perylene-based phosphors can be preferably used. As the phosphors particularly preferably used in the present invention, inorganic phosphors can be cited. The inorganic phosphor used in the present invention is described below.

Examples of phosphors that emit green light include [SrAl ₂ O ₄ : Eu], [Y ₂ SiO ₅ : Ce, Tb], [MgAl ₁₁ O ₁₉ : Ce, Tb], [Sr ₇ Al ₁₂ O ₂₅ : Eu], [(at least one or more of Mg, Ca, Sr, and Ba) Ga ₂ S ₄ : Eu].

Examples of phosphors that emit blue light include [Sr ₅ (PO ₄ ) ₃ Cl: Eu], [(SrCaBa) ₅ (PO ₄ ) ₃ Cl: Eu], [(BaCa) ₅ (PO ₄ ) ₃ Cl : Eu], [(at least one of Mg, Ca, Sr, Ba) ₂ B ₅ O ₉ Cl: Eu, Mn], [(at least one of Mg, Ca, Sr, Ba) (PO ₄ ) ₆ Cl ₂ : Eu, Mn].

As a phosphor that emits green to yellow light, there is at least yttrium activated with cerium. Aluminum oxide phosphor, at least yttrium activated with cerium.釓. Aluminum oxide phosphor, at least yttrium activated with cerium. aluminum. Garnet oxide phosphor, and at least yttrium activated with cerium. gallium. Aluminum oxide phosphors, etc. (so-called YAG-based phosphors). Specifically, [Ln ₃ M ₅ O ₁₂ : R (Ln is at least one selected from Y, Gd, and La, M includes at least any of Al and Ca, and R is a lanthanide series)], [ (Y1-xGax) ₃ (Al1-yGay) ₅ O ₁₂ : R(R is at least one selected from Ce, Tb, Pr, Sm, Eu, Dy, Ho, 0<Rx<0.5, 0<y< 0.5)].

Examples of phosphors that emit red light include [Y ₂ O ₂ S: Eu], [La ₂ O ₂ S: Eu], [Y ₂ O ₃ : Eu], and [Gd ₂ O ₂ S: Eu].

In addition, as a phosphor that emits light corresponding to the current mainstream blue LED, [Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Gd) ₃ Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : Ce, Y ₃ Al ₅ O ₁₂ : Ce] and other YAG-based phosphors, [Tb ₃ Al ₅ O ₁₂ : Ce] and other TAG-based phosphors, [(Ba, Sr) ₂ SiO ₄ : Eu ]-Based phosphors or [Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce]-based phosphors, [(Sr, Ba, Mg) ₂ SiO ₄ : Eu] and other silicate-based phosphors, [(Ca, Sr) ₂ Si ₅ N ₈ : Eu], [(Ca, Sr)AlSiN ₃ : Eu], [CaSiAlN ₃ : Eu] and other nitride-based phosphors, [Cax(Si, Al) ₁₂ (O, N) ₁₆ : Nitrogen oxide-based phosphors such as Eu], and further examples include [(Ba, Sr, Ca)Si ₂ O ₂ N ₂ : Eu]-based phosphors, [Ca ₈ MgSi ₄ O ₁₆ C ₁₂ : Eu] It is a phosphor, [SrAl ₂ O ₄ : Eu, Sr ₄ Al ₁₄ O ₂₅ : Eu] and other phosphors.

Among these, in terms of luminous efficiency, brightness, etc., YAG-based phosphors, TAG-based phosphors, and silicate-based phosphors can be preferably used. In addition, in addition to this, a well-known phosphor can also be used according to the purpose or target emission color.

Next, the case where the inorganic compound is a metal oxide will be described. As the metal oxide, silicon dioxide, aluminum oxide, yttrium oxide, zinc oxide, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, etc. can be preferably used.

When titanium oxide or aluminum oxide is used in the thermosetting resin composition of the present invention, it can also be suitably used as a material for a reflector. In addition, in the thermosetting resin composition of the present invention, it is preferable to add silica for the purpose of preventing precipitation of the phosphor.

The proportion of silicon dioxide in the thermosetting resin composition of the present invention is preferably 0.1% to 40%, more preferably 1% to 20%, based on the weight ratio to the total amount of the thermosetting resin composition. More preferably, it is 1% to 10%.

Silica can be obtained by finely granulating naturally occurring silica (natural silica), or industrially synthesized silica (synthetic silica). In the case of natural silica, it has a crystal axis because it is crystalline. Therefore, although optical characteristics derived from crystals can be expected, since the specific gravity is slightly higher than that of synthetic silica, it may affect the dispersion in the thermosetting resin composition. In addition, in the case of obtaining by pulverizing a natural product, there are cases where it becomes particles of an indeterminate shape, or there are cases where the material has a wide particle size distribution.

Synthetic silicon dioxide includes wet synthetic silicon dioxide and dry synthetic silicon dioxide, and there is no particular limitation for use in the present invention. However, in the synthesis of silicon dioxide, no matter Regardless of the production method, there is a case of crystal water. When the crystal water may have some influence on the thermosetting resin composition or hardened product, or the LED element, it is preferable to also consider the crystal Choose the amount of water.

Synthetic silicon dioxide is not crystalline, but amorphous, so it has no crystal axis, and optical characteristics derived from crystallization cannot be particularly expected. However, in addition to the control of particle distribution, features such as extremely reduced particle size can be effectively utilized.

In particular, fumed silica has a nanometer-level particle size and has excellent particle dispersion. Furthermore, in the case of comparison with the same weight, the smaller the particle size, the larger the total surface area, and therefore the light reflection direction is more diversified, so it can be used better.

In addition, in general, silica has a large surface area and is made hydrophilic by the effect of silanol present on the surface (hydrophilic silica). It can also be chemically modified to form hydrophobic silica. Which type of silica to use is selected according to the purpose, but in the present invention, it is preferable to use hydrophilic silica in experimental verification.

The method for producing the thermosetting resin composition of the present invention is not particularly limited. For example, the following methods can be mentioned: using a homodisperser, homomixer, universal mixer, planetary mixer , Kneader, three-roller or bead mill (beads mill) and other mixers, at room temperature or heating, the hardening accelerator, silicone resin and if necessary the thermal hardener, anti Mix the specified amount of oxidizer, etc.

The thermosetting resin composition of the present invention is in a soft state (semi-cured State) molding, can be made into any shape. The molding method is not limited, and examples thereof include molding machines such as hot press molding, film coating machines, and extrusion molding, or printing methods such as screen printing, gravure printing, and offset printing. In addition, the molded product can also be reprocessed and used in the next step. For example, it can be formed into a flat shape such as a coating film or a sheet, and cut into thin pieces to form a wafer-like shape, which can be used as a material for sealing or bonding. In addition, by using injection molding or compression molding, it can be used as a reflective LED housing material and reflector material. In addition, in this specification, what can mold a thermosetting resin composition regardless of the shape is expressed as a prepreg.

In the case of molding the prepreg into a flat shape such as a coating film or a sheet, the thickness can be determined according to the content of the phosphor and the required optical properties. Specifically, if it is in the form of a coating film, it is 0.1 μm or more, and if it is in the form of a sheet, it can be molded to about 10 μm to 3000 μm. When the thickness after curing changes, the thickness can be determined by considering it. To improve optical properties. From the viewpoint of heat resistance, the film thickness of the phosphor sheet is preferably 1000 μm or less, more preferably 200 μm or less, and still more preferably 100 μm or less. By making the phosphor sheet into a film thickness of 1000 μm or less, light absorption or light scattering due to the binder resin can be reduced, and it becomes a phosphor sheet with excellent optical properties.

Heat treatment is performed on the thermosetting resin composition of the present invention or its prepreg to obtain a target cured product (article). As a condition for obtaining a hardened product, the temperature is preferably 60°C to 200°C, more preferably 80°C to 160°C. In addition, the time is preferably from 1 hour to 24 hours, and more preferably from 2 hours to 5 hours from the viewpoint of economy.

Furthermore, in addition to the function of an item itself as a product, it also includes For example, it contains what is present in a specific structure like a sealing material and hardened as a part of a member.

The use of the thermosetting resin composition of the present invention or its prepreg is not particularly limited. For example, it can be used as a sealant, a housing material, and a bonding material for connection with lead electrodes, heat sinks, etc. , Underfill material and passivation film on the light-emitting element in the case of flip chip packaging of light-emitting elements such as light-emitting diodes and optical semiconductor elements. Among them, an optical semiconductor device that can efficiently extract light emitted from an optical semiconductor element can be manufactured, and therefore, it can be suitably used as a sealant, reflector material, phosphor sheet, underfill material, or die bonding material.

The hardness of the cured product obtained by curing the thermosetting resin composition of the present invention is preferably in the range of 45 or less in D hardness and 30 or more in A hardness. The thermosetting resin composition of the present invention can further improve gas barrier performance. When high gas barrier properties are desired, the D hardness is preferably 45 or more. In addition, the refractive index is preferably a high refractive index of 1.5 or more. If the refractive index is 1.5 or more, a cured product with excellent light extraction efficiency of the LED is formed.

The method for sealing a light-emitting element with the composition for an optical semiconductor of the present invention is not particularly limited. For example, the following method may be mentioned: the composition for an optical semiconductor of the present invention is preliminarily injected into a molding die, and the lead of the light-emitting element is immersed and fixed therein A method of hardening a frame, etc., and a method of injecting and hardening the optical semiconductor composition of the present invention into a mold in which a light-emitting element is inserted.

Examples of methods for injecting the optical semiconductor composition of the present invention include: Injection, transfer molding and injection molding with dispensers. Further, other sealing methods include, for example, the following method: the composition for optical semiconductors of the present invention is dropped on the light-emitting element, stencil printing, screen printing, and coating through a mask, and then cured Method; and using a dispenser or the like to inject the optical semiconductor composition of the present invention into a cup with a light-emitting element arranged at the bottom and harden it.

In addition, an optical semiconductor element including the composition for an optical semiconductor element of the present invention as a sealing agent is also one of the present invention.

[Example]

Based on examples, the present invention will be described in more detail. In addition, the present invention is not limited to the following examples.

<Measurement of number average molecular weight and weight average molecular weight>

The number average molecular weight and weight average molecular weight of the polymer synthesized in the present invention are measured in the following manner. Using the high-performance liquid chromatography system CO-2065plus manufactured by JASCO Corporation, 20μL of tetrahydrofuran (THF) solution with a sample concentration of 1% by mass was used as the analysis sample. The column: Shodex KF804L [Showa Denko Co., Ltd. Made by the company] (2 connected in series), column temperature: 40°C, detector: RI, eluent: THF, and eluent flow rate: 1.0 mL per minute, using gel permeation chromatography (gelpermeation chromatography) , GPC) method to determine the polystyrene conversion.

(A) A thermosetting resin containing SiH groups and alkenyl groups as a reaction product of silsesquioxane having SiH groups and organopolysiloxane having two alkenyl groups fat

The thermosetting resin containing SiH groups and alkenyl groups as the component (A) of the present invention uses the following silsesquioxane derivative base polymer 1 produced by the method disclosed in International Publication No. 2011/145638.

[Ssesquioxane Derivative Base Polymer 1]

The compound in formula (1) where a[formula (XI)]=2.34, b[formula (X-II)]=0, c[formula (X-III)]=1.66 and m=1 is the following chemical formula The compound shown is the silsesquioxane derivative base polymer 1.

The silsesquioxane derivative base polymer 1 was synthesized by the following method according to the following reaction formula. Put 50 g (0.0384 mol) of silsesquioxane derivative (DD-4H), 51.3 g (0.197 mol) in a 200 mL reaction vessel equipped with a thermometer, reflux cooler, and agitator (relative 5 times mol in DD-4H) 1,5-divinyl-1,1,3,3,5,5-hexamethyltrisiloxane (DVTS), 37.5g of toluene as a solvent.

In a nitrogen environment, start heating and stirring. When the content reaches 115°C, add it so that the Pt concentration becomes 0.005ppm relative to DD-4H, and perform heating and stirring. mix. The reaction was tracked by GPC, and the heating was stopped after 7 hours to stop the reaction. The reaction solution was transferred to an eggplant-shaped flask, and toluene and excess DVTS were distilled off using an evaporator at 70°C and 0.13kPa under reduced pressure to obtain 58g of a viscosity at 25°C of 95Pa. s colorless and transparent liquid. The molecular weight was analyzed by GPC, and as a result, the number average molecular weight: Mn=1200, and the weight average molecular weight: Mw=1400. According to the analysis result, it can be determined as a compound with a[formula (X-I)]=2.34, b[formula (X-II)]=0, c[formula (X-III)]=1.66, and m=1.

(B) A linear compound having an alkenyl group or SiH group at both ends, at least one aryl group in the main chain, and a siloxane chain as the main structure.

As the component (B) of the present invention, the linear compound having alkenyl groups at both ends, at least one aryl group in the main chain, and having a siloxane chain as the main structure is the following compound.

[Methyl phenyl polysiloxane containing vinyl groups at both ends: molecular weight 3000] (B-1)

Use formula (2) where R ⁰ = vinyl (expressed as Vi), R ⁷ = methyl (expressed as Me), R ⁸ = methyl and phenyl (expressed as Ph), n=20, the following The number average molecular weight represented by the formula is 3000 methyl phenyl polysiloxane containing vinyl groups at both ends (manufactured by Gelest Co., Ltd.), which is obtained by removing the cyclic siloxane component by washing with a methanol solvent.

[Diphenyltrisiloxane (DVDPTS) with vinyl groups on both ends] (B-2)

Use formula (2) where R ⁰ = vinyl, R ⁷ = methyl, R ⁸ = phenyl, n=1, 1,5-divinyl-3,3-diphenyl represented by the following formula -1,1,5,5-Tetramethyltrisiloxane (manufactured by Bio-Gen).

[Diphenyltetrasiloxane containing both terminal vinyl groups (DV4P4S)] (B-3)

Use the following method to produce 1,7-divinyl-3 represented by the following formula in the ^{formula (2) where R 0} = vinyl, R ⁷ = methyl, R ^{8 = phenyl, n=2,} Derived from 3,5,5-tetraphenyl-1,1,7,7-tetramethyltetrasiloxane.

Set up a 500mL three-necked flask, stirrer, cooling tube, dropping funnel, and thermometer protection tube. Put 93g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (DVDS) and 16g of methanol into the flask. Add 2.5 g of concentrated sulfuric acid at a liquid temperature of 3°C, and stir for 30 minutes. Next, 91.6 g of diphenyldimethoxysilane was added dropwise at a liquid temperature of 6°C, and the mixture was stirred for 1 hour. 26.4 g of pure water was added over 1 hour, and stirred for 2.5 hours. Draw out the water layer. At room temperature, 34.9 g of concentrated sulfuric acid was added from the dropping funnel over 15 minutes. After stirring for 1 hour, the sulfuric acid layer was removed and washed with water until the pH value became 7, and 143.6 g of the reaction liquid was obtained. The reaction liquid was distilled at a temperature of 100° C. and a pressure of 0.4 kPa to obtain 78.6 g of the distillation component DVDPTS and 7.2 g of the kettle residual component DV4P4S.

[Diphenyltrisiloxane containing vinyl groups at both ends: molecular weight 1100] (B-4)

In the formula (3), a compound having a number average molecular weight of 1100, represented by the following formula, ^{in which R 0} = vinyl, R ⁷ = methyl, R ^{8 = phenyl, j=1, and k=2 is used.}

The compound (B-4) uses the following formula and uses two siloxanes (DVDPTS (1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyl Trisiloxane): DHDPTS (3,3-Diphenyl-1,1,5,5-tetramethyltrisiloxane): manufactured by Korea Bio-Gen Corporation) Hydrosilylation Synthesized by polymerization. Hydrosilation is carried out by the following method: Put DVDPTS and DHDPTS into a flask, add 2 ppm of Pt catalyst, and heat at 70°C for 8 hours.

[Diphenyltrisiloxane containing vinyl groups at both ends: molecular weight 1800] (B-5)

In the formula (3), a compound having a number average molecular weight of 1,800, represented by the following formula, ^{in which R 0} =vinyl, R ⁷ =methyl, R ^{8 =phenyl, j=1, and k=4 was used.}

[Diphenyltrisiloxane containing vinyl groups at both ends: molecular weight 4000] (B-6)

In the formula (3), a compound having a number average molecular weight of 4000, represented by the following formula, ^{in which R 0} = vinyl, R ⁷ = methyl, R ^{8 = phenyl, j=1, and k=10 was used.}

[Diphenyltrisiloxane containing vinyl groups at both ends: molecular weight 60,000] (B-7)

In formula (3), a compound having R ⁰ =vinyl, R ⁷ =methyl, R ⁸ =phenyl, j=1, k=168, and a number average molecular weight of 60,000 represented by the following formula is used.

Compound (B-5), compound (B-6), compound (B-7) are all used with (B-4)

In the same way, it was synthesized by changing the molar ratio of the two silicones DVDPTS and DHDPTS. The molar ratios of DVDPTS and DHDPTS are shown below.

As the component (B) of the present invention, the linear compound having SiH groups at both ends, at least one aryl group in the main chain, and having a siloxane chain as the main structure is the following compound.

[Diphenyltrisiloxane (DHDPTS) containing both terminal SiH groups] (B-8)

Use formula (2) where R ⁰ = hydrogen, R ⁷ = methyl, R ⁸ = phenyl, n=1, 1,5-divinyl-3,3-diphenyl- represented by the following formula: 1,1,5,5-Tetramethyltrisiloxane (manufactured by Bio-Gen).

[Diphenyltrisiloxane containing both terminal SiH groups: molecular weight 1050] (B-9)

In the formula (3), R ⁰ = hydrogen, R ⁷ = methyl, R ⁸ = phenyl, j=1, k=2, and a compound having a number average molecular weight of 1050 represented by the following formula is used.

The compound (B-10) was synthesized by changing the molar ratio of the two silicones DVDPTS and DHDPTS by the same method as (B-4). The molar ratio of DVDPTS/DHDPTS is implemented at 0.5.

(C) Pt catalyst

As the Pt catalyst as the component (C) of the present invention, Caster catalyst, brand name Pt-VTS-3.0X [3 wt% xylene solution, manufactured by Umicore Co., Ltd.] was used.

(D) The SiH group is obtained by reacting a silsesquioxane having an SiH group, an organopolysiloxane having two alkenyl groups, an epoxy compound having an alkenyl group, and a silyl compound having an alkenyl group. compound of

[Ssesquioxane Derivative Base Polymer 2]

The SiH group-containing compound as the component (D) of the present invention uses the formula (D1) where A'[formula (a)]=1.32, B'[formula (b)]=0.69, C'[formula (ci) ]=0.65, D'[Formula (di)]=0.65, m=8.8 silsesquioxane derivative base polymer 2 represented by the following formula.

The silsesquioxane derivative base polymer 2 was synthesized by the following method according to the following reaction formula. Add 50g (0.0384 mol) of silsesquioxane derivative (DD-4H) and 18.6g (0.0266 mol) of vinyl in a reaction vessel with an internal volume of 300 mL equipped with a thermometer, reflux cooler, and agitator. Silicone (FM-2205), 7.47 g (0.0252 mol) of monoallyl diglycidyl isocyanurate (MA-DGIC: manufactured by Shikoku Chemical Industry Co., Ltd.), 3.7 g (0.0252 mol) ) Vinyl trimethoxysilane (S210: manufactured by JNC Co., Ltd.), and 50 g of toluene as a solvent.

In a nitrogen environment, start heating and stirring. When the content reached 100°C, it was added in such an amount that the Pt concentration would become 1 ppm with respect to DD-4H, and heating and stirring were performed directly for 5 hours. The disappearance of MA-DGIC was confirmed by gas chromatography (GC), and the reaction was terminated. After cooling to room temperature, 1.6 g of activated carbon was added, stirred for more than 3 hours, and then filtered to remove the activated carbon. Using an evaporator for the filtrate, toluene as a solvent was distilled off at 90°C and a reduced pressure of 0.13 kPa. Obtained 74 g of syrup-like colorless and transparent liquid.

The molecular weight of the obtained product was analyzed by GPC, and the result was the number average molecular weight: Mn=3900, and the weight average molecular weight: Mw=18200.

(E1) to (E4), which are organosiloxane compounds having three or more alkenyl groups or SiH groups, are used as additives (E).

(E1) Organosiloxane compound represented by the following formula having 3 vinyl groups

(E2) Organosiloxane compound represented by the following formula having 4 vinyl groups

(E3) Organosiloxane compound represented by the following formula having 3 SiH groups

(E4) the average composition in terms of M _'8 Q _4, the molecule having an average of 8 SiH groups comprising M' units, Q silicone units ketone resin as a partial structure

As the additive (F), a linear dimethylpolysiloxane having a number average molecular weight of 700 and having two vinyl groups at both ends (Silaplane FM-2205: manufactured by JNC Co., Ltd.) was used .

As the additive (G), a linear dimethylpolysiloxane with a number average molecular weight of 1000 having one SiH group at a single end (Silaplane FM-0111: manufactured by JNC Co., Ltd.) was used .

As the alkoxysilane compound (H), 3-glycidoxypropyltrimethoxysilane (Sila-Ace S510: manufactured by JNC Co., Ltd.) was used (in formula (H), R ⁸ Is 3-glycidoxypropyl, R ⁹ is methyl, and h, i, and j are 1, 3, and 0 respectively).

<Preparation of thermosetting resin composition 1>

Put the compound synthesized in the embodiment or organopolysiloxane in the spiral tube A mixture of alkanes. The spiral tube was set on a rotation and revolution mixer ["Defoaming Nintaro (registered trademark)" ARE-250 manufactured by Thinky Co., Ltd.], and mixing and defoaming were performed. Table 1 shows the ratio of each component.

The Custer catalyst manufactured by Umicore [trade name Pt-VTS-3.0X: xylene solution with 3% Pt concentration] is added so that the Pt concentration becomes a predetermined amount, and the curing retarder: MVS is used. -H [trade name, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane: manufactured by JNC Co., Ltd.] diluted to 10 times, again The mixing and defoaming were carried out with a rotation and revolution mixer, and the composition at and the comparative composition xy as the thermosetting resin composition were obtained. Table 1 shows the mass% of each thermosetting resin composition and the addition amount (ppm) of the Pt catalyst.

In addition, in the comparative composition x and the comparative composition y, 0.25% of the total compounding weight of glycidyl ether trimethoxysilane was used as the adhesion-imparting material: brand name S510 [manufactured by JNC Co., Ltd.] as the epoxy group-containing material Silane coupling agent.

<Hardened Object 1>

Put the prepared thermosetting resin composition at and the comparative curable composition xy into a mold, heat at 120°C for 1 hour, and heat at 160°C for 3 hours to perform heat curing to obtain 4mm thick hardened material AT and comparative hardened material XY. In addition, liquid A and liquid B of OE-6630 (manufactured by Toray Dow Corning Silicone) were mixed at a ratio of 1:5, and heat-cured in the same manner to obtain a comparative cured product Z with a thickness of 4 mm.

All are transparent hardened products, and the transmittance at 400nm is above 94%.

<Measurement of moisture permeability>

The thermosetting resin composition at and the comparative curable composition xy were put into a mold, heated at 120°C for 1 hour, and then heated at 160°C for 3 hours to heat and harden to obtain a thickness of 1 mm The cured product film AT and the comparative cured product film XY. The moisture permeability measurement is performed using the film and in accordance with JIS Z 0208 under the conditions of 40° C. and humidity of 90%. Table 2 shows the obtained moisture permeability.

<Production of Hardened Package 1>

Use the dispenser MEASURING MASTER MPP-1 manufactured by Musashi Engineering (stock) to inject the thermosetting composition at, the comparatively hardening composition xy, and OE-6630 into the copy (Enomoto) (stock) ) In the lead frame 5050D/G PKG manufactured with a blue LED chip and a metal wire mounted, it is cured in the same way to produce a cured package of a cured product AR and a comparative cured product XZ.

<Sulfur resistance test 1>

Sulfur resistance test 1 was implemented by the following method: the hardened package made by the method was put into a 450ml airtight container containing 5g of sulfur powder, and after leaving it at 70°C for 16 hours, it was observed The degree of blackening caused. The color change was not observed as ⊚, the light gray was changed to ○, the dark gray was changed to △, and the dark gray was changed to ×. The obtained results are shown in Table 2.

Furthermore, the gas barrier properties can be confirmed based on the sulfur resistance test.

<Cold and hot shock test 1>

Thermal shock test 1 is to put the hardened package made by the method into the test area of the thermal shock device TSE-11-A manufactured by Aspec Co., Ltd. Exposure at -40°C for 30 minutes and exposure at 105°C for 30 minutes constitutes one cycle, which is implemented by repeating 100 cycles. Furthermore, the movement time between the two exposure temperatures is 5 minutes. After 200 cycles, a lighting test was performed, setting all lighting to ◎, setting more than half of the lighting to ○, setting less than half of the lighting to △, and setting all non-lighting to ×. The obtained results are shown in Table 2.

"Table 1"

As shown in Table 2, it is clear that the cured product A-T using the composition a-t of the present invention is a sealing material that has good gas barrier properties and good cold and thermal shock resistance, and can have both of the above characteristics.

Table 3 shows the results of the sulfur resistance test and thermal shock test of the cured package of the cured product H, cured product S, cured product T, and comparative cured product X-Z. In addition, the refractive index at 25°C of the cured product H, cured product S, cured product T, and comparative cured product X-Z having a thickness of 4 mm after curing was measured. Regarding the refractive index, the cured product was cut with a band saw, and a test piece was produced in accordance with JIS K7142 (2008). Using the test piece, an Abbe refractometer [manufactured by Atago Co., Ltd. NAR-2T], and use the D-ray (586nm) of a sodium lamp to measure the refractive index. Diiodomethane is used as the intermediate liquid. In addition, as heat resistance evaluation, the cured product was placed in an oven at 180°C for 1000 hours, and the transmittance retention rate at 400 nm was measured. The results are shown in Table 3.

As shown in Table 3, it is clear that the cured product using the composition of the present invention is gas A sealing material that has good body barrier properties, good thermal shock resistance, and excellent heat resistance. It can be seen that it is particularly excellent in lighting applications.

<Preparation of thermosetting resin composition 2>

As in Preparation 1 of the thermosetting resin composition, a mixture of the compound synthesized in the above-mentioned Example and the organopolysiloxane was added to the spiral tube. The spiral tube was set on a rotation and revolution mixer ["Defoaming Nintaro (registered trademark)" ARE-250 manufactured by Thinky Co., Ltd.], and mixing and defoaming were performed. The Custer catalyst manufactured by Umicore [trade name Pt-VTS-3.0X: xylene solution with 3% Pt concentration] is added so that the Pt concentration becomes a predetermined amount, and the curing retarder: MVS is used. -H [trade name, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane: manufactured by JNC Co., Ltd.] diluted to 10 times, again Mixing and defoaming were carried out with a rotating and revolving mixer, and a composition uw as a thermosetting resin composition was obtained. Table 4 shows the mass% of each thermosetting resin composition and the addition amount (ppm) of the Pt catalyst.

<Hardened Object 2>

In the same way as the cured product 1, the prepared thermosetting resin composition uw is put into a mold, heated at 120°C for 1 hour, and heated at 160°C for 3 hours to perform heat curing to obtain Hardened UW with a thickness of 4mm. In addition, OE-7651 and OE-7662 (manufactured by Toray Dow Corning Silicone) liquid A and B were mixed in a predetermined ratio, and heat-cured in the same manner to obtain a comparative cured product AA and a comparative cured product AB with a thickness of 4 mm.

<Production of Hardened Package 2>

As with the hardened package 1, the thermosetting composition uw, and OE-7651 and OE-7662 were injected using a dispenser MEASURING MASTER MPP-1 manufactured by Musashi Engineering Co., Ltd. If the lead frame 5050D/G PKG manufactured by Enomoto (stock) is equipped with blue LED chips and metal wires, it is cured in the same way to make the cured product UW, the comparative cured product AA, and the comparative cured product AB. Package body.

<Sulfur resistance test 2>

The sulfur resistance test 2 was set to more severe conditions than the sulfur resistance test 1.

Sulfur resistance test 2 was implemented by the following method: the hardened package made by the method was placed in a 450 ml airtight container containing 5 g of sulfur powder, and after leaving it at 80°C for 24 hours, the The degree of blackening caused. The color change was not observed as ⊚, the light gray was changed to ○, the dark gray was changed to △, and the dark gray was changed to ×. The obtained results are shown in Table 5.

<Cold and hot shock test 2>

Similar to the thermal shock test 1, the thermal shock test 2 is to put the hardened package produced by the above method into the test area of the thermal shock device TSE-11-A manufactured by the company, and it will be- Exposure at 40°C for 30 minutes and exposure at 105°C for 30 minutes constitutes 1 cycle, which is implemented by repeating 100 cycles. Furthermore, the movement time between the two exposure temperatures is 5 minutes. After 200 cycles, a lighting test was performed, setting all lighting to ◎, setting more than half of the lighting to ○, setting less than half of the lighting to △, and setting all non-lighting to ×. The obtained results are shown in Table 5.

<Refractive Index>

The refractive index at 25°C of the cured product U-W having a thickness of 4 mm, the comparative cured product AA, and the comparative cured product AB were measured. Regarding the refractive index, the hardened material was cut with a band saw in the same manner as described above, and a test piece was produced in accordance with JIS K7142 (2008). Using the test piece, an Abbe refractometer was used [Atago Co., Ltd. Manufactured NAR-2T], and measured the refractive index using the D-ray (586nm) of a sodium lamp. Diiodomethane is used as the intermediate liquid. The obtained results are shown in Table 5.

<Hardness>

The hardness at 25°C of the cured product U-W having a thickness of 4 mm, the comparative cured product AA, and the comparative cured product AB were measured. Regarding the hardness, it was measured using a D-type durometer in accordance with JIS K6253. The obtained results (D hardness) are shown in Table 5.

<Evaluation of heat resistance>

As an evaluation of heat resistance, the cured product was placed in an oven at 180°C for 1000 hours, The transmittance retention rate at 400 nm was measured. The results are shown in Table 5.

The comparative cured product X and the comparative cured product Z in Table 5 are the same as the comparative cured product X and the comparative cured product Z in Table 3.

As shown in Table 5, it can be seen that a cured product using the composition of the present invention having a D hardness of 45 or more exhibits excellent performance even under a more severe sulfur resistance test, and therefore has better gas barrier properties. In addition, it can be seen that it is a sealing material that maintains thermal shock resistance and is also excellent in heat resistance. The sealing material for optical semiconductors containing the composition of the present invention is particularly useful for high-output lighting applications.

[Industrial availability]

The thermosetting resin composition of the present invention can provide a cured product with good gas barrier properties and excellent thermal shock resistance, and therefore is very useful as a sealing material for optical semiconductor elements such as LEDs.

Claims (21)

A thermosetting resin composition containing the following (A), (B), (C) and (D): (A) as a silsesquioxane having a SiH group and an organic polymer having two alkenyl groups A thermosetting resin containing SiH groups and alkenyl groups; (B) has an alkenyl group or SiH group at both ends, at least one aryl group in the main chain, and a silicone chain as the reaction product The linear compound of the main structure; (C) Pt catalyst; and (D) by making a silsesquioxane having a SiH group, an organopolysiloxane having two alkenyl groups, and an epoxy resin having an alkenyl group A compound having a SiH group obtained by reacting a compound and a silyl compound having an alkenyl group; the hardness of the cured product obtained by curing the thermosetting resin composition is measured with a D-type durometer and the D hardness is 50 or more. The thermosetting resin composition as described in claim 1, wherein (B) is a straight chain having alkenyl groups at both ends, at least one aryl group in the main chain, and a silicone chain as the main structure状 Compounds. The thermosetting resin composition described in item 1 of the patent application, wherein (B) is a straight chain having SiH groups at both ends, at least one aryl group in the main chain, and a silicone chain as the main structure状 Compounds. The thermosetting resin composition according to any one of items 1 to 3 in the scope of the patent application, wherein the silsesquioxane in (A) is a double-layer silsesquioxane. The thermosetting resin composition according to any one of items 1 to 3 in the scope of the patent application, wherein (A) is a compound represented by formula (1):

In formula (1), X is independently a group represented by formula (XI), formula (X-II) or formula (X-III), and the compound represented by formula (1) per molecule [the When the compound is a mixture of the group represented by the formula (XI), the ratio of the group represented by the formula (X-II) and the group represented by the formula (X-III) is different, it is said compound The number of groups represented by formula (XI) of 1 molecule average] is a, the number of groups represented by formula (X-II) is b, and the number of groups represented by formula (X-III) In the case of c, a+2b+c=4, 0<a≦3, 0≦b≦1, 0<c≦3; R ^{1 is} independently an alkyl group with 1 to 4 carbon atoms, or a cyclopentyl group Or cyclohexyl; m is an average value satisfying 1~100; -H (XI)

In formula (X-II), R ² and R ^{3 are} independently alkyl with 1 to 4 carbons, cyclopentyl, cyclohexyl or phenyl; r is ^{the repeating number of -OSi(R 3} ) ₂ -, which is Meet the average value of 2-20;

In formula (X-III), R ⁴ and R ^{5 are} independently alkyl with 1 to 4 carbons, cyclopentyl, cyclohexyl or phenyl; s is ^{the repeating number of -OSi(R 5} ) ₂ -, which is which the mean value of from 2 to 20; R & lt ⁰ carbon atoms having one double bond unsaturated hydrocarbon group having 2 to 5, R ^{'is 0} carbon atoms and R & lt same saturated hydrocarbon ^0. The thermosetting resin composition according to any one of items 1 to 3 in the scope of patent application, wherein (B) is a compound represented by formula (2):

In formula (2), R ⁶ and R ^{7 are} independently alkyl with 1 to 4 carbons, cyclopentyl, cyclohexyl, or aryl with 6 to 12 carbons; n is -OSi(R ⁷ ) _2- The repetition number is an average value that satisfies 1-50; R ⁰ is hydrogen or an unsaturated hydrocarbon group with 2-5 carbons with a double bond. In the thermosetting resin composition described in claim 6, wherein in the compound represented by formula (2), 50% or more of ^{2n R 7 are aryl groups.} The thermosetting resin composition according to any one of items 1 to 3 in the scope of patent application, wherein (B) is a compound represented by formula (3):

In formula (3), R ⁶ and R ^{7 are} independently alkyl with 1 to 4 carbons, cyclopentyl, cyclohexyl, or aryl with 6 to 12 carbons; j is a number satisfying 1 to 5, and k is 0 or meet the average value of 1-50; R ⁰ is hydrogen or an unsaturated hydrocarbon group with 2 to 5 carbons with a double bond, R ^0'is a saturated hydrocarbon group with 2 to 5 carbons, and R ⁰ is not In the case of hydrogen, R ^0'and R ^{0 have} the same carbon number. In the thermosetting resin composition described in item 8 of the scope of patent application, in the compound represented by formula (3), 50% or more of ^{2n R 7 are aryl groups.} The thermosetting resin composition described in item 1 of the scope of patent application, wherein (D) is a compound represented by formula (D1):

In formula (D1), X'is independently formula (a), formula (b), formula (ci), formula (c-ii), formula (c-iii), formula (di), formula (d-ii) ) Or the group represented by the formula (d-iii), when the compound represented by the formula (D1) per molecule [the compound is the group represented by the formula (a) and the formula (b), formula (ci) ), in the case of a mixture of compounds having different ratios of groups represented by formula (c-ii), formula (c-iii), formula (di), formula (d-ii) or formula (d-iii), The number of groups represented by formula (a) of the compound 1 molecule is set to A', the number of groups represented by formula (b) is set to B', formula (ci), formula (c- ii) or the number of groups represented by formula (c-iii) is set to C', and the number of groups represented by formula (di), formula (d-ii) or formula (d-iii) is set to D' in the case where, a '+ 2B' + C '+ D' = 4,0.5 ≦ a '≦ 3.0,0.5 ≦ 2B' ≦ 2.0,0.1 ≦ C '≦ 2,0 ≦ D' ≦ 1.0; R 1 ' is independently Ground is an alkyl group with 1 to 4 carbons, cyclopentyl or cyclohexyl; m'is an average value satisfying 1 to 100; -H (a)

In the formula (b), R ^{2 'and} R ^3' are independently alkyl carbon atoms, a cyclopentyl group, a cyclohexyl group or a phenyl group having 1 to 4; t is -OSi (R ^{3 ')} ₂ - a number of repetitions, It is an average value that satisfies 1-20;

Formula (di) R ^{4 ',} in Formula (d-ii) R ^{4 "and} of formula ^{(d-iii) R 4'} '' is independently selected from methyl, ethyl, butyl and isobutyl The group in the propyl group; the x in the formula (d-ii) is the ^{repeating number of -OSi(R 4"} ) ₂ -, which is an average value satisfying 1 to 20; the y in the formula (d-iii) is- The number of repetitions of OSi(R ^4''' ) ₂ -is an average value satisfying 1 to 10; R ⁰ in formula (d-iii) is an unsaturated hydrocarbon group with 2 to 5 carbons and one double bond. The thermosetting resin composition as described in item 10 of the scope of patent application, wherein in formula (D1), R ^1'is a methyl group, m'is an average value satisfying 1 to 25, and X'independently represents a formula (a ), a group represented by formula (b), formula (ci) or formula (di). The thermosetting resin composition described in any one of items 1 to 3 in the scope of the patent application, wherein the ratio of (A) is 50% to 95% by mass based on the total amount of the thermosetting resin composition %, the ratio of (B) is 2% by mass to 50% by mass. The thermosetting resin composition according to any one of items 1 to 3 in the scope of the patent application, wherein the ratio of (A) is 70% by mass to 95% by mass based on the total amount of the thermosetting resin composition %, the ratio of (B) is 2% by mass to 30% by mass. In the thermosetting resin composition described in the first item of the scope of patent application, the ratio of (D) is 1% by mass to 20% by mass based on the total amount of the thermosetting resin composition. The thermosetting resin composition as described in any one of items 1 to 3 in the scope of the patent application, in which an inorganic compound is further dispersed. The thermosetting resin composition as described in item 15 of the scope of patent application, The inorganic compound is at least one of a phosphor or a metal oxide. A prepreg obtained by molding the thermosetting resin composition as described in any one of items 1 to 16 in the scope of the patent application. A hardened product obtained by hardening the thermosetting resin composition described in any one of the scope of the patent application item 1 to the 16th, or the prepreg described in the scope of the patent application item 17. The cured product described in item 18 of the scope of patent application is in the form of a coating film or sheet, and has a thickness of 0.1 μm to 3,000 μm. A composition for optical semiconductors, which contains the thermosetting resin composition described in any one of the scope of the patent application item 1 to item 16, or the prepreg described in the scope of the patent application item 17. An optical semiconductor element comprising the composition for an optical semiconductor as described in item 20 of the scope of patent application as a sealing agent.