JP6323086B2 - Thermosetting resin composition and article using the same - Google Patents

Description

  The present invention relates to a thermosetting resin composition comprising silsesquioxane and organopolysiloxane excellent in storage stability, high heat resistance, high transparency, and heat-resistant yellowing, and molding the thermosetting resin composition. And a light emitting device including the cured molded body.

  Examples of the member constituting the white LED package include a metal lead frame, reflector resin, LED chip, gold wire, sealing resin, and phosphor. Although the market for LEDs is expanding for applications such as lighting, heat generation in the LED package has become a problem as the output increases, and high heat resistance is also required for components. . As for the sealing resin, when an epoxy resin is used, yellowing due to its heat generation is unavoidable. Therefore, instead of the epoxy resin, a silicone resin having higher heat resistance and light resistance is sealed in the white LED. It has been used as a stopping material. The silicone sealing resin generally used is a two-component mixed type that applies an addition reaction. In this method, two compositions having different compositions are mixed, and an addition reaction is initiated by the action of a catalyst contained in one composition to be cured.

  In this case, after mixing, the viscosity gradually increases because the curing reaction proceeds even at room temperature, and since there is a change in viscosity in the subsequent steps such as phosphor dispersion process and package dispensing process, There is a problem in that the dispersion state of the phosphor and the change in the dispense amount occur in the product quality in the latter period, and as a result, it is difficult to make a homogeneous product. In addition, the viscosity continues to increase and eventually becomes gelled or solidified and cannot be dispensed. As a result, the yield of the sealing resin and phosphor decreases. Furthermore, it has been pointed out that in the two-liquid mixing operation, the hardness and elastic modulus of the resin change due to a slight shift in the mixing ratio, resulting in a difference in performance between production lots.

  In order to solve such a problem, in recent years, a product in which two liquids are mixed in advance and stored at a low temperature of about −30 ° C. to suppress an increase in viscosity has been sold, but it is necessary to return to room temperature before use. However, since a change in viscosity occurs immediately after returning to room temperature, no fundamental solution has been reached.

  In addition, a phosphor sheet has been developed in order to improve the dispersion state of the phosphor due to the change in viscosity and the optical variation due to the change in the dispense amount. Since the phosphor sheet is mounted on a chip that emits light, heat resistance and light resistance are required in the same manner as the sealing resin. In many cases, such a sheet forming material is a suitable material or sealing material for the sealing resin. The resin itself is diverted and used (Patent Document 1).

  In this way, when the phosphor sheet is completely cured, it is necessary to use an adhesive layer to adhere to the LED chip, which complicates the process. When the adhesive layer is not used, after the sheet is formed, it is once cured to a semi-cured state to form the sheet, and then placed on a chip to be fully cured and the phosphor sheet is adhered. In this case, the semi-cured phosphor sheet gradually cures at room temperature in the same manner as the sealing resin and has the disadvantage of causing poor adhesion during the main curing. (Patent Document 2).

  Further, Patent Document 1 describes that the curing proceeds to an extent that is excellent in processing, but in order to finally adhere to the LED chip at a temperature higher than the sheet forming temperature, it may still be in a semi-cured state. is necessary. As is apparent from the examples, the diverted sealing resin has a film formed at a temperature lower than the temperature required for curing by the manufacturer. As described above, the semi-cured resin also needs to be stored at a very low temperature so that the curing does not proceed any more.

JP2013-1792A JP 2009-235368 A

  As mentioned above, the LED sealant and phosphor sheet use a two-component silicone resin, so there are limitations on workability due to the progress of the addition reaction after mixing, and low temperature storage is required for storage. It is necessary. Therefore, the present invention is a thermosetting resin composition that can be stored at room temperature, is not subject to work restrictions due to viscosity changes or pot life, and does not cause performance variation due to a quantity error that occurs in the conventional two-liquid mixing process. It is another object of the present invention to provide an article using the same.

  The present inventors have intensively studied to solve the above problems. As a result, a thermosetting resin comprising a thermosetting resin containing a SiH group and an alkenyl group obtained from a reaction of a silsesquioxane having a SiH group and an organopolysiloxane having two alkenyl groups, a Pt catalyst, and a curing retarder. The storage resin composition has high storage stability at room temperature, and can be cured by heat, and can be suitably used as a sealing material, has high storage stability as a molded product, and gives a cured product suitably by post-cure, Moreover, it discovered that it had adhesiveness. In the present invention, the thermosetting resin composition is reacted with silsesquioxane having SiH group, organopolysiloxane having two alkenyl groups, epoxy compound having alkenyl groups, and silyl compound having alkenyl groups. It was found that the above-mentioned problems can be solved by including a thermosetting resin having a SiH group obtained by the above and an organopolysiloxane having a SiH group only at one end, and the present invention has been completed. .

That is, the present invention is as follows.
1. A thermosetting resin composition containing (A) and (B).
(A) A thermosetting resin that is a reaction product of a silsesquioxane having a SiH group and an organopolysiloxane having two alkenyl groups and having a SiH group and an alkenyl group.
(B) Pt catalyst.

2. Furthermore, the thermosetting resin composition of the preceding clause 1 containing (C).
(C) Curing inhibitor.
Here, (C) the curing inhibitor is 250 to 200,000 times the blending amount (mass) of (B) Pt catalyst.

3. 3. The thermosetting resin composition according to item 1 or 2, wherein the silsesquioxane is a double-decker silsesquioxane.

4). The thermosetting resin composition according to any one of items 1 to 3, further comprising at least one of (D) to (F).
(D) Thermosetting having a SiH group obtained by reacting a silsesquioxane having a SiH group, an organopolysiloxane having two alkenyl groups, an epoxy compound having an alkenyl group and a silyl compound having an alkenyl group Resin.
(E) An organopolysiloxane compound having two or more alkenyl groups.
(F) A linear organopolysiloxane compound having a SiH group only at one end.

5. 4. The thermosetting resin composition according to any one of items 1 to 3, wherein the thermosetting resin (A) is a compound represented by the following formula (1).

In Formula (1), each X is independently
It is a group represented by the following formula (XI), formula (X-II) or formula (X-III), and per molecule of the compound represented by formula (1) [the compound is represented by formula (XI ), A group represented by the formula (X-II), and a group represented by the formula (X-III), the compound is a mixture of different compounds. When the number of groups represented by 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,
a + 2b + c = 4, 0 <a ≦ 3, 0 ≦ b ≦ 1, and 0 <c ≦ 3.
R ¹ is each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, and cyclohexyl, and m is an average value satisfying 1 to 100.

In the formula (X-II), ^{R 1} is the same as ^{R 1} in formula (1), ^{R 2} and ^{R 3} are each independently selected from alkyl of 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl R is the number of repeating -OSi (R ³ ) _2- , and r is an average value satisfying 2-20.

In the formula (X-III), R ⁴ and R ⁵ are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and s is —OSi (R ⁵ ) ₂ —. S is an average value satisfying 2 to 20.

6). The thermosetting resin composition according to item 4, wherein the thermosetting resin (D) is a compound represented by the following formula (D1).

In the formula (D1), each X ′ independently represents the following formula (a), formula (b), formula (ci), formula (c-ii), formula (c-iii), formula (d- i) a group represented by the formula (d-ii) or the formula (d-iii), and per molecule of the compound represented by the formula (1) [the compound is represented by the formula (a) In the case of a mixture of compounds in which the proportions of groups represented by formula (b) to formula (d-iii) are different, the compound averages 1 molecule]
The number of groups represented by formula (a) is A,
The number of groups represented by formula (b) is B,
The number of groups represented by formula (ci), formula (c-ii) or formula (c-iii) is C,
When the number of groups represented by formula (d-i), formula (d-ii) or formula (d-iii) is D, A + 2B + C + D = 4, and 0.5 ≦ A ≦ 3.0 Yes, 0.5 ≦ 2B ≦ 2.0, 0.1 ≦ C ≦ 2, and 0 ≦ D ≦ 1.0.
R ^{1 ′} is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, and cyclohexyl, and m ′ is an average value satisfying 1 to 100.

In formula (b), R ^{1 'is} R ¹ in Formula ^(D1)' is the same as, R ^{2 'and} R ^3' are each independently alkyl of 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl And t is the number of repeating -OSi (R ^{3 '} ) _2- and is an average value satisfying 1-20.

In the formulas (di) to (d-iii), R ⁴ , R ^{4 ′} and R ^{4 ″} are each independently a group selected from methyl, ethyl, butyl and isopropyl. x is the number of repetitions of -OSi (R4 ^' ) _2- and is an average value satisfying 1-20. y is the number of repetitions of -OSi (R ^{4 ''} ) _2- and is an average value satisfying 1 to 10.

7). 5. The thermosetting resin composition according to item 4, wherein the thermosetting resin (D) is a compound represented by the following formula (D2).

  In formula (D2), R ″ is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and r is an integer of 0 to 100. aii is 0.1 ≦ aii ≦ 3.5, Xii is 0 ≦ 2Xii ≦ 2.0, Yii is 0 ≦ Yii ≦ 3.0, and Zii is 0.1 ≦ Zii ≦ 3.5.

8). 5. The thermosetting resin composition according to item 4, wherein the linear organopolysiloxane compound (F) having a SiH group only at one end is a compound represented by the following formula (2).

R ⁶ and R ⁷ are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, m is the number of repeating -OSi (R ⁷ ) ₂ —, and 1 to 20 The average value satisfying

9. The thermosetting resin composition according to item 4, wherein the organopolysiloxane compound (E) having two or more alkenyl groups is a compound represented by the formula (3).

In the formula (3), R ⁸ and R ⁹ are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and n is —OSi (R ⁹ ) ₂ —. It is the number of repetitions and is an average value satisfying 1-50.

10. Reacting (D) silsesquioxane having SiH group, organopolysiloxane having two alkenyl groups, epoxy compound having alkenyl groups and silyl compound having alkenyl groups on the basis of the total amount of the thermosetting resin composition. 10. The thermosetting resin composition according to any one of the preceding items 1 to 9, which comprises a thermosetting resin having a SiH group, obtained at 1 to 50% by mass.

11. 11. The thermosetting resin composition according to any one of items 1 to 10, which contains the thermosetting resin (E) at a ratio of 1 to 10% by mass on the basis of the total amount of the thermosetting resin composition.

12 12. The method according to any one of 1 to 11 above, containing 2 to 20% by mass of a linear organopolysiloxane compound having a SiH group only at one end of the (F), based on the total amount of the thermosetting resin composition. Thermosetting resin composition.

13. Furthermore, the thermosetting resin composition of any one of the preceding clauses 1-12 by which the inorganic compound was disperse | distributed.

14 14. The thermosetting resin composition according to item 13, wherein the inorganic compound is a phosphor and / or a metal oxide.

15. The thermosetting resin composition according to any one of items 1 to 14, wherein the rate of increase in viscosity under a storage condition of 30 days at a temperature of 80 ° C. is within 50%.

16. A prepreg obtained by molding the thermosetting resin composition according to any one of items 1 to 15.

17. Item obtained by heat-curing the prepreg according to Item 16.

18. 18. The article according to item 17 above, which is in the form of a coating film or a sheet and has a thickness of 0.1 μm to 3,000 μm.

  Since the thermosetting resin composition of the present invention is excellent in storage stability, it does not cause a change in viscosity or chemical change at room temperature, and has a high refractive index, high heat resistance, and excellent adhesiveness. A cured product can be provided. Therefore, the silicone sealing resin (sealing agent) using the thermosetting resin composition of the present invention does not need to be used by mixing two liquids just before as in the conventional case.

  Furthermore, the thermosetting resin composition of the present invention can be easily molded into an arbitrary shape in a semi-cured state to form a prepreg. Due to excellent storage stability, the semi-cured state is maintained for a long period of time, and the degree of freedom of use is extremely high. Furthermore, the thermosetting resin composition of the present invention can be used by dispersing an inorganic compound.

  Furthermore, the prepreg can be heat-treated and thermally cured. Since the thermosetting resin composition of the present invention has a silsesquioxane skeleton as a main component, the cured product is excellent in heat resistance and UV resistance. In addition, it exhibits excellent adhesion to housing base materials such as polyphthalamide resin, silver or ceramics, and can withstand rigorous reliability tests such as moisture reflow, heat cycle tests, and sulfur resistance tests, and is stored at room temperature. A stable resin composition and an excellent molded cured product comprising the resin composition can be obtained.

Hereinafter, the present invention will be described in detail.
In addition, when written alone as (A), it means what is defined in (A) in this document, but it may be re-expressed as appropriate, for example, thermosetting resin (A). This rule is the same for (B) to (F).

The thermosetting resin composition of the present invention is characterized by containing the following (A) and (B).
(A) A thermosetting resin comprising a SiH group and an alkenyl group, which is a reaction product of a silsesquioxane having a SiH group and an organopolysiloxane having two alkenyl groups.
(B) Pt catalyst.

  The thermosetting resin defined by (A) (hereinafter also referred to as thermosetting resin (A)) is a reaction product of silsesquioxane having SiH groups and organopolysiloxane having two alkenyl groups. . Examples of silsesquioxanes having SiH groups include double-decker silsesquioxanes and cage-type silsesquioxanes having a T8 structure. The cage silsesquioxane having a T8 structure has eight functional groups, whereas the double-decker silsesquioxane used in the present invention has only four functional groups. Easy to control the structure. Unlike the fully condensed cage silsesquioxane, the double-decker silsesquioxane preferably used in the present invention is incompletely condensed, has a relatively high degree of molecular freedom, and is excellent in flexibility. . From such a viewpoint, double-decker silsesquioxane is preferable.

  As a thermosetting resin (A), the compound represented by following formula (1) is mentioned, for example.

In the formula (1), each X is independently a group represented by the following formula (XI), formula (X-II) or formula (X-III). R ¹ is each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, and m is an average value satisfying 1 to 100. Among these, m is preferably 1.

In the formula (X-II), ^{R 1} is the same as ^{R 1} in formula (1), ^{R 2} and ^{R 3} are each independently selected from alkyl of 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl R is the number of repeating -OSi (R ³ ) _2- , and r is an average value satisfying 2-20. r is preferably 2 to 10. R ¹ is the same as ^{R 1} in Formula (1).

In the formula (X-III), R ⁴ and R ⁵ are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and s is —OSi (R ⁵ ) ₂ —. S is an average value satisfying 2 to 20. As for s, 2-10 are preferable and 2-4 are more preferable.

  Per molecule of the compound represented by the formula (1) [the compound is represented by the group represented by the formula (XI), the group represented by the formula (X-II), and the formula (X-III) In the case of a mixture of compounds having different group ratios, the number of groups represented by the formula (XI) of the compound 1 molecule average] is a, and the number of groups represented by the formula (X-II) is b When the number of groups represented by formula (X-III) is c, a + 2b + c = 4, 0 <a ≦ 3, 0 ≦ b ≦ 1, and 0 <c ≦ 3. .

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

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

  As the thermosetting resin (A), it is preferable to use a SiH-based thermosetting resin. The a is preferably 1.0 to 3.0, and more preferably 1.5 to 2.5 from the viewpoint of conspicuous excellent characteristics when cured. A, b, and c in the compound represented by the general formula (1) can be adjusted by the inventor's discretion, for example, by conforming to the production method described in International Publication No. 2011/145638.

  The thermosetting resin composition of the present invention preferably contains 50 to 95% by mass, and preferably 80 to 90% by mass of the thermosetting resin (A) based on the total amount of the thermosetting resin composition. More preferred. By setting the blending ratio of the thermosetting resin (A) to 80% by mass or more, the characteristics possessed by the double-decker silsesquioxane, that is, characteristics such as heat resistance, UV resistance, and high refractive index are maintained. Is possible. Moreover, the hardness of hardened | cured material can be D45 or less by making the mixture ratio of a thermosetting resin (A) into 95 mass% or less.

  The Pt catalyst of (B) (hereinafter also referred to as Pt catalyst (B)) is a catalyst containing platinum that can cure the thermosetting resin (A) under heating, and even if platinum is not oxidized. It may be oxidized. Examples of oxidized platinum include platinum oxide. Examples of the partially oxidized platinum include an Adams catalyst.

  Examples of the platinum catalyst include a Karstedt catalyst, a Spear catalyst, and hexachloroplatinic acid. These are generally well known catalysts. Of these, a non-oxidized type Karsted catalyst is preferably used.

  The blending ratio of the platinum catalyst (B) in the total thermosetting resin composition is preferably an amount sufficient to advance the curing of the curable resin composition of the present invention. Depending on the blending ratio with the agent, after the mixing, the curing reaction proceeds further than the temperature rises above a certain temperature while maintaining a stable viscosity or semi-cured in addition to the temperature rising above a certain temperature. First, as a blending ratio capable of retaining hardness and reactivity, 10 ppb to 200 ppb in terms of pure platinum is preferable. Preferably they are 30 ppb-150 ppb, More preferably, they are 50 ppb-100 ppb.

  In addition to the thermosetting resin (A) and the Pt catalyst (B) described above, the thermosetting resin composition of the present invention further includes (C) a curing inhibitor, thereby further improving storage stability. For this reason, it is preferable that the thermosetting resin composition of this invention contains (C) hardening inhibitor.

(C) The curing inhibitor (hereinafter also referred to as component (C)) will be described.
The curing reaction starts when the Pt catalyst (B) is blended with the thermosetting resin (A), but a curing inhibitor is blended to inhibit this reaction up to a predetermined temperature.

  As the curing inhibitor, known ones used in addition-type curable compositions with hydrosilylation catalysts can be used. Specific examples include compounds containing two or more alkenyl groups, compounds containing aliphatic unsaturated bonds, organophosphorus compounds, tin compounds, and organic peroxides. These may be used alone or in combination of two or more.

  Examples of the compound containing two or more alkenyl groups include disiloxanes containing both vinyl groups, trisiloxanes, and vinyl group-containing cyclic siloxanes such as 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane. Can be mentioned.

  Examples of the compound containing an aliphatic unsaturated bond include 3-methyl-1-dodecin-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynyl-1-cyclohexanol and the like. Mention may be made of propargyl alcohols, ene-yne compounds, maleic acid esters such as maleic anhydride and dimethyl maleate.

  Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite.

  Examples of tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

  Of these, 1,3-divinyldisiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane or 1-ethynyl-1-cyclohexanol is preferred.

  (C) As a compounding quantity of a component, until the curable resin composition of this invention hold | maintains the stable viscosity until it raises more than a certain temperature, or it rises above a certain temperature in the semi-hardened state The amount is such that the curing reaction does not proceed further. Specifically, it is 250 to 200,000 times, preferably 500 to 100,000 times the blending amount (mass) of the Pt catalyst (B). More preferably, it is 5000 to 50,000 times.

In addition, the present invention, as necessary,
(D) Thermosetting having SiH group obtained by reacting silsesquioxane having SiH group, organopolysiloxane having two alkenyl groups, epoxy compound having alkenyl group and silyl compound having alkenyl group Resin (hereinafter, also referred to as thermosetting resin (D)),
(E) an organopolysiloxane compound having two or more alkenyl groups (hereinafter also referred to as compound (E)),
(F) a linear organopolysiloxane compound having a SiH group only at one end (hereinafter also referred to as compound (F)),
It is also possible to include one or more of these.

  As a thermosetting resin (D), the compound represented by a following formula (D1) is mentioned, for example.

In the formula (D1), each X ′ independently represents the following formula (a), formula (b), formula (ci), formula (c-ii), formula (c-iii), formula (d- i) a group represented by the formula (d-ii) or the formula (d-iii), and per molecule of the compound represented by the formula (1) [the compound is represented by the formula (a) In the case of a mixture of compounds in which the proportions of groups represented by formula (b) to formula (d-iii) are different, the compound averages 1 molecule]
The number of groups represented by formula (a) is A,
The number of groups represented by formula (b) is B,
The number of groups represented by formula (ci), formula (c-ii) or formula (c-iii) is C,
When the number of groups represented by formula (d-i), formula (d-ii) or formula (d-iii) is D, A + 2B + C + D = 4, and 0.5 ≦ A ≦ 3.0 Yes, 0.5 ≦ 2B ≦ 2.0, 0.1 ≦ C ≦ 2, and 0 ≦ D ≦ 1.0.

R ^{1 ′} is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, and cyclohexyl, and m ′ is an average value satisfying 1 to 100.

In the formula (b), R ^{2 ′} and R ^{3 ′} are each independently a group selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl, and t is —OSi (R ^{3 ′} ) _2. It is the number of repetitions of-and is an average value satisfying 1-20.

In the formulas (di) to (d-iii), R ⁴ , R ^{4 ′} and R ^{4 ″} are each independently a group selected from methyl, ethyl, butyl and isopropyl. x is the number of repetitions of -OSi (R4 ^' ) _2- and is an average value satisfying 1-20. y is the number of repetitions of -OSi (R ^{4 ''} ) _2- and is an average value satisfying 1 to 10.

  The group represented by the formula (a) is a silsesquioxane-derived group having the SiH group, a compound corresponding to the group represented by the formula (b), and formulas (ci) to An epoxy derivative corresponding to the group represented by (c-iii), and a compound corresponding to the group represented by formula (d-i) to (d-iii) used as necessary after the reaction SiH group residue. Therefore, the group represented by the formula (a) can react with a thermosetting resin that is a reaction product of silsesquioxane and an organopolysiloxane to which the compound of the present invention is applied as an adhesion promoter. It has a role to reinforce the function of the compound of the invention as an adhesion-imparting material.

  The group represented by the formula (b) is a cross-linking component of silsesquioxane, and can give flexibility to the compound of the present invention. Specifically, for example, a polymer structure is taken like a compound represented by the following formula (1-1).

In Formula (1-1), X1 is each independently represented by Formula (a), Formulas (ci) to (c-iii), and Formulas (di) to (d-iii). X2 is a group represented by the formula (b). R ¹⁷ is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, and is preferably methyl. u is an average value satisfying 0 to 1000.

  As the value of B, which is the number of groups represented by formula (b), increases, the cross-linking component between molecules increases, and the compound of the present invention becomes a high molecular weight compound. If B = 0, there is no cross-linking component. In the range of 0 <B <1, the crosslinking component increases and the molecular weight increases as the value of B increases. In the range of B> 1, the cross-linking of molecules is in a very advanced state, and it cannot be used as a thermosetting resin because it becomes a gel. The molecular weight of the compound of the present invention can be adjusted by changing the value of B within the range of 0 <B ≦ 1.

  The groups represented by the formulas (c-i) to (c-iii) are epoxy groups bonded to SiH residues in the cross-linked product of the silsesquioxane and the organopolysiloxane, and the housing substrate for LED It has a role to improve adhesion. The component (ci) is a group having an isocyanuric ring skeleton in addition to an epoxy group, and also has a role of improving adhesion with a metal.

  The groups represented by the formulas (di) to (d-iii) are an alkoxysilyl group or a trialkylsilyl group bonded to a SiH residue in the cross-linked product of the silsesquioxane and the organopolysiloxane. Vinylsilyl group.

  The group represented by the following formula (di) is a group derived from the thermosetting resin (D) and is an arbitrary component. The group represented by the formula (d-i) is used for the purpose of improving the adhesion with a metal or the compatibility with a resin.

In formula (di), each R ⁴ is independently a group selected from methyl, ethyl, butyl and isopropyl.

  The group represented by the following formula (d-ii) is a group derived from the thermosetting resin (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, the purpose of adjusting the viscosity, or the purpose of adjusting the hardness after curing the curable resin composition.

In the formula (d-ii), each R ^{4 ′} is independently a group selected from methyl, ethyl, butyl and isopropyl, preferably methyl. x is the number of repetitions of -OSi (R ^{4 '} ) _2- . x is an average value satisfying 1 to 20, and preferably an average value satisfying 1 to 10.

  The group represented by the following formula (d-iii) is a group derived from the thermosetting resin (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, the purpose of adjusting the viscosity, or the purpose of adjusting the hardness after curing the curable resin composition.

In the formula (d-iii), each R ^{4 ″} is independently a group selected from methyl, ethyl, butyl and isopropyl, preferably methyl. y is the number of repetitions of -OSi (R4 ^" ) _2- . y is an average value satisfying 1 to 10.

  A + 2B + C + D = 4, 0.5 ≦ A ≦ 3.0, 0.5 ≦ 2B ≦ 2.0, 0.1 ≦ C ≦ 2, and 0 ≦ D ≦ 1.0. The values of A to D can be arbitrarily adjusted according to the properties of the thermoplastic resin composition to which the compound of the present invention is applied as an adhesion promoter.

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

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

  As shown in the following reaction formula, an equimolar reaction of excess moles of divinyltetradisiloxane (DVDS) and hexamethyldisiloxane (MM) in the presence of an acid catalyst with respect to cyclic octamethyltetracyclosiloxane (D4). And an equilibrated mixture of compound a, compound b, and compound c is obtained, and used as a reaction reagent for obtaining a group represented by formula (d-ii) or a group represented by formula (d-iii).

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

  The molar ratio of the combined reaction of DVDS and MM with respect to D4 is preferably 2 or more. If the molar ratio is 2 or more, the molecular weight of the resulting siloxane chain is short and becomes a component that can be removed by distillation, and in the subsequent purification step, excess compound a, compound b, and compound c that were not involved in the reaction. Easy to remove.

It describes about the method of reaction in order to obtain group represented by a formula (d-ii) or a formula (d-iii).
Thermosetting resin (D) which is a compound having an isocyanuric ring skeleton of the present invention and having an epoxy group and having a group represented by the above formula (d-ii) or formula (d-iii) ) -Derived group is a group represented by the formula (ci).

  As shown in the following reaction formula, in the first reaction, DD-4H which is a double-decker compound having four SiH groups and MA-DGIC which is (ci) are first hydrosilylated. First, a compound having a group represented by the formula (ci) is obtained. The compound of the formula (ci) is sold as MA-DGIC by Shikoku Kasei Co., Ltd. DD-4H can be synthesized according to the method described in International Publication No. 2004/024741.

  In the reaction formula, ai is 0.1 to 3.5.

  Next, as shown in the following reaction formula, in the second-stage reaction, the moles of vinyl groups in the mixture of the compound a, the compound b, and the compound c with respect to the number of moles of SiH groups in the first-stage compound. The following product is obtained by hydrosilylation reaction so that the number becomes excessive.

  In the above 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. , Wi is 0 ≦ Wi ≦ 3.0.

  The hydrosilylation reaction is performed so that the number of moles of vinyl groups is excessive, but the remaining SiH groups remain without disappearing even in a high temperature region of 100 ° C. or higher, and further 120 ° C. or higher.

  Excess compound a, compound b, and compound c not involved in the reaction can be distilled off by distillation using a thin film evaporator. Alternatively, it can be removed by a solvent extraction method. Alternatively, it may be left as it is at the discretion of the inventor. The temperature when distilling off excess compound a, compound b, and compound c in 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.

  A preferable solvent for removing excess compound a, compound b, and compound c in the solvent extraction method is a solvent having a large dissolving power and a relatively low boiling point. A preferred solvent is a lower alcohol. A particularly preferred solvent is methanol. In order to further increase the degree of purification, the number of repeated solvent extraction operations may be increased.

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

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

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

  As the reactant used in the second stage reaction, a compound represented by the formula (G) is used.

  In the formula (G), R ′ and R ″ are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and r is an integer of 0 to 100. R ′ and R ″ are preferably methyl. r is preferably 1 to 100, and more preferably 2 to 20.

  As shown in the following reaction formula, the hydrosilylation reaction is performed so that the number of moles of the vinyl group of the compound represented by the formula (G) is excessive with respect to the number of moles of the SiH group in the first-stage compound. To obtain the following product.

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

  The hydrosilylation reaction is performed so that the number of moles of the vinyl group of the compound represented by the formula (G) is excessive, but the residual SiH does not disappear even in a high temperature region of 100 ° C. or higher, more preferably 120 ° C. or higher. The group remains.

  Since the excess organopolysiloxane not involved in the reaction is a compound having a vinyl group, it may be left as it is as a thermosetting resin component. Or you may remove by solvent extraction etc. suitably. A preferred solvent for removing excess organopolysiloxane is a solvent having a high dissolving power and a relatively low boiling point. A preferred solvent is a lower alcohol. A particularly preferred solvent is methanol. In order to further increase the degree of purification, the number of repeated solvent extraction operations may be increased.

  Moreover, as a thermosetting resin (D), the compound represented by a following formula (D2) is mentioned, for example.

  In formula (D2), R ″ is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and r is an integer of 0 to 100. aii is 0.1 ≦ aii ≦ 3.5, Xii is 0 ≦ 2Xii ≦ 2.0, Yii is 0 ≦ Yii ≦ 3.0, and Zii is 0.1 ≦ Zii ≦ 3.5.

  The thermosetting resin composition of the present invention preferably contains 1 to 50% by mass, more preferably 2 to 15% by mass of the curable resin (D) based on the total amount of the thermosetting resin composition. . By setting the blending ratio of the thermosetting resin (D) having a SiH group to 1% by mass or more, it is possible to improve the adhesion strength with the LED housing substrate.

  In addition, since the epoxy part in a thermosetting resin (D) can be used arbitrarily, the sum total of an epoxy part will be 0.01-10 mass% on the thermosetting resin composition whole quantity reference | standard. It is preferable to contain by a mass part, and it is more preferable to contain by a mass part which will be 0.05-5 mass%.

  The thermosetting resin composition of the present invention may contain (E) an organosiloxane compound (compound E) having two or more alkenyl groups as required. Examples of the organopolysiloxane having two or more alkenyl groups of the present invention include compounds represented by the following general formula (3).

In the formula (3), R ⁸ and R ⁹ are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and n is —OSi (R ⁹ ) ₂ —. The average value satisfying 1 to 50.

The compound (E) is a component for adjusting the viscosity of the cured composition of the present invention and assisting the cured product with strength or flexibility. In the formula (3), when R ⁸ and R ⁹ are all alkyl having 1 to 4 carbon atoms, methyl is preferably used and is represented by the following general formula (4).

  In the formula (4), n ′ is an average value satisfying 1-20. When n 'is 20 or less, the compatibility with the cured composition of the present invention is good, which is preferable. In terms of imparting flexibility, 5 or more is preferable, and 10 or less is preferable from the viewpoint of a gas barrier. 5 to 8 is particularly preferable from the viewpoints of flexibility and gas barrier.

Moreover, the following general formula (5) or (6) in which at least a part of R ⁸ and R ⁹ in the formula (3) is a phenyl group can also be suitably used.

  In said Formula (5), x is an average value which satisfy | fills 1-50, Preferably it is 1-20.

  In the formula (6), y + z is an average value satisfying 1 to 50, and a value satisfying y / (y + z) <0.5 is preferable from the viewpoint of refractive index and gas barrier. In the sense of imparting flexibility to the cured product, y + z is preferably 10 or more.

  These compounds (E) may be optionally used in combination.

  Compound (E) can be produced by a known and commonly used method. The organosiloxane compound represented by the formula (4) is obtained by, for example, subjecting tetramethylvinyldisiloxane and octamethylcyclotetrasiloxane to an equilibration reaction in the presence of a solid acid catalyst such as activated clay and then filtering the solid acid catalyst. Then, low boiling cutting is performed under a vacuum condition of about 0.13 kPa and a temperature condition of 100 to 120 ° C. The organosiloxane compound represented by formula (5) or formula (6) can also be produced by a known and commonly used method. It is also industrially available from GELEST.

  The compounding ratio of the compound (E) is preferably 1% by mass to 10% by mass or less in the total thermosetting resin composition of the present invention. By making the compounding ratio of the compound (E) within the above range, heat resistance is improved and resin strength is increased, which is preferable.

(F) A linear organopolysiloxane compound (compound (F)) having a SiH group only at one end will be described.
Examples of the compound (F) include a compound represented by the following formula (2).

In the formula (2), R ⁶ and R ⁷ are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, preferably methyl or butyl. m is the number of repetitions of -OSi (R ⁷ ) _2- . m is an average value satisfying 1 to 20, and preferably an average value satisfying 2 to 15.

  The compound (F) is used for reducing the hardness. That is, it can be made to react with the alkenyl group which the said thermosetting resin (A) has, and low hardness can be achieved by reducing the whole crosslinking density by this.

  The more compound (F) is blended, the lower the hardness of the cured product. The content of (F) in the thermosetting resin composition of the present invention is preferably such a content that the cured product can maintain a refractive index of 1.5 or more. By setting the content such that the refractive index of the cured product can maintain 1.5 or more, light extraction efficiency as an LED sealing agent can be improved, and adhesion can be enhanced.

  The number average molecular weight of the compound (F) is preferably 148 to 2000, and more preferably 400 to 1000. When the number average molecular weight of (F) is 400 or less, the volatility is high, and there is a risk of dispersal in the stage of blending and curing the cured composition, so a number average molecular weight of 400 or more is more preferable.

  Further, by setting the number average molecular weight of the compound (F) to 2000 or less, a reaction product of a silsesquioxane having a SiH group and an organopolysiloxane having two alkenyl groups, wherein the SiH group and the alkenyl group It is possible to maintain compatibility with the thermosetting resin containing, maintain the transparency of the cured product, and maintain adhesion performance.

  The compounding ratio of the compound (F) is preferably 2 to 20% by mass and more preferably 5 to 15% by mass in the total thermosetting resin composition of the present invention. By setting the compounding ratio of the compound (F) to 2% by mass or more, the hardness of the cured product can be lowered to D45 or less. Moreover, by setting the compounding ratio of the compound (F) to 20% by mass or less, a cured product having a low hardness can be obtained effectively while maintaining various properties such as heat resistance, UV resistance, and adhesion of the cured product. Is possible.

  The thermosetting resin composition of the present invention can be used by further dispersing an inorganic compound in accordance with any purpose such as imparting thixotropy or imparting optical properties. There is no limitation in the inorganic compound to be used, A well-known material can be used. Further, the structure of the inorganic compound may be amorphous or may be crystallized. The combination of inorganic compounds to be dispersed is not limited. As the inorganic compound, various phosphors and metal oxides can be suitably used. Of course, phosphors and metal oxides may be used in combination.

  By dispersing the phosphor in the thermosetting resin composition of the present invention, it has a light emitting function and can be used as a composition for LED. The phosphor content in the thermosetting resin composition of the present invention is preferably 1 to 90% by mass, and more preferably 2 to 50% by mass.

  There is no restriction | limiting in the fluorescent substance which can be used for the thermosetting resin composition of this invention. Further, the concentration distribution of the phosphor in the composition may be uniform or different. The type of phosphor to be used, the presence / absence of the phosphor concentration distribution, and the conditions for the distribution may be determined according to the use environment, application, and purpose of the LED.

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

  The phosphors as described above include various 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. Specific phosphors used in the present invention include known phosphors such as organic phosphors, inorganic phosphors, fluorescent pigments, and fluorescent dyes. Examples of organic phosphors include allylsulfoamide / melamine formaldehyde co-condensed dyes and perylene phosphors. Perylene phosphors are preferably used because they can be used for a long period of time. Examples of the fluorescent material that is particularly preferably used in the present invention include inorganic phosphors. 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], and [Sr ₇ Al ₁₂ O ₂₅ : Eu. ] [(At least one of Mg, Ca, Sr, 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], and [(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 phosphors emitting green to yellow, at least cerium-activated yttrium / aluminum oxide phosphors, at least cerium-enriched yttrium / gadolinium / aluminum oxide phosphors, at least cerium-activated yttrium / aluminum There are garnet oxide phosphors and at least cerium activated yttrium gallium aluminum oxide phosphors (so-called YAG phosphors). Specifically, [Ln ₃ M ₅ O ₁₂ : R (Ln is at least one selected from Y, Gd, La, M includes at least one of Al and Ca, and R is a lanthanoid a _{system)], [(Y1-xGax} ) 3 (Al1-yGay) 5 O 12:. R (R is at least one or more of Ce, Tb, Pr, Sm, Eu, Dy, selected from 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]. .

Moreover, as a fluorescent substance corresponding to the blue LED currently in the mainstream, [Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Gd) ₃ Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : YAG phosphor such as Ce, Y ₃ A ₁₅ O ₁₂ : Ce], TAG phosphor such as [Tb ₃ Al ₅ O ₁₂ : Ce], [(Ba, Sr) ₂ SiO ₄ : Eu] phosphor Body, [Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce] phosphor, silicate phosphor such as [(Sr, Ba, Mg) ₂ SiO ₄ : Eu], [(Ca, Sr) ₂ Si ₅ N ₈ : Eu], [(Ca, Sr) AlSiN ₃ : Eu], nitride phosphors such as [CaSiAlN ₃ : Eu], and oxy such as [Cax (Si, Al) ₁₂ (O, N) ₁₆ : Eu] Nitride phosphors, and [ _{Ba, Sr, Ca) Si 2} O 2 N 2: Eu] _{phosphor, [Ca 8 MgSi 4 O 16} Cl 2: Eu] _{phosphor, [SrAl 2 O 4: Eu} , Sr 4 Al 14 O 25: And a phosphor such as Eu].

Among these, YAG-based phosphors, TAG-based phosphors, and silicate-based phosphors are preferably used in terms of light emission efficiency and luminance. In addition to these, known phosphors can be used depending on the intended use and the intended emission color.

Next, a case where the inorganic compound is a metal oxide will be described. As the metal oxide, silica, alumina, yttrium oxide, zinc oxide, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide and the like are preferably used.
The ratio of the metal oxide in the thermosetting resin composition of the present invention is preferably 1 to 70% by mass, more preferably 1 to 40% by mass, and still more preferably the mass ratio with respect to the total amount of the thermosetting resin composition. Is 1-20 mass%.

  When titanium oxide or aluminum oxide is used in the thermosetting resin composition of the present invention, it can be suitably used as a reflector material. Regarding the reflector material, polyphthalamide resin is widely used. However, it has been pointed out that polyphthalamide resins are liable to deteriorate, especially discoloration, due to long-term use, and the thermosetting resin composition of the present invention can solve this problem.

  In addition, for example, as silica, a naturally produced silica stone (natural silica) may be used, or industrially synthesized silica (synthetic silica) may be used. Since natural silica is a crystal, it has a crystal axis. For this reason, although the optical characteristic derived from a crystal | crystallization can be anticipated, since specific gravity is a little high compared with a synthetic silica, it may influence the dispersion | distribution in a thermosetting resin composition. Further, when a natural product is pulverized, it may be an irregularly shaped particle or a material having a wide particle size distribution.

  Synthetic silica includes wet synthetic silica and dry synthetic silica, but the use is not particularly limited in the present invention. However, synthetic silica may have water of crystallization regardless of the production method, and if this water of crystallization may affect the thermosetting resin composition or cured product, LED element, etc., the number of water of crystallization It is preferable to select in consideration of the above.

  Since synthetic silica is amorphous rather than crystalline, it has no crystal axis and optical characteristics derived from crystals cannot be expected. However, in addition to controlling the particle distribution, it is possible to take advantage of features such as extremely small particle size.

  In particular, fumed silica has a nano-order particle size and excellent particle dispersibility. Further, when compared with the same weight, the smaller the particle diameter, the larger the total surface area, so that the light reflection direction becomes more diversified, so that it can be used more preferably.

  In general, silica has a large surface area and is a hydrophilic material (hydrophilic silica) due to the effect of silanol present on the surface, but can also be made into hydrophobic silica by chemical modification. Which type of silica is used is selected depending on the purpose, but in the present invention, it is preferable to use hydrophilic silica in experimental verification.

  The method for preparing and mixing the thermosetting resin composition of the present invention is not particularly limited. For example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, a triple roll or a bead mill, Or the method of mixing each predetermined amount of the said hardening accelerator, a silicone resin, and the said thermosetting agent, antioxidant, etc. as needed under heating is mentioned.

  The thermosetting resin composition of the present invention is very excellent in storage stability, and has a viscosity increase rate of 50% or less when stored for 30 days in an environment at a temperature of 80 ° C. In addition, the thermoplastic resin composition of the present invention is thermosetting and does not consider humidity conditions that do not affect curing because of storage in a container. If the rate of increase in viscosity is within 50%, the soft state is maintained, which is preferable without affecting the subsequent molding operation. In the future, the soft state may be referred to as a semi-cured state.

  The thermosetting resin composition of the present invention can be molded in a semi-cured state into an arbitrary shape. There is no limitation on the molding method, and examples thereof include molding machines such as hot press molding, film coater, and extrusion molding, and printing methods such as screen printing, gravure printing, and lithographic printing. The molded product can be reprocessed like a prepreg and used in the next step. For example, a prepreg molded into a flat shape such as a coating film or a sheet can be cut out finely to form a chip-like shape as a material for sealing or adhesion. Further, by using an injection molding or a compression molding method, it is possible to obtain an LED housing material or a reflector material having a reflection function. In addition, in this book, what shape | molded the thermosetting resin composition irrespective of the shape is expressed as a prepreg.

  The thickness of the prepreg molded into a flat shape such as a coating film or a sheet is determined from the phosphor content and desired optical characteristics. Specifically, it is 0.1 μm or more in the case of a coating film, and about 10 μm to 3000 μm can be molded in the case of a sheet. From the viewpoint of improving optical properties and heat resistance, the thickness of the phosphor sheet is preferably 1000 μm or less, more preferably 200 μm or less, and even more preferably 100 μm or less. By setting the phosphor sheet to a film thickness of 1000 μm or less, light absorption and light scattering by the binder resin can be proposed, so that the phosphor sheet is optically excellent.

The thermosetting resin composition of this invention or this prepreg is heat-processed, and the target article (cured material) is obtained. As conditions for obtaining a cured product, the temperature is preferably 60 to 200 ° C, more preferably 80 to 160 ° C. Moreover, it is preferable that time is 1 to 24 hours, and it is more preferable that it is 2 to 5 hours from an economical viewpoint.
In addition to articles that function as a single product, articles that exist in a specific structure such as a sealing material and are cured as a part of a member are also included in the article.

  The use of the thermosetting resin composition or the prepreg of the present invention is not particularly limited. For example, a die bonding material for connecting to a sealant, a housing material, a lead electrode, a heat sink, or the like, an optical semiconductor element such as a light emitting diode When the light emitting element is flip-chip mounted, it can be used as an underfill material or a passivation film on the light emitting element. Especially, since an optical semiconductor device capable of efficiently extracting light generated by light emission from the optical semiconductor element can be manufactured, it can be suitably used as a sealant, a reflector material, a phosphor sheet, an underfill material, or a die bond 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 refractive index is preferably a high refractive index of 1.5 or more. When the refractive index is 1.5 or more, the cured product is excellent in LED light extraction efficiency.

  The method for sealing the light emitting element with the thermosetting resin composition of the present invention is not particularly limited. For example, the composition for optical semiconductor of the present invention is injected in advance into a mold mold, and the light emitting element is fixed thereto. Examples include a method of immersing the prepared lead frame and then curing, and a method of injecting and curing the composition for optical semiconductors of the present invention into a mold in which a light emitting element is inserted.

  Examples of the method for injecting the thermosetting resin composition of the present invention include injection by a dispenser, transfer molding, and injection molding. Further, as other sealing methods, for example, the optical semiconductor composition of the present invention is dropped onto a light emitting device, stencil printing, screen printing, a method of applying and curing through a mask, and a light emitting device on the bottom. A method of injecting the composition for optical semiconductor of the present invention into a cup or the like with a dispenser or the like and curing it.

  An optical semiconductor element containing the thermosetting resin composition of the present invention as a sealant is also one aspect of the present invention.

  The cured product of the thermosetting resin composition of the present invention is excellent in, for example, transparency, heat resistance, and heat yellowing. Therefore, an article containing a cured product can be suitably used for applications such as a semiconductor sealing material, an optical semiconductor sealing material, a phosphor sheet, a reflector, an insulating film, a sealant, and an optical lens. Also, transparent materials, optical materials, optical films, optical sheets, adhesives, electronic materials, insulating materials, interlayer insulating films, paints, inks, coating materials, molding materials, potting materials, liquid crystal sealants, display device sealants, Solar cell sealing material, resist material, color filter, electronic paper material, hologram material, solar cell material, fuel cell material, display material, recording material, waterproof material, moisture proof material, battery solid electrolyte, gas separation Can be used for membranes. Moreover, it can use for the additive etc. to other resin.

  The present invention will be described in more detail based on examples. 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 the weight average molecular weight of the polymer synthesized in the present invention were measured as follows.
Using a high-performance liquid chromatograph system CO-2065plus manufactured by JASCO Corporation and using 20 μL of a THF solution having a sample concentration of 1 mass% as an analysis sample, a column: Shodex KF804L [manufactured by Showa Denko KK] (two in series) Connection), column temperature: 40 ° C., detector: RI, eluent: THF, eluent flow rate: 1.0 mL per minute, measured by GPC method, and determined by polystyrene conversion.

The reagents used in the examples are as follows.
FM-2205 (polydimethylsiloxane having vinyl groups at both ends and having a number average molecular weight of 700): MA-DGIC (monoallyl diglycidyl isoannulate): S210 (vinyltrimethoxysilane) manufactured by Shikoku Kasei Kogyo Co., Ltd .: JNC Made by Co., Ltd.

(A) Thermosetting resin comprising a silsesquioxane having a SiH group and an organopolysiloxane having two alkenyl groups, which is a component (A) of the present invention. The following silsesquioxane derivative base polymer 1 or silsesquioxane derivative base polymer 2 produced by the method disclosed in International Publication No. 2011/145638 is used as a thermosetting resin containing a SiH group and an alkenyl group. Using.

[Silsesquioxane derivative base polymer 1]
In the above formula (1), a [formula (XI)] = 2.34, b [formula (X-II)] = 0, c [formula (X-III)] = 1.66, The compound represented by the following chemical formula was designated as silsesquioxane derivative base polymer 1.

[Silsesquioxane derivative base polymer 2]
In the formula (1), a [formula (XI)] = 2.37, 2b [formula (X-II)] = 0.48, c [formula (X-III)] = 1.14. The compound represented by the following chemical formula was designated as silsesquioxane derivative base polymer 2.

(D) Thermosetting having SiH group obtained by reacting silsesquioxane having SiH group, organopolysiloxane having two alkenyl groups, epoxy compound having alkenyl groups and silyl compound having alkenyl groups resin

[Silsesquioxane derivative base polymer 3]
As the thermosetting resin having a SiH group as the component (D) of the present invention, in the above formula (D1), A [formula (a)] = 1.32, 2B [formula (b)] = 1.38, A silsesquioxane derivative base polymer 3 represented by the following formula, in which C [formula (ci)] = 0.65 and D [formula (di)] = 0.65, was used.

  The silsesquioxane derivative base polymer 3 was synthesized by the following method according to the following reaction formula. 50 g of silsesquioxane derivative (DD-4H) and 18.6 g (0.0266 mol) of vinyl silicone (FM-2205) in a 300 mL internal reaction vessel equipped with a thermometer, reflux condenser, and stirrer Then, 7.47 g (0.0252 mol) of monoallyl diepoxy isocyanurate (MA-DGIC), 3.7 g (0.0252 mol) of S210, and 50 g of toluene as a solvent were added.

  Heating and stirring were started under a nitrogen atmosphere. After the contents reached 100 ° C., an amount that the Pt concentration became 1 ppm with respect to DD-4H was added, and the mixture was heated and stirred as it was for 5 hours. The reaction was completed after confirming the disappearance of MA-DGIC from GC. After cooling to room temperature, 1.6 g of activated carbon was added and stirred for 3 hours or more, and then the activated carbon was removed by filtration. Toluene, which is a solvent, was distilled off from the filtrate under reduced pressure conditions of 90 ° C. and 0.13 kPa using an evaporator. 74 g of a water-like colorless and transparent liquid was obtained.

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

(F) Linear organopolysiloxane compound having a SiH group only at one end As the organopolysiloxane having a SiH group only at one end, which is the component (F) of the present invention, the number average molecular weight manufactured by JNC Corporation A 900 or 500 single-ended SiH silicone was used. In addition, as a comparative compound of the component (F), both-end SiH silicone having a number average molecular weight of 500 was used.

  The organopolysiloxanes having number average molecular weights of 900 and 500 having SiH groups only at one end were prepared by referring to the method described in Japanese Patent Application Laid-Open No. 2000-273178. Moreover, what was manufactured by referring the method described in Japan Unexamined-Japanese-Patent No. 2003-252995 was used for the both-ends SiH silicone of the number average molecular weight 500.

[One-end SiH silicone with a number average molecular weight of 900]
In the above formula (2), R ⁶ = butyl, R ⁷ = methyl, m = 11, a compound represented by the following chemical formula was used as a one-terminal SiH silicone having a number average molecular weight of 900.

[One-end SiH silicone having a number average molecular weight of 500]
In the above formula (2), R ⁶ = butyl, R ⁷ = methyl, m = 5, a compound represented by the following chemical formula was used as a one-terminal SiH silicone having a number average molecular weight of 500.

[SiH silicone at both ends with a number average molecular weight of 500]
As a comparative component of the component (F) of the present invention, a both-end SiH silicone having a number average molecular weight of 500 represented by the following formula was used.

(B) Pt catalyst As a Pt catalyst which is the component (B) of the present invention, a Karsted catalyst trade name Pt-VTS 3 wt% xylene solution (manufactured by Umicore) was used.

(E) Organopolysiloxane compound having two or more alkenyl groups As a compound having two or more alkenyl groups as the component (E) of the present invention, in the formula (3), R ⁸ = methyl, R ⁹ = methyl, The both-end vinyl silicone having a number average molecular weight of 700 represented by the following chemical formula, where n = 8, was used.

Epoxy group-containing silane coupling agent Further, in the comparative examples, glycidyl ether trimethoxysilane: trade name S510 (manufactured by JNC Corporation) was used as an epoxy group-containing silane coupling agent as an adhesion imparting material.

<Preparation of thermosetting resin composition>
The compound synthesized in the above example or a mixture of polyorganosiloxane was placed in a screw tube. The screw tube is set in a rotating / revolving mixer ["Awatori Nertaro (registered trademark)" ARE-250 manufactured by Sinky Co., Ltd.], mixed and defoamed, and intermediate compositions a to d as intermediate resin compositions are prepared. Obtained. Table 1 shows the mass% of each thermosetting resin composition.

  In addition to the above intermediate compositions a to d, a rusted catalyst (trade name: Pt-VTS: xylene solution having a Pt concentration of 3% by mass) manufactured by Umicore is used as a curing inhibitor: MVS-H (trade name, 1, 3, 5). , 7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (manufactured by JNC Corporation) diluted 100 times (mass) so that the Pt concentration becomes a predetermined amount, and further prohibition of curing The agent is added to a predetermined amount, mixed and defoamed again with a rotation / revolution mixer, and compositions A1 to A8, B1, C1 to C5, D1 to D2, and thermosetting resin compositions, and Comparative compositions A9 to A12 and C6 to C7 were obtained. Table 2 shows the mass% of each thermosetting resin composition and the blending amounts of the Pt catalyst and the curing inhibitor.

  About the obtained composition A1-A8, B1, C1-C5, D1-D2, and comparative composition A9-A12, C6-C7, the storage stability and sclerosis | hardenability were evaluated with the following method. The results are shown in Table 2.

<Storage stability>
The storage stability is evaluated by measuring the viscosity after taking the above composition in a storage container and putting them in an 80 ° C. constant temperature bath for 30 days. It was investigated whether the viscosity increase rate after the test was 50% or less compared with the viscosity before the test. ○ indicates a viscosity increase rate of 50% or less, and x indicates a viscosity increase rate of 50% or more.

<Curability of thermosetting resin composition>
The curability was examined by putting the composition into a PFA petri dish and heating at 160 ° C. for 1 hour to cure. If it was cured and a film was obtained, it was marked as ◯, and if it was not cured and was liquid or waxy, it was marked as x.

<Production of cured product>
About each of the thermosetting resin compositions A1, B1, C1, and D1, sandwiched by Nichias Co., Ltd. Naflon SP packing (4 mm diameter) between two glasses, the thermosetting resin composition is poured into this, After degassing under reduced pressure, curing is carried out by heating in order of 1 hour at 80 ° C. and then 4 hours at 150 ° C., and the cured products A1, B1, C1, and D1 having a smooth surface of 4 mm thickness are obtained by removing the glass. It was.

  About the obtained hardened | cured material A1, B1, C1, D1, the physical property was evaluated with the following method. The results are shown in Table 3.

<Viscosity>
The viscosity of the thermosetting resin compositions A1, B1, C1, and D1 before curing of the cured products A1, B1, C1, and D1 uses a TV-22 type viscometer cone plate type manufactured by Toki Sangyo Co., Ltd. The measurement was performed at a constant temperature of 25 ° C.

<Light transmittance>
A cured product having a thickness of 4 mm was prepared, and the light transmittance at a wavelength of 400 nm was measured with an ultraviolet-visible spectrophotometer UV-1650 manufactured by Shimadzu Corporation.

<Heat resistant transmittance>
The heat resistance test was performed and evaluated by the following method. A cured product having a thickness of 4 mm was prepared, and the light transmittance at a wavelength of 400 nm was measured with an ultraviolet-visible spectrophotometer UV-1650 manufactured by Shimadzu Corporation to obtain an initial transmittance. The cured product was placed in an oven at 180 ° C. [constant temperature dryer: DX302 manufactured by Yamato Scientific Co., Ltd.] and heat-treated for a certain time (1000 hours in Table 2).

  The light transmittance of the cured product after the heat resistance test was measured with an ultraviolet-visible spectrophotometer. From the transmittance at a wavelength of 400 nm, the retention at this wavelength (transmittance after heat treatment for a certain time / initial transmittance at each wavelength × 100 ) Was calculated and evaluated. When the transmittance retention at 400 nm after a heat resistance test at 180 ° C. of 1000 hours was 85% or more, “Yes”, when it was 75% or more, Δ, and when it was 75% or less, ×.

<UV resistance>
With respect to UV transmittance, UV light was irradiated on a cured product having a thickness of 4 mm using a Deep UV Lamp manufactured by Ushio Co., Ltd. through a 365 nm bandpass filter at an irradiation intensity of 550 to 600 mW / cm ² . When the retention rate of 400 nm after irradiation for 2000 hours was 99% or more, it was evaluated as ◯, when 97% or more, Δ, and when 97 or less, ×.

<Refractive index>
The test piece cut the hardened | cured material with the band saw, and produced the test piece according to JISK7142 (2008). Using this test piece, the refractive index was measured with an Abbe refractometer [NAR-2T manufactured by Atago Co., Ltd.] using a D line (586 nm) of a sodium lamp. The intermediate solution was methylene iodide.

<Hardness of cured product>
In accordance with JIS K6253 (2006), the D hardness was measured with a durometer WR-105D manufactured by Nishitokyo Seimitsu Co., Ltd., and the A hardness was measured with a WR-104A.

<Adhesive strength test PPA>
The test was conducted according to JIS K6850 (1999). The test piece is a thermosetting resin between polyphthalamide resin [Amodel (trade name) A-4122NLWH905 manufactured by Solvay Advanced Polymers Co., Ltd.] adjusted as a substrate according to JIS K6850 (1999). The composition was sandwiched and heated at 80 ° C. for 1 hour and then heated and cured at 150 ° C. for 4 hours. The adhesion test was measured using a 5 kN load cell with a tensile and compression tester [Autograph AGS-500B manufactured by Shimadzu Corporation].

<Adhesion strength test PA9T>
The test was conducted according to JIS K6850 (1999). The test piece has a thermosetting resin composition sandwiched between polyphthalamide resin [Kuraray Co., Ltd. Genesta (trade name) PA9T] adjusted in accordance with JIS K6850 (1999) as a base material. After heating at 80 ° C. for 1 hour, heat curing was performed under the conditions of heating at 150 ° C. for 4 hours. The adhesion test was measured using a 5 kN load cell with a tensile and compression tester [Autograph AGS-500B manufactured by Shimadzu Corporation].

<Adhesive strength test Ag>
The test was conducted according to JIS K6850 (1999). The test piece sandwiched a thermosetting resin composition between silver-plated standard test substrates [manufactured by Nippon Test Panel Co., Ltd.], heated at 80 ° C. for 1 hour, and then at 150 ° C. for 4 hours. It was made by heat curing under heating conditions. The adhesion test was measured using a 5 kN load cell with a tensile and compression tester [Autograph AGS-500B manufactured by Shimadzu Corporation].

<Hygroscopic reflow test>
A thermosetting resin composition is dispensed into 16 PPA resin packages [Model No. 5050 D / G, manufactured by Enomoto Co., Ltd.] with a silver-plated bottom side, using a dispenser (Model No. MPP-1 manufactured by Musashi Engineering Co., Ltd.). After the injection, the mixture was heated at 80 ° C. for 1 hour, and further heated and cured at 150 ° C. for 4 hours. These PPA resin packages are absorbed in an environmental tester (model number SH-241 manufactured by Espec Corp.) under conditions of moisture absorption at a temperature of 30 ° C., a relative humidity of 60% and 192 hours, and then a simulated reflow machine [Malcom Corp. Reflow was performed twice under the temperature condition (260 ° C.) according to the JEDEC standard with the product model SRS-1C]. The number of peeled pieces and the number of cracks generated in 16 pieces are shown.

<Heat cycle test PPA peeling / cracking>
A thermosetting resin composition is dispensed into 16 PPA resin packages [Model No. 5050 D / G, manufactured by Enomoto Co., Ltd.] with a silver-plated bottom side, using a dispenser (Model No. MPP-1 manufactured by Musashi Engineering Co., Ltd.). After the injection, the mixture was heated at 80 ° C. for 1 hour, and further heated and cured at 150 ° C. for 4 hours. These PPA resin packages were reflowed once in a simulated reflow machine [model SRS-1C manufactured by Malcolm Co., Ltd.] under temperature conditions (260 ° C.) according to JEDEC standards. Then, it put into the test area of the thermal shock apparatus [Espec Co., Ltd. model number TSE-11], and exposed by -40 degreeC for 30 minutes, and carrying out for 30 minutes at 105 degreeC was implemented by repeating 500 cycles. In addition, the movement time between both exposure temperatures was 2 minutes. The occurrence of peeling and cracking was observed with a microscope. The defect rate in 16 pieces is shown.

<Heat cycle test PA9T peeling / cracking>
A thermosetting resin composition is injected into 15 PA9T resin packages [Model No. SMD5050N-TA112 manufactured by I-CHIUN Co., Ltd.] for power LEDs with a silver-plated bottom portion using a dispenser (Model No. MPP-1 manufactured by Musashi Engineering Co., Ltd.). Then, after heating at 80 ° C. for 1 hour, it was further cured by heating at 150 ° C. for 4 hours. These PA9T resin packages were reflowed once under a temperature condition (260 ° C.) according to the JEDEC standard using a simulated reflow machine [model SRS-1C manufactured by Malcolm Co., Ltd.]. These PA9T resin packages are put in a test area of a thermal shock apparatus [manufactured by ESPEC Co., Ltd., Model No. TSE-11], exposed to −40 ° C. for 30 minutes, and exposed to 105 ° C. for 30 minutes as one cycle and repeated 500 cycles. Was carried out. In addition, the movement time between both exposure temperatures was 2 minutes. The occurrence of peeling and cracking was observed with a microscope. Tables 2 and 4 show the failure rate in 15 pieces.

<Heat cycle test, wire breakage>
LED resin package [Enomoto Co., Ltd. Model No. 5050 D / G, 32 pieces of thermosetting resin composition, mounted with blue LED chip [Product No. B1515ACA0 manufactured by GeneLite] and Gold Wire [Product No. SR-25 manufactured by Tanaka Kikinzoku Co., Ltd.] After injecting with a dispenser [Model number MPP-1 manufactured by Musashi Engineering Co., Ltd.], it was heated and cured at 80 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours. This LED resin package was reflowed once under a temperature condition (260 ° C.) according to the JEDEC standard using a reflow simulator [model SRS-1C manufactured by Malcolm Co., Ltd.]. Furthermore, it put into the test area of the thermal shock apparatus [Espec Co., Ltd. product type | model number TSE-11], and exposed by -40 degreeC for 30 minutes, and carrying out for 30 minutes at 105 degreeC, and implemented by repeating 500 cycles. In addition, the movement time between both exposure temperatures was 2 minutes. The LED was turned on. Tables 2 and 4 show the lighting failure rate.

As shown in Table 2, the compositions A1 to A8, B1, C1 to C5, and D1 to D2 of the present invention have storage stability and curability by strictly controlling the amounts of the Pt catalyst and the curing inhibitor. It was found that the thermosetting composition was compatible.
On the other hand, it was found that Comparative Compositions A9 to A12 and C6 to C7 were compositions that were not used as thermosetting compositions as they were because of poor storage stability or poor curability.

  As shown in Table 3, cured products A to D using the compositions A to D of the present invention have a refractive index of 1.5 or more, and further have heat resistant transmittance and UV transmittance possessed by silsesquioxane. In addition, it was found that the adhesion to the polyphthalamide resin (PPA, PA9T) or silver which is a reflector base material is good, and further, the moisture absorption reflow resistance and the heat cycle resistance are excellent.

<Create semi-cured resin sheet>
The thermosetting composition A4 was placed in a PFA petri dish so as to have a thickness of 0.5 mm and heated at 100 ° C. for 60 minutes. A semi-cured resin sheet having surface tackiness was obtained.

  Similarly, the thermosetting composition A4 was placed between SUS molds having a release agent coated on the surface, and heated at 160 ° C. for 5 minutes with a hot press machine. A semi-cured resin molded sheet having a surface tackiness of 1 mm in thickness was obtained.

<Curing semi-cured resin sheet>
The semi-cured resin sheet obtained above was placed on a SUS plate with a surface mirror finish and heated at 160 ° C. for 120 minutes. The semi-cured resin sheet was once softened and then cured and adhered to the SUS plate.

<LED bare chip sealing with semi-cured resin sheet>
The semi-cured resin sheet obtained above was placed on the mounting surface on which the LED bare chip was mounted and heated at 160 ° C. for 120 minutes. The semi-cured resin sheet was once softened and then cured and adhered to the plate, and a package in which the surface of the LED bare chip was sealed was obtained.

  Although the invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention.

  The thermosetting resin composition of the present invention has high heat resistance and high UV resistance, high adhesion to the substrate, and excellent toughness, so it has excellent moisture absorption reflow resistance, heat cycle resistance, and sulfur resistance. In particular, it is very useful as a sealing material for an optical semiconductor element such as a high-power LED, a phosphor sheet, and a reflector material. Moreover, the thermosetting resin composition of the present invention is easy to mold, and a molded cured product can be easily created by heating to a high temperature after molding. Furthermore, after molding, the semi-cured molded product that is completely cured by heating is kept at room temperature as a semi-cured molded product without further reaction even if stored at room temperature in this state. In addition, when this is used, it is possible to obtain a completely cured product by re-curing at a higher temperature than when a semi-cured molded product is prepared. For example, a phosphor and / or an inorganic compound is added to the thermosetting resin composition of the present invention, and after sufficiently mixing it, it is molded into a sheet. The resulting molded product is semi-cured in a short time at a temperature lower than fully cured, that is, from 80 ° C. to 140 ° C. or 150 ° C., so that it is excellent in stability even when stored at room temperature by cooling once. A phosphor sheet can be created. Since these phosphor sheets are stable at room temperature, they can be easily stocked after production, and the distribution cost can be suppressed without requiring a refrigerated warehouse or a refrigerated vehicle in the distribution route. In addition, when using the sheet, it is placed on the LED chip and heated to a higher temperature or longer time than when the semi-cured product is created, and once softened and gelled, adhesion occurs, and the chip and its A semiconductor light-emitting device capable of suitably converting the light wavelength, which is completely cured after being in close contact with the surrounding members and is easily covered with a phosphor, can be produced.

Claims (17)

A thermosetting resin composition containing (A) , (B) , (C), and (F) .
(A) A thermosetting resin that is a reaction product of a silsesquioxane having a SiH group and an organopolysiloxane having two alkenyl groups and having a SiH group and an alkenyl group.
(B) Pt catalyst.
(C) Curing inhibitor.
(F) A linear organopolysiloxane compound having a SiH group only at one end.
Here, (C) the curing inhibitor is 250 to 200,000 times the blending amount (mass) of (B) Pt catalyst. The thermosetting resin composition according to claim 1 , wherein the silsesquioxane is a double-decker silsesquioxane. Furthermore, the thermosetting resin composition of Claim 1 or 2 containing (D) or (E) .
(D) Thermosetting having a SiH group obtained by reacting a silsesquioxane having a SiH group, an organopolysiloxane having two alkenyl groups, an epoxy compound having an alkenyl group and a silyl compound having an alkenyl group Resin.
(E) An organopolysiloxane compound having two or more alkenyl groups. The thermosetting resin composition according to any one of claims 1 to 3, wherein the thermosetting resin (A) is a compound represented by the following formula (1).

In Formula (1), each X is independently
It is a group represented by the following formula (XI), formula (X-II) or formula (X-III), and per molecule of the compound represented by formula (1) [the compound is represented by formula (XI ), A group represented by the formula (X-II), and a group represented by the formula (X-III), the compound is a mixture of different compounds. When the number of groups represented by 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,
a + 2b + c = 4, 0 <a ≦ 3, 0 ≦ b ≦ 1, and 0 <c ≦ 3.
R ¹ is each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, and cyclohexyl, and m is an average value satisfying 1 to 100.

In the formula (X-II), ^{R 1} is the same as ^{R 1} in formula (1), ^{R 2} and ^{R 3} are each independently selected from alkyl of 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl R is the number of repeating -OSi (R ³ ) _2- , and r is an average value satisfying 2-20.

In the formula (X-III), R ⁴ and R ⁵ are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and s is —OSi (R ⁵ ) ₂ —. S is an average value satisfying 2 to 20. The thermosetting resin composition according to claim 3 , wherein the thermosetting resin (D) is a compound represented by the following formula (D1).

In the formula (D1), each X ′ independently represents the following formula (a), formula (b), formula (ci), formula (c-ii), formula (c-iii), formula (d- i) a group represented by the formula (d-ii) or the formula (d-iii), and per molecule of the compound represented by the formula (1) [the compound is represented by the formula (a) In the case of a mixture of compounds in which the proportions of groups represented by formula (b) to formula (d-iii) are different, the compound averages 1 molecule]
The number of groups represented by formula (a) is A,
The number of groups represented by formula (b) is B,
The number of groups represented by formula (ci), formula (c-ii) or formula (c-iii) is C,
When the number of groups represented by formula (d-i), formula (d-ii) or formula (d-iii) is D, A + 2B + C + D = 4, and 0.5 ≦ A ≦ 3.0 Yes, 0.5 ≦ 2B ≦ 2.0, 0.1 ≦ C ≦ 2, and 0 ≦ D ≦ 1.0.
R ^{1 ′} is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, and cyclohexyl, and m ′ is an average value satisfying 1 to 100.

In formula (b), R ^{1 'is} R ¹ in Formula ^(D1)' is the same as, R ^{2 'and} R ^3' are each independently alkyl of 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl And t is the number of repeating -OSi (R ^{3 '} ) _2- and is an average value satisfying 1-20.

In the formulas (di) to (d-iii), R ⁴ , R ^{4 ′} and R ^{4 ″} are each independently a group selected from methyl, ethyl, butyl and isopropyl. x is the number of repetitions of -OSi (R4 ^' ) _2- and is an average value satisfying 1-20. y is the number of repetitions of -OSi (R ^{4 ''} ) _2- and is an average value satisfying 1 to 10. The thermosetting resin composition according to claim 3 , wherein the thermosetting resin (D) is a compound represented by the following formula (D2).

In the formula (D2), R ″ is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and r is an integer of 0 to 100. aii is 0.1 ≦ aii ≦ 3.5, Xii is 0 ≦ 2Xii ≦ 2.0, Yii is 0 ≦ Yii ≦ 3.0, and Zii is 0.1 ≦ Zii ≦ 3.5. The thermosetting resin composition according to claim 1 , wherein the linear organopolysiloxane compound (F) having a SiH group only at one end is a compound represented by the following formula (2).

R ⁶ and R ⁷ are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, m is the number of repeating -OSi (R ⁷ ) ₂ —, and 1 to 20 The average value satisfying The thermosetting resin composition according to claim 3 , wherein the organopolysiloxane compound (E) having two or more alkenyl groups is a compound represented by the formula (3).

In the formula (3), R ⁸ and R ⁹ are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and n is —OSi (R ⁹ ) ₂ —. It is the number of repetitions and is an average value satisfying 1-50. Reacting the silsesquioxane having (D) SiH group, the organopolysiloxane having two alkenyl groups, the epoxy compound having alkenyl groups, and the silyl compound having alkenyl groups on the basis of the total amount of the thermosetting resin composition. The thermosetting resin composition according to any one of claims 1 to 8 , which comprises a thermosetting resin having a SiH group, obtained in a ratio of 1 to 50% by mass. The thermosetting resin composition according to any one of claims 1 to 9 , which contains the thermosetting resin (E) at a ratio of 1 to 10% by mass based on the total amount of the thermosetting resin composition. In the thermosetting resin composition the total amount of the (F) containing 2-20 wt% of straight-chain organopolysiloxane compound having SiH groups only at one end, any one of claims 1 to 1 0 Thermosetting resin composition according to Furthermore, the thermosetting resin composition of any one of Claims 1-11 in which the inorganic compound was disperse | distributed. Inorganic compound is a fluorescent substance and / or metal oxides, a thermosetting resin composition according to claim 1 2. 80 ° C. The viscosity increase rate in the 30 days storage conditions at a temperature of is within 50%, thermosetting resin composition according to any one of claims 1 to 1 3. The prepreg obtained by molding the claims 1 to 1 4 thermosetting resin composition according to any one of. Articles obtained by thermally curing the prepreg of claim 1 5. A coating or sheet form, the thickness is 0.1Myuemu～3,000myuemu, article of claim 1 6.