JP6672123B2 - Curable silicone resin composition - Google Patents

Description

  The present invention relates to a curable silicone resin composition.

  To date, condensation-curable organopolysiloxanes have been widely used in applications such as adhesives, waterproof and moisture-proof coatings, electrical insulating films, and building sealants. In recent years, from the viewpoints of high heat resistance, light resistance, transparency, and the like, utilization as a sealing material for a photodiode (LED) has been attracting attention. In such industrial applications, the curing speed of the resin is important, but the productivity of the condensation-curable organopolysiloxane is inferior to that of the addition-curable organopolysiloxane due to its low reactivity. In addition, when a large amount of condensation catalyst is used to improve the reactivity, the deterioration of the silicone resin is accelerated, so that there is a problem that the inherent high heat resistance and light resistance of the silicone resin cannot be exhibited. Further, the catalyst itself may be colored, or the catalyst may exhibit color due to deterioration, and many catalysts are unsuitable for fields where transparency is important.

  Various attempts have been made to improve and commercialize condensation-curable organopolysiloxanes. For example, Patent Document 1 discloses an organopolysiloxane having two or more silanol groups in one molecule and an organopolysiloxane having two or more silicon-bonded alkoxy groups in one molecule, and a metal catalyst such as aluminum or zinc. In addition, it describes that by adding a condensation catalyst of a phosphoric acid ester or a boron compound, the deterioration of the resin is minimized while improving the curing speed. In addition, Patent Document 2 discloses that a partially hydrolyzed product of tetraalkoxysilane or trialkoxysilane and a linear organopolysiloxane containing silanol groups at both ends are cured by adding a volatile amine catalyst to the cured product. It is described that the remaining catalyst is reduced. Further, Patent Document 3 describes that gelation can be achieved with a small number of reactions by increasing the molecular weight of the condensable organopolysiloxane in advance.

In addition, condensation-curable organopolysiloxane resins generally have a low curing rate and are not suitable for continuous molding, and also have a problem that voids are likely to remain in molded products due to generation of outgas during curing. Therefore, the curable polyorganosiloxane resin composition used in a lens or an LED element sealing material (molded product) molded by a molding apparatus such as a transfer mold, a compression mold, and an injection mold is almost an addition-curable type (patented). References 4, 5, 6, and 7). Further, as described in Patent Document 8, solids are easier to handle than liquids when they are not cured and are preferred for molding. However, in order to be solids when they are not cured, the crosslink density must be high. As a result, the cured product obtained after curing becomes hard and brittle.

JP 2011-219729 A JP-A-2006-8246 JP 2007-119569 A JP 2007-182549 A JP 2007-316612 A JP 2008-19424 A JP 2008-27966 A JP 2009-275214A

  As described above, the curable organopolysiloxane resin composition has not been satisfactory in the field where high heat resistance and light resistance are required as well as moldability. For example, as described above, the condensation-curable resin compositions described in Patent Documents 1 to 3 are not suitable for molding because a large amount of gas is generated during curing. Moreover, since the cured products obtained from the addition-curable resin compositions described in Patent Documents 4 to 8 have a carbon-carbon bond, heat resistance and light resistance are required in fields requiring high reliability, such as LED sealing materials. Insufficiency.

  The present invention has been made in view of the above circumstances, and is a curable resin composition that is solid or semi-solid at 25 ° C., is easy to handle at room temperature, cures quickly, and reduces the amount of gas generated during curing. An object of the present invention is to provide a curable resin composition which gives a cured product having a small amount and excellent heat resistance and light resistance.

The present inventors have made intensive studies to solve the above problems, (A) has a melting or softening point in the range of 30 to 250 ° C. under 1 atm, of human unity _^(R 1 ₂ SiO 2 _{/ 2} ) A solid or semi-solid resin composition at 25 ° C. comprising a branched organosilicon compound having at least one unit in the molecule, (B) a cyclic organopolysiloxane solid at 25 ° C. and a specific catalyst. It has been found that the product is excellent in handling properties at room temperature and is quickly cured by heating to give a cured product having high heat resistance and light resistance.

  In the present invention, a semi-solid at 25 ° C. refers to a substance which has a certain degree of fluidity at 25 ° C. but has a very high viscosity and is difficult to measure viscosity at 25 ° C. with a rotational viscometer, or a solid at 25 ° C. It is not in a state, but has a shape retaining property that does not have fluidity.

That is, the present invention
(A) has a melting or softening point in the range of 30 to 250 ° C. at 760 ^mmHg, branched _{organo (R} 1 _{2 SiO 2/2)} units having at least one structure in which successive two or more in a molecule in the polysiloxane (wherein, R ^1, independently of one another, Ri substituted or unsubstituted monovalent hydrocarbon radical der having 1 to 12 carbon atoms, provided that more than 10 mol% relative to the total moles of siloxane repeating units is a cyclosiloxane Not including the forming structure )
100 parts by mass (B) cyclic organopolysiloxane having a melting point in the range of 30 to 250 ° C. at 760 mmHg
5-200 parts by weight, and (C) an amine, and, silazane bonds _(Si-NR 2), ammonium siloxanolate structure _{^{(SiO - N + R 4)}} , and the metal siliconate at least one bond (SiO-M) At least one selected from organic or inorganic silicon compounds having one or more (R is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms, and M is an alkali metal atom)
Provided is a curable silicone resin composition containing 0.05 to 30 parts by mass based on 100 parts by mass in total of the component (A) and the component (B).

  The melting point is a temperature at which a solid becomes a liquid by heating. The softening point is a temperature at which a substance which is solid or semi-solid and does not have a certain melting point starts to be deformed and softened by heating. The melting point and softening point in the present invention are the temperature of the melting peak top measured by a differential scanning calorimeter (DSC) under 760 mmHg. More specifically, it is the temperature of the melting peak top measured by raising the temperature of a 10 mg sample at 760 mmHg at 20 ° C./min.

The curable silicone resin composition of the present invention is cured by an equilibrium polycondensation reaction by breaking and recombining Si—O—Si bonds. Therefore, less gas is generated at the time of curing, and the curing speed is high. In addition, since the cured product is not an addition reaction type, the obtained cured product has no carbon-carbon bond. Further, the curable silicone resin composition of the present invention has a melting point or softening point within a range of 30 to 250 ° C. under 760 mmHg. That is, the curable silicone resin composition of the present invention is solid or semi-solid at 25 ° C. By being solid or semi-solid at 25 ° C., the composition has excellent handling properties when uncured, and can be molded into a complicated shape by being sufficiently liquefied or softened during heat molding. In particular, by molding the curable silicone resin composition of the present invention into a sheet or a tablet, a semiconductor device can be easily sealed. The cured product obtained becomes rubbery with elongation because they contain a large amount of _^(R 1 _{2 SiO 2/2)} units.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[(A) Branched-chain organopolysiloxane]

The component (A) in the present invention is a branched organopolysiloxane having a melting point or softening point in the range of 30 to 250 ° C at 760 mmHg, and may have a melting point or softening point in the range of 50 to 200 ° C. It preferably has a melting point or softening point in the range of 70 to 180 ° C. This means that the branched organopolysiloxane in the present invention is solid or semi-solid at 760 mmHg and 25 ° C. The definition of semi-solid is as described above. In particular, it is preferably solid at 25 ° C. and has a melting point within the above-mentioned temperature range. Component (A) is a branched-chain organopolysiloxane containing, as essential to have at least one structural successive (R 1 ² _{SiO 2/2)} units 2 or more in the molecule. Thus, the organopolysiloxane has one or more (R ¹ SiO _3/2 ) units and / or (SiO _4/2 ) units. The ^(R ₁ 2 _{SiO 2/2)} units is two or more successive structures, and it is preferably of 2 to 1000 amino _^(R 1 _{2 SiO 2/2)} are continuous.

By organopolysiloxane is (R 1 ² _{SiO 2/2)} units having a structure that two or more successive, cleavage and recombination of siloxane bonds by later-described component (C) (i.e., equilibration reaction) easily And the curing reaction can be performed more quickly.

The branched-chain organopolysiloxane preferably has a total of 3 to 500 (R ¹ SiO _3/2 ) units [T units] and / or (SiO _4/2 ) units [Q units] in the molecule. The _^(R 1 _{3 SiO 1/2)} ^0~500 pieces of unit [M Units, and not continuous _^(R 1 _{2 SiO 2/2)} units have at 0-500 pieces of [D Units Good.

The component (A) is preferably an organopolysiloxane represented by the following general formula (1).
^{_{(R 1 3 SiO 1/2) a}} (R 1 2 SiO 2/2) b [(R 1 2 SiO 2/2) m] b '(R 1 SiO 3/2) c (SiO 4/2) d (O _1/2 R ² ) _e (1)
(R ¹ is independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ² is independently a hydrogen atom or a 1 to 6 carbon atom, A monovalent hydrocarbon group which may have an oxygen atom, a is an integer of 0 to 500, b is an integer of 0 to 500, m is an integer of 10 to 1,000, and b 'is An integer of 1 to 100, c is an integer of 0 to 500, d is an integer of 0 to 500, c + d is 3 to 500, e is an integer of 0 to 100, and siloxane units represented may form a block be bonded randomly. the ^{_{[(R 1 2 SiO 2/2)}} m] siloxane units in the parentheses in the attached to the m continuously cage, and, as shown above _^(R 1 _{2 SiO 2/2) b} in parentheses Shi Loxane units are not continuous but are randomly linked).

In the above formula (1), R ¹ is independently of each other a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; a phenyl group, a tolyl group, and a naphthyl group. Aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group; part or all of the hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms such as fluorine, bromine and chlorine or cyano groups Those substituted with a (meth) acryloxy group, a glycidyloxy group, a mercapto group, an amino group or the like, for example, a halogenated monovalent hydrocarbon group such as a trifluoropropyl group or a chloropropyl group; a β-cyanoethyl group; cyanoalkyl group such as γ-cyanopropyl group, 3-methacryloxypropyl group, 3-glycidyloxy Examples thereof include a propyl group, a 3-mercaptopropyl group, and a 3-aminopropyl group. Among them, a methyl group or a phenyl group is preferable. R ³ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6, preferably 1 to 3 carbon atoms, for example, a hydrogen atom; methyl, ethyl, propyl, isopropyl, butyl and hexyl An alkyl group such as a group; an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group and an ethoxymethyl group, and preferably a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group.

In the above formula (1), a is an integer of 0 to 500, preferably an integer of 0 to 300, b is an integer of 0 to 500, preferably an integer of 0 to 300, and m is 10 An integer of ~ 1,000, preferably an integer of 15 ~ 750, more preferably an integer of 20 ~ 500, b 'is an integer of 1 ~ 100, preferably an integer of 1 ~ 75, Preferably, it is an integer of 1 to 50, c is an integer of 0 to 500, preferably an integer of 0 to 300, and d is an integer of 0 to 500, preferably an integer of 0 to 300. c + d is 3 to 500, preferably 5 to 300, and e is an integer of 0 to 100, preferably 0 to 50. In the above formula (1), the bonding order of each siloxane unit shown in parentheses is not limited. As described above, the organopolysiloxane (A) of the present ^invention, it is necessary to have at least one structural successive _(R 1 _{2 SiO 2/2)} units 2 or more in the molecule.

Organopolysiloxane having the structure above-described (R 1 ² _{SiO 2/2)} units is two or more successive, besides obtainable by hydrolytic condensation of halogenated silane or alkoxysilane, siloxane bonds cyclic siloxanes Can also be obtained by cleaving in the presence of an acid or alkali to polymerize. (A) organopolysiloxane may be synthesized by hydrolytic condensation of a successive (R 1 ² _{SiO 2/2)} units and a halogenated silane or an alkoxysilane obtained as described above. Further, it can be synthesized by other known methods, or a commercially available product may be used.

[(B) Cyclic organopolysiloxane]
The component (B) is a cyclic organopolysiloxane having a melting point in the range of 30 to 250 ° C at 760 mmHg, preferably having a melting point in the range of 50 to 200 ° C, more preferably in the range of 60 to 180 ° C. Preferably have a melting point. This means that the cyclic organopolysiloxane is solid at 25 ° C. under 760 mmHg. The cyclic organopolysiloxane may be a conventionally known one. By the component (B) and component (A) ring-opening and re-SiO-Si bonds bonds (equilibrated) at the time of curing, the composition is ^cured, the _(R 1 _{2 SiO 2/2)} units A cured product containing a large amount is obtained. The cured product is particularly rubbery.

上記式（２）において、Ｒ^１は互いに独立に、水素原子または、置換又は非置換の、炭素数１〜１２、好ましくは１〜６の一価炭化水素であり、上記（Ａ）成分の説明にて記載したＲ^１の例示から選択される基である。但し、上記（Ａ）成分におけるＲ^１とは独立している。Ｒ^１は互いに独立に、好ましくはメチル基又はフェニル基である。ｎは３〜８の整数であり、好ましくは３〜５の整数であり、更に好ましくは３である。 Preferred is a cyclic organopolysiloxane represented by the following general formula (2).

In the above formula (2), R ¹ is independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms. Is a group selected from the examples of R ¹ described in above. However, it is independent of R ^{1 in the} component (A). R ¹ are, independently of ^one another, preferably a methyl or phenyl group. n is an integer of 3 to 8, preferably an integer of 3 to 5, and more preferably 3.

  Examples of the cyclic organopolysiloxane include hexamethylcyclotrisiloxane, 1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane, hexaphenylcyclotrisiloxane, 1,1-diphenyl-3, 3,5,5-tetramethylcyclotrisiloxane, 1,1,3,3-tetraphenyl-5,5-dimethylcyclotrisiloxane, 1,3,5,7-tetraphenyl-1,3,5,7 -Tetramethylcyclotetrasiloxane, 1,1,5,5-tetraphenyl-3,3,7,7-tetramethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, decaphenylcyclopentasiloxane, and dodecaphenylcyclohexasiloxane And the like. Above all, from the viewpoint of reactivity, hexamethylcyclotrisiloxane and 1,1-diphenyl-3,3,5,5-tetramethylcyclotrisiloxane are preferable.

  The amount of the component (B) is 5 to 200 parts by mass, preferably 7.5 to 100 parts by mass, and more preferably 10 to 50 parts by mass, per 100 parts by mass of the component (A). If the amount of the component (B) is too small, the cured product may become brittle. On the other hand, if the amount of the component (B) is too large, the tackiness of the surface of the cured product becomes high, and there is a possibility that the cured product cannot be released from the mold.

[(C) Curing catalyst]
(C) component, an amine, and, silazane bonds _(Si-NR 2), ammonium siloxanolate structure _{^{(SiO - N + R 4)}} , and at least one metal siliconate bond (SiO-M), 1 piece One or more selected from the organosilicon compounds (R is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms, and M is an alkali metal atom). These compounds function as a curing catalyst for the curable silicone resin composition. Hereinafter, each compound will be described.

  As the amine, a compound conventionally known as a curing catalyst can be used. For example, monoamine, diamine, amino alcohol, aminoalkoxy and salts thereof can be used. It is preferably an amine compound having a boiling point at 760 mmHg in the range of 60 to 200 ° C, particularly preferably 80 to 180 ° C. Those having a boiling point of less than the lower limit tend to volatilize at room temperature and thus are difficult to handle, and have a strong tendency to volatilize from the curable resin composition of the present invention before acting as a curing catalyst. Further, those exceeding the upper limit tend to remain in the cured product, and the heat resistance and light resistance of the cured product are impaired.

Examples of the amine include triethylamine, di-n-propylamine, tri-n-propylamine, diisopropylamine, diisopropylethylamine, di-n-butylamine, ethylpropylamine, diisobutylamine, di-t-butylamine, and n-butylamine. Monoamines such as pentylamine, neopentylamine, methylpentylamine, n-hexylamine, cyclohexylamine, n-heptylamine, cycloheptylamine, aminomethylcyclohexane, amylamine and cumylamine; ethylenediamine, 1,3-diaminopropane, Diamines such as 2-diamino-2-methylpropane, 1,4-diaminobutane, 1,3-diaminopentane and 1,5-diaminopentane; 2-aminoethanol, 1-amino-2-propano And amino alcohols such as Le, and the like.

In the present invention, the silazane bond _(Si-NR 2), ammonium siloxanolate structure _{^{(SiO - N + R 4)}} , an inorganic or organic silicon compound having at least one of either one metal siliconate bond (SiO-M) is It functions particularly suitably as a catalyst for the equilibrium reaction of the curable silicone resin composition and reacts quickly to give a cured product. For example, it is considered that the silazane compound decomposes upon heating to produce an amine compound, and the amine compound acts as a catalyst. The silazane bond among the above-mentioned organic silicon compound (Si-NR 2 _^2), and / or ammonium siloxanolate structure - a compound having a (SiO ^N + ^R 2 _⁴⁾ is promptly hydrolyzed nitrogen atoms during curing Evaporates into ammonia. Therefore, no catalyst remains in the obtained cured product, and a cured product having high heat resistance and light resistance can be provided. Further, since the catalyst is a silazane compound, a change in viscosity when handling the silicone resin composition can be reduced. More preferred as the curing catalyst of the present invention is a compound having at least one silazane bond.

（式（３）、（５）、及び（６）中、Ｒ^３は、互いに独立に、水素原子または置換又は非置換の炭素数１〜１２の一価炭化水素基であり、Ｒ^４は、互いに独立に、水素原子または炭素数１〜１２の一価炭化水素基、又は下記式（４）で表される基であり、

式（４）中、Ｒ^３は互いに独立に、水素原子または置換又は非置換の炭素数１〜１２の一価炭化水素基であり、式（５）においてｍは３〜８の整数であり、式（６）においてｆは１〜５００の整数であり、ｇは０〜５００の整数であり、及びｈは０〜２００の整数であり、但し、ｆ＋ｇ＋ｈは１０〜５００であり、上記各括弧内に示される各シラザン単位の結合順序は制限されない）。

（式（７）中、Ｒ^３は互いに独立に、水素原子、または置換又は非置換の、炭素数１〜１２の一価炭化水素基であり、Ｘは、互いに独立に、炭素数１〜６の一価炭化水素基、水酸基、炭素数１〜６の酸素原子を有する一価炭化水素基、−ＮＲ_２、−Ｏ⁻Ｎ^＋Ｒ_４、又は−Ｏ−Ｍであり、但し、少なくとも１のＸは−ＮＲ_２、−Ｏ⁻Ｎ^＋Ｒ_４、又は−Ｏ−Ｍであり、Ｒ及びＭは上記の通りであり、及びｎは０〜１，０００の整数である）。 Silazane bonds _(Si-NR 2), ammonium siloxanolate structure _{^{(SiO - N + R 4)}} , and at least one selected from metal siliconate bond (SiO-M), inorganic or organic silicon compound having one or more A conventionally known one may be used. Preferably, silazane represented by the following general formula (3), cyclic silazane represented by the following general formula (5), polysilazane represented by the following general formula (6), and represented by the following general formula (7) At least one selected from organosilicon compounds.

(In the formulas (3), (5), and (6), R ³ is independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ⁴ is Independently of each other, a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms, or a group represented by the following formula (4);

In the formula (4), R ³ is independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and in the formula (5), m is an integer of 3 to 8, In the formula (6), f is an integer of 1 to 500, g is an integer of 0 to 500, and h is an integer of 0 to 200, provided that f + g + h is 10 to 500, and Is not limited.

(In the formula (7), R ³ is, independently of each other, a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms; A monovalent hydrocarbon group, a hydroxyl group, a monovalent hydrocarbon group having an oxygen atom having 1 to 6 carbon atoms, —NR ₂ , —O ^— N ⁺ R ₄ , or —OM, provided that at least one of X is _{^{-NR 2, -O - n + R}} 4, or a -O-M, R and M are as defined above, and n is an integer of 0 to 1,000).

In the formulas (3) to (6), R ³ is a group selected from the options of R ¹ described in the description of the component (A). Among them, a methyl group or a phenyl group is preferable. R ⁴ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms, or a group represented by the above formula (4). Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include those exemplified for R ¹ above. In the cyclic silazane represented by the above formula (5), m is an integer of 3 to 8, and is preferably an integer of 3 to 5. In the polysilazane compound represented by the formula (6), f is an integer of 1 to 500, preferably an integer of 5 to 400, more preferably an integer of 10 to 200, and g is 0 to 500. , Preferably an integer of 0 to 250, more preferably an integer of 1 to 140, h is an integer of 0 to 200, preferably an integer of 0 to 100, more preferably 1 An integer of from 50 to 50, where f + g + h is from 10 to 500, preferably from 20 to 350.

  The silazane compound represented by the above formula (3), (5) or (6) can be produced by a known method. For example, it can be synthesized by subjecting a halogenated silane and an amine compound to a dehydrochlorination reaction. Also, commercially available products may be used.

In the above formula (7), R ³ is a group selected from the options of R ¹ described in the description of the component (A). Among them, a methyl group or a phenyl group is preferable. X, independently of one another, a monovalent hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, a monovalent hydrocarbon group having an oxygen atom having 1 to 6 carbon _{^{atoms, -NR 2, -O - N +}} R 4, or a -O-M, provided that at least one _{^{X -NR 2, -O - N +}} R 4, or -O-M. Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include those exemplified for R ¹ in the description of the above component (A). Among them, a methyl group or a phenyl group is preferable. The monovalent hydrocarbon group having an oxygen atom is, for example, an alkoxy group or an alkoxyalkoxy group, and is preferably an alkoxy group. Preferably, one of X is a monovalent hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, -NR _2, or ^-O - a ^N + _{R 4,} other X is good in the range of -NR _2. R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12, preferably 1 to 8 carbon atoms, and is preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include the groups exemplified for R ¹ in the description of the component (A). If the number of carbon atoms exceeds 12, it becomes an amine compound having low volatility after hydrolysis and may remain in the cured product.

M is an alkali metal atom and is any of lithium, sodium, potassium, rubidium, cesium, and francium, with lithium being preferred. However, since these metal atoms would remain in the cured product, and more preferred embodiments, X is -NR ₂ or ^-O - a ^N + _{R 4,} at least one of -NR ₂ and more preferably at the end Is preferred. The ^-O - structure represented by ^N + _{R 4} is particularly preferably ^-O - is ^{_{N + (H 2) R 2}} . n is an integer of 0 to 1,000, preferably 0 or an integer of 3 to 750, and more preferably an integer of 5 to 600.

  The compound represented by the above formula (7) may be synthesized by a known method, or a commercially available compound may be used. Examples of known synthesis methods include a method in which a silazane compound is obtained by a dehydrochlorination reaction of a halogen-terminated polyorganosiloxane with an arbitrary amine compound, and a method in which a cyclic polyorganosiloxane is converted into an amine compound or an alkali metal hydroxide, or alkylated. When a cyclic polyorganosiloxane is subjected to ring-opening polycondensation by the action of an alkali metal or the like, a silazane compound, an ammonium siloxanolate compound, or an alkali metal siliconate is obtained.

  Examples of the silazane compound represented by the above formula (3) include trimethylsilylamine, bis (trimethylsilyl) amine, tris (trimethylsilyl) amine, methyldiphenylsilylamine, bis (methyldiphenylsilyl) amine, and tris (methyldiphenylsilyl) amine And the like. Examples of the cyclic silazane represented by the above formula (5) include hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, decamethylcyclopentasilazane, trimethyltriphenylcyclotrisilazane, tetramethyltetraphenylcyclotetrasilazane, and pentamethylpentane Examples include phenylcyclopentasilazane, hexaphenylcyclotrisilazane, octaphenylcyclotetrasilazane, and decaphenylcyclopentasilazane. Examples of the polysilazane represented by the above formula (6) include inorganic polysilazane such as perhydropolysilazane, and organic polysilazane such as methyl polysilazane. Among them, bis (trimethylsilyl) amine, tris (trimethylsilyl) amine, hexamethylcyclotrisilazane, and perhydropolysilazane are preferable from the viewpoint of availability.

上記各式において、ｎ、Ｒ^１及びＭは上記の通りであり、Ｒ’は炭素数１〜１２、好ましくは１〜８の一価炭化水素基であり、Ｒは炭素数１〜６の一価炭化水素基、水酸基、又は炭素数１〜６の酸素原子を有する一価炭化水素基である。 Preferred examples of the organosilicon compound represented by the above formula (7) include the following compounds.

In each of the above formulas, n, R ¹ and M are as described above, R ′ is a monovalent hydrocarbon group having 1 to 12, preferably 1 to 8 carbon atoms, and R is a monovalent hydrocarbon group having 1 to 6 carbon atoms. It is a monovalent hydrocarbon group, a hydroxyl group, or a monovalent hydrocarbon group having 1 to 6 carbon atoms.

  More specifically, as the compound represented by the above formula (7), diaminodimethylsilane, di (N, N-dimethylamino) dimethylsilane, diaminodiphenylsilane, di (N, N-dimethylamino) diphenylsilane, 1,3-diaminotetramethyldisiloxane, 1,3-di (N, N-diethylamino) tetramethyldisiloxane, 1,5-diaminohexamethyltrisiloxane, 1,5-diamino-1,3,5-trimethyl Α, ω-diaminopolydimethylsiloxanes wherein n is 1 to 250, α, ω-diaminopolymethylphenylsiloxanes, such as -1,3,5-triphenyltrisiloxane, 1,9-diaminodecamethylpentasiloxane, 1-amino-5-aminooxy-1,1,3,3,5,5-hexamethyltrisiloxane, 1- (N N-dimethylamino) -5- (N, N-dimethylaminooxy) -1,1,3,3,5,5-hexamethyltrisiloxane, 1-amino-5-aminooxy-1,1,5 Α-amino-ω-aminooxypolydimethylsiloxanes such as 5-tetramethyl-3,3-diphenyltrisiloxane and α-amino-ω-aminooxypolymethylphenylsiloxanes. Among them, bis (trimethylsilyl) amine, tris (trimethylsilyl) amine, hexamethylcyclotrisilazane, perhydropolysilazane, di (N, N-dimethylamino) dimethylsilane, and di (N, N-dimethylamino) diphenylsilane are preferable. It is.

  The amount of the component (C) in the present invention is 0.05 to 30 parts by mass, preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the components (A) and (B) in total. Preferably it is 0.5 to 10 parts by mass. When the amount of the component (C) is within the above range, a cured product can be obtained promptly upon heating without adversely affecting the handleability of the composition.

[Other ingredients]
The silicone resin composition of the present invention may further optionally contain a rare earth element compound. By containing the rare earth element compound, deterioration of the cured product can be further suppressed when used under conditions where heat resistance and light resistance are required. Examples of the rare earth element compound include a rare earth element organic complex, a rare earth element alkoxide, and a rare earth element organic acid salt. One of these may be used alone, or two or more kinds may be used in combination. Is also good.

  As the rare earth element compound, for example, a rare earth element organic complex with acetylacetonate, triscyclopentadienyl and the like; a rare earth element alkoxide having an alkoxy group such as an isopropoxy group, an n-butoxy group and an isobutoxy group; octylic acid; Rare earth element organic acid salts such as lauric acid and pivalic acid are exemplified. The rare earth element in these is, for example, lanthanum, cerium, neodymium, europium, ytterbium and the like, and preferably cerium.

  Although the amount of the rare earth element compound in the composition of the present invention is not particularly limited, the amount of the rare earth element contained in the rare earth element compound is 10 parts by mass with respect to 100 parts by mass of the total of the components (A) to (C). The amount is preferably from 3,000 ppm to 3,000 ppm, more preferably from 50 to 1,000 ppm. This range is preferable because the effect of suppressing the deterioration of the resin can be sufficiently obtained.

  As other components other than the rare earth element compound, for example, inorganic fillers such as white pigment, silica, and phosphor, a diluent, a pH adjuster, an antioxidant, and a release agent can be included. The content of these other components may be appropriately adjusted within the range not impairing the effects of the present invention in accordance with the conventional condensation-curable silicone composition, and is not particularly limited.

  As the inorganic filler, for example, Si, Al, Ti, Zr, Fe, Ca, Mg, Sr, Ba, Y, Zn, Cu, Cr, Nb, Ni, Ce, Mn, Sn, Cd, Se, Li, Examples include oxides, nitrides, sulfides, various complex oxides, and complex compounds thereof containing metals or nonmetal elements such as Co, Eu, and Ga. Specific examples include silica, alumina, titanium dioxide, zirconia, barium titanate, yttrium alumina garnet, cerium-doped yttrium alumina garnet, europium-doped barium aluminum sulfide, and gallium nickel nitride.

  Examples of the diluent include solvents such as aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as cyclohexanone and methyl isobutyl ketone, and glycol ether solvents such as polyethylene glycol monomethyl ether, or non-reactive. Short-chain silicone oils having 1 to 10 silicon atoms are exemplified.

  Examples of the pH adjuster include organic acids such as acetic acid and citric acid, and organic bases such as pyridine and N, N-dimethylaniline.

  Antioxidants include, for example, benzoic acid, isopropylmethylphenol, ethylhexanediol, lysozyme chloride, chlorhexidine hydrochloride, octylphenoxyethanol, orthophenylphenol, and the like.

The release agent can be added in order to remove the molded article from the mold without damage after pressure-molding and curing the resin composition in the mold. The release agent needs to be completely compatible with each component contained in the curable silicone resin composition described above. In particular, when producing a transparent molded product such as a lens, it is required to provide a colorless and transparent cured product. Further, when the cured product of the silicone resin composition of the present invention is used as an LED lens for blue, white, etc., high durability is required not only for transparency but also for deterioration due to short-wavelength light and discoloration at high temperatures. Can be Any release agent that satisfies such requirements can be used.

Examples of the releasing agent include fatty acids (Rikemar AZ-01, Rikemar B-100, Rikemar HC-100, Rikemar HC-200, Rikemar S-95, Rikemar S-200, Rikemar TG-12, Riquestar TG-12, manufactured by Riken Vitamin). EW-100, RIQUESTAR EW-200, RIQUESTER EW-250, RIQUESTER EW-400, RIQUESTER EW-440A, RIQUESTER HT-10), polyethylene type (manufactured by Clariant: LICOWAX PED 136, LICOWAX PED 153, LICOWAX PED 371FPo, 371FPh : HOE WAX PE 130 PDR, HOE WAX PED 191 PDR, HOE WAX PE 191 PDR, HOE WAX PE 191 Flakes, HOE WAX PE 52 Powder), carnauba system (Toa Kasei: YTS-040625-03, carnauba candelilla, refined granulated carnauba) or montanic acid ester (manufactured by Clariant: etc. Licolub WE40) and the like. Among these, the fatty acid-based release material is excellent in compatibility with the silicone resin, transparency after curing, and further, discoloration resistance after being left at a high temperature.

The amount of the release agent is usually 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass based on 100 parts by mass of the components (A) to (C) and optionally the component (D). is there. By blending in an amount within the above range, a molded product such as a lens molded by injection molding or the like can be easily taken out of the mold. If the amount of the release agent is too small, the molded product may not be able to be properly released from the mold. If the amount of the release agent is too large, the release agent may ooze onto the surface of the molded product, and when the molded product is a lens or the like, properties such as transparency may be impaired.

The method for producing the curable silicone resin composition of the present invention is not particularly limited. The silicone resin composition of the present invention has a melting point or softening point within the range of 30 to 250 ° C. at 760 mmHg. This means that the silicone resin composition of the present invention is solid or semi-solid at 760 mmHg and 25 ° C. Therefore, the silicone resin composition of the present invention can be molded into a sheet or tablet (flat plate) even if it is not cured. For example, the above-mentioned components are blended at a predetermined composition ratio, and after mixing them sufficiently uniformly by a mixer or the like, a melt-mixing process is performed by a hot roll, a kneader, an extruder, etc., and then cooled and solidified to obtain an appropriate size. The mixture is pulverized into pieces and then, if necessary, tableted with a tableting machine to obtain a sheet- or tablet-shaped molded product. By using such a molded product, sealing of a semiconductor device or the like can be easily performed. Preferably, the curing catalyst (C) is added after melt-mixing the branched-chain organopolysiloxane and the cyclic organopolysiloxane and then cooling the mixture. Although the cooling temperature is not particularly limited, it is about −60 to 20 ° C. The resulting composition is further cooled and solidified and used as described above.

As described above, in the present invention, a semi-solid at 25 ° C. refers to a substance that has a certain degree of fluidity at 25 ° C. but has a very high viscosity and is difficult to measure the viscosity at 25 ° C. with a rotational viscometer, or 25 ° C. Which is not in a solid state but has a shape-retaining property that does not have fluidity. In particular, in the present invention, when the molded article made of the obtained resin composition is left on a horizontal table at 25 ° C. for 8 hours, and further left at 25 ° C. for one week, when a change in dimensions is observed, Those that have not changed in size for one week or more are called solids. Up to 8 hours, there was no change in dimensions (had shape retention), but one week after the change in dimensions, it was called semi-solid. Those having a change in dimensions within 8 hours are referred to as liquids (including highly viscous liquids).

The curable silicone resin composition of the present invention is cured by heating. Further, a molded product having a required shape and dimensions can be obtained by a molding method such as compression molding, transfer molding, or injection molding. The molding conditions are not particularly limited, but curing can be performed at a temperature of 80 ° C to 180 ° C for about 30 seconds to 600 seconds. Further, post-curing (secondary curing) can be performed at 50 to 200 ° C., particularly 80 to 180 ° C. for 1 to 24 hours, particularly 1 to 12 hours.

By curing the curable silicone resin composition of the present invention, a colorless and transparent molded product can be obtained. In the present invention, the colorless and transparent cured product means a cured product having a light transmittance at 450 nm with respect to a thickness of 1 mm of 80% or more, preferably 85% or more, particularly preferably 90% or more.

  The condensation-curable silicone resin composition of the present invention gives a cured product having high light transmittance. Therefore, the condensation-curable silicone resin composition of the present invention is useful for encapsulating LED elements, particularly for encapsulating blue LEDs and ultraviolet LEDs. The method for encapsulating an LED element or the like with the condensation-curable silicone resin composition of the present invention may be in accordance with a conventionally known method. For example, a dispensing method, a compression molding method, or the like can be used.

  Furthermore, the condensation-curable silicone resin composition of the present invention has excellent handling properties, and provides a cured product having crack resistance, heat resistance, light resistance, and transparency. It is also useful for applications such as materials, optical equipment materials, optical component materials, optical fiber materials, organic materials for optical / electronic functions, and peripheral materials for semiconductor integrated circuits.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
The components (A) to (C) used in Examples and Comparative Examples are as follows. In the following, Me represents a methyl group, iPr represents an isopropyl group, nBu represents an n-butyl group, nPe represents an n-pentyl group, and Ph represents a phenyl group. In addition, the bonding order of each siloxane unit shown in parentheses of the following organopolysiloxane is not limited to the following description. In addition, each melting point described below is a melting peak top temperature measured by heating a 10 mg sample at 760 mmHg at 20 ° C./min using DSC EXSTAR6000 manufactured by Seiko Instruments Inc.

(A) Branched-chain silicone (A-1) Branched-chain silicone represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd.) Melting point 65 ° C
[(Me ₂ SiO _1.0 ) ₅ ] ₂ (PhSiO _1.5 ) ₉ (O _0.5 H) ₂
(A-2) Branched-chain silicone represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd.): melting point 55 ° C.
[(MePhSiO _1.0 ) ₂₀ ] ₂ (PhSiO _1.5 ) ₁₈ (O _0.5 H) ₄
(A-3) Branched-chain silicone represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd.) Melting point 94 ° C.
(Me ₃ SiO _0.5 ) ₆₀ [(Me ₂ SiO _1.0 ) ₁₂₀ ] ₁ (SiO _2.0 ) ₉₀ (O _0.5 R) ₈
Mixture of compounds wherein R = H or iPr (A-4) Branched silicone represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd.): melting point 82 ° C.
(Me ₃ SiO _0.5 ) ₃₀ [(Me ₂ SiO _1.0 ) ₂ ] ₈₀ (MeSiO _1.5 ) ₁₆₀ (O _0.5 R) ₃₀
Mixture of compounds where R = H or Me

(Comparative A ′) Branched silicone represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd.), melting point 72 ° C.
(Me ₂ SiO _1.0 ) ₁₀ (PhSiO _1.5 ) ₉ (O _0.5 H) ₂
The (Me ₂ SiO _1.0 ) units are randomly linked and not continuous.

（Ｂ−２）下記構造式で表される、１，３，５，７−テトラメチル−１，３，５，７−テトラフェニルシクロテトラシロキサン（信越化学工業株式会社製）融点９８℃

（Ｂ−３）下記構造式で表される、ヘキサメチルシクロトリシロキサン（信越化学工業株式会社製）融点６３℃

(B) Cyclic silicone (B-1) 1,1,3,3-tetramethyl-5,5-diphenylcyclotrisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following structural formula, melting point 61 ° C.

(B-2) 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclotetrasiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following structural formula, melting point: 98 ° C.

(B-3) Hexamethylcyclotrisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following structural formula, melting point 63 ° C.

(Comparative B ′) Octamethylcyclotetrasiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following structural formula and liquid at 25 ° C.

（Ｃ−２）トリメチルトリフェニルシクロトリシラザン（信越化学工業株式会社製）

（Ｃ−３）下記シラザン単位で構成される無機ポリシラザン（信越化学工業株式会社製）

（Ｃ−４）下記シラザン単位で構成される有機ポリシラザン（信越化学工業株式会社製）

（Ｃ−５）ヘプチルアミン（東京化成工業株式会社製） （沸点１５７℃）
（Ｃ−６）下記片末端シラザン／片末端アンモニウムシロキサノレート化合物（信越化学工業株式会社製）

（Ｃ−７）下記両末端シラザン化合物（信越化学工業株式会社製）

（Ｃ−８）下記両末端リチウムシリコネート化合物（信越化学工業株式会社製）

（Ｃ−９）下記両末端シラザン化合物（信越化学工業株式会社製）
（ｎＢｕ）_２Ｎ−（Ｍｅ_２Ｓｉ）−Ｎ（ｎＢｕ）_２
（Ｃ−１０）下記リチウムシリコネート化合物（信越化学工業株式会社製）
Ｐｈ_２ＭｅＳｉＯＬｉ (C) Curing catalyst (C-1) Tris (trimethylsilyl) amine (manufactured by Shin-Etsu Chemical Co., Ltd.)

(C-2) Trimethyltriphenylcyclotrisilazane (manufactured by Shin-Etsu Chemical Co., Ltd.)

(C-3) Inorganic polysilazane composed of the following silazane units (manufactured by Shin-Etsu Chemical Co., Ltd.)

(C-4) Organic polysilazane composed of the following silazane units (manufactured by Shin-Etsu Chemical Co., Ltd.)

(C-5) Heptylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) (boiling point: 157 ° C.)
(C-6) Silazane at one end / ammonium siloxanolate compound at one end (Shin-Etsu Chemical Co., Ltd.)

(C-7) The following silazane compound at both ends (manufactured by Shin-Etsu Chemical Co., Ltd.)

(C-8) Lithium siliconate compound at both ends shown below (Shin-Etsu Chemical Co., Ltd.)

(C-9) The following silazane compound at both ends (manufactured by Shin-Etsu Chemical Co., Ltd.)
_{(NBu) 2 N- (Me 2} Si) -N (nBu) 2
(C-10) The following lithium siliconate compound (manufactured by Shin-Etsu Chemical Co., Ltd.)
Ph ₂ MeSiOLi

[Examples 1 to 10, Comparative Examples 1 and 2]
The components (A) and (B) are placed in a Henschel mixer according to the blending amounts shown in Table 1, melt-mixed at 110 ° C., cooled to 70 ° C., added with a catalyst (C), and further mixed. A curable silicone resin composition was obtained.
In Comparative Example 1, the components (A ′) and (B-1) were placed in a Henschel mixer according to the amounts shown in Table 1, melt-mixed at 110 ° C., and then cooled to 70 ° C. The catalyst was added and further mixed to obtain a curable silicone resin composition.
In Comparative Example 2, the components (A-4) and (B ') were placed in a Henschel mixer according to the blending amounts shown in Table 1, melt-mixed at 110 ° C, cooled to 70 ° C, and cooled to (C). The catalyst was added and further mixed to obtain a curable silicone resin composition.

Each of the curable silicone resin compositions was freeze-pulverized at -30 ° C. 1.5 g of the silicone resin composition powder was placed in a tableting machine of φ20 mm to form a tablet. The following evaluation was performed about each curable silicone resin composition prepared by the Example and the comparative example. The composition of Comparative Example 2 was a highly viscous liquid at 25 ° C. and did not form a tablet.

[(1) Properties of curable resin composition at 25 ° C]
After the prepared tablet was left on a horizontal table at 25 ° C. for 8 hours to observe whether there was any change in dimensions, it was further left at 25 ° C. for one week to observe the change in dimensions. Those having no change in size for one week or more were solid, and those having no change in size for 8 hours but having changed one week later were semi-solid. The results are shown in Tables 2 and 3.
The composition of Comparative Example 2 was a highly viscous liquid at 25 ° C., and changed its dimensions within 8 hours.

[(2) Melting point of curable resin composition]
Using DSC EXSTAR6000 manufactured by Seiko Instruments Inc., the temperature of the melting peak top measured by raising the temperature of 10 mg of the composition under the condition of 760 mmHg at 20 ° C./min. The results are shown in Tables 2 and 3.

  Regarding the following evaluations, in addition to the compositions of Examples 1 to 10 and Comparative Examples 1 and 2, as Comparative Example 3, an addition-curable silicone resin composition (liquid at 25 ° C. under 760 mmHg) LPS-5557 ( Shin-Etsu Chemical Co., Ltd.) was also evaluated.

[(3) Curing speed]
A graph in which the change over time of the storage modulus G ′ (Pa) at 120 ° C. of the resin composition was measured by a rheometer ALPHA TECHNOLOGIES APA 2000, and the value of Tan δ derived from the obtained storage modulus was plotted against time. The time of the peak top was read from, and this time was defined as the gel time. The measurement was performed at a frequency of 100 cpm and an amplitude angle of 0.75 degrees. The results are shown in Tables 2 and 3.

[(4) Hardness of cured product]
One prepared tablet was placed in a Teflon (registered trademark) mold having a diameter of 20 mm x 3 mm and cured by a hot press machine at 10 MPa, 150 ° C for 5 minutes, and the obtained cured product was further heated at 150 ° C for 4 hours. Post cured. The hardness (Shore D, TYPE A) of the cured product was measured according to JIS K 6253-3: 2012. For Comparative Examples 2 and 3, the resin composition was poured into a Teflon (registered trademark) mold and cured under the same conditions as described above. The results are shown in Tables 2 and 3.

[(4) Light transmittance of cured product]
Place a 50mm x 20mm x 1mm thick glass epoxy plate on a stainless steel plate, place one prepared tablet in the hole, sandwich it with another stainless plate from the top, and press hot After curing at 10 MPa and 150 ° C. for 5 minutes by a machine, the obtained cured product was further post-cured at 150 ° C. for 4 hours. The compositions of Comparative Examples 2 and 3 were prepared by pouring a resin composition into a glass epoxy plate and curing the composition under the same conditions as above.
The light transmittance at 450 nm of each of the obtained cured products was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). The results are shown in Tables 2 and 3.

[(5) Heat resistance test]
After the sample prepared in the above test (3) was left at 200 ° C. for 1,000 hours, the light transmittance at 450 nm was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). The results are shown in Tables 2 and 3.
[(6) Outgassing evaluation]
In the same manner as in the above test (4), a glass epoxy plate having a 50 mm × 20 mm × 1 mm thick hole was placed on a stainless steel plate, one prepared tablet was placed in the hole, and another tablet was placed from above. After being sandwiched between stainless steel plates, it was cured by a hot press machine at 10 MPa, 150 ° C. for 5 minutes. The compositions of Comparative Examples 2 and 3 were prepared by pouring a resin composition into a glass epoxy plate and curing the composition under the same conditions as above. The number of voids contained in one obtained sheet sample was visually measured. A sheet having a thickness of 50 mm × 20 mm × 1 mm having 0 voids was evaluated as excellent, a sheet having 1 to 5 holes as good, and a sheet having 5 or more voids as poor. The larger the number of voids, the more gas was generated during curing. The results are shown in Tables 2 and 3.

As shown in Table 3, the cured product obtained from the addition-curable silicone resin composition (Comparative Example 3) has poor heat resistance. In addition, the composition of Comparative Example 1 containing a branched organopolysiloxane having no structure in which two or more (Me ₂ SiO _1.0 ) units are continuous has a slow curing rate at 120 ° C. Since the composition of Comparative Example 2 is in a liquid state at 25 ° C., it is inferior in handleability at the time of molding. Further, the compositions of Comparative Examples 1 and 2 generate gas at the time of curing, and many voids are generated in the cured product.
On the other hand, as shown in Table 2, the curable silicone resin composition of the present invention (Examples 1 to 10) is excellent in handleability because it is solid at 25 ° C., and the addition-curable silicone resin composition It has a curing speed equivalent to that of the product (Comparative Example 3), that is, cures rapidly by heating at 120 ° C. to give a colorless and transparent cured product, and the obtained cured product is extremely excellent in heat resistance. Furthermore, since the amount of gas generated at the time of curing is small, generation of voids in the cured product can be suppressed, and a cured product excellent in moldability can be provided.

  The curable silicone resin composition of the present invention provides a cured product having excellent handling properties and excellent reliability such as heat resistance. Therefore, by sealing a semiconductor element with the cured product, a semiconductor device having excellent reliability can be provided. In particular, since the curable silicone resin composition of the present invention is solid or semi-solid at 25 ° C., the composition is easily molded into a sheet or tablet to easily seal a semiconductor device. be able to. Further, the curable silicone resin composition of the present invention provides a cured product having high light transmittance, and thus is useful as a material for encapsulating LED elements, particularly for encapsulating blue LEDs and ultraviolet LEDs.

Claims (13)

(A) has a melting or softening point in the range of 30 to 250 ° C. at 760 ^mmHg, branched _{organo (R} 1 _{2 SiO 2/2)} units having at least one structure in which successive two or more in a molecule in the polysiloxane (wherein, R ^1, independently of one another, Ri substituted or unsubstituted monovalent hydrocarbon radical der having 1 to 12 carbon atoms, provided that more than 10 mol% relative to the total moles of siloxane repeating units is a cyclosiloxane Not including the forming structure )
100 parts by mass (B) cyclic organopolysiloxane having a melting point in the range of 30 to 250 ° C. at 760 mmHg
5-200 parts by weight, and (C) an amine, and, silazane bonds _(Si-NR 2), ammonium siloxanolate structure _{^{(SiO - N + R 4)}} , and the metal siliconate at least one bond (SiO-M) At least one selected from organic or inorganic silicon compounds having one or more (R is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms, and M is an alkali metal atom)
A curable silicone resin composition containing 0.05 to 30 parts by mass based on 100 parts by mass of the total of the components (A) and (B). (A) component is represented by the following general formula (1), the curable silicone resin composition according to claim _{^{1 (R 1 3 SiO 1/2)}} a (R 1 2 SiO 2/2) b [( _{^{R 1 2 SiO 2/2) m]}} b '(R 1 SiO 3/2) c (SiO 4/2) d (O 1/2 R 2) e (1)
(R ¹ is independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ² is independently a hydrogen atom or a 1 to 6 carbon atom, A monovalent hydrocarbon group which may have an oxygen atom, a is an integer of 0 to 500, b is an integer of 0 to 500, m is an integer of 10 to 1,000, and b 'is An integer of 1 to 100, c is an integer of 0 to 500, d is an integer of 0 to 500, c + d is 3 to 500, e is an integer of 0 to 100, and siloxane units represented may form a block be bonded randomly, the _{^{[(R 1 2 SiO 2/2)}} m] siloxane units in the parentheses in the attached to the m continuously cage, and, as shown above _^(R 1 _{2 SiO 2/2) b} in parentheses Shi The oxane units are not continuous but are linked at random , provided that 10 mol% or more of the total moles of siloxane repeating units do not include a structure in which cyclosiloxane is formed . The curable silicone resin composition according to claim 1, wherein the component (B) is represented by the following general formula (2).

(R ¹ is independently of each other a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and n is an integer of 3 to 8). The curable silicone resin composition according to claim 3, wherein n in the formula (2) is 3. The curable silicone resin composition according to claim 3, wherein R ¹ in the formula (2) is independently a methyl group or a phenyl group.   The component (C) is an amine and a silazane bond (Si-NR ₂ The compound according to any one of claims 1 to 5, wherein the compound is at least one member selected from the group consisting of an organosilicon compound having one or more (R is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms). 9. The curable silicone resin composition according to claim 1. The component (C) is a silazane represented by the following general formula (3), a cyclic silazane represented by the following general formula (5), a polysilazane represented by the following general formula (6), and a following general formula (7) The curable silicone resin composition according to any one of claims 1 to 6 , which is at least one selected from organosilicon compounds represented by the following formula:

(In the formula (3), (5), and (6), ^{R 3} is, independently, a hydrogen atom or a substituted or unsubstituted, monovalent hydrocarbon group having 1 to 12 carbon atoms, ^{R 4} Are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms, or a group represented by the following formula (4):

In the formula (4), R ³ is independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and in the formula (5), m is an integer of 3 to 8 In the formula (6), f is an integer of 1 to 500, g is an integer of 0 to 500, and h is an integer of 0 to 200, provided that f + g + h is 10 to 500; In (6), the siloxane units shown in the parentheses may be randomly bonded or form block units.)

(In the formula (7), R ³ is, independently of each other, a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms; A monovalent hydrocarbon group, a hydroxyl group, a monovalent hydrocarbon group having an oxygen atom having 1 to 6 carbon atoms, —NR ₂ , —O ^— N ⁺ R ₄ , or —OM, provided that at least one of X is _{^{-NR 2, -O - n + R}} 4, or a -O-M, R and M are as defined above, and n is an integer of 0 to 1,000). In the organic silicon compound having the metal siliconate bond (SiO-M), M is lithium, curable silicone resin composition according to any one of claims 1 to 5 and 7. The curable silicone resin composition according to any one of claims 1 to 6 , wherein (C) the amine has a boiling point in the range of 60 to 200 ° C at 760 mmHg. In the general formula (7), one X is a monovalent hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, -NR ₂ or -O ^- N ⁺ R ₄ ; the other of X is -NR _2, curable silicone resin composition according to claim 7. The curable silicone resin composition according to any one of claims 1 to 10 , which has a melting point or a softening point within a range of 30 to 250C at 760 mmHg. A sheet comprising the curable silicone resin composition according to any one of claims 1 to 11 . A tablet comprising the curable silicone resin composition according to any one of claims 1 to 11 .