KR101136643B1 - Silicone Resin Composition for Light Emitting Diode - Google Patents

Abstract

This invention provides the composition which is excellent in transparency and provides the hardened | cured material with little discoloration with time.

(A) organopolysiloxane with a viscosity of 10 mPa · s or more of formula (1)

(B) organohydrogenpolysiloxanes having a viscosity of formula 2 below 1,000 mPa · s and / or organohydrogensilanes of formula 3

(C) addition reaction catalyst

(D) a silicon compound having an epoxy group and at least one group selected from an Si-H group, an organooxysilyl group and an alkenyl group bonded to a silicon atom

(E) The silicone resin composition for light emitting diodes containing liquid acid anhydride is provided.

<Formula 1>

R _n SiO _{(4-n) / 2}

Wherein R is a monovalent hydrocarbon group, an alkoxy group or a hydroxyl group, wherein 0.1 to 80 mole% of the total R is an alkenyl group, and n is 1 ≦ n <2.

<Formula 2>

R ' _a H _b SiO _{(4-ab) / 2}

In the formula, R 'is a monovalent hydrocarbon group, 0.7≤a≤2.1, 0.002≤b≤1.0, and 0.8≤a + b≤2.6.

 <Formula 3>

_{R 'c SiH (4-c} )

In the formula, c is 1 or 2.

Light emitting diodes, silicone resins, organopolysiloxanes, silicon compounds

Description

Silicone resin composition for light emitting diodes {Silicone Resin Composition for Light Emitting Diode}

[Patent Document 1] Japanese Unexamined Patent Publication No. 10-228249

[Patent Document 2] Japanese Unexamined Patent Publication No. 10-242513

[Patent Document 3] Japanese Unexamined Patent Publication No. 2000-123981

TECHNICAL FIELD This invention relates to the silicone resin composition for light emitting diodes used for protection of a light emitting diode (LED) element, wavelength change and adjustment, and a lens.

Conventionally, epoxy resin is generally used as a sealing material of a light emitting diode element. As for the silicone resin, Japanese Patent Application Laid-Open No. 10-228249 or Japanese Patent Application Laid-Open No. 10-242513, etc., is used as a lens material, and Japanese Patent Application Laid-Open No. 2000-123981 uses a wavelength adjusting coating. Although use is attempted, there are few practical uses.

On the other hand, while white LEDs are attracting attention, problems such as yellowing caused by ultraviolet rays or the like during the actual use of epoxy sealing materials, which have not been a problem until now, and cracks caused by an increase in the amount of heat generated by miniaturization, have arisen.

This invention is made | formed in view of the said situation, and an object of this invention is to provide the silicone resin composition for light emitting diodes which provides the hardened | cured material which is excellent in transparency and little discoloration with time, and excellent in the characteristic as a sealing material.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, (A) organo or liquid phase which is represented by following General formula (1) and has a viscosity at 25 degreeC which has two or more alkenyl groups in 1 molecule is 10 mPa * s or more Polysiloxane, (B) An organohydrogenpolysiloxane represented by the following formula (2) and having two or more Si-H bonds in one molecule and having a viscosity at 25 ° C. of 1,000 mPa · s or less and / or represented by the following formula (3): Organohydrogensilane, (C) addition reaction catalyst, (D) an epoxy group in one molecule, a hydrogen atom (Si-H group) bonded to a silicon atom, an organooxysilyl group, and an alkenyl group bonded to a silicon atom The silicone resin composition for light-emitting diodes containing a silicon compound having at least one group selected from (E) and a liquid acid anhydride (E) has excellent transparency, less discoloration with time, and characteristics as a sealing material. It found that there can be a good cured article, and thus completing the present invention.

Therefore, the present invention

(A) 100 parts by mass of a liquid or solid organopolysiloxane represented by Formula 1 below and having a viscosity at 25 ° C. having two or more alkenyl groups in one molecule of 10 mPa · s or more,

(B) an organohydrogenpolysiloxane represented by the following formula (2) and having two or more Si-H bonds in one molecule and having a viscosity at 25 ° C. of 1,000 mPa · s or less and / or represented by the following formula (3): 2 to 100 parts by mass of ganohydrogensilane,

(C) addition reaction catalyst catalyst amount,

(D) 0.1-40 mass of the silicon compound which has an epoxy group and 1 or more types chosen from the hydrogen atom (Si-H group) couple | bonded with the silicon atom, the organooxysilyl group, and the alkenyl group couple | bonded with the silicon atom in 1 molecule. Wealth, and

(E) The silicone resin composition for light emitting diodes containing 0-5 mass parts of liquid acid anhydrides is provided.

R _n SiO _{(4-n) / 2}

Wherein R is the same or different substituted or unsubstituted monovalent hydrocarbon group, alkoxy group or hydroxyl group, wherein 0.1 to 80 mol% of the total R is an alkenyl group, and n is a positive number satisfying 1 ≦ n <2.

R ' _a H _b SiO _{(4-ab) / 2}

Wherein R 'is the same or different substituted or unsubstituted monovalent hydrocarbon group excluding aliphatic unsaturated hydrocarbon group, a and b satisfy 0.7≤a≤2.1, 0.002≤b≤1.0, and 0.8≤a + b≤2.6 It is positive.

_{R 'c SiH (4-c} )

In formula, R 'is the same as the above and c is 1 or 2.

The silicone resin composition of this invention is used as transparent resin materials, such as a protection of a light emitting diode element, wavelength change and adjustment, and a lens, and can provide the hardened | cured material which is excellent in transparency and discoloration resistance, and excellent in the characteristic as a sealing material.

BEST MODE FOR CARRYING OUT THE INVENTION [

The silicone resin composition for light emitting diodes (LED) according to the present invention,

(A) a liquid or solid organopolysiloxane represented by the formula (1) having a viscosity of at least 10 mPa? S at 25 ° C. having two or more alkenyl groups in one molecule,

(B) an organohydrogenpolysiloxane represented by the formula (2) and having two or more Si-H bonds in one molecule, and having a viscosity at 25 ° C. of 1,000 mPa · s or less and / or represented by the formula (3) Rosensilane,

(C) an addition reaction catalyst,

(D) a silicon compound having at least one group selected from an epoxy group and a hydrogen atom (Si-H group) bonded to a silicon atom, an organooxysilyl group and an alkenyl group bonded to a silicon atom in one molecule,

(E) Contains liquid acid anhydride.

Component (A) used in the present invention is the main agent (base polymer) of the present composition, which is represented by the following general formula (1) and has a branched or three-dimensional network structure of liquid or solid phase having a viscosity at 25 ° C. of 10 mPa · s or more (that is, , Organopolysiloxane resin of trifunctional siloxane units (RSiO _3/2 , R is the same as in formula 1) and / or SiO _4/2 units essentially.

<Formula 1>

R _n SiO _{(4-n) / 2}

Wherein R is the same or different substituted or unsubstituted monovalent hydrocarbon group, alkoxy group or hydroxyl group, wherein 0.1 to 80 mole% of the total R is an alkenyl group, n is 1 ≦ n <2, preferably 1 ≦ n A positive number satisfying ≤1.8, more preferably 1≤n≤1.5.

In the above formula (1), examples of the substituted or unsubstituted monovalent hydrocarbon group bonded to the silicon atom represented by R include those having 1 to 12 carbon atoms, preferably 1 to 9 carbon atoms, specifically, methyl group, ethyl group, Alkyl groups such as propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, phenyl group, tolyl group, Aryl groups such as xylyl and naphthyl groups, aralkyl groups such as benzyl, phenylethyl and phenylpropyl groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, hexenyl groups, cyclohexenyl groups, Derived from an octenyl group, or vinylnorbornene

(Wherein the chain line represents a bonding position), or a part or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine and chlorine, cyano groups, for example, chloromethyl group, Halogen-substituted alkyl groups, such as a chloropropyl group, a bromoethyl group, and a trifluoropropyl group, a cyanoethyl group, etc. are mentioned. Examples of the alkoxy group include lower alkoxy groups having usually 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group and tert-butoxy group. have.

In this case, two or more of R are required to be an alkenyl group (preferably having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms). Further, the content of alkenyl groups is 0.1 to 80 mol%, preferably 0.5 to 50 mol%, in all organic groups (i.e., the above-mentioned substituted or unsubstituted monovalent hydrocarbon groups except for hydroxyl and alkoxy groups), In particular, it is preferable to set it as about 1-30 mol%.

In the organopolysiloxane, in order to obtain a high refractive index, introduction of a phenyl group into the organopolysiloxane of the present invention is effective, and it is particularly preferable to use an organopolysiloxane containing a large amount of phenyl groups represented by the following general formula (1a).

R _p (C ₆ H ₅ ) _q SiO _{(4-pq) / 2}

Wherein R is the same as above, p and q are 1 ≦ p + q <2, preferably 1 ≦ p + q ≦ 1.8, more preferably 1 ≦ p + q ≦ 1.5, and 0.20 ≦ q /(p+q)≦0.95, preferably 0.30 ≦ q / (p + q) ≦ 0.80, more preferably 0.45 ≦ q / (p + q) ≦ 0.70.

In addition, content of an alkoxy group and a hydroxyl group is 0-5 mass% normally with respect to the organopolysiloxane resin of (A) component in total, especially about 0.1-3 mass%.

As the organopolysiloxane, a liquid or solid phase having a viscosity at 25 ° C. of 10 mPa · s or more, preferably 100 to 100,000,000 mPa · s, more preferably 10,000 to 10,000,000 mPa · s is used as the base polymer.

In addition, the component (A) may optionally contain a silicon atom at the molecular chain terminal, a silicon atom during the molecular chain, or a molecular chain terminal and the molecular chain during the purpose of adjusting the viscosity of the composition or the hardness of the cured product. It contains, or contains, an alkenyl group (e.g., vinyl group) bonded to a silicon atom, the main chain contains repetitions of diorganosiloxane units, and both ends of the molecular chain contain a phenyl group sealed with a triorganosiloxy group. Straight diorganopolysiloxane which is not provided can also be mix | blended.

Subsequently, the organohydrogenpolysiloxane and / or organohydrogensilane of component (B) act as a crosslinking agent that cures the composition by hydrosilylation with an alkenyl group-containing organopolysiloxane of component (A). 2 or more, preferably 3 or more (usually 3 to 300, especially 3 to 150) SiH bond in one molecule represented by the following formula (2), and the viscosity at 25 ° C. is 1,000 mPa? organohydrogenpolysiloxane which is s or less, and / or organohydrogensilane represented by following formula (3).

<Formula 2>

R ' _a H _b SiO _{(4-ab) / 2}

Wherein R 'is the same or different substituted or unsubstituted monovalent hydrocarbon group excluding aliphatic unsaturated hydrocarbon groups, a and b are 0.7 ≦ a ≦ 2.1, 0.002 ≦ b ≦ 1.0, and also 0.8 ≦ a + b ≦ 2.6, preferably Preferably, it is a positive number satisfying 0.8 ≦ a ≦ 2, 0.01 ≦ b ≦ 1, and 1 ≦ a + b ≦ 2.4.

<Formula 3>

_{R 'c SiH (4-c} )

In formula, R 'is the same as the above and c is 1 or 2.

Here, as R ', although the group similar to the unsubstituted or substituted monovalent hydrocarbon group in R in Formula 1 is mentioned, it is preferable that it does not have an aliphatic unsaturated bond.

Examples of the organohydrogensilane and organohydrogenpolysiloxane include (CH ₃ ) SiH ₃ , (CH ₃ ) ₂ SiH ₂ , (C ₆ H ₅ ) SiH ₃ , 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, both terminal trimethylsiloxy group blocking methylhydrogenpolysiloxane, both terminal trimethylsiloxy group blocking dimethylsiloxane-methylhydrogensiloxane copolymer, both terminal dimethylhydrogensiloxy group blocking dimethyl Polysiloxane, both terminal dimethylhydrogensiloxy group blockage dimethylsiloxane methylmethyl siloxanesiloxane copolymer, both terminal trimethylsiloxy group blockade methylhydrogensiloxane diphenylsiloxane copolymer, both terminal trimethylsiloxy group blockade methylhydrogensiloxane di Phenylsiloxane-dimethylsiloxane copolymers, copolymers containing (CH ₃ ) ₂ HSiO _1/2 units and SiO _4/2 units, (CH ₃ ) ₂ HSiO _1/2 units, SiO _4/2 units and And the like (C ₆ H ₅₎ copolymer comprising SiO _3/2 units.

The molecular structure of the organohydrogenpolysiloxane may be any of linear, cyclic, branched or three-dimensional network structure, but the number (or degree of polymerization) of silicon atoms in one molecule is 3 to 1,000, especially 3 to 300. Can be used.

Moreover, it is preferable that the viscosity at 25 degrees C of this organohydrogen polysiloxane is 1,000 mPa * s or less, More preferably, it is 0.1-500 mPa * s, More preferably, it is 0.5-300 mPa * s.

When the organopolysiloxane of the component (A) has a phenyl group, the organohydrogensilane and / or the organohydrogenpolysiloxane of the component (B) also have a phenyl group for the purpose of securing transparency and preventing separation during storage. desirable. In this case, in R 'of the above formula (2), 5 mol% or more, more preferably 8 to 50 mol%, more preferably of all the groups (R' and hydrogen atoms bonded to the silicon atom) bonded to the silicon atom. It is preferable that 10-30 mol% is a phenyl group. Further, in the general formula (2), less than 15 mol%, preferably 10 mol% or more of the total groups (R 'and hydrogen atoms bonded to the silicon atom) bonded to the silicon atom are organohydrogenpolysiloxanes in which a phenyl group, and silicon Organohydrogenpolysiloxanes in which at least 15 mol%, preferably at most 50 mol%, of the total groups (R 'and hydrogen atoms bonded to silicon atoms) bonded to the atoms are phenyl groups are weight ratios 1: 9 to 9: 1, in particular It is preferable to use it together with 3: 7-7: 3.

The compounding quantity of the organohydrogenpolysiloxane and / or organohydrogensilane of the said (B) component is 2-100 mass parts with respect to 100 mass parts of organopolysiloxane of (A) component, Preferably it is 10-100 mass It is wealth. When the amount of the component (B) is too small, the viscosity may be high and workability may be poor, or the crosslinking may be insufficient and the strength of the cured product may be poor. When the amount of the component is too high, the reinforcing effect of the resin of the component (A) is insufficient. There is a possibility that the strength of the cured product decreases.

In addition, this organohydrogenpolysiloxane and / or organohydrogensilane are in sum total with the organopolysiloxane of (A) component or the said organopolysiloxane, and the alkenyl-group containing linear diorganopolysiloxane as said arbitrary components. The molar ratio of hydrogen atoms (ie, Si—H groups) bonded to silicon atoms in component (B) to alkenyl groups bonded to silicon atoms is 0.5 to 5 mol / mol, preferably 0.8 to 4 mol / mol, more Preferably, it can also mix | blend in the quantity used as 1-3 mol / mol.

The addition reaction catalyst of the component (C) is a catalyst for promoting hydrosilylation addition reaction of the alkenyl group in the component (A) and the Si—H group in the component (B), and as the addition reaction catalyst, platinum black and platinum chloride And platinum group metal catalysts such as chloroplatinic acid, reactants of chloroplatinic acid with monohydric alcohols, complexes of chloroplatinic acid with olefins, platinum catalysts such as platinum bisacetoacetate, palladium catalysts, and rhodium catalysts. Among these, the platinum compound which is easy to obtain industrially and can reach the objective by addition of a small amount is preferable.

In addition, although the compounding quantity of this addition reaction catalyst is a catalytic amount, it is usual to mix | blend about 0.1-1,000 ppm with respect to the total weight of (A) and (B) component as a platinum group metal, especially 1-500 ppm, especially about 2-100 ppm. Do.

Epoxy group in one molecule of component (D), hydrogen atom (Si-H group) bonded to silicon atom, organooxysilyl group (Si-OR ¹ group (R ¹ is unsubstituted or substituted monovalent hydrocarbon group) ) And a silicon compound having at least one group selected from alkenyl groups (eg, Si—CH═CH ₂ groups) bonded to silicon atoms are used for the purpose of improving adhesion to the substrate used in the LED. . Although the molecular weight of this organosilicon compound is not specifically defined, too large a molecular weight is unsuitable for use in LEDs because of poor compatibility and turbidity when mixed with the organopolysiloxane of component (A). For example, generally referred to as a silane coupling agent such as epoxy functional alkoxysilanes such as 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; Preference is given to those derived from organopolysiloxanes having a linear or cyclic structure represented by 4.

In the above formula, R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert -Aryl groups such as butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl and decyl groups, aryl groups such as phenyl, tolyl, xylyl and naphthyl, benzyl and phenyl Aralkyl groups, such as an aralkyl group, such as an ethyl group and a phenylpropyl group, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, butenyl group, a hexenyl group, a cyclohexenyl group, an octenyl group, and some hydrogen atoms of these groups Or all substituted with halogen atoms such as fluorine, bromine, chlorine, cyano group, etc., for example, halogen-substituted alkyl groups such as chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group, cyanoethyl group, etc. Can be mentioned. In the organooxy group represented by R ¹ O-, R ¹ is preferably an alkyl group, an alkenyl group, or an aryl group, and particularly preferably an alkyl group.

(여기서, a는 1 내지 4, 바람직하게는 2 내지 3의 정수, b는 1 내지 3, 바람직하게는 2 내지 3의 정수)이다. X is -OR ¹ or

(Where a is an integer of 1 to 4, preferably 2 to 3, and b is an integer of 1 to 3, preferably 2 to 3).

w, x, y, z are any integer of 0 or more, y is an integer of 1 or more, and any one of w, x, z is 1 or more. However, when x and z are 0, one or more R <^1> contained in a compound needs to be an alkenyl group, such as a vinyl group. w + x + y + z becomes like this. Preferably it is 20 or less (usually 2-20), More preferably, it is 2-10, Most preferably, it is 4-7. Further, in the formula (4), if the siloxane is linear, the terminal is a hydroxyl group, an alkoxy group (OR ^{1 _{group), R 1 2 (H)}} Si group, R ¹ ₂ (H) SiO group, R ¹ ₃ Si group It is preferable that the group is sealed with a R ¹ ₃ SiO group, a (R ¹ O) ₃ Si group, or a (R ¹ O) ₃ SiO group.

As addition amount of (D) component, it is 0.1-40 mass parts with respect to 100 mass parts of (A) component, Preferably it is 1-20 mass parts, More preferably, it is 2-10 mass parts. If it is less than this range, sufficient adhesiveness will not be acquired, and when it adds more than this, the possibility of a yellowing problem will arise at the temperature of 150 degreeC or more.

The liquid acid anhydride of (E) component is added arbitrarily, and it plays the role of improving the activity of the reactive group of (D) component at the time of hardening of a composition, and improving adhesiveness. As such a liquid acid anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, etc. are mentioned, for example.

The addition amount in the case of using (E) liquid acid anhydride is 5 mass parts or less (that is, 0-5 mass parts) with respect to 100 mass parts of (A) component. When added more than this, there exists a possibility that the flexural modulus may fall extremely, and the target physical property may not be obtained, and a yellowing problem arises at the temperature of 150 degreeC or more. Therefore, it is preferable to add in the range of 0-4 mass parts preferably. Moreover, in order to provide this compounding effect, it is preferable to use a compounding quantity of 0.1 mass part or more.

The composition of the present invention includes not only the above-mentioned (A) to (E) components, but also any of the above-mentioned components such as dimethylpolysiloxane for controlling the addition reaction controlling agent, hardness and viscosity to provide curing properties and pot life as optional components. In addition to the linear diorganopolysiloxane having an alkenyl group with or without a phenyl group, the non-reactive organopolysiloxane of linear form, the linear or cyclic low molecular organopolysiloxane having about 2 to 10 silicon atoms, etc. It can also be added in a range that does not impair the effect of.

In addition, an inorganic filler such as fumed silica may be blended in order to improve the strength within a range that does not affect the transparency, and if necessary, a wavelength adjusting agent, a dye, a pigment, a flame retardant, a heat resistant agent, an oxidation resistant agent, and the like may be added. It can also mix | blend.

Moreover, although the hardening conditions of the said composition are not specifically limited, It is preferable to set it as the conditions of 30 to 180 minutes at 120-180 degreeC.

<Examples>

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to a following example. In addition, in a following example, a part represents a mass part.

&Lt; Example 1 >

Toluene, phenyltrichlorosilane, vinylmethyldichlorosilane and dimethyldichlorosilane were added, co-hydrolyzed, polycondensed, and (C ₆ H ₅ ) SiO _3/2 units, (CH ₂ = CH) (CH ₃ ) SiO _{2 / 2} units, and (CH ₃ ) ₂ SiO _2/2 units, wherein the average composition is represented by (CH ₃ ) _0.7 (C ₆ H ₅ ) _0.55 (CH ₂ = CH) _0.20 SiO _1.28 A 50 mass% toluene solution of organopolysiloxane (silicone resin) was prepared (this silicone resin itself was solid at 25 ° C.).

Viscosity of 2 mPa? S in which 90 parts of the solid content (organopolysiloxane) in the solution has a hydrogen gas generation amount of 200 ml / g having a phenyl group of 10 mol% based on the total of hydrogen atoms, phenyl groups and methyl groups bonded to silicon atoms. 13 parts of phenylmethylhydrogenpolysiloxane and 10 parts of adhesion | attachment provision components represented by following formula (5) were added, and the uniform transparent liquid composition was obtained.

<Example 2>

To 113 parts of the composition of Example 1, 1 part of Rikacid MH-700 (comprising the compound represented by the following formula (6) manufactured by Shin-Nipbon Lika was added as a main component) was added to obtain a uniform transparent liquid.

<Example 3>

Three parts of lycaside MH-700 was added to 113 parts of the composition of Example 1 to obtain a uniform transparent liquid.

<Example 4>

Toluene, phenyltrichlorosilane, vinylmethyldichlorosilane and dimethyldichlorosilane were added, co-hydrolyzed, polycondensed, and (C ₆ H ₅ ) SiO _3/2 units, (CH ₂ = CH) (CH ₃ ) SiO ₂ Orthogonal structure of three-dimensional network comprising _{/ 2} units and (CH ₃ ) ₂ SiO _2/2 units, the average composition of which is represented by (CH ₃ ) _0.7 (C ₆ H ₅ ) _0.55 (CH ₂ = CH) _0.20 SiO _1.28 A 50 mass% toluene solution of ganopolysiloxane (silicone resin) was prepared (this silicone resin itself was solid at 25 ° C.).

90 parts of the solid content (organopolysiloxane) in the solution is a phenyl having a viscosity of 2 mPa? S having 10 mol% of phenyl groups and 200 ml / g of hydrogen gas generated relative to the sum of hydrogen atoms, phenyl groups and methyl groups bonded to silicon atoms. 18 parts of methylhydrogenpolysiloxane and 3 parts of 3-glycidoxypropyltrimethoxysilane were added to obtain a uniform transparent liquid composition.

Comparative Example 1

Using the same silicone resin as in Example 1, 18 parts of the same phenylmethylhydrogenpolysiloxane as in Example 1 was added to 100 parts of the resin solid content to obtain a uniform composition.

Comparative Example 2

Three parts of lycaside MH-700 was added to Comparative Example 1 to obtain a uniform composition.

&Lt; Comparative Example 3 &

7 parts of lycaside MH-700 was added to 113 parts of the composition of Example 1 to obtain a uniform transparent liquid composition.

To 100 parts of the composition of Examples and Comparative Examples obtained as described above, 20 ppm of a platinum catalyst containing a vinylsiloxane complex of platinum chloride was added as a platinum atom, stirred and mixed to form a frame of 30 mm × 40 mm × 2 mm thickness. On, and cured in an oven at 150 ° C. for 1 hour to obtain a cured sample. The hardness was measured at Shore D using the cured sample, and the flexural modulus and flexural strength were measured by the method according to JIS K6911. Subsequently, a silicone rubber frame of 2 mm × 2 mm × 1 mm (thickness) was installed on the glass plate, and the sample was potted therein and cured at 150 ° C. for 1 hour, followed by removing the silicone rubber frame. As a result, a block having a height of 2 mm and a height of 2 mm was formed on the glass plate, and the adhesive strength was measured by a push-pull gauge. The results are shown in Table 1 below.

Next, the light transmittance of the said Example and the comparative example was evaluated by the following method. The results are shown in Table 2 below.

Assessment Methods:

The light transmittance of the prepared sample was measured at 400 nm to make an initial value. This was irradiated with ultraviolet rays with a shunt shine weather meter (Suga tester), and the light transmittance after 100 hours and 500 hours was measured.

The silicone resin composition of this invention is used as transparent resin materials, such as a protection of a light emitting diode element, wavelength change and adjustment, and a lens, and can provide the hardened | cured material which is excellent in transparency and discoloration resistance, and excellent in the characteristic as a sealing material.

Claims (3)

(A) 100 parts by mass of a liquid or solid organopolysiloxane represented by the following formula (1) and having a viscosity at 25 ° C. having at least 2 alkenyl groups of 2 to 8 carbon atoms in one molecule of 10 mPa · s or more; (B) an organohydrogenpolysiloxane represented by the following formula (2) and having two or more Si-H bonds in one molecule and having a viscosity at 25 ° C. of 1,000 mPa · s or less and / or represented by the following formula (3): 2 to 100 parts by mass of ganohydrogensilane, (C) addition reaction catalyst catalyst amount, (D) Silicon having an epoxy group and at least one group selected from hydrogen atoms (Si-H groups) bonded to silicon atoms, organooxysilyl groups bonded to silicon atoms, and alkenyl groups having 2 to 8 carbon atoms bonded to silicon atoms in one molecule (D) 0.1 to 40 parts by mass of the compound, and (E) Silicone resin composition for light emitting diodes containing 0.1-5 mass parts of liquid acid anhydrides. <Formula 1> R _n SiO _{(4-n) / 2} (Wherein R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, alkoxy group having 1 to 6 carbon atoms or hydroxyl group substituted with the same or different unsubstituted or halogen atom or cyano group, and 0.1 to 80 mol% of total R Alkenyl group, n is a positive number satisfying 1≤n <2) <Formula 2> R ' _a H _b SiO _{(4-ab) / 2} (Wherein R ′ is a monovalent hydrocarbon group having 1 to 12 carbon atoms substituted with the same or different unsubstituted or halogen atom or cyano group except for aliphatic unsaturated hydrocarbon group, a and b are 0.7 ≦ a ≦ 2.1, 0.002 ≦ b ≤ 1.0, and positive integer that satisfies 0.8 ≤ a + b ≤ 2.6) <Formula 3> _{R 'c SiH (4-c} ) (Wherein R 'is the same as above and c is 1 or 2) The silicone resin composition for light emitting diodes according to claim 1, wherein the organopolysiloxane of component (A) is a liquid or solid organopolysiloxane represented by the following formula (1a) and having a viscosity at 25 ° C. of 100 mPa · s or more. <Formula 1a> R _p (C ₆ H ₅ ) _q SiO _{(4-pq) / 2} Wherein R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydroxyl group substituted with the same or different unsubstituted or halogen atom or cyano group, and 0.1 to 80 mol% of the total R is alke P and q are positive numbers satisfying 1 ≦ p + q <2 and 0.20 ≦ q / (p + q) ≦ 0.95. The silicone resin composition for light emitting diodes according to claim 2, wherein 5 mol% or more of the organohydrogenpolysiloxane of the component (B) is a phenyl group in the total amount of the total R ′ of the general formula (2) and H bonded to the silicon atom.