JP6981933B2 - A curable composition, a cured product of the composition, and a semiconductor device using the cured product. - Google Patents

Description

The present invention relates to a curable composition, a cured product thereof, and a semiconductor device using the cured product.

Conventionally, an epoxy resin is generally used as a material for an optical device or an optical component, particularly as a sealing material for a light emitting diode (LED) element. Further, it has been attempted to use a silicone resin as a mold member or the like for an LED element (Patent Documents 1 and 2) and as a color filter material (Patent Document 3), but there are few practical examples of use. ..

In recent years, while white LEDs have been attracting attention, yellowing of epoxy encapsulants due to ultraviolet rays, etc., which has not been a problem until now, and cracks due to an increase in calorific value due to miniaturization have become problems. Is an urgent need. As a countermeasure against these, it is considered to use a cured silicone resin having a large amount of phenyl groups in the molecule. However, the substrate used for the current LED is often a silver substrate, and silver is corroded by sulfur compounds existing in the air, which may reduce the luminous efficiency of the LED. This phenomenon can be suppressed to some extent even with a cured silicone resin having a phenyl group, but it is inferior to the epoxy encapsulant. As a countermeasure against this, a material having both silver corrosion and heat resistance has been proposed by using a cured composition having a polycyclic hydrocarbon group (Patent Document 4). However, since the change point of this composition as a resin is near room temperature, cracks are likely to occur due to temperature changes at high and low temperatures.

Japanese Unexamined Patent Publication No. 10-228249 Japanese Unexamined Patent Publication No. 10-242513 Japanese Unexamined Patent Publication No. 2000-123981 Japanese Unexamined Patent Publication No. 2005-133073

The present invention has been made to solve the above problems, and has a curable composition that provides a cured product having high hardness, mechanical strength, crack resistance, light transmission in a short wavelength region, and gas barrier properties. The purpose is to provide things.

（式中、Ｒ^１は独立に置換または非置換の炭素数１〜１２の２価炭化水素基である。）

（式中、Ｒ^２は独立に置換または非置換の炭素数１〜１２の１価炭化水素基であり、Ｒ^３は単結合または非置換の炭素数１〜４の２価炭化水素基である。）
（Ｂ）アルケニル基を１分子中に２個以上有するオルガノシロキサン化合物、
（Ｃ）ヒドロシリル化反応触媒：組成物全体の質量に対して白金族金属原子として１〜５００ｐｐｍ In order to achieve the above problems, the present invention provides a curable composition containing the following (A), (B) and (C).
(A) An addition reaction product of an organosilicon compound represented by the following formula (1) and an organosilicon compound represented by the following formula (2), which has three or more SiH groups in one molecule. Reactant,

(In the formula, R ¹ is an independently substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)

(In the formula, R ² is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ³ is a single bond or unsubstituted divalent hydrocarbon group having 1 to 4 carbon atoms. .)
(B) An organosiloxane compound having two or more alkenyl groups in one molecule,
(C) Hydrosilylation reaction catalyst: 1 to 500 ppm as a platinum group metal atom with respect to the total mass of the composition.

The curable composition of the present invention can provide a curable composition having high hardness, mechanical strength, and crack resistance, and providing a cured product having excellent light transmission and gas barrier properties in a short wavelength region.

In the curable composition of the present invention, the above R ¹ can be a phenylene group and the above R ² can be a methyl group or a phenyl group.

（式中、Ｒ^４は独立に非置換または置換の１価炭化水素基であり、Ｒ^５は独立にメチル基又はフェニル基であり、ａは０〜５０の整数であり、ｂは０〜１００の整数である。ただし、ａが０のときＲ５はフェニル基であり、かつ、ｂは１〜１００である。括弧が付されたシロキサン単位の配列順は任意である。） The curable composition of the present invention is preferably a compound in which the above (B) is represented by the following formula (3).

(In the formula, R ⁴ is an independently unsubstituted or substituted monovalent hydrocarbon group, R ⁵ is an independently methyl group or phenyl group, a is an integer of 0 to 50, and b is 0 to 100. However, when a is 0, R5 is a phenyl group and b is 1 to 100. The order of arrangement of the siloxane units in parentheses is arbitrary.)

The present invention also provides a cured product obtained by curing the curable composition.

The cured product of the present invention has high hardness, mechanical strength, and crack resistance, and is excellent in light transmission in the short wavelength region and gas barrier property.

The cured product of the present invention preferably has a light transmittance (25 ° C.) of 80% or more at a wavelength of 400 nm at a thickness of 2 mm.

A cured product having such a light transmittance can be suitably used for applications such as protection, sealing or adhesion of a light emitting diode element, wavelength change or adjustment, or a lens.

Further, the present invention provides a semiconductor device in which a semiconductor element is coated with the cured product.

The semiconductor device of the present invention has high hardness, mechanical strength, and crack resistance of the cured product used, and has excellent gas barrier properties, so that the semiconductor device has high durability. Further, since it is excellent in light transmission in a short wavelength region, it is also useful as a semiconductor device such as a light emitting diode element that requires light transmission.

The curable composition of the present invention can provide a cured product having high hardness, mechanical strength, and crack resistance, and excellent light transmission and gas barrier properties in a short wavelength region. Therefore, it can be suitably used for applications such as protection, sealing or adhesion, wavelength change or adjustment, or a lens of a light emitting diode element. It is also useful as a lens material, a sealing material for an optical device or an optical component, a material for various optical components such as a display material, an insulating material for an electronic device or an electronic component, and a coating material.

It is a schematic sectional drawing which shows an example of the optical semiconductor device which used the cured product of the curable composition of this invention. ^{6 is a 1} H-NMR spectrum of the addition reaction product (A-1) obtained in Synthesis Example 1. 6 is a GPC chart of the addition reaction product (A-1) obtained in Synthesis Example 1. ^{6 is a 1} H-NMR spectrum of the addition reaction product (A-2) obtained in Synthesis Example 2. 6 is a GPC chart of the addition reaction product (A-2) obtained in Synthesis Example 2. ^{6 is a 1} H-NMR spectrum of the addition reaction product (A-3) obtained in Synthesis Example 3. 3 is a GPC chart of the addition reaction product (A-3) obtained in Synthesis Example 3.

As described above, there has been a demand for the development of a curable composition which has high hardness, mechanical strength, and crack resistance, and which provides a cured product having excellent light transmission and gas barrier properties in a short wavelength region.

As a result of diligent studies on the above problems, the present inventors have found that a curable composition containing a specific component can solve the above problems, and have completed the present invention.

（式中、Ｒ^１は独立に置換または非置換の炭素数１〜１２の２価炭化水素基である。）

（式中、Ｒ^２は独立に置換または非置換の炭素数１〜１２の１価炭化水素基であり、Ｒ^３は単結合または非置換の炭素数１〜４の２価炭化水素基である。）
（Ｂ）アルケニル基を１分子中に２個以上有するオルガノシロキサン化合物、
（Ｃ）ヒドロシリル化反応触媒：組成物全体の質量に対して白金族金属原子として１〜５００ｐｐｍ That is, the present invention is a curable composition containing the following (A), (B) and (C).
(A) An addition reaction product of an organosilicon compound represented by the following formula (1) and an organosilicon compound represented by the following formula (2), which has three or more SiH groups in one molecule. Reactant,

(In the formula, R ¹ is an independently substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)

(In the formula, R ² is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ³ is a single bond or unsubstituted divalent hydrocarbon group having 1 to 4 carbon atoms. .)
(B) An organosiloxane compound having two or more alkenyl groups in one molecule,
(C) Hydrosilylation reaction catalyst: 1 to 500 ppm as a platinum group metal atom with respect to the total mass of the composition.

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

[Curable composition]
The curable composition of the present invention contains the following components (A) to (C). The curable composition (additional curable silicone composition) of the present invention can be prepared by mixing the following components (A) to (C) and, if necessary, other components by a conventionally known method. ..
Hereinafter, each component will be described in detail.

[(A) component]
The component (A) in the curable composition of the present invention functions as a cross-linking agent by causing a hydrosilylation reaction with the component (B) described later.

The component (A) is an addition reaction product of an organosilicon compound represented by the following formula (1) and an organosilicon compound represented by the following formula (2), and has three SiH groups in one molecule. It is an addition reaction product having the above.

（式中、Ｒ^１は独立に置換または非置換の炭素数１〜１２の２価炭化水素基である。）

（式中、Ｒ^２は独立に置換または非置換の炭素数１〜１２の１価炭化水素基であり、Ｒ^３は単結合または非置換の炭素数１〜４の２価炭化水素基である。）、

(In the formula, R ¹ is an independently substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)

(In the formula, R ² is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ³ is a single bond or unsubstituted divalent hydrocarbon group having 1 to 4 carbon atoms. .),

Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms represented by R ¹ include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group and a cyclohexylene group. Examples include alkylene groups such as n-octylene groups, arylene groups such as phenylene groups and naphthylene groups, and those in which some or all of the hydrogen atoms of these groups are replaced with halogen atoms such as fluorine, bromine and chlorine. is, as the ^{R 1,} a phenylene group is particularly preferred.

The monovalent hydrocarbon group having 1 to 12 carbon atoms represented by R ^2, a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, isobutyl group, tert- butyl group, a pentyl group, a neopentyl group, a hexyl Alkyl group such as group, octyl group, cycloalkyl group such as cyclohexyl group, alkenyl group such as vinyl group, allyl group and propenyl group, aryl group such as phenyl group, trill group, xylyl group and naphthyl group, benzyl group and phenyl. Examples thereof include an aralkyl group such as an ethyl group and a phenylpropyl group, and a group in which a part or all of the hydrogen atom of these groups is substituted with a halogen atom such as fluorine, bromine or chlorine, and R ² is methyl or A phenyl group is preferable, and a phenyl group is particularly preferable.

Examples of the unsubstituted divalent hydrocarbon group having 1 to 4 carbon atoms represented by R ³ include an alkylene group such as a methylene group, an ethylene group, an n-propylene group and an n-butylene group. When R ³ is a single bond, it represents an organosilicon compound in which a vinyl group is directly bonded to a silicon atom. As R ³ is a single bond or an ethylene group it is particularly preferred.

Suitable specific examples of the organosilicon compound represented by the above formula (1) are shown below, but the present invention is not limited thereto. Further, the organosilicon compound represented by the above formula (1) can be used alone or in combination of two or more.

Suitable specific examples of the compound represented by the above formula (2) are shown below, but the present invention is not limited thereto. Further, the compound represented by the above formula (2) can be used alone or in combination of two or more.

（式中、ｎは１〜１０の整数である。） A preferable example of the component (A) which is an addition reaction product of the organosilicon compound represented by the above formula (1) and the organosilicon compound represented by the above formula (2) is a compound represented by the following unit formula. Can be mentioned.

(In the formula, n is an integer of 1 to 10.)

Specific examples of the compound represented by the unit formula include, but are not limited to, compounds represented by the following formula.

Further, the component (A) can be used alone or in combination of two or more of the compounds represented by the above unit formulas.

[Preparation of (A) component]
The component (A) in the curable composition of the present invention contains an excess amount, preferably 3 mol, of the compound represented by the above formula (1) with respect to 1 mol of the compound represented by the above formula (2). It can be obtained by mixing 30 mol or less, more preferably 4.5 mol or more and 15 mol or less, and carrying out a hydrosilylation reaction in the presence of both.

A known catalyst can be used as the catalyst used for the hydrosilylation reaction. For example, carbon powder carrying platinum metal, platinum black, second platinum chloride, platinum chloride acid, reaction product of platinum chloride acid and monovalent alcohol, complex of platinum chloride acid and olefins, platinum bisacetoacetate, etc. Platinum-based catalysts; examples thereof include platinum-based metal-based catalysts such as palladium-based catalysts and rhodium-based catalysts. Further, the addition reaction conditions, purification conditions, use of solvent and the like are not particularly limited, and known methods may be used.

The component (A) in the curable composition of the present invention may be composed of one kind of compound or a combination (mixture) of two or more kinds of compounds.

(A) It can be confirmed by selecting an appropriate measuring means that one molecule of the compound constituting the component has three or more SiH groups. (A) When there are two or more compounds constituting the component, a SiH group can be added to one molecule for each compound by selecting an ^{appropriate combination of measuring means (for example, 1 H-NMR and GPC).} It can be confirmed that there are three or more.

[(B) component]
The component (B) in the curable composition of the present invention is an organosiloxane compound having two or more alkenyl groups in one molecule.

Specific examples of the component (B) are not particularly limited, but are trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer at both ends of the molecular chain, and trimethylsiloxy group-blocked dimethylsiloxane / diphenylsiloxane / methylvinylsiloxane at both ends of the molecular chain. Examples thereof include a copolymer, a dimethylvinylsiloxy group-sealed dimethylsiloxane / diphenylsiloxane copolymer at both ends of the molecular chain, and the component (B) can be used alone or in combination of two or more.

（式中、Ｒ^４は独立に非置換または置換の１価炭化水素基であり、Ｒ^５は独立にメチル基又はフェニル基であり、ａは０〜５０の整数であり、ｂは０~１００の整数である。ただし、ａが０のときＲ^５はフェニル基であり、かつ、ｂは１〜１００である。括弧が付されたシロキサン単位の配列順は任意である。） The component (B) is preferably a linear organopolysiloxane represented by the following formula (3).

(In the formula, R ⁴ is an independently unsubstituted or substituted monovalent hydrocarbon group, R ⁵ is an independently methyl group or phenyl group, a is an integer of 0 to 50, and b is 0 to 100. However, when a is 0, R ⁵ is a phenyl group and b is 1 to 100. The order of arrangement of the siloxane units in parentheses is arbitrary.)

The monovalent hydrocarbon radical unsubstituted or substituted, represented by R ^4, the aliphatic unsaturated group, and a monovalent hydrocarbon group other than the aliphatic unsaturated group, e.g., methyl group, ethyl group, propyl Alkyl groups having 1 to 6 carbon atoms such as groups, isopropyl groups, butyl groups, isobutyl groups, sec-butyl groups and t-butyl groups; carbon atoms such as chloromethyl groups and 3,3,3-trifluoropropyl groups. Examples thereof include a haloalkyl group having a number of 1 to 4; an aryl group having 6 to 10 carbon atoms such as a phenyl group and a trill group. Of these, an alkyl group having 1 to 6 carbon atoms, a phenyl group and a vinyl group are preferable, and a methyl group is particularly preferable.

In the above formula (3), a is an integer of 0 to 50, preferably 1 to 10, more preferably 1 to 7, and even more preferably 2 to 4. b is an integer of 0 to 100, preferably 0 to 50, more preferably 1 to 10, and even more preferably 2 to 4.

The organopolysiloxane represented by the formula (3) is, for example, after hydrolyzing / condensing a bifunctional silane such as dichlorodiphenylsilane or dialkoxydiphenylsilane, or at the same time as hydrolysis / condensation, aliphatic unsaturated. It is obtained by blocking the end with a siloxane unit containing a group.

The blending amount of the component (B) can be such that the molar ratio of SiH groups (SiH group / aliphatic unsaturated group) to the aliphatic unsaturated group in the composition is 0.5 or more and 5 or less. The amount is preferably 0.8 or more and 2 or less. When the molar ratio (SiH group / aliphatic unsaturated group) is 0.5 or more and 5 or less, the composition of the present invention can be sufficiently cured.

[(C) component]
As the hydrosilylation reaction catalyst which is the component (C) of the present invention, the same catalyst as that used for the preparation of the component (A) can be used.

The blending amount of the component (C) in the curable composition of the present invention is 1 to 500 ppm, preferably about 1 to 100 ppm, more preferably 2 to 12 ppm as a platinum group metal atom with respect to the total mass of the composition. Is the amount. If the blending amount of the component (C) is less than 1 ppm as a platinum group metal atom or more than 500 ppm with respect to the total mass of the composition, the time required for the curing reaction becomes too long or too short. , The cured product may be colored.

[Other ingredients]
In addition to the above-mentioned components (A) to (C), components such as an antioxidant and an inorganic filler may be added to the curable composition of the present invention, if necessary.

[Antioxidant]
In the cured product of the curable composition of the present invention, the addition-reactive carbon-carbon double bond in the component (B) may remain unreacted due to oxygen in the atmosphere. Oxidation can cause the cured product to become colored. Therefore, such coloring can be prevented in advance by adding an antioxidant to the curable composition of the present invention, if necessary.

As the antioxidant, known ones can be used, for example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-amylhydroquinone, 2,5-di-. t-Butylhydroquinone, 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4- Ethyl-6-t-butylphenol) and the like. These can be used alone or in combination of two or more.

When this antioxidant is used, the blending amount thereof is not particularly limited, but it is usually 1 to 10,000 ppm, particularly 10 to 1 with respect to the total mass of the component (A) and the component (B). It is preferable to add about 000 ppm. By setting the blending amount within the above range, the antioxidant ability is sufficiently exhibited, and a cured product having excellent optical properties can be obtained without the occurrence of coloring, cloudiness, oxidative deterioration and the like.

[Inorganic filler]
In order to adjust the viscosity of the curable composition of the present invention, the hardness of the cured product obtained from the curable composition of the present invention, the strength, and the dispersion of the phosphor, nanosilica, Inorganic fillers such as fused silica, crystalline silica, titanium oxide, nanoalumina, and alumina may be added.

[Adhesive improver]
An adhesiveness improver may be added to the curable composition of the present invention. Examples of the adhesiveness improving agent include a silane coupling agent, an oligomer thereof, and a polysiloxane having a reactive group similar to that of the silane coupling agent.

（式中、ｓは１〜３の整数であり、ｔは０〜３の整数であり、ｕは０〜３の整数であり、但しｓ＋ｔ＋ｕは４〜５の整数である。括弧が付されたシロキサン単位の配列順は任意である。） The adhesiveness improving agent is preferably a compound represented by the following formula (4).

(In the formula, s is an integer of 1 to 3, t is an integer of 0 to 3, u is an integer of 0 to 3, but s + t + u is an integer of 4 to 5. Parentheses are added. The order of arrangement of siloxane units is arbitrary.)

The adhesiveness improver is an optional component added to the curable composition of the present invention and the cured product to improve the adhesiveness to the substrate. Here, the base material refers to a metal material such as gold, silver, copper, and nickel, a ceramic material such as aluminum oxide, aluminum nitride, and titanium oxide, and a polymer material such as a silicone resin and an epoxy resin. The adhesiveness improver can be used alone or in combination of two or more.

When the adhesiveness improving agent is used, the blending amount is preferably 1 to 30 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total of the component (A) and (B). be. With such a blending amount, the thermosetting silicone composition of the present invention and the cured product thereof effectively improve the adhesiveness to the substrate and are less likely to cause coloring.

Preferable specific examples of the adhesiveness improver include, but are not limited to, those represented by the following formulas.

[others]
Further, in order to secure the pot life, an addition reaction control agent such as 1-ethynylcyclohexanol and 3,5-dimethyl-1-hexyne-3-ol can be blended.

Further, it is also possible to use a light stabilizer in order to impart resistance to photodegradation due to light energy of sunlight, fluorescent lamps and the like. As this photostabilizer, a hindered amine-based stabilizer that captures radicals generated by photooxidation deterioration is suitable, and when used in combination with an antioxidant, the antioxidant effect is further improved. Specific examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyl-2,2,6,6-tetramethylpiperidine and the like.

[Cursed product]
The curable composition of the present invention is cured to obtain a cured product of the present invention. The cured product has high hardness, mechanical strength, and crack resistance, and is excellent in light transmission in a short wavelength region and gas barrier property. The curing conditions of the curable composition of the present invention are not particularly limited, but are preferably 60 to 180 ° C. and 5 to 180 minutes.

In the cured product obtained from the curable composition of the present invention, it is preferable that the refractive index (25 ° C.) of light having a wavelength of 589 nm is 1.5 or more.

Further, the cured product obtained from the curable composition of the present invention preferably has a light transmittance (25 ° C.) of 80% or more at a wavelength of 400 nm at a thickness of 2 mm.

The cured product of the present invention having such optical characteristics can be suitably used for applications such as protection, sealing or adhesion, wavelength change or adjustment, or lens of a light emitting diode element, as well as a lens material, an optical device, or optics. It is a useful material as a sealing material for parts, a material for various optical parts such as a display material, an insulating material for an electronic device or an electronic part, and a coating material.

[Semiconductor device]
The present invention further provides a semiconductor device in which a semiconductor element is coated with a cured product obtained from the above curable composition.

Hereinafter, a semiconductor device using a cured product of the curable composition of the present invention (hereinafter, also referred to as “semiconductor device of the present invention”) will be described with reference to FIG. 1, but the present invention is limited thereto. It's not a thing.

FIG. 1 is a schematic cross-sectional view showing an example of the semiconductor device of the present invention. In the semiconductor device 1 of the present invention, a semiconductor chip 4 is die-bonded on a package 3 on which a silver-plated substrate 2 is formed, and the semiconductor chip 4 is wire-bonded by a bonding wire 5. The semiconductor chip 4 is coated with the cured product 6 of the curable composition of the present invention described above. The coating of the semiconductor chip 4 is performed by applying the above-mentioned curable composition of the present invention (additional curable silicone composition) and curing the curable composition by heating. In addition, you may cure by a known curing method under other known curing conditions.

In this case, from the viewpoint of making it less susceptible to the influence of external stress and suppressing the adhesion of dust and the like as much as possible, the curable composition forms a cured product having a hardness of 30 or more in ShoreD specified in JIS by curing. It is preferable that the product is used.

Since the curable composition of the present invention forms a cured product having high hardness and crack resistance and excellent light transmission and gas barrier properties in a short wavelength region, the semiconductor device of the present invention using this curable composition is used. Is highly reliable.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Further, in the example, ¹ H-NMR measurement used AVANCE III manufactured by Bruker Biospin. GPC (gel permeation chromatography) measurement was carried out using HLC-8320GPC manufactured by Tosoh Corporation, using tetrahydrofuran (THF) as a mobile phase, in terms of polystyrene.

[Synthesis Example 1] Preparation of (A-1) Components In a 1 L 4-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer, 1,4-bis (dimethylsilyl) benzene (Shinetsu Chemical Industry Co., Ltd.) 350.0 g (1.8 mol) of 5% Pt carbon powder (manufactured by N.E.Chemcat Co., Ltd.) 0.18 g was added, and the mixture was heated to 85 ° C. using an oil bath. To this, 74.5 g (0.4 mol) of trivinylphenylsilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise. After completion of the dropping, the mixture was stirred at 90 to 100 ° C. for 5 hours. After stirring, the temperature was returned to 25 ° C., 4.2 g of activated carbon was added, and the mixture was stirred for 1 hour. After stirring, the mixture was filtered and concentrated under reduced pressure to obtain 250.7 g (colorless and transparent, yield 81%, viscosity at 25 ° C.: 400 Pa · s) of the component (A-1).

As a result of analyzing the reaction product by ¹ H-NMR (FIG. 2), GPC (FIG. 3), etc., the obtained reaction product is a compound having a structure represented by the following formulas (a) to (e). It was a mixture, and the ratio of each compound was (a) :( b) :( c) :( d) :( e) = 30: 20: 15: 10: 25 (mol%). Further, each of the above compounds was a compound having 3 or more SiH groups in one molecule, and the content ratio of SiH groups in the whole mixture was 0.0030 mol / g.

[Synthesis Example 2] Preparation of (A-2) Components In a 1 L 4-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer, 1,4-bis (dimethylsilyl) benzene (Shinetsu Chemical Industry Co., Ltd.) 194.4 g (1.0 mol) of 5% Pt carbon powder (manufactured by N.E.Chemcat Co., Ltd.) 0.097 g was added, and the mixture was heated to 85 ° C. using an oil bath. 37.3 g (0.2 mol) of trivinylphenylsilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise thereto. After completion of the dropping, the mixture was stirred at 90 to 100 ° C. for 5 hours. After stirring, the temperature was returned to 25 ° C., 4.2 g of activated carbon was added, and the mixture was stirred for 1 hour. After stirring, the mixture was filtered and concentrated under reduced pressure to obtain 131.0 g of the component (A-2) (colorless and transparent, yield 85%, viscosity at 25 ° C.: 150 Pa · s).

As a result of analyzing the reaction product by ¹ H-NMR (FIG. 4), GPC (FIG. 5), etc., the obtained reaction product is a compound having a structure represented by the above formulas (a) to (e). The ratio of each compound was (a) :( b) :( c) :( d) :( e) = 36: 24: 15: 10: 15 (mol%). Further, each of the above compounds was a compound having 3 or more SiH groups in one molecule, and the content ratio of SiH groups in the whole mixture was 0.0032 mol / g.

[Synthesis Example 3] Preparation of (A-3) Components In a 1 L 4-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer, 1,4-bis (dimethylsilyl) benzene (Shinetsu Chemical Industry Co., Ltd.) 262.8 g (1.35 mol) of 5% Pt carbon powder (manufactured by N.E.Chemcat Co., Ltd.) 0.12 g was added, and the mixture was heated to 85 ° C. using an oil bath. 28.0 g (0.15 mol) of trivinylphenylsilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise thereto. After completion of the dropping, the mixture was stirred at 90 to 100 ° C. for 5 hours. After stirring, the temperature was returned to 25 ° C., 2.9 g of activated carbon was added, and the mixture was stirred for 1 hour. After stirring, the mixture was filtered and concentrated under reduced pressure to obtain 99.7 g of the component (A-3) (colorless and transparent, yield 87%, viscosity at 25 ° C.: 30 Pa · s).

As a result of analyzing the reaction product by ¹ H-NMR (FIG. 6), GPC (FIG. 7), etc., this compound has a structure represented by the following formulas (a) to (c) and (f). The ratio of each compound was (a) :( b) :( c) :( f) = 55: 25: 10: 10 (mol%). Further, each of the above compounds was a compound having 3 or more SiH groups in one molecule, and the content ratio of SiH groups in the whole mixture was 0.0035 mol / g.

[Examples 1 to 4, Comparative Examples 1 to 3]
The following components were mixed at the composition ratios shown in Tables 1 and 2 (numerical values represent parts by mass) to prepare a silicone composition. In the example below, the symbols representing the composition of the organopolysiloxane are as follows.
M ^Vi : (CH ₂ = CH) (CH ₃ ) ₂ SiO _1/2
M ^ΦVi : (CH ₂ = CH) (CH ₃ ) (C ₆ H ₅ ) SiO _1/2
^MH : H (CH ₃ ) ₂ SiO _1/2
D ^2Φ : (C ₆ H ₅ ) ₂ SiO _2/2
T ^Φ : (C ₆ H ₅ ) SiO _3/2
Q: SiO _4/2

(A) Component (A-1) Compound obtained in Synthetic Example 1 (A-2) Compound obtained in Synthetic Example 2 (A-3) Compound comparative component obtained in Synthetic Example 3 (A) -4) Branched organopolysiloxane represented by ^MH ₃ T ^Φ ₁

(B) Component (B-1) Average unit formula M ^ΦVi ₂ D ^2Φ ₃ Organopolysiloxane (B-2) Average unit with a viscosity of 2,000 mPa · s and 0.23 mol of vinyl group per 100 g Organopolysiloxane (B-3) with a viscosity of 10 mPa · s, represented by the formula M ^Vi ₂ D ^{2Φ , having 0.50 mol of vinyl group per 100 g. Average unit formula M Φ Vi} ₂₀ D ^2Φ _37.5 Q _42.5 . Represented, an organopolysiloxane solid at 25 ° C. with 0.16 mol of vinyl group per 100 g

(C) Component Polysiloxane diluted product of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 1% by weight)

(D) Component Adhesive improver represented by the following structural formula (5)

<Performance evaluation method>
With respect to the curable compositions obtained in the above Examples and Comparative Examples, the performance of the cured product was evaluated according to the following method.

(1) Hardness A curable composition was poured into a mold assembled from a glass plate to a thickness of 6 mm, and post-cured at 150 ° C. for 4 hours to obtain a cured product. Table 3 shows the results of measuring the hardness (Shore D or Type A) of each cured product at 23 ° C. according to ASTM D 2240. For Shore D hardness, D is added before the value, and for Type A hardness, A is added before the value.

(2) Light Transmittance With respect to the cured product having a thickness of 2 mm prepared in the same manner as in the above hardness measurement, the 400 nm light transmittance of each cured product was measured using a spectrophotometer. The measurement results are shown in Table 3.

(3) Elongation and tensile strength With respect to the cured product having a thickness of 2 mm prepared in the same manner as in the above hardness measurement, the elongation and tensile strength of each cured product were measured at 23 ° C. according to JIS-K-6249. The measurement results are shown in Table 3.

(4) Crack resistance A curable composition was poured into the semiconductor device (LED device) shown in FIG. 1, held at 100 ° C. for 1 hour, and then cured at 150 ° C. for 4 hours. The obtained LED device was exposed to 260 ° C. for 3 minutes, and the presence or absence of cracks in the cured product was confirmed. After that, each LED device was placed in a thermal shock tester having a cycle of -40 ° C for 15 minutes and 125 ° C for 15 minutes, and it was confirmed whether or not there was a crack in the cured product portion of the curable composition in each LED device after 500 cycles. did. The results are shown in Table 3.

(5) Oxygen gas permeability Oxygen gas permeation device for the cured product obtained by pouring the curable composition into a mold made of a glass plate to a thickness of 1 mm and post-curing at 150 ° C. for 4 hours. The measurement was performed using (Model 8000 manufactured by Illinois Instruments). The results are shown in Table 3.

Table 3 shows that the cured product of the curable composition of the present invention is excellent in transparency, elongation, tensile strength, crack resistance, and gas barrier property. Therefore, the cured product of the transparent thermosetting silicone composition of the present invention is useful as a sealing material for an optical element, particularly a white LED.

As shown in Comparative Examples 1 to 3, when (A-4), which is a cross-linking agent having a siloxane bond, is used, the result is inferior in elongation and oxygen gas permeability as compared with the curable composition of the present invention. It became.

The present invention is not limited to the above embodiment. The above-described embodiment is an example, and any of the above-described embodiments having substantially the same configuration as the technical idea described in the claims of the present invention and having the same effect and effect is the present invention. Is included in the technical scope of.

1 ... semiconductor device, 2 ... silver-plated substrate, 3 ... package, 4 ... semiconductor chip,
5 ... Bonding wire, 6 ... Cured product of curable composition

Claims (5)

A curable composition comprising the following (A), (B) and (C).
(A) An addition reaction product of an organosilicon compound represented by the following formula (1) and an organosilicon compound represented by the following formula (2), which has three or more SiH groups in one molecule. Reactant,

(In the formula, R ¹ is a phenylene group.)

(Wherein, ^{R 2} is phenyl group, ^{R 3} is Tan'yui if.)
(B) An organosiloxane compound having two or more alkenyl groups in one molecule,
(C) Hydrosilylation reaction catalyst: 1 to 500 ppm as a platinum group metal atom with respect to the total mass of the composition. The curable composition according to claim 1, wherein the (B) is a compound represented by the following formula (3).

(In the formula, R ⁴ is an independently unsubstituted or substituted monovalent hydrocarbon group, R ⁵ is an independently methyl group or phenyl group, a is an integer of 0 to 50, and b is 0 to 100. However, when a is 0, R ⁵ is a phenyl group and b is 1 to 100. The order of arrangement of the siloxane units in parentheses is arbitrary.) A cured product obtained by curing the curable composition according to claim 1 or 2. The cured product according to claim 3 , wherein the light transmittance (25 ° C.) at a wavelength of 400 nm at a thickness of 2 mm is 80% or more. A semiconductor device characterized in that the semiconductor element is coated with the cured product according to claim 3 or 4.

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