JP2021059682A - Curable composition, cured product thereof, and semiconductor device - Google Patents

Abstract

To provide a curable composition which gives a cured product having high hardness and toughness and excellent light transmissivity in a short wavelength region.SOLUTION: The curable composition contains the following (A), (B) and (C): (A) an addition reaction product of an organosilicon compound having a bis(dimethylsilyl) group and at least one of a linear siloxane having unsaturated groups at both terminals and a cyclic siloxane having an unsaturated group, the addition reaction product having two or more SiH groups in one molecule; (B) a compound having two or more alkenyl groups in one molecule; and (C) a hydrosilylation reaction catalyst.SELECTED DRAWING: Figure 1

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, white LEDs have been attracting attention, and problems such as yellowing of epoxy encapsulants due to ultraviolet rays 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, such a composition has low toughness and is prone to cracking.

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

The present invention has been made to solve the above problems, and an object of the present invention is to provide a curable composition which gives a cured product having high hardness and toughness and excellent light transmission in a short wavelength region.

（式中、Ｒ^１は置換または非置換の炭素原子数１〜１２の２価炭化水素基である。）

（式中、Ｒ^２、Ｒ^４は独立に置換または非置換の炭素原子数１〜１２の１価炭化水素基であり、Ｒ^３は独立に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。ａは１〜３の整数であり、ｂは０〜１００の整数である。）

（式中、Ｒ^３は上記のとおりであり、Ｒ^５は独立にメチル基又はフェニル基であり、Ｒ^６は独立に置換または非置換の炭素原子数１〜１２の１価炭化水素基であり、ｃは１または２であり、ｄは２〜１０の整数であり、ｅは０〜１０の整数である。シロキサン単位の配列は任意であってよい。）
（Ｂ）アルケニル基を１分子中に２個以上有する化合物、
（Ｃ）ヒドロシリル化反応触媒 In order to achieve the above object, the present invention provides a curable composition containing the following (A), (B) and (C).
(A) Addition reaction between an organosilicon compound represented by the following formula (1) and at least one of a linear siloxane represented by the following formula (2) and a cyclic siloxane represented by the following formula (3). An addition reaction product having two or more SiH groups in one molecule.

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

(In the formula, R ² and R ⁴ are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R ³ is independently single-bonded or unsubstituted carbon atoms 1 to 4-2. It is a valent hydrocarbon group. A is an integer of 1 to 3 and b is an integer of 0 to 100.)

(In the formula, R ³ is as described above, R ⁵ is an independently methyl or phenyl group, and R ⁶ is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. , C is 1 or 2, d is an integer of 2 to 10, e is an integer of 0 to 10. The sequence of siloxane units may be arbitrary.)
(B) A compound having two or more alkenyl groups in one molecule,
(C) Hydrosilylation reaction catalyst

The curable composition of the present invention can provide a curable composition having high hardness and toughness and excellent light transmission in a short wavelength region.

In the curable composition of the present invention, it is preferable that R ¹ is a phenylene group, R ² , R ⁴ , and R ⁶ are independently methyl groups or phenyl groups, and R ³ is a single bond.

（式中、Ｒ^７は独立にメチル基又はフェニル基であり、Ｒ^８は独立に置換または非置換の炭素原子数１〜１２の１価炭化水素基であり、ｆは０〜５０の整数であり、ｇは０〜１００の整数である。ただし、ｆが０のときＲ^７はフェニル基であり、かつ、ｇは１〜１００の整数である。括弧が付されたシロキサン単位の配列は任意であってよい。） The curable composition of the present invention is preferably a compound in which the above (B) is represented by the following formula (4).

(In the formula, R ⁷ is an independently methyl or phenyl group, R ⁸ is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and f is an integer of 0 to 50. Yes, g is an integer from 0 to 100, where when f is 0, R ⁷ is a phenyl group and g is an integer from 1 to 100. The parenthesized sequence of siloxane units is arbitrary. May be.)

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

The cured product of the present invention has high hardness and toughness, and is excellent in light transmission in the short wavelength region.

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 light transmittance can be suitably used for protection, sealing or adhesion of light emitting diode elements, wavelength change or adjustment, lenses, etc., and for lens materials, optical devices or optical components. It is a useful material as a material for various optical parts such as a sealing material and a display material, an insulating material for an electronic device or an electronic part, and a coating material.

Further, the cured product of the present invention preferably has a hardness specified in ASTM D 2240 of 30 or more in the durometer A.

Such a cured product is less susceptible to the influence of external stress, and it is possible to suppress the adhesion of dust and the like as much as possible.

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 is a semiconductor device having excellent durability because the hardness and toughness of the cured product used are high. 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 and toughness and excellent light transmission in a short wavelength region. Therefore, it can be suitably used for applications such as protection, sealing or adhesion, wavelength change or adjustment, or lens of a light emitting diode element. Therefore, the cured product obtained from the curable composition of the present invention can be suitably used for applications such as protection, sealing or adhesion of light emitting diode elements, wavelength change or adjustment, or lenses. 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. Further, the semiconductor device of the present invention using such a curable composition has excellent reliability.

It is schematic cross-sectional view which shows an example of the optical semiconductor device using the cured product of the curable composition of this invention. 6 is a GPC chart of the addition reaction product (A-1) obtained in Synthesis Example 1. It is a GPC chart of the addition reaction product (A-2) obtained in Synthesis Example 2. 6 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 that provides a cured product having high hardness and toughness and excellent light transmission in the 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は置換または非置換の炭素原子数１〜１２の２価炭化水素基である。）

（式中、Ｒ^２、Ｒ^４は独立に置換または非置換の炭素原子数１〜１２の１価炭化水素基であり、Ｒ^３は独立に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。ａは１〜３の整数であり、ｂは０〜１００の整数である。）

（式中、Ｒ^３は上記のとおりであり、Ｒ^５は独立にメチル基又はフェニル基であり、Ｒ^６は独立に置換または非置換の炭素原子数１〜１２の１価炭化水素基であり、ｃは１または２であり、ｄは２〜１０の整数であり、ｅは０〜１０の整数である。シロキサン単位の配列は任意であってよい。）
（Ｂ）アルケニル基を１分子中に２個以上有する化合物、
（Ｃ）ヒドロシリル化反応触媒 That is, the present invention is a curable composition containing the following (A), (B) and (C).
(A) Addition reaction between an organosilicon compound represented by the following formula (1) and at least one of a linear siloxane represented by the following formula (2) and a cyclic siloxane represented by the following formula (3). An addition reaction product having two or more SiH groups in one molecule.

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

(In the formula, R ² and R ⁴ are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R ³ is independently single-bonded or unsubstituted carbon atoms 1 to 4-2. It is a valent hydrocarbon group. A is an integer of 1 to 3 and b is an integer of 0 to 100.)

(In the formula, R ³ is as described above, R ⁵ is an independently methyl or phenyl group, and R ⁶ is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. , C is 1 or 2, d is an integer of 2 to 10, e is an integer of 0 to 10. The sequence of siloxane units may be arbitrary.)
(B) A compound having two or more alkenyl groups in one molecule,
(C) Hydrosilylation reaction catalyst

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

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

（式中、Ｒ^１は置換または非置換の炭素原子数１〜１２の２価炭化水素基である。）

（式中、Ｒ^２、Ｒ^４は独立に置換または非置換の炭素原子数１〜１２の１価炭化水素基であり、Ｒ^３は独立に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。ａは１〜３の整数であり、ｂは０〜１００の整数である。）

（式中、Ｒ^３は上記のとおりであり、Ｒ^５は独立にメチル基又はフェニル基であり、Ｒ^６は独立に置換または非置換の炭素原子数１〜１２の１価炭化水素基であり、ｃは１または２であり、ｄは２〜１０の整数であり、ｅは０〜１０の整数である。シロキサン単位の配列は任意であってよい。） The component (A) in the curable composition of the present invention is represented by an organosilicon compound represented by the following formula (1), a linear siloxane represented by the following formula (2), and a following formula (3). It is an addition reaction product with at least one of the cyclic siloxanes, and is an addition reaction product having two or more SiH groups in one molecule.

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

(In the formula, R ² and R ⁴ are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R ³ is independently single-bonded or unsubstituted carbon atoms 1 to 4-2. It is a valent hydrocarbon group. A is an integer of 1 to 3 and b is an integer of 0 to 100.)

(In the formula, R ³ is as described above, R ⁵ is an independently methyl or phenyl group, and R ⁶ is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. , C is 1 or 2, d is an integer of 2 to 10, e is an integer of 0 to 10. The sequence of siloxane units may be arbitrary.)

In the above formula (2), b is an integer of 0 to 100, preferably 0 to 10, and more preferably 0. If b exceeds 100, the hardness of the cured product may be insufficient.

In the above formula (3), d is an integer of 2 to 10, preferably 3 to 10. If d is less than 2, the function of the component (A) as a cross-linking agent is insufficient, and if d is more than 10, the cured product may become brittle and have poor toughness. e is an integer from 0 to 10, preferably 0 to 2. If e exceeds 10, the hardness of the cured product may be insufficient.

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. , N-octylene group and other alkylene groups, phenylene group, naphthylene group and other arylene groups, and some or all of the hydrogen atoms of these groups substituted with halogen atoms such as fluorine, bromine and chlorine. As R ¹ , a phenylene group is particularly preferable.

The monovalent hydrocarbon group R ^{2, R 4} and the carbon atoms represented by ^{R 6} 1 to 12, a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, isobutyl group, tert- butyl group, Alkyl groups such as pentyl group, neopentyl group, hexyl group and octyl group, cycloalkyl group such as cyclohexyl group, alkenyl group such as vinyl group, allyl group and propenyl group, phenyl group, tolyl group, xylyl group, naphthyl group and the like. Examples thereof include aralkyl groups such as an aryl group, a benzyl group, a phenylethyl group and a phenylpropyl group, and those in which a part or all of the hydrogen atoms of these groups are replaced with halogen atoms such as fluorine, bromine and chlorine. , Methyl or phenyl group is preferred.

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 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 linear siloxane 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、シロキサン単位の配列は任意であってよい。） Suitable specific examples of the cyclic siloxane represented by the above formula (3) are shown below, but the present invention is not limited thereto. Further, the compound represented by the above formula (3) can be used alone or in combination of two or more.

(In the formula, the arrangement of siloxane units may be arbitrary.)

（式中、ｎは１〜１０の整数であり、破線は結合手を表す。） It is an addition reaction product of an organosilicon compound represented by the above formula (1) and at least one of a linear siloxane represented by the above formula (2) and a cyclic siloxane represented by the above formula (3). A preferable example of the component (A) is a compound having a constituent unit ratio represented by the following formula.

(In the formula, n is an integer of 1 to 10, and the broken line represents the bond.)

Specific examples of the compound having such a structural unit ratio include, but are not limited to, compounds represented by the following structural formulas.

[Preparation of (A) component]
The component (A) in the curable composition of the present invention comprises 1 mol of an alkenyl group contained in the linear siloxane represented by the above formula (2) and / or the cyclic siloxane represented by the above formula (3). On the other hand, the compound represented by the above formula (1) is mixed in an excess amount, preferably more than 1 mol and 10 mol or less, more preferably more than 1.5 mol and 5 mol or less, and hydrosilylated in the presence of both. It can be obtained by carrying out a reaction.

An unreacted alkenyl group derived from the linear siloxane represented by the above formula (2) and / or the cyclic siloxane represented by the above formula (3) may be present in the component (A). , It is preferable that all alkenyl groups undergo a hydrosilylation reaction.

A known catalyst can be used as the catalyst used for the hydrosilylation reaction. For example, carbon powder carrying platinum metal, platinum black, secondary 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-group 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.

It can be confirmed by selecting an appropriate measuring means that one molecule of the compound constituting the component (A) has two 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 1 H-NMR and GPC).} It can be confirmed that there are two or more.

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

Examples of the alkenyl group include a linear alkenyl group such as a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group and an octenyl group, and a cyclic alkenyl group such as a norbornenyl group and a cyclohexenyl group. , Vinyl group and allyl group are preferable.

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 copolymers, dimethylvinylsyloxy group-blocking dimethylsiloxane / diphenylsiloxane copolymers at both ends of the molecular chain.

（ｈは０〜１０の整数である。） In addition, examples other than siloxane include compounds represented by the following formulas, but are not limited thereto.

(H is an integer from 0 to 10.)

The component (B) can be used alone or in combination of two or more.

（式中、Ｒ^７は独立にメチル基又はフェニル基であり、Ｒ^８は独立に置換または非置換の炭素原子数１〜１２の１価炭化水素基であり、ｆは０〜５０の整数であり、ｇは０〜１００の整数である。ただし、ｆが０のときＲ^７はフェニル基であり、かつ、ｇは１〜１００の整数である。括弧が付されたシロキサン単位の配列は任意であってよい。） The component (B) is preferably a linear organopolysiloxane represented by the following formula (4).

(In the formula, R ⁷ is an independently methyl or phenyl group, R ⁸ is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and f is an integer of 0 to 50. Yes, g is an integer from 0 to 100, where when f is 0, R ⁷ is a phenyl group and g is an integer from 1 to 100. The parenthesized sequence of siloxane units is arbitrary. May be.)

Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms represented by R ⁸ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group and a neopentyl group. Alkyl group such as hexyl group and 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, xsilyl group and naphthyl group, benzyl group, Examples thereof include aralkyl groups such as a phenylethyl group and a phenylpropyl group, and those in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine and chlorine. Among them, the number of carbon atoms The alkyl group, phenyl group, and vinyl group of 1 to 6 are preferable, and the methyl group is particularly preferable.

In the above formula (4), f can be an integer of 0 to 50, preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 4. g can be an integer of 0 to 100, preferably 0 to 50, more preferably 0 to 10, and even more preferably 0 to 4.

The organopolysiloxane represented by the formula (4) is aliphatic unsaturated, for example, after hydrolysis / condensation of a bifunctional silane such as dichlorodiphenylsilane or dialkoxydiphenylsilane, or at the same time as hydrolysis / condensation. It is obtained by blocking the end with a siloxane unit containing a group.

The amount of the component (B) is preferably such that the molar ratio of SiH groups (SiH groups / aliphatic unsaturated groups) to the aliphatic unsaturated group in the composition is 0.5 or more and 5 or less, more preferably. It is an amount of 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.

[Component (C)]
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 amount of the component (C) blended in the curable composition of the present invention may be an effective amount as a catalyst and is not particularly limited, but is preferably a platinum group metal atom with respect to the total mass of the composition. It is preferable to add an amount of 1 to 500 ppm, more preferably 1 to 100 ppm, still more preferably 2 to 12 ppm. By setting the blending amount within the above range, the time required for the curing reaction becomes appropriate, and the coloring of the cured product can be suppressed.

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

Known antioxidants 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 components (A) and (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 characteristics 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 improver include a silane coupling agent, an oligomer thereof, and a polysiloxane having a reactive group similar to that of the silane coupling agent.

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 improver 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). is there. With such a blending amount, the thermosetting silicone composition of the present invention and the cured product thereof are effectively improved in adhesiveness to the base material, and coloring is unlikely to occur.

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

[Other]
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 light stabilizer, 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.

When the composition of the present invention is used as a sealing material, a silane coupling agent may be added to improve the adhesiveness to the base material, or a plasticizer may be added to prevent cracks. Good.

[Cured 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 and toughness, and is excellent in light transmission in a short wavelength region. 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.

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. Then, 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 curable composition of the present invention (additional curable silicone composition) described above 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 has a hardness of 30 or more specified in JIS or ASTM D 2240 by curing. It is preferable that it forms a cured product of.

Since the curable composition of the present invention forms a cured product having high hardness and toughness and excellent light transmission in a short wavelength region, the semiconductor device of the present invention using this curable composition is reliable. It will be excellent.

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. The GPC (gel permeation chromatography) measurement was carried out using HLC-8320GPC manufactured by Tosoh Corporation, using tetrahydrofuran (THF) as the mobile phase, in terms of polystyrene.

[Synthesis Example 1] Preparation of component (A-1) 1,4-bis (dimethylsilyl) benzene (Hokuko Chemical Industry Co., Ltd.) in a 1 L four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer. 660 g (3.4 mol) of 5% Pt carbon powder (manufactured by NECMCAT Co., Ltd.) of 0.30 g was added, and the mixture was heated to 85 ° C. using an oil bath. 47 g (0.2 mol) of hexavinyldisiloxane (manufactured by Hokuko Chemical Industry Co., Ltd.) was added dropwise thereto. After completion of the dropping, the mixture was stirred at 90 to 100 ° C. for 3 hours. After stirring, the temperature was returned to 25 ° C., and the peak disappearance of the vinyl group was confirmed by ^{1 H-NMR spectrum measurement.} After adding 11 g of activated carbon and stirring for 1 hour, Pt carbon powder and activated carbon are separated by filtration, and excess 1,4-bis (dimethylsilyl) benzene is removed by concentration under reduced pressure to remove 240 g (colorless) component (A-1). Transparent, viscosity at 23 ° C.: 49 Pa · s) was obtained.

As a result of analyzing the reaction product by GPC (FIG. 2) or the like, the obtained reaction product is a mixture of compounds having structures represented by the following formulas (a1) to (e1), and the ratio of each compound. Was (a1) :( b1) :( c1) :( d1) :( e1) = 40: 20: 14: 13: 8 (mol%). The content ratio of SiH groups in the whole mixture was 0.0038 mol / g.

（ｎ＝５〜１０、破線は結合手を表す。）

(N = 5-10, broken line represents a bond)

[Synthesis Example 2] Preparation of component (A-2) 1,4-bis (dimethylsilyl) benzene (Hokuko Chemical Industry Co., Ltd.) in a 1 L four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer. 496 g (2.6 mol) of 5% Pt carbon powder (manufactured by NECMCAT Co., Ltd.) (0.24 g) was added, and the mixture was heated to 85 ° C. using an oil bath. 78 g (0.3 mol) of 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane (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., and the peak disappearance of the vinyl group was confirmed by ^{1 H-NMR spectrum measurement.} After adding 9 g of activated carbon and stirring for 1 hour, Pt carbon powder and activated carbon are separated by filtration, and excess 1,4-bis (dimethylsilyl) benzene is removed by concentration to remove 220 g (colorless and transparent) component (A-2). , Viscosity at 23 ° C.: 2.9 Pa · s) was obtained.

As a result of analyzing the reaction product by GPC (FIG. 3) or the like, the obtained reaction product is a mixture of compounds having structures represented by the following formulas (a2) to (d2), and the ratio of each compound. Was (a2) :( b2) :( c2) :( d2) = 57: 24: 10: 7 (mol%). The content ratio of SiH groups in the whole mixture was 0.0032 mol / g.

（ｎ＝４〜１０、破線は結合手を表す。）

(N = 4 to 10, the broken line represents the bond.)

[Synthesis Example 3] Preparation of component (A-3) 1,4-bis (dimethylsilyl) benzene (Hokuko Chemical Industry Co., Ltd.) in a 500 mL four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer. 175 g (0.9 mol) of 5% Pt carbon powder (manufactured by NECMCAT Co., Ltd.) (0.11 g) was added, and the mixture was heated to 85 ° C. using an oil bath. 93 g (0.3 mol) of dimethyldiphenyldivinyldisiloxane (manufactured by Hokuko Chemical Industry 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., and the peak disappearance of the vinyl group was confirmed by ^{1 H-NMR spectrum measurement.} After adding 4.0 g of activated carbon and stirring for 1 hour, Pt carbon powder and activated carbon are separated by filtration, and excess 1,4-bis (dimethylsilyl) benzene is removed by concentration to remove 182 g (A-3) component (A-3). Colorless and transparent, viscosity at 23 ° C.: 1.5 Pa · s) was obtained.

As a result of analyzing the reaction product by GPC (FIG. 4) or the like, the obtained reaction product is a mixture of compounds having structures represented by the following formulas (a3) to (d3), and the ratio of each compound. Was (a3) :( b3) :( c3) :( d3) = 43: 25: 15: 6 (mol%). The content ratio of SiH groups in the whole mixture was 0.0022 mol / g.

（ｎ＝４〜１０、破線は結合手を表す。）

(N = 4 to 10, the broken line represents the bond.)

[Examples 1 to 6, Comparative Examples 1 and 2]
The following components are mixed at the composition ratios shown in Table 1 (numerical values represent parts by mass), and the molar ratio of SiH groups to alkenyl groups in the composition ([SiH groups] / [alkenyl groups]) is 1.1. The curable composition was prepared so as to be. In the example below, the symbols representing the constituent units of the organopolysiloxane are as follows.
M ^Vi : (CH ₂ = CH) (CH ₃ ) ₂ 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

(A) Component (A-1) Addition reaction product obtained in the above Synthesis Example 1 (A-2) Addition reaction product obtained in the above Synthesis Example 2 (A-3) Addition reaction product obtained in the above Synthesis Example 3 Reactant comparison component (A-4) Branched organopolysiloxane represented by ^MH ₃ T ^Φ ₁

(B) Component (B-1) ^{Linear organopolysiloxane represented by M Vi} ₂ D ^2Φ ₁ (B-2) Bisphenol diallyl ether (manufactured by Hokuko Chemical Industry Co., Ltd .: product name "BPA-AE")

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

[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. In Comparative Example 2, the cross-linking agent and the main agent (component (B)) were incompatible with each other, and a cured product could not be obtained.

(1) Hardness The curable composition was poured into a mold assembled from a glass plate and cured at 150 ° C. for 4 hours to obtain a cured product. Table 2 shows the results of measuring the hardness (Shore D or Type A) of each cured product at 23 ° C. according to ASTM D 2240. The ShoreD hardness was measured with a cured product having a thickness of 2 mm, and D was added before the value. The Type A hardness was measured with a cured product having a thickness of 6 mm, and A was 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 2.

(3) Evaluation of toughness Similar to the above hardness measurement, a cured product having a thickness of 2 mm was prepared in Examples 1, 3 and 5 and Comparative Example 1, and a cured product having a thickness of 0.3 mm was prepared in Examples 2, 4 and 6. did. The state when each cured product was bent at a right angle at 23 ° C. along a metal rod having a diameter of 1 mm was evaluated as 〇 (bending without cracking) and × (breaking).

(4) 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: 2003. The measurement results are shown in Table 2. The hardness of the cured products of Examples 2, 4 and 6 was very high, and the elongation and tensile strength could not be measured.

As shown in Tables 1 and 2, the curable composition of the present invention has good compatibility between the components (A) and (B), and is a cured product having excellent hardness, toughness and transparency. Gave.

^{On the other hand, a composition using an organopolysiloxane represented by MH} ₃ T ^Φ ₁ instead of the component (A) of the present invention is inferior in toughness, elongation and tensile strength (Comparative Example 1) and does not have siloxane (Comparative Example 1). B) The compatibility when the component was used was insufficient (Comparative Example 2).

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

[Synthesis Example 1] Preparation of component (A-1) 1,4-bis (dimethylsilyl) benzene (Hokuko Chemical Industry Co., Ltd.) in a 1 L four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer. 660 g (3.4 mol) of 5% Pt carbon powder (manufactured by NECMCAT Co., Ltd.) of 0.30 g was added, and the mixture was heated to 85 ° C. using an oil bath. 47 g (0.2 mol) of hexavinyldisiloxane (manufactured by Hokuko Chemical Industry Co., Ltd.) was added dropwise thereto. After completion of the dropping, the mixture was stirred at 90 to 100 ° C. for 3 hours. Back to撹拌終After the completion 25 ° ^C., was confirmed peak disappearance of the vinyl group in 1 H-NMR spectrum measurement. After adding 11 g of activated carbon and stirring for 1 hour, Pt carbon powder and activated carbon are separated by filtration, and excess 1,4-bis (dimethylsilyl) benzene is removed by concentration under reduced pressure to remove 240 g (colorless) component (A-1). Transparent, viscosity at 23 ° C.: 49 Pa · s) was obtained.

[Synthesis Example 2] Preparation of component (A-2) 1,4-bis (dimethylsilyl) benzene (Hokuko Chemical Industry Co., Ltd.) in a 1 L four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer. 496 g (2.6 mol) of 5% Pt carbon powder (manufactured by NECMCAT Co., Ltd.) (0.24 g) was added, and the mixture was heated to 85 ° C. using an oil bath. 78 g (0.3 mol) of 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane (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. Back to撹拌終After the completion 25 ° ^C., was confirmed peak disappearance of the vinyl group in 1 H-NMR spectrum measurement. After adding 9 g of activated carbon and stirring for 1 hour, Pt carbon powder and activated carbon are separated by filtration, and excess 1,4-bis (dimethylsilyl) benzene is removed by concentration to remove 220 g (colorless and transparent) component (A-2). , Viscosity at 23 ° C .: 2.9 Pa · s) was obtained.

[Synthesis Example 3] Preparation of component (A-3) 1,4-bis (dimethylsilyl) benzene (Hokuko Chemical Industry Co., Ltd.) in a 500 mL four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer. 175 g (0.9 mol) of 5% Pt carbon powder (manufactured by NECMCAT Co., Ltd.) (0.11 g) was added, and the mixture was heated to 85 ° C. using an oil bath. 93 g (0.3 mol) of dimethyldiphenyldivinyldisiloxane (manufactured by Hokuko Chemical Industry Co., Ltd.) was added dropwise thereto. After completion of the dropping, the mixture was stirred at 90 to 100 ° C. for 5 hours. Back to撹拌終After the completion 25 ° ^C., was confirmed peak disappearance of the vinyl group in 1 H-NMR spectrum measurement. After adding 4.0 g of activated carbon and stirring for 1 hour, Pt carbon powder and activated carbon are separated by filtration, and excess 1,4-bis (dimethylsilyl) benzene is removed by concentration to remove 182 g (A-3) component (A-3). Colorless and transparent, viscosity at 23 ° C.: 1.5 Pa · s) was obtained.

Claims (7)

A curable composition comprising the following (A), (B) and (C).
(A) Addition reaction between an organosilicon compound represented by the following formula (1) and at least one of a linear siloxane represented by the following formula (2) and a cyclic siloxane represented by the following formula (3). An addition reaction product having two or more SiH groups in one molecule.

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

(In the formula, R ² and R ⁴ are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R ³ is independently single-bonded or unsubstituted carbon atoms 1 to 4-2. It is a valent hydrocarbon group. A is an integer of 1 to 3 and b is an integer of 0 to 100.)

(In the formula, R ³ is as described above, R ⁵ is an independently methyl or phenyl group, and R ⁶ is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. , C is 1 or 2, d is an integer of 2 to 10, e is an integer of 0 to 10. The sequence of siloxane units may be arbitrary.)
(B) A compound having two or more alkenyl groups in one molecule,
(C) Hydrosilylation reaction catalyst The curable composition according to claim 1, wherein R ¹ is a phenylene group, R ² , R ⁴ , and R ⁶ are independently methyl or phenyl groups, and R ^{3 is a single bond.} The curable composition according to claim 1 or 2, wherein the (B) is a compound represented by the following formula (4).

(In the formula, R ⁷ is an independently methyl or phenyl group, R ⁸ is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and f is an integer of 0 to 50. Yes, g is an integer from 0 to 100, where when f is 0, R ⁷ is a phenyl group and g is an integer from 1 to 100. The parenthesized sequence of siloxane units is arbitrary. May be.) A cured product obtained by curing the curable composition according to any one of claims 1 to 3. The cured product according to claim 4, wherein the light transmittance (25 ° C.) at a wavelength of 400 nm at a thickness of 2 mm is 80% or more. The cured product according to claim 4 or 5, wherein the hardness specified in ASTM D 2240 is 30 or more in the durometer A. A semiconductor device characterized in that the semiconductor element is coated with the cured product according to any one of claims 4 to 6.

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