JP7401247B2 - Curable composition, cured product thereof, and semiconductor device - Google Patents

Description

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

BACKGROUND OF THE INVENTION Conventionally, epoxy resins have generally been used as materials for optical devices or optical components, particularly as encapsulating materials for light emitting diode (LED) elements. Regarding silicone resin, attempts have been made to use it as a molding member for LED elements (Patent Documents 1 and 2) and as a color filter material (Patent Document 3), but there are few actual examples of its use. .

In recent years, as white LEDs have attracted attention, issues such as yellowing of the epoxy sealant due to ultraviolet rays, etc., which had not been a problem in the past, and the occurrence of cracks due to the increase in heat generation due to miniaturization have become problems, and these issues are being addressed. is an urgent need. As a countermeasure to these problems, the use of cured silicone resins having a large amount of phenyl groups in the molecule is being considered. However, such compositions have low toughness and are prone to cracking.

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

The present invention was made to solve the above problems, and an object of the present invention is to provide a curable composition that provides a cured product that has high hardness and toughness and excellent light transmittance in the 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 a single bond or unsubstituted 2 to 4 carbon atoms. It is a valence 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 independently a methyl group or a phenyl group, and R ⁶ is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. , c is 1 or 2, d is an integer from 2 to 10, and e is an integer from 0 to 10. The arrangement of the 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 that provides a cured product with high hardness and toughness and excellent light transmittance in the 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 a methyl group or a phenyl group, 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。） In the curable composition of the present invention, the above (B) is preferably a compound represented by the following formula (4).

(In the formula, R ⁷ is independently a methyl group or phenyl group, R ⁸ is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and f is an integer of 0 to 50. , and g is an integer from 0 to 100. However, when f is 0, R ⁷ is a phenyl group, and g is an integer from 1 to 100. The 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 and toughness, and is excellent in light transmittance in a short wavelength region.

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

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

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

Such a cured product can be made less susceptible to external stress and can suppress the adhesion of dust and the like as much as possible.

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

The semiconductor device of the present invention has excellent durability because the hardened material used has high hardness and toughness. Furthermore, since it has excellent light transmittance in a short wavelength region, it is also useful as a semiconductor device that requires light transmittance, such as a light emitting diode element.

The curable composition of the present invention has high hardness and toughness, and can provide a cured product with excellent light transmittance in a short wavelength region. Therefore, it can be suitably used for purposes such as protecting, sealing or adhering light emitting diode elements, changing or adjusting wavelength, or as lenses. Therefore, the cured product obtained from the curable composition of the present invention can be suitably used for purposes such as protecting, sealing or adhering light emitting diode elements, changing or adjusting the wavelength, or as lenses. It is also useful as a lens material, a sealing material for optical devices or optical components, a material for various optical components such as a display material, an insulating material for electronic devices or electronic components, and a coating material. Furthermore, the semiconductor device of the present invention using such a curable composition has excellent reliability.

FIG. 1 is a schematic cross-sectional view showing an example of an optical semiconductor device using a cured product of the curable composition of the present invention. 1 is a GPC chart of addition reaction product (A-1) obtained in Synthesis Example 1. 1 is a GPC chart of addition reaction product (A-2) obtained in Synthesis Example 2. 1 is a GPC chart of addition reaction product (A-3) obtained in Synthesis Example 3.

As mentioned above, there has been a need to develop a curable composition that provides a cured product with high hardness and toughness and excellent light transmittance in the short wavelength region.

As a result of extensive studies on the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a curable composition containing specific components, 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 a single bond or unsubstituted 2 to 4 carbon atoms. It is a valence 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 independently a methyl group or a phenyl group, and R ⁶ is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. , c is 1 or 2, d is an integer from 2 to 10, and e is an integer from 0 to 10. The arrangement of the 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 explained in detail, but the present invention is not limited thereto.

[Curable composition]
[(A) Component]
Component (A) in the curable composition of the present invention functions as a crosslinking agent that causes a hydrosilylation reaction with component (B) described below.

（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。） Component (A) in the curable composition of the present invention includes an organosilicon compound represented by the following formula (1), a linear siloxane represented by the following formula (2), and a linear siloxane represented by the following formula (3). It is an addition reaction product with at least one of the cyclic siloxanes 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 a single bond or unsubstituted 2 to 4 carbon atoms. It is a valence 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 independently a methyl group or a phenyl group, and R ⁶ is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. , c is 1 or 2, d is an integer from 2 to 10, and e is an integer from 0 to 10. The arrangement of the 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. When d is less than 2, the function of component (A) as a crosslinking agent is insufficient, and when d exceeds 10, the cured product may become brittle and have poor toughness. e is an integer from 0 to 10, preferably from 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 methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, and cyclohexylene group. , alkylene groups such as n-octylene groups, arylene groups such as phenylene groups, naphthylene groups, etc., and those in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, chlorine, etc. As R ¹ , a phenylene group is particularly preferred.

Monovalent hydrocarbon groups having 1 to 12 carbon atoms represented by R ² , R ⁴ and R ⁶ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, Alkyl groups such as pentyl group, neopentyl group, hexyl group, octyl group, cycloalkyl group such as cyclohexyl group, alkenyl group such as vinyl group, allyl group, propenyl group, phenyl group, tolyl group, xylyl group, naphthyl group, etc. Examples include aralkyl groups such as aryl groups, benzyl groups, phenylethyl groups, and phenylpropyl groups, 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. , methyl or phenyl groups are preferred.

Examples of the unsubstituted divalent hydrocarbon group having 1 to 4 carbon atoms represented by R ³ include alkylene groups such as methylene group, ethylene group, n-propylene group, and 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. A single bond is particularly preferred as ^R3 .

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

Preferred specific examples of the linear siloxane represented by the above formula (2) are shown below, but the invention is not limited thereto. Furthermore, the compounds 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。） Preferred specific examples of the cyclic siloxane represented by the above formula (3) are shown below, but the invention is not limited thereto. Furthermore, the compounds 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). Preferred examples of component (A) include compounds having a structural unit ratio represented by the following formula.

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

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

[Preparation of component (A)]
Component (A) in the curable composition of the present invention is based on 1 mole of alkenyl groups 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 mole and less than 10 moles, more preferably more than 1.5 moles and less than 5 moles, and hydrosilylated in the presence of both. It can be obtained by carrying out a reaction.

In component (A), unreacted alkenyl groups 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. , it is preferred that all alkenyl groups undergo a hydrosilylation reaction.

As the catalyst used in the hydrosilylation reaction, known catalysts can be used. For example, carbon powder supporting platinum metal, platinum black, platinum chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohol, complexes of chloroplatinic acid and olefins, platinum bisacetoacetate, etc. Platinum-based catalysts include platinum group metal catalysts such as palladium-based catalysts and rhodium-based catalysts. Further, addition reaction conditions, purification conditions, use of solvent, etc. are not particularly limited, and known methods may be used.

Component (A) in the curable composition of the present invention may consist of one type of compound or a combination (mixture) of two or more types of compounds.

The presence of two or more SiH groups in one molecule of the compound constituting component (A) can be confirmed by selecting an appropriate measuring means. (A) When there are two or more types of compounds constituting the component, SiH groups can be added to one molecule for each compound by selecting an appropriate combination of measurement methods (for example, ¹ H-NMR and GPC, etc.). It can be confirmed that there are two or more.

[(B) Component]
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 linear alkenyl groups such as vinyl group, allyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, and octenyl group, and cyclic alkenyl groups such as norbornenyl group and cyclohexenyl group. , vinyl group, and allyl group are preferred.

Specific examples of component (B) include, but are not limited to, dimethylsiloxane/methylvinylsiloxane copolymer with trimethylsiloxy groups endblocked at both molecular chain ends, dimethylsiloxane/diphenylsiloxane/methylvinylsiloxane endblocked with trimethylsiloxy groups at both molecular chain ends. Copolymers, dimethylsiloxane/diphenylsiloxane copolymers with dimethylvinylsiloxy groups endblocked at both molecular chain ends, and the like.

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

(h is an integer from 0 to 10.)

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。） Component (B) is preferably a linear organopolysiloxane represented by the following formula (4).

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

The monovalent hydrocarbon group having 1 to 12 carbon atoms represented by R ⁸ includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, Alkyl groups such as hexyl groups and octyl groups, cycloalkyl groups such as cyclohexyl groups, alkenyl groups such as vinyl groups, allyl groups, and propenyl groups, aryl groups such as phenyl groups, tolyl groups, xylyl groups, and naphthyl groups, benzyl groups, Examples include aralkyl groups such as phenylethyl groups and phenylpropyl groups, and those in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, chlorine, etc. Among them, the number of carbon atoms 1 to 6 alkyl groups, phenyl groups, and vinyl groups are preferred, and methyl groups are particularly preferred.

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 from 0 to 100, preferably from 0 to 50, more preferably from 0 to 10, even more preferably from 0 to 4.

The organopolysiloxane represented by formula (4) can be produced by hydrolyzing and condensing a bifunctional silane such as dichlorodiphenylsilane or dialkoxydiphenylsilane, or simultaneously with aliphatic unsaturation. It is obtained by capping the ends with group-containing siloxane units.

The blending amount of component (B) is preferably such that the molar ratio of SiH groups to aliphatic unsaturated groups in the composition (SiH groups/aliphatic unsaturated groups) is 0.5 or more and 5 or less, more preferably The amount is 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]
The hydrosilylation reaction catalyst which is component (C) of the present invention can be the same as that used in the preparation of component (A) above.

The amount of component (C) blended into the curable composition of the present invention is not particularly limited as long as it is an effective amount as a catalyst, but it is preferably in terms of platinum group metal atoms based on the mass of the entire composition. It is preferable to blend the amount in 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 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 optionally contain components such as an antioxidant, an inorganic filler, and an adhesion improver.

[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, and this may be caused by oxygen in the atmosphere. Oxidation may cause the cured product to become discolored. Therefore, such coloring can be prevented by incorporating an antioxidant into the curable composition of the present invention, if necessary.

As the antioxidant, known antioxidants can be used, such as 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-amylhydroquinone, and 2,5-di-t-amylhydroquinone. 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 using this antioxidant, its amount is not particularly limited, but it is usually 1 to 10,000 ppm, especially 10 to 1 ppm, based on the total mass of components (A) and (B). ,000 ppm is preferable. By incorporating the amount within the above range, the antioxidant ability is fully exhibited, and a cured product with excellent optical properties without coloration, cloudiness, oxidative deterioration, etc. can be obtained.

[Inorganic filler]
Nanosilica, Inorganic fillers such as fused silica, crystalline silica, titanium oxide, nano-alumina, and alumina may be added.

[Adhesion improver]
The curable composition of the present invention may contain an adhesion improver. Examples of the adhesion improver include a silane coupling agent, an oligomer thereof, and a polysiloxane having the same reactive group as the silane coupling agent.

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

When using an adhesion improver, the blending amount is preferably 1 to 30 parts by mass, more preferably 1 to 10 parts by mass, based on the total of 100 parts by mass of components (A) and (B). be. With such a blending amount, the thermosetting silicone composition of the present invention and its cured product effectively improve the adhesion to the substrate, and are less likely to be colored.

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

[others]
Further, in order to ensure pot life, addition reaction control agents such as 1-ethynylcyclohexanol and 3,5-dimethyl-1-hexyn-3-ol can be added.

Furthermore, it is also possible to use a light stabilizer to impart resistance to photodeterioration caused by light energy such as sunlight and fluorescent lamps. As this light stabilizer, a hindered amine stabilizer that captures radicals generated by photooxidative 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.

Furthermore, when the composition of the present invention is used as a sealing material, a silane coupling agent may be added to improve adhesion to the base material, or a plasticizer may be added to prevent cracking. 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 excellent light transmittance in a short wavelength region. The curing conditions for the curable composition of the present invention are not particularly limited, but preferably conditions are 60 to 180°C and 5 to 180 minutes.

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

The cured product of the present invention having such optical properties can be suitably used for protection, sealing or adhesion of light emitting diode elements, wavelength change or adjustment, lenses, etc., as well as lens materials, optical devices or optical The material is useful as a sealing material for components, a material for various optical components such as a display material, an insulating material for electronic devices or electronic components, and even 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-mentioned curable composition.

Hereinafter, with reference to FIG. 1, 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, but the present invention is limited thereto. It's not a thing.

FIG. 1 is a schematic cross-sectional view showing an example of a semiconductor device of the present invention. In the semiconductor device 1 of the present invention, a semiconductor chip 4 is die-bonded onto a package 3 on which a silver-plated substrate 2 is formed, and this semiconductor chip 4 is wire-bonded with 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 semiconductor chip 4 is coated by applying the above-described curable composition of the present invention (addition-curable silicone composition) and curing the curable composition by heating. In addition, it may be cured by a known curing method under other known curing conditions.

In this case, from the viewpoint of making it less susceptible to external stress and minimizing the adhesion of dust, etc., the above-mentioned curable composition has a hardness of 30 or more in durometer A as specified in JIS or ASTM D 2240 by curing. It is preferable that the cured product is formed.

The curable composition of the present invention has high hardness and toughness, and forms a cured product with excellent light transmittance in the short wavelength region. Therefore, the semiconductor device of the present invention using this curable composition has high reliability. It will be excellent.

Hereinafter, the present invention will be specifically explained using Examples and Comparative Examples, but the present invention is not limited thereto.

Furthermore, in the examples, AVANCE III manufactured by Bruker Biospin was used for ¹ H-NMR measurement. GPC (gel permeation chromatography) measurements were performed using HLC-8320GPC manufactured by Tosoh Corporation, using tetrahydrofuran (THF) as a mobile phase, and using polystyrene standards.

[Synthesis Example 1] Preparation of component (A-1) In a 1L four-necked flask equipped with a stirrer, cooling tube, dropping funnel, and thermometer, 1,4-bis(dimethylsilyl)benzene (Hokuko Chemical Industry Co., Ltd.) 660 g (3.4 mol) of 5% Pt carbon powder (manufactured by N.E. Chemcat Co., Ltd.) and 0.30 g of 5% Pt carbon powder (manufactured by N.E. Chemcat Co., Ltd.) were added, and the mixture was heated to 85° C. using an oil bath. 47 g (0.2 mol) of hexavinyldisiloxane (manufactured by Hokko Chemical Industry Co., Ltd.) was added dropwise to this. After the dropwise addition was completed, the mixture was stirred at 90 to 100°C for 3 hours. After the stirring was completed, the temperature was returned to 25°C, and disappearance of the vinyl group peak 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 were filtered out, and excess 1,4-bis(dimethylsilyl)benzene was removed by vacuum concentration, resulting in 240 g of component (A-1) (colorless). It was transparent and had a viscosity of 49 Pa·s at 23°C.

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

（ｎ＝５～１０、破線は結合手を表す。）

(n=5 to 10, the dashed line represents the bond.)

[Synthesis Example 2] Preparation of component (A-2) In a 1 L four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel, and a thermometer, 1,4-bis(dimethylsilyl)benzene (Hokuko Chemical Industry Co., Ltd.) was added. 496 g (2.6 mol) of 5% Pt carbon powder (manufactured by N.E. Chemcat Co., Ltd.) and 0.24 g of 5% Pt carbon powder (manufactured by N.E. Chemcat Co., Ltd.) were added, and the mixture was heated to 85° C. using an oil bath. To this, 78 g (0.3 mol) of 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise. After the addition was completed, the mixture was stirred at 90 to 100°C for 5 hours. After the stirring was completed, the temperature was returned to 25°C, and disappearance of the vinyl group peak was confirmed by ¹ H-NMR spectrum measurement. After adding 9g of activated carbon and stirring for 1 hour, Pt carbon powder and activated carbon were filtered out, and excess 1,4-bis(dimethylsilyl)benzene was removed by concentration, resulting in 220g of component (A-2) (colorless and transparent). , viscosity at 23°C: 2.9 Pa·s).

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

（ｎ＝４～１０、破線は結合手を表す。）

(n=4 to 10, the dashed line represents the bond.)

[Synthesis Example 3] Preparation of component (A-3) In a 500 mL four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel, and a thermometer, 1,4-bis(dimethylsilyl)benzene (Hokuko Chemical Industry Co., Ltd.) was added. 175 g (0.9 mol) of 5% Pt carbon powder (manufactured by N.E. Chemcat Co., Ltd.) and 0.11 g of 5% Pt carbon powder (manufactured by N.E. Chemcat Co., Ltd.) were 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 to this. After the addition was completed, the mixture was stirred at 90 to 100°C for 5 hours. After the stirring was completed, the temperature was returned to 25°C, and disappearance of the vinyl group peak 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 were filtered out, and excess 1,4-bis(dimethylsilyl)benzene was removed by concentration, resulting in 182 g of component (A-3) ( A colorless and transparent product with a viscosity of 1.5 Pa·s at 23° C. was obtained.

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

（ｎ＝４～１０、破線は結合手を表す。）

(n=4 to 10, the dashed line represents the bond.)

[Examples 1 to 6, Comparative Examples 1 and 2]
The following components were mixed at the composition ratios shown in Table 1 (numbers represent parts by mass), and the molar ratio of SiH groups to alkenyl groups in the composition ([SiH groups]/[alkenyl groups]) was 1.1. A curable composition was prepared as follows. In the examples below, the symbols representing the structural units of organopolysiloxane are as follows.
M ^Vi :( _CH2 =CH)( _CH3 )2SiO1 _{/ 2}
M ^H :H( _CH3 ) _{2SiO1 /2}
^D2Φ : _{( C6H5} )2SiO2 _{/ 2}
^TΦ : ( _C6H5 )SiO3 _{/ 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 M ^H ₃ T ^Φ ₁

(B) Component (B-1) Linear organopolysiloxane represented by M ^Vi ₂ D ^2Φ ₁ (B-2) Bisphenol A 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]
Regarding the curable compositions obtained in the above Examples and Comparative Examples, the performance of the cured products was evaluated according to the following method. In addition, in Comparative Example 2, the crosslinking agent and the main ingredient (component (B)) were not compatible, and a cured product could not be obtained.

(1) Hardness A curable composition was poured into a mold made of glass plates, 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 in accordance with ASTM D 2240. The Shore D hardness was measured using a 2 mm thick cured product, and D was added before the value. Moreover, Type A hardness was measured using a 6 mm thick cured product, and A was added in front of the value.

(2) Light transmittance The 400 nm light transmittance of each cured product was measured using a spectrophotometer for a 2 mm thick cured product prepared in the same manner as the hardness measurement above. The measurement results are shown in Table 2.

(3) Toughness evaluation Similarly to the above hardness measurement, 2 mm thick cured products were created in Examples 1, 3, and 5 and Comparative Example 1, and 0.3 mm thick cured products were created in Examples 2, 4, and 6. did. The state of each cured product when bent at a right angle at 23° C. along a metal rod with a diameter of 1 mm was evaluated as 〇 (bends without cracking) and × (breaks).

(4) Elongation and tensile strength The elongation and tensile strength of each cured product were measured at 23°C in accordance with JIS-K-6249:2003 for 2 mm thick cured products prepared in the same manner as the hardness measurement above. The measurement results are shown in Table 2. The hardness of the cured products of Examples 2, 4, and 6 was so high that 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 components (A) and (B), and produces a cured product with excellent hardness, toughness, and transparency. Gave.

On the other hand, a composition using an organopolysiloxane represented by M ^H ₃ T ^Φ ₁ in place of component (A) of the present invention has poor toughness, elongation, and tensile strength (Comparative Example 1), and does not contain siloxane ( Compatibility was insufficient when component B) was used (Comparative Example 2).

Note that the present invention is not limited to the above embodiments. The above-mentioned embodiments are illustrative, and any embodiment that has substantially the same configuration as the technical idea stated in the claims of the present invention and has similar effects is the present invention. covered within 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 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) which has 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 a single bond or unsubstituted 2 to 4 carbon atoms. It is a valence 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 independently a methyl group or a phenyl group, and R ⁶ is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. , c is 1 or 2, d is an integer from 2 to 10, and e is an integer from 0 to 10. The arrangement of the siloxane units may be arbitrary.)
The organosilicon compound represented by the above formula (1) is 1,4-bis(dimethylsilyl)benzene, and the linear siloxane represented by the above formula (2) is hexavinyldisiloxane or dimethyl The addition reaction product (B) M is diphenyldivinyldisiloxane, and the cyclic siloxane represented by the above formula (3) is 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane. Linear organopolysiloxane represented by ^Vi ₂ D ^{2 Φ} ₁ (M ^Vi is (CH ₂ = CH) (CH ₃ ) ₂ SiO _1/2 , and D ^{2 Φ} is (C ₆ H ₅ ) ₂ SiO _2/2 ) or bisphenol A diallyl ether (C) Hydrosilylation reaction catalyst A cured product obtained by curing the curable composition according to claim 1. The cured product according to claim 2, having a light transmittance (25° C.) at a wavelength of 400 nm at a thickness of 2 mm of 80% or more. The cured product according to claim 2 or 3, wherein the hardness specified in ASTM D 2240 is 30 or more in terms of durometer A. A semiconductor device comprising a semiconductor element coated with the cured product according to any one of claims 2 to 4.

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