TWI854043B - Curable composition, cured product thereof, and semiconductor device - Google Patents

Abstract

The subject of the present invention is to provide a curable composition that imparts high hardness and toughness and excellent light transmittance in the short wavelength region to a cured product. The solution is a curable composition that contains the following (A), (B) and (C): (A) an addition reaction product of an organic silicon compound represented by formula (1) and at least one of the siloxanes represented by formula (2) and (3), and the addition reaction product is an addition reaction product having two or more SiH groups in one molecule ( ^R1 is a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms, ^R2 , ^R4 , and ^R6 are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, ^R3 is independently a single bond or unsubstituted divalent hydrocarbon group having 1 to 4 carbon atoms, ^R5 is independently a methyl group or a phenyl group, a is an integer of 1 to 3, b is an integer of 0 to 100, c is 1 or 2, d is an integer of 2 to 10, and e is an integer of 0 to 10; the arrangement of siloxane units is arbitrary); (B) a compound having two or more alkenyl groups in one molecule; (C) a catalyst for hydrosilylation reaction.

Description

Curable composition, cured product thereof, and semiconductor device

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

Conventionally, epoxy resins are generally used as materials for optical devices or optical parts, especially as sealing materials for light-emitting diode (LED) components. In addition, attempts have been made to use silicone resins as molding components for LED components (Patent Documents 1 and 2) or as color filter materials (Patent Document 3), but there are few actual examples of their use.

In recent years, white LEDs have attracted much attention. Yellowing of epoxy sealing materials due to ultraviolet rays, etc., which has not been a problem so far, and cracking due to increased heat generation due to miniaturization have become problems, and it is urgent to deal with them. The strategy for such a response is to explore the use of polysilicone resin cured products with a large number of phenyl groups in the molecule. However, such a composition has low toughness and is prone to cracking. [Prior technical literature] [Patent literature]

[Patent Document 1] Japanese Patent Publication No. 10-228249 [Patent Document 2] Japanese Patent Publication No. 10-242513 [Patent Document 3] Japanese Patent Publication No. 2000-123981

[The problem that the invention wants to solve]

The present invention is made to solve the above-mentioned problem, and its purpose is to provide a hardening composition that imparts high hardness and toughness and excellent light transmittance in the short-wavelength region to the hardened material. [Means for solving the problem]

In order to achieve the above-mentioned object, the present invention provides a curable composition comprising the following (A), (B) and (C). (A) An addition reaction product of an organic silicon 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), wherein the addition reaction product has two or more SiH groups in one molecule. (wherein, ^R1 is a substituted or unsubstituted divalent alkyl group having 1 to 12 carbon atoms); (wherein, R ² and R ⁴ are independently substituted or unsubstituted monovalent hydrocarbon groups with 1 to 12 carbon atoms, R ³ is independently a single bond or unsubstituted divalent hydrocarbon group with 1 to 4 carbon atoms; a is an integer from 1 to 3, and b is an integer from 0 to 100); (wherein, ^R3 is as described above, ^R5 is independently methyl or phenyl, ^R6 is 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, and e is an integer of 0 to 10; the arrangement of siloxane units may be arbitrary); (B) a compound having two or more alkenyl groups in one molecule; (C) a catalyst for a hydrosilylation reaction.

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

In the curable composition of the present invention, it is preferred 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.

The curable composition of the present invention is further preferably a compound represented by the following formula (4) in which (B) is mentioned above. (In the formula, ^R7 is independently a methyl group or a phenyl group, ^R8 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, f is an integer from 0 to 50, and g is an integer from 0 to 100. However, when f is 0, ^R7 is a phenyl group, and g is an integer from 1 to 100. The arrangement of the siloxane units in the brackets may be arbitrary).

Furthermore, the present invention provides a hardened product obtained by hardening the hardening composition.

The cured product of the present invention has high hardness and toughness and excellent light transmittance 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 400nm with a thickness of 2mm.

If the cured product has such a light transmittance, it can be suitably used for the protection, sealing or bonding of light-emitting diode elements, wavelength change or adjustment, or lens, etc. In addition, it is also useful as a lens material, a sealing material for optical devices or optical parts, a material for various optical parts such as a display material, an insulating material for electronic devices or electronic parts, and a coating material.

Furthermore, the hardness of the cured product of the present invention is preferably 30 or more when measured with a rubber durometer A as specified in ASTM D 2240.

Such a hardened material is less susceptible to external stress and can greatly suppress the adhesion of dust and the like.

Furthermore, the present invention provides a semiconductor device in which a semiconductor element is covered with the aforementioned hardened material.

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

The curable composition of the present invention can give a cured product with high hardness and toughness and excellent light transmittance in the short wavelength region. Therefore, it can be suitably used for the protection, sealing or bonding of LED elements, wavelength change or adjustment, or lens. Therefore, the cured product obtained from the curable composition of the present invention can be suitably used for the protection, sealing or bonding of LED elements, wavelength change or adjustment, or lens. In addition, it is also useful as a lens material, a sealing material for optical devices or optical parts, a display material, and other materials for various optical parts, an insulating material for electronic devices or electronic parts, and further a coating material. Furthermore, the semiconductor device of the present invention using such a curable composition becomes one with excellent reliability.

As described above, there is a demand for the development of a curable composition that imparts high hardness and toughness to a cured product and excellent light transmittance in a short wavelength region.

As a result of repeated and in-depth research on the above-mentioned subject, the inventors of the present invention have found that a hardening composition containing specific ingredients can solve the above-mentioned subject, and thus completed the present invention.

That is, the present invention is a curable composition comprising the following (A), (B) and (C). (A) An addition reaction product of an organic silicon 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), wherein the addition reaction product has two or more SiH groups in one molecule. (wherein, ^R1 is a substituted or unsubstituted divalent alkyl 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 divalent hydrocarbon group having 1 to 4 carbon atoms. a is an integer of 1 to 3, and b is an integer of 0 to 100). (wherein, ^R3 is as described above, ^R5 is independently methyl or phenyl, ^R6 is 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, and e is an integer of 0 to 10. The arrangement of siloxane units may be arbitrary); (B) a compound having two or more alkenyl groups in one molecule; (C) a catalyst for a hydrosilylation reaction.

The present invention is described in detail below, but the present invention is not limited thereto.

[Curing composition] [(A) component] The (A) component in the curable composition of the present invention functions as a crosslinking agent that triggers a silylation reaction with the (B) component described later.

The component (A) in the curable composition of the present invention is an addition reaction product of an organic silicon 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), and the addition reaction product has two or more SiH groups in one molecule. (wherein, ^R1 is a substituted or unsubstituted divalent alkyl 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 divalent hydrocarbon group having 1 to 4 carbon atoms. a is an integer of 1 to 3, and b is an integer of 0 to 100). (wherein, ^R3 is as described above, ^R5 is independently a methyl group or a phenyl group, ^R6 is independently a 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, and e is an integer of 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. When 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 of 0 to 10, preferably 0 to 2. When e exceeds 10, the hardness of the cured product may be insufficient.

The divalent alkyl group having 1 to 12 carbon atoms represented by ^R1 may be alkylene groups such as methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, cyclohexylene, and n-octylene; arylene groups such as phenylene and naphthylene, or groups in which a part or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, and chlorine. ^R1 is particularly preferably phenylene.

The monovalent alkyl group having 1 to 12 carbon atoms represented by ^R2 , ^R4 and ^R6 may be alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl and octyl; cycloalkyl groups such as cyclohexyl; alkenyl groups such as vinyl, allyl and propenyl; aryl groups such as phenyl, tolyl, xylyl and naphthyl; aralkyl groups such as benzyl, phenylethyl and phenylpropyl, or groups wherein a part or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine and chlorine, etc., preferably methyl or phenyl.

R ³ represents an unsubstituted divalent alkyl group having 1 to 4 carbon atoms, and examples thereof include alkylene groups such as methylene, ethylene, n-propylene, and n-butylene. When R ³ is a single bond, it represents an organic silicon compound in which a vinyl group is directly bonded to a silicon atom. R ³ is particularly preferably a single bond.

Suitable specific examples of the organosilicon compound represented by the above formula (1) are shown below, but are not limited thereto. The organosilicon compound represented by the above formula (1) may 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 are not limited thereto. The compound represented by the above formula (2) may be used alone or in combination of two or more.

Suitable specific examples of the cyclosiloxane represented by the above formula (3) are shown below, but are not limited thereto. The compound represented by the above formula (3) may be used alone or in combination of two or more. (In the formula, the arrangement of the siloxane units can be arbitrary).

Preferred examples of the component (A) of the addition reaction product of the organic silicon compound represented by the above formula (1) and at least one of the linear siloxane represented by the above formula (2) and the cyclic siloxane represented by the above formula (3) include compounds having a constituent unit ratio represented by the following formula. (In the formula, n is an integer between 1 and 10, and the dotted line represents the bonding site).

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

[Preparation of component (A)] The component (A) in the curable composition of the present invention can be obtained by mixing an excess amount of the compound represented by the above formula (1), preferably more than 1 mol and less than 10 mol, more preferably more than 1.5 mol and less than 5 mol, with respect to 1 mol of alkenyl contained in the linear siloxane represented by the above formula (2) and/or the cyclic siloxane represented by the above formula (3), and performing a silylation reaction in the presence of both.

In the component (A), there may be 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), and preferably all the alkenyl groups are subjected to the hydrosilylation reaction.

The catalyst used in the aforementioned hydrosilylation reaction can be a known catalyst. For example, platinum-based catalysts such as carbon powder carrying platinum metal, platinum black, platinum (IV) chloride, platinum chloride acid, reaction products of platinum chloride acid and monohydric alcohol, complexes of platinum chloride acid and olefins, and platinum diacetate; and platinum group metal catalysts such as palladium catalysts and rhodium catalysts can be listed. In addition, the addition reaction conditions, purification conditions, use of solvents, etc. are not particularly limited, and known methods can be used.

The component (A) in the curable composition of the present invention may include one compound or a combination (mixture) of two or more 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. When there are two or more compounds constituting component (A), the presence of two or more SiH groups in one molecule can be confirmed for each compound by selecting a combination of appropriate measuring means (e.g., ¹ H-NMR and GPC, etc.).

[Component (B)] 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 straight-chain alkenyl groups such as vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, etc.; and cyclic alkenyl groups such as norbornyl, cyclohexenyl, etc., preferably vinyl and allyl.

Specific examples of the component (B) are not particularly limited, and examples thereof include dimethylsiloxane/methylvinylsiloxane copolymers having trimethylsiloxy end-capped molecular chains, dimethylsiloxane/diphenylsiloxane/methylvinylsiloxane copolymers having trimethylsiloxy end-capped molecular chains, and dimethylsiloxane/diphenylsiloxane copolymers having dimethylvinylsiloxane end-capped molecular chains.

Furthermore, examples other than siloxane include compounds represented by the following formulas, but are not limited thereto. (h is an integer between 0 and 10).

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

The component (B) is preferably a linear organic polysiloxane represented by the following formula (4). (In the formula, ^R7 is independently a methyl group or a phenyl group, ^R8 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, f is an integer from 0 to 50, and g is an integer from 0 to 100. However, when f is 0, ^R7 is a phenyl group, and g is an integer from 1 to 100. The arrangement of the siloxane units in the brackets may be arbitrary).

The monovalent alkyl group having 1 to 12 carbon atoms represented by ^R8 may be alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, octyl, etc.; cycloalkyl groups such as cyclohexyl, etc.; alkenyl groups such as vinyl, allyl, propenyl, etc.; aryl groups such as phenyl, tolyl, xylyl, naphthyl, etc.; aralkyl groups such as benzyl, phenylethyl, phenylpropyl, etc., or groups in which a part or all of the hydrogen atoms are substituted with halogen atoms such as fluorine, bromine, chlorine, etc., among which alkyl groups having 1 to 6 carbon atoms, phenyl, and vinyl are preferred; and methyl is 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 of 0 to 100, preferably 0 to 50, more preferably 0 to 10, and even more preferably 0 to 4.

The organopolysiloxane represented by formula (4) can be obtained by, for example, hydrolyzing/condensing a difunctional silane such as dichlorodiphenylsilane or dialkoxydiphenylsilane, and then capping the terminal with a siloxane unit containing an aliphatic unsaturated group, or simultaneously with the hydrolysis/condensation.

The blending amount of the 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 to 5, more preferably 0.8 to 2. When the molar ratio (SiH groups/aliphatic unsaturated groups) is 0.5 to 5, the composition of the present invention can be sufficiently cured.

[Component (C)] The catalyst for the hydrosilylation reaction of the component (C) of the present invention may be the same as that used in the preparation of the component (A) above.

The amount of component (C) added to the curable composition of the present invention is not particularly limited as long as it is an effective amount as a catalyst. It is preferably added in an amount of 1 to 500 ppm, more preferably 1 to 100 ppm, and even more preferably 2 to 12 ppm in terms of platinum group metal atoms relative to the mass of the entire composition. By making the amount of addition 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 also contain antioxidants, inorganic fillers, adhesion enhancers, and other ingredients as needed.

[Antioxidant] In the hardened material of the hardening composition of the present invention, there are cases where the addition-reactive carbon-carbon double bonds in the above-mentioned component (B) remain unreacted, which may become the cause of coloration of the hardened material due to oxidation by oxygen in the atmosphere. Therefore, by adding an antioxidant to the hardening composition of the present invention as needed, such coloration can be prevented in advance.

As the antioxidant, 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'-butylenebis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), etc. These can be used alone or in combination of two or more.

Furthermore, when the antioxidant is used, the blending amount is not particularly limited. Generally, 1 to 10,000 ppm, particularly preferably 10 to 1,000 ppm, relative to the total mass of the above-mentioned components (A) and (B). By making the blending amount within the above-mentioned range, the antioxidant ability is fully exerted, and a cured product with excellent optical properties and no coloring, white turbidity, oxidation degradation, etc. can be obtained.

[Inorganic filler] In order to adjust the viscosity of the curable composition of the present invention or the hardness of the cured product obtained from the curable composition of the present invention, or to improve the strength, or to make the dispersion of the fluorescent body better, inorganic fillers such as nanosilica, fused silica, crystalline silica, titanium oxide, nanoalumina, and aluminum oxide may be added.

[Adhesion enhancer] An adhesion enhancer may also be blended into the curable composition of the present invention. Examples of adhesion enhancers include silane coupling agents or oligomers thereof, polysiloxanes having the same reactive groups as silane coupling agents, and the like.

Adhesion enhancers are any components mixed into the composition in order to enhance the adhesion of the curable composition of the present invention and its cured product to the substrate. Here, the substrate refers to metal materials such as gold, silver, copper, nickel, etc.; ceramic materials such as aluminum oxide, aluminum nitride, titanium oxide, etc.; polymer materials such as polysilicon resin, epoxy resin, etc. Adhesion enhancers can be used alone or in combination of two or more.

When the adhesion improver is used, the blending amount is preferably 1 to 30 parts by mass, more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the total of the above-mentioned components (A) and (B). If it is such a blending amount, the thermosetting polysilicone composition of the present invention and its cured product can effectively improve the adhesion to the substrate and is not easy to cause coloration.

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

[Others] In order to ensure pot life, addition reaction control agents such as 1-ethynylcyclohexanol and 3,5-dimethyl-1-hexyn-3-ol may be added.

Furthermore, in order to impart resistance to light degradation caused by light energy such as sunlight and fluorescent lamps, light stabilizers can also be used. The light stabilizer is preferably a hindered amine stabilizer that captures free radicals generated by photo-oxidative degradation. By using it in combination with an antioxidant, the antioxidant effect is further improved. Specific examples of light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 4-benzyl-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 mixed in order to improve adhesion to a substrate, and a plasticizer may be added in order to prevent cracking.

[Hardened product] Harden the curable composition of the present invention to form the cured product of the present invention. The cured product has high hardness and toughness and excellent light transmittance in the short wavelength region. There is no special restriction on the curing conditions of the curable composition of the present invention, and the conditions of 60~180℃ and 5~180 minutes are preferred.

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 and a thickness of 2 mm.

If the cured product of the present invention has such optical properties, it can be suitably used for the protection, sealing or bonding of light-emitting diode elements, wavelength change or adjustment, or lens, etc. In addition, it is also useful as a lens material, a sealing material for optical devices or optical parts, a material for various optical parts such as a display material, an insulating material for electronic devices or electronic parts, and a coating material.

[Semiconductor device] The present invention further provides a semiconductor device covered with a semiconductor element by a hardened material obtained from the above-mentioned hardening composition.

A semiconductor device using a cured product of the curable composition of the present invention (hereinafter also referred to as "the semiconductor device of the present invention") will be described below with reference to FIG. 1, but the present invention is not limited thereto.

FIG1 is a schematic cross-sectional view showing an example of a semiconductor device of the present invention. The semiconductor device 1 of the present invention is a semiconductor chip 4 bonded to a package 3 formed with a silver-plated substrate 2, and the semiconductor chip 4 is wire-bonded by bonding wires 5. Next, the semiconductor chip 4 is coated with a hardened material 6 of the hardening composition of the present invention. The coating of the semiconductor chip 4 is performed by applying the hardening composition of the present invention (addition-hardening polysilicone composition) and curing the hardening composition by heating. Furthermore, it can also be cured by a known curing method under other known curing conditions.

In this case, it is not easily affected by external stress, and from the viewpoint of maximally suppressing the adhesion of dust, etc., the above-mentioned curable composition is preferably a cured product having a hardness of 30 or more as measured by a rubber durometer A specified in JIS or ASTM D 2240.

The curable composition of the present invention forms a hardened material with high hardness and toughness and excellent light transmittance in the short wavelength region. Therefore, the semiconductor device of the present invention using the curable composition has excellent reliability. [Example]

The present invention is specifically described below using embodiments and comparative examples, but the present invention is not limited thereto.

In the examples, ¹ H-NMR measurement was performed using AVANCE III manufactured by Bruker BioSpin. GPC (gel permeation chromatography) measurement was performed using HLC-8320GPC manufactured by Tosoh Corporation and tetrahydrofuran (THF) as a mobile phase in terms of polystyrene.

[Synthesis Example 1] Preparation of component (A-1) In a 1L 4-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer, add 660g (3.4 mol) of 1,4-bis(dimethylsilyl)benzene (produced by Beixing Chemical Industry Co., Ltd.) and 0.30g of 5% Pt carbon powder (produced by NE CHEMCAT Co., Ltd.), and heat to 85°C using an oil bath. 47g (0.2 mol) of hexavinyldisiloxane (produced by Beixing Chemical Industry Co., Ltd.) was dripped into it. After the dripping was completed, the mixture was stirred at 90-100°C for 3 hours. After the stirring was completed, the mixture was returned to 25°C, and the peak of the vinyl group was confirmed to disappear by ¹ H-NMR spectroscopy. 11 g of activated carbon was added, and after stirring for 1 hour, the Pt carbon powder and activated carbon were filtered out, and the remaining 1,4-bis(dimethylsilyl)benzene was removed by concentration under reduced pressure to obtain 240 g of component (A-1) (colorless and transparent, viscosity at 23°C: 49 Pa･s).

The reaction product was analyzed by GPC (Figure 2) and the obtained reaction product was 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%). In addition, the content ratio of SiH groups in the entire mixture was 0.0038 mol/g.

(n=5~10, dotted lines indicate the binding sites).

[Synthesis Example 2] Preparation of component (A-2) In a 1L four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer, 496g (2.6 mol) of 1,4-bis(dimethylsilyl)benzene (produced by Hokko Chemical Industry Co., Ltd.) and 0.24g of 5% Pt carbon powder (produced by NE CHEMCAT Co., Ltd.) were added, and heated to 85°C using an oil bath. 78g (0.3 mol) of 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane (produced by Shin-Etsu Chemical Co., Ltd.) was dripped into the mixture. After the dripping was completed, the mixture was stirred at 90-100°C for 5 hours. After the stirring was completed, the mixture was returned to 25°C, and the peak of the vinyl group was confirmed to disappear by ¹ H-NMR spectroscopy. 9 g of activated carbon was added and stirred for 1 hour, then the Pt carbon powder and activated carbon were filtered out and the remaining 1,4-bis(dimethylsilyl)benzene was removed by concentration to obtain 220 g of component (A-2) (colorless and transparent, viscosity at 23°C: 2.9 Pa･s).

The reaction product was analyzed by GPC (Figure 3) and the obtained reaction product was 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%). In addition, the content ratio of SiH groups in the entire mixture was 0.0032 mol/g.

(n=4~10, dotted lines indicate the bonding sites).

[Synthesis Example 3] Preparation of component (A-3) In a 500 mL 4-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer, 175 g (0.9 mol) of 1,4-bis(dimethylsilyl)benzene (produced by Beixing Chemical Industry Co., Ltd.) and 0.11 g of 5% Pt carbon powder (produced by NE CHEMCAT Co., Ltd.) were added, and heated to 85°C using an oil bath. 93 g (0.3 mol) of dimethyldiphenyldivinyldisiloxane (produced by Beixing Chemical Industry Co., Ltd.) was dripped into the mixture. After the dripping was completed, the mixture was stirred at 90-100°C for 5 hours. After the stirring was completed, the mixture was returned to 25°C, and the peak of the vinyl group was confirmed to disappear by ¹ H-NMR spectroscopy. 4.0 g of activated carbon was added and stirred for 1 hour, then the Pt carbon powder and activated carbon were filtered out, and the remaining 1,4-bis(dimethylsilyl)benzene was removed by concentration to obtain 182 g of component (A-3) (colorless and transparent, viscosity at 23°C: 1.5 Pa･s).

The reaction product was analyzed by GPC (Figure 4) and the like, and the obtained reaction product was 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%). In addition, the content ratio of SiH groups in the entire mixture was 0.0022 mol/g.

(n=4~10, dotted lines indicate the bonding sites).

[Examples 1 to 6, Comparative Examples 1 and 2] The following components were mixed in the composition ratios shown in Table 1 (the values represent parts by mass) to prepare a curable composition in such a manner that the molar ratio of SiH groups to alkenyl groups in the composition ([SiH groups]/[alkenyl groups]) was 1.1. In the following examples, 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) The addition reaction product obtained in the above Synthesis Example 1 (A-2) The addition reaction product obtained in the above Synthesis Example 2 (A-3) The addition reaction product obtained in the above Synthesis Example 3 Comparative Component (A-4) Branched organic polysiloxane represented by M ^H ₃ T ^Φ ₁

(B) Component (B-1) Linear organic polysiloxane represented by M ^Vi ₂ D ^2Φ ₁ (B-2) Bisphenol diallyl ether (produced by Beixing Chemical Industry Co., Ltd.: product name "BPA-AE")

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

[Performance Evaluation Method] For the curable compositions obtained in the above-mentioned examples and comparative examples, the performance of the cured products was evaluated according to the following method. In Comparative Example 2, the crosslinking agent and the main agent (component (B)) were not miscible, and no cured product could be obtained.

(1) Hardness The curable composition was poured into a mold assembled with glass plates and cured at 150°C for 4 hours to obtain a hardened product. The hardness (Shore D or Type A) of each hardened product was measured at 23°C according to ASTM D 2240 and the results are shown in Table 2. The Shore D hardness was measured with a 2 mm thick hardened product, and D was added before the value. The Type A hardness was measured with a 6 mm thick hardened product, and A was added before the value.

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

(3) Toughness evaluation Similar to the above hardness test, Examples 1, 3, 5 and Comparative Example 1 produced 2 mm thick hardened products, and Examples 2, 4, and 6 produced 0.3 mm thick hardened products. The hardened products were bent at right angles along a 1 mm diameter metal rod at 23°C and evaluated as 0 (bent but not cracked) or × (cracked).

(4) Elongation and tensile strength For 2 mm thick hardened products prepared in the same manner as the above hardness measurement, the elongation and tensile strength of each hardened product were measured at 23°C in accordance with JIS-K-6249:2003. The measurement results are shown in Table 2. In addition, for the hardened products of Examples 2, 4, and 6, the hardness was very high and the elongation and tensile strength could not be measured.

As shown in Table 1 and Table 2, the curable composition of the present invention is one in which the components (A) and (B) have good compatibility, and can provide a cured product with excellent hardness, toughness and transparency.

On the other hand, the composition using ^the _{organopolysiloxane} represented by ^MH3TΦ1 instead of the component (A) _of the present invention has poor toughness, elongation and tensile strength (Comparative Example 1), and the compatibility is insufficient when the component (B) without siloxane is used (Comparative Example 2).

Furthermore, the present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are for illustration only, and those having substantially the same structure as the technical concept described in the scope of the patent application of the present invention and exerting the same function and effect are all included in the technical scope of the present invention.

1: Semiconductor device 2: Silver-plated substrate 3: Package 4: Semiconductor chip 5: Bonding wire 6: Cured material of curable composition

[Figure 1] A schematic cross-sectional view showing an example of a photoconductor device using a cured product of the curable composition of the present invention. [Figure 2] A GPC chart of the addition reaction product (A-1) obtained in Synthesis Example 1. [Figure 3] A GPC chart of the addition reaction product (A-2) obtained in Synthesis Example 2. [Figure 4] A GPC chart of the addition reaction product (A-3) obtained in Synthesis Example 3.

1:Semiconductor devices

2: Silver-plated substrate

3: Packaging

4: Semiconductor chip

5: Joining wires

6: Hardened material of hardening composition

Claims (7)

A curable composition comprising the following (A), (B) and (C): (A) an addition reaction product of 1,4-bis(dimethylsilyl)benzene and at least one of a linear siloxane represented by the following formula (2) and a cyclic siloxane represented by the following formula (3), wherein the addition reaction product has two or more SiH groups in one molecule

(wherein, R ² and R ⁴ are independently substituted or unsubstituted monovalent hydrocarbon groups with 1 to 12 carbon atoms, R ³ is independently a single bond or unsubstituted divalent hydrocarbon group with 1 to 4 carbon atoms; a is an integer from 1 to 3, and b is an integer from 0 to 100);

(wherein, ^R3 is as described above, ^R5 is independently methyl or phenyl, ^R6 is 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, and e is an integer of 0 to 10; the arrangement of siloxane units may be arbitrary); (B) a compound having two or more alkenyl groups in one molecule; (C) a catalyst for a hydrosilylation reaction. The curable composition of claim 1, wherein R ² , R ⁴ , and R ⁶ are independently methyl or phenyl, and R ³ is a single bond. The curable composition of claim 1 or 2, wherein the aforementioned (B) is a compound represented by the following formula (4);

(wherein, ^R7 is independently a methyl group or a phenyl group, ^R8 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, f is an integer from 0 to 50, and g is an integer from 0 to 100; however, when f is 0, ^R7 is a phenyl group, and g is an integer from 1 to 100; the arrangement of the siloxane units in the brackets may be arbitrary). A hardened material, characterized in that it is formed by hardening a hardening composition as in any one of claims 1 to 3. For example, the hardened material of claim 4 has a light transmittance of 80% or more at a wavelength of 400nm and a thickness of 2mm (25°C). For the hardened material of claim 4 or claim 5, the Type A hardness measured by rubber durometer A specified in ASTM D 2240 is 30 or more. A semiconductor device characterized in that a semiconductor element is covered by a hardened material as described in any one of claim 4 to 6.

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