TW202128845A - Curable composition, cured product thereof, and semiconductor device - Google Patents

Abstract

The purpose 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. The curable composition contains the following (A), (B) and (C): (A) an addition reaction product of an organosilicon compound represented by formula (1) and at least one siloxane represented by formula (2) and formula (3), 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. (H2C = CH-R3)c(3)R1 is a substituted or unsubstituted divalent hydrocarbon group having 1-12 carbon atoms, R2, R4, and R6 are independently a substituted or unsubstituted monovalent hydrocarbon group having 1-12 carbon atoms, R3 is independently a single bond or an unsubstituted divalent hydrocarbon group having 1-4 carbon atoms, R5 is independently a methyl group or a phenyl group, a is an integer of 1-3, b is an integer of 0-100, c is 1 or 2, d is an integer of 2-10, and e is an integer of 0-10. The arrangement of the siloxane units may be arbitrary.

Description

Curable composition, its cured product, and semiconductor device

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

In the past, as a material for optical devices or optical parts, especially a sealing material for light-emitting diode (LED) elements, epoxy resin is generally used. In addition, there have been attempts to use silicone resin as a molding member of LED elements (Patent Documents 1 and 2) or as a color filter material (Patent Document 3), but there are few practical examples of use.

In recent years, white LEDs have received attention. Epoxy sealing materials, which have not been a problem until now, have caused problems such as yellowing due to ultraviolet rays, or cracks caused by increased heat generation due to miniaturization. Top priority. The corresponding strategy is to explore the use of a cured polysiloxane resin with a large amount of phenyl groups in the molecule. However, such a composition system has low toughness and is prone to cracks. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-228249 [Patent Document 2] Japanese Patent Application Laid-Open No. 10-242513 [Patent Document 3] JP 2000-123981 A

[The problem to be solved by the invention]

The present invention was made in order to solve the above-mentioned problems, and its object is to provide a curable composition that imparts a cured product with high hardness and toughness and excellent light transmittance in the short wavelength region. [Means to solve the problem]

(式中，R¹ 為取代或非取代之碳原子數1~12之2價烴基)；

(式中，R² 、R⁴ 係獨立地為取代或非取代之碳原子數1~12之1價烴基，R³ 係獨立地為單鍵或非取代之碳數1~4之2價烴基；a為1~3之整數，b為0~100之整數)；

(式中，R³ 係如上述，R⁵ 係獨立地為甲基或苯基，R⁶ 係獨立地為取代或非取代之碳原子數1~12之1價烴基，c為1或2，d為2~10之整數，e為0~10之整數；矽氧烷單位之排列可為任意)； (B)1分子中具有2個以上的烯基之化合物； (C)矽氫化反應觸媒。In order to achieve the aforementioned problems, the present invention provides a curable composition containing the following (A), (B), and (C). (A) The addition of the organosilicon compound represented by the following formula (1) with at least one of the linear siloxane represented by the following formula (2) and the cyclic siloxane represented by the following formula (3) Reactant, and is an addition reactant with more than 2 SiH groups in a molecule

(In the formula, R ¹ is a substituted or unsubstituted divalent hydrocarbon group with 1-12 carbon atoms);

(In the formula, R ² and R ⁴ are independently substituted or unsubstituted monovalent hydrocarbon groups with 1 to 12 carbon atoms, and 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, b is an integer from 0 to 100);

(In the formula, R ³ is as above, R ⁵ is independently methyl or phenyl, R ⁶ is independently a substituted or unsubstituted monovalent hydrocarbon group with 1 to 12 carbon atoms, c is 1 or 2, d is an integer from 2 to 10, e is an integer from 0 to 10; the arrangement of siloxane units can be arbitrary); (B) Compounds with more than 2 alkenyl groups in 1 molecule; (C) Hydrosilation reaction Media.

If it is the curable composition of the present invention, it is possible to provide a curable composition that imparts 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 the above-mentioned 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，R⁷ 係獨立地為甲基或苯基，R⁸ 係獨立地為取代或非取代之碳原子數1~12之1價烴基，f為0~50之整數，g為0~100之整數。惟，f為0時R⁷ 為苯基，且，g為1~100之整數。括弧中之矽氧烷單位之排列可為任意)。In the curable composition of the present invention, it is further preferred that the aforementioned (B) is a compound represented by the following formula (4).

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

In addition, the present invention provides a cured product obtained by curing the aforementioned curable composition.

If it is the cured product of the present invention, the hardness and toughness are high, and the light transmittance in the short-wavelength region is excellent.

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

If it is a cured product with 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. In addition, it is also useful as a lens material, optical Various materials for optical parts such as sealing materials for devices or optical parts, display materials, insulating materials for electronic devices or electronic parts, and materials for coating materials.

In addition, the hardness of the cured product of the present invention is preferably 30 or more as measured by a rubber durometer A in accordance with ASTM D 2240.

If it is such a hardened material, it is less susceptible to external stress, and it is possible to 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 by the aforementioned cured product.

In the case of the semiconductor device of the present invention, since the hardness and toughness of the cured product used are high, it becomes a semiconductor device with excellent durability. Furthermore, since the light transmittance in the short-wavelength region is also excellent, it is also used as a light-emitting diode element and other semiconductor devices that require light transmittance. [Effects of Invention]

The curable composition of the present invention can impart 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 light-emitting diode 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 applications such as protection, sealing or bonding of light-emitting diode elements, wavelength change or adjustment, and lenses. In addition, it is also used as a lens material, sealing material for optical devices or optical parts, materials for various optical parts such as display materials, insulating materials for electronic devices or electronic parts, and further coating materials. Furthermore, the semiconductor device of the present invention using such a curable composition has excellent reliability.

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

The inventors of the present invention have repeatedly studied the above-mentioned problems, and found that the above-mentioned problems can be solved by a curable composition containing specific components, and the present invention has been completed.

(式中，R¹ 為取代或非取代之碳原子數1~12之2價烴基)；

(式中，R² 、R⁴ 係獨立地為取代或非取代之碳原子數1~12之1價烴基，R³ 係獨立地為單鍵或非取代之碳數1~4之2價烴基。a為1~3之整數，b為0~100之整數)。

(式中，R³ 係如上述，R⁵ 係獨立地為甲基或苯基，R⁶ 係獨立地為取代或非取代之碳原子數1~12之1價烴基，c為1或2，d為2~10之整數，e為0~10之整數。矽氧烷單位之排列可為任意)； (B)1分子中具有2個以上的烯基之化合物； (C)矽氫化反應觸媒。That is, the present invention is a curable composition containing the following (A), (B), and (C). (A) The addition of the organosilicon compound represented by the following formula (1) with at least one of the linear siloxane represented by the following formula (2) and the cyclic siloxane represented by the following formula (3) The reactant is an addition reactant having two or more SiH groups in a molecule.

(In the formula, R ¹ is a substituted or unsubstituted divalent hydrocarbon group with 1-12 carbon atoms);

(In the formula, R ² and R ⁴ are independently substituted or unsubstituted monovalent hydrocarbon groups with 1 to 12 carbon atoms, and 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, b is an integer from 0 to 100).

(In the formula, R ³ is as above, R ⁵ is independently methyl or phenyl, R ⁶ is independently a substituted or unsubstituted monovalent hydrocarbon group with 1 to 12 carbon atoms, c is 1 or 2, d is an integer from 2 to 10, e is an integer from 0 to 10. The arrangement of siloxane units can be arbitrary); (B) Compounds with more than 2 alkenyl groups in one molecule; (C) Hydrosilation reaction Media.

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

[Curable composition] [(A) Ingredient] The component (A) in the curable composition of the present invention functions as a crosslinking agent that initiates a hydrosilation reaction with the component (B) described later.

(式中，R¹ 為取代或非取代之碳原子數1~12之2價烴基)；

(式中，R² 、R⁴ 係獨立地為取代或非取代之碳原子數1~12之1價烴基，R³ 係獨立地為單鍵或非取代之碳數1~4之2價烴基。a為1~3之整數，b為0~100之整數)。

(式中，R³ 係如上述，R⁵ 係獨立地為甲基或苯基，R⁶ 係獨立地為取代或非取代之碳原子數1~12之1價烴基，c為1或2，d為2~10之整數，e為0~10之整數。矽氧烷單位之排列可為任意)。The component (A) in the curable composition of the present invention is an organosilicon compound represented by the following formula (1), and a linear siloxane represented by the following formula (2) and represented by the following formula (3) The addition reactant of at least one of the cyclic siloxanes is an addition reactant having two or more SiH groups in one molecule.

(In the formula, R ¹ is a substituted or unsubstituted divalent hydrocarbon group with 1-12 carbon atoms);

(In the formula, R ² and R ⁴ are independently substituted or unsubstituted monovalent hydrocarbon groups with 1 to 12 carbon atoms, and 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, b is an integer from 0 to 100).

(In the formula, R ³ is as above, R ⁵ is independently methyl or phenyl, R ⁶ is independently a substituted or unsubstituted monovalent hydrocarbon group with 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 siloxane units can be arbitrary).

In the above formula (2), b is an integer of 0-100, preferably 0-10, more preferably 0. When b exceeds 100, the hardness of the hardened product may be insufficient.

In the above formula (3), d is an integer of 2-10, preferably 3-10. When d is less than 2, the function of the component (A) as a crosslinking agent is insufficient, and when d exceeds 10, the hardened product may become brittle and the toughness may deteriorate. e is an integer of 0-10, preferably 0-2. When e exceeds 10, the hardness of the hardened product may be insufficient.

R ¹ represents a divalent hydrocarbon group with 1 to 12 carbon atoms, including methylene, ethylene, n-propylene, n-butyl, n-pentylene, n-hexylene, ring extension Alkylene groups such as hexyl and n-octyl; aryl groups such as phenyl and naphthyl groups, or part or all of the hydrogen atoms of these groups are passed through halogen atoms such as fluorine, bromine, chlorine, etc. As a substituent, R ^{1 is} particularly preferably a phenylene group.

R ² , R ⁴ and R ⁶ represent monovalent hydrocarbon groups with 1 to 12 carbon atoms, including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and pentyl , Neopentyl, hexyl, octyl, etc. alkyl; cyclohexyl, etc. cycloalkyl; vinyl, allyl, propenyl, etc. alkenyl; phenyl, tolyl, xylyl, naphthyl, etc. Aryl; benzyl, phenylethyl, phenylpropyl, etc., aralkyl groups, etc., or those where part or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, chlorine, etc., preferably It is methyl or phenyl.

The ^{unsubstituted divalent hydrocarbon group having 1 to 4 carbon atoms represented by R 3} includes alkylene groups such as methylene, ethylene, n-propylene, and n-butylene. When R ³ is a single bond, it represents an organosilicon 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 to these. In addition, the organosilicon compound represented by the above formula (1) may be used singly or in combination of two or more kinds.

Suitable specific examples of the linear siloxane represented by the above formula (2) are shown below, but are not limited to these. Moreover, the compound represented by the said formula (2) may be used individually by 1 type, and may be used in combination of 2 or more types.

(式中，矽氧烷單位之排列可為任意)。Suitable specific examples of the cyclic siloxane represented by the above formula (3) are shown below, but are not limited to these. Moreover, the compound represented by the said formula (3) may be used individually by 1 type, and may be used in combination of 2 or more types.

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

(式中，n為1~10之整數，虛線表示鍵結部位)。(A) of the addition reactant of the organosilicon compound represented by the above formula (1) with at least one of the linear siloxane represented by the above formula (2) and the cyclic siloxane represented by the above formula (3) Preferred examples of the components include compounds having a ratio of constituent units represented by the following formula.

(In the formula, n is an integer from 1 to 10, and the dashed line indicates the bonding site).

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

[Preparation of (A) component] The component (A) in the curable composition of the present invention may be contained in the linear siloxane represented by the above formula (2) and/or the cyclic siloxane represented by the above formula (3) 1 mol of the alkenyl group, mixed with the excess amount of the compound represented by the above formula (1), preferably more than 1 mol and 10 mol or less, more preferably more than 1.5 mol and 5 mol or less, in the presence of both Under the hydrosilylation reaction.

In 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 it is preferably All alkenyl groups undergo hydrosilation reaction.

As the catalyst used in the aforementioned hydrosilation reaction, a known catalyst can be used. For example, carbon powder containing platinum metal, platinum black, platinum (IV) chloride, chloroplatinic acid, the reaction product of chloroplatinic acid and monohydric alcohol, and the complex of chloroplatinic acid and olefins Platinum-based catalysts such as palladium-based catalysts and rhodium-based catalysts. In addition, addition reaction conditions, purification conditions, use of solvents, etc. are not particularly limited, and known methods can be used.

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

The compound constituting the component (A) has two or more SiH groups in one molecule, which can be confirmed by selecting an appropriate measurement method. When there are two or more compounds constituting the component (A), it is possible to confirm that each compound has two or more SiH groups per molecule ^{by selecting a combination of appropriate measurement means (for example, 1 H-NMR and GPC).}

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

Examples of alkenyl groups include linear alkenyl groups such as vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, and octenyl; norbornyl and cyclohexenyl Cyclic alkenyl groups such as vinyl groups and allyl groups are preferred.

(B) The specific examples of component (B) are not particularly limited. Examples include dimethylsiloxane/methylvinylsiloxane copolymers in which both ends of the molecular chain are terminated with trimethylsilyloxy groups, and Trimethylsilyloxy-terminated dimethylsiloxane/diphenylsiloxane/methylvinylsiloxane copolymer, the two ends of the molecular chain are blocked by dimethylvinylsilyloxy group II Methylsiloxane/diphenylsiloxane copolymer, etc.

(h為0~10之整數)。Moreover, other than siloxane, the compound etc. which are represented by the following formula are mentioned, but it is not limited to these.

(h is an integer from 0 to 10).

(B) A component may be used individually by 1 type, and may be used in combination of 2 or more types.

(式中，R⁷ 係獨立地為甲基或苯基，R⁸ 係獨立地為取代或非取代之碳原子數1~12之1價烴基，f為0~50之整數，g為0~100之整數。惟，f為0時R⁷ 為苯基，且，g為1~100之整數。括弧中之矽氧烷單位之排列可為任意)。The component (B) is preferably a linear organopolysiloxane represented by the following formula (4).

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

R ⁸ represents a monovalent hydrocarbon group with 1 to 12 carbon atoms, including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, and hexyl Alkyl groups such as, octyl; cycloalkyl groups such as cyclohexyl; alkenyl groups such as vinyl, allyl, propenyl, etc.; aryl groups such as phenyl, tolyl, xylyl, naphthyl, etc.; benzyl, Phenylethyl, phenylpropyl and other aralkyl groups, etc., or the hydrogen atoms of these groups are partially or completely substituted by halogen atoms such as fluorine, bromine, chlorine, etc., especially with carbon atoms of 1~ Alkyl group, phenyl group and vinyl group of 6 are preferred; especially methyl group is preferred.

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

The organopolysiloxane represented by formula (4) can be obtained by, for example, hydrolyzing/condensing bifunctional silanes such as dichlorodiphenylsilane or dialkoxydiphenylsilane, or when it is combined with hydrolysis/condensation Ground, it is obtained by blocking the end with a siloxane unit containing an aliphatic unsaturated group.

(B) The blending amount of the component is preferably such that the molar ratio of the SiH group to the aliphatic unsaturated group (SiH group/aliphatic unsaturated group) in the composition becomes 0.5 or more and 5 or less. It is preferably 0.8 or more and 2 or less. If 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 hardened.

[(C) Ingredient] The catalyst for the hydrosilation reaction of the component (C) of the present invention can be the same as that used for the preparation of the component (A).

The blending amount of the component (C) to the curable composition of the present invention is not particularly limited, as long as it is an effective amount as a catalyst. Relative to the mass of the entire composition, it is calculated as platinum group metal atoms. The best blending composition is 1~500ppm, more preferably 1~100ppm, and even more preferably 2~12ppm. By setting the blending amount within the aforementioned range, the time required for the curing reaction becomes moderate, and the coloration of the cured product can be suppressed.

[Other ingredients] In the curable composition of the present invention, in addition to the above-mentioned (A) to (C) components, components such as antioxidants, inorganic fillers, and adhesiveness enhancers may be blended as needed.

[Antioxidants] In the cured product of the curable composition of the present invention, the addition-reactive carbon-carbon double bond in the above-mentioned component (B) remains unreacted. It may be oxidized by atmospheric oxygen. Become the cause of coloring of the hardened material. Therefore, by blending antioxidants in the curable composition of the present invention as needed, such coloring can be prevented in advance.

Known antioxidants can be used, such as 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-pentylhydroquinone, and 2,5-di-t-butyl Hydroquinone, 4,4'-butylene bis(3-methyl-6-t-butylphenol), 2,2'-methylene bis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol) and the like. These can be used singly or in combination of two or more kinds.

In addition, when the antioxidant is used, there is no particular limitation on the amount of it blended. Relative to the total mass of the above-mentioned (A) component and (B) component, it is usually blended at 1 to 10,000 ppm, and especially blended at 10 to 10 ppm. About 1,000 ppm is preferable. By setting the blending amount within the aforementioned range, the antioxidant capacity is fully exhibited, and a cured product with excellent optical properties without coloration, white turbidity, oxidative deterioration, 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 increase the strength, or to make the dispersion of the phosphor good, nanosilica may be added or melted Inorganic filler for silica, crystalline silica, titania, nano alumina, alumina, etc.

[Adhesion improver] In the curable composition of the present invention, an adhesive enhancer may also be blended. Examples of the adhesion improver include a silane coupling agent or its oligomer, polysiloxane having the same reactive group as the silane coupling agent, and the like.

Adhesion enhancer is an optional component blended in the composition in order to improve the adhesion of the curable composition of the present invention and its cured product to the substrate. Here, the base material refers to metal materials such as gold, silver, copper, and nickel; ceramic materials such as alumina, aluminum nitride, and titanium oxide; and polymer materials such as polysiloxane resin and epoxy resin. The adhesiveness enhancer may be used singly or in combination of two or more kinds.

The blending amount when using the adhesiveness improver is preferably 1 to 30 parts by mass, more preferably 1 to 10 parts by mass relative to the total of 100 parts by mass of the above-mentioned (A) component and (B). If it is such a blending amount, the thermosetting silicone composition of the present invention and its cured product can effectively improve the adhesion to the substrate, and it is unlikely to cause coloration.

Suitable specific examples of the adherability improver include those represented by the following formulas, but are not limited to these.

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

Further, in order to impart resistance to light degradation caused by light energy of sunlight, fluorescent lamps, etc., a light stabilizer may also be used. The light stabilizer is a hindered amine stabilizer that captures free radicals generated by photooxidation 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-tetramethyl Piperidine and others.

In addition, when using the composition of the present invention as a sealing material, in order to improve the adhesion to the substrate, a silane coupling agent may be blended, and a plasticizer may be added to prevent cracking.

[Hardened material] The curable composition of the present invention is cured to become the cured product of the present invention. The aforementioned hardened product has high hardness and toughness, and excellent light transmittance in the short-wavelength region. Furthermore, there are no special restrictions on the curing conditions of the curable composition of the present invention, and the conditions of 60 to 180°C for 5 to 180 minutes are preferred.

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

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

[Semiconductor device] In the present invention, there is further provided a semiconductor device covered with a semiconductor element by a cured product obtained from the above-mentioned curable composition.

Hereinafter, a semiconductor device using the 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 not limited to this.

FIG. 1 is a schematic cross-sectional view showing an example of the semiconductor device of the present invention. The semiconductor device 1 of the present invention is formed on a package 3 on which a silver-plated substrate 2 is formed, and a semiconductor chip 4 is die-bonded, and the semiconductor chip 4 is wire-bonded by bonding wires 5. Next, the semiconductor chip 4 is covered with the cured product 6 of the curable composition of the present invention. The coating of the semiconductor wafer 4 is performed by applying the curable composition of the present invention (addition curable polysiloxy composition), and curing the curable composition by heating. Furthermore, it can also be cured by a known curing method under other known curing conditions.

In this case, it is less susceptible to external stress, and from the viewpoint of suppressing the adhesion of dust and the like as much as possible, the above-mentioned curable composition is preferably cured to form a rubber hardness meter A measured by JIS or ASTM D 2240. Hardened products with a hardness of 30 or more.

The curable composition of the present invention forms a cured product 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 following examples and comparative examples are used to specifically illustrate the present invention, but the present invention is not limited to these.

In the examples, the ¹ H-NMR measurement system used AVANCE III manufactured by Bruker BioSpin. GPC (Gel Permeation Chromatography) measurement was performed in terms of polystyrene using HLC-8320GPC manufactured by Tosoh Co., Ltd., using tetrahydrofuran (THF) as a mobile phase.

[Synthesis example 1] Preparation of (A-1) component is in a 1L 4-necked flask equipped with a stirring device, cooling tube, dropping funnel and thermometer, and 1,4-bis(dimethylsilyl)benzene (Beixing) is added 660 g (3.4 mol) of Chemical Industry Co., Ltd., 0.30 g of 5% Pt carbon powder (manufactured by NE CHEMCAT Co., Ltd.), and heated to 85° C. using an oil bath. Into this, 47 g (0.2 mol) of hexavinyldisiloxane (manufactured by Beixing Chemical Industry Co., Ltd.) was dropped. After the dripping is finished, stir at 90-100°C for 3 hours. After the stirring, the temperature was returned to 25°C, and it was ^{confirmed by 1} H-NMR spectrum measurement that the peak of the vinyl group disappeared. Add 11 g of activated carbon, stir for 1 hour, filter off Pt carbon powder and activated carbon, and concentrate under reduced pressure to remove the remaining 1,4-bis(dimethylsilyl)benzene to obtain component (A-1) 240g (colorless and transparent, viscosity at 23°C: 49Pa･s).

As a result of analyzing the reaction product by GPC (Figure 2), etc., the reaction product obtained is a mixture of compounds having the structure represented by the following formulas (a1) to (e1), and the ratio of each compound is (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，虛線表示鍵結部位)。

(n=5~10, the dotted line indicates the bonding position).

[Synthesis example 2] Preparation of (A-2) component is in a 1L 4-necked flask equipped with a stirring device, cooling tube, dropping funnel and thermometer, and 1,4-bis(dimethylsilyl)benzene (Beixing) is added Chemical Industry Co., Ltd. make) 496g (2.6 mol), 5% Pt carbon powder (NE CHEMCAT Co., Ltd. make) 0.24g, use an oil bath to heat to 85°C. Into this, 78 g (0.3 mol) of 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) was dropped. After the dripping, it was stirred at 90-100°C for 5 hours. After the stirring, the temperature was returned to 25°C, and it was ^{confirmed by 1} H-NMR spectrum measurement that the peak of the vinyl group disappeared. Add 9g of activated carbon, stir for 1 hour, filter off the Pt carbon powder and activated carbon, and remove the remaining 1,4-bis(dimethylsilyl)benzene by concentration to obtain 220g of component (A-2) ( Colorless and transparent, viscosity at 23°C: 2.9Pa･s).

As a result of analyzing the reaction product by GPC (Figure 3), etc., the reaction product obtained is a mixture of compounds having the structure represented by the following formulas (a2) to (d2), and the ratio of each compound is (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、虛線表示鍵結部位)。

(n=4~10, the dotted line indicates the bonding position).

[Synthesis Example 3] Preparation of (A-3) component is in a 500 mL 4-necked flask equipped with a stirring device, cooling tube, dropping funnel and thermometer, and 1,4-bis(dimethylsilyl)benzene (Beixing) is added Chemical Industry Co., Ltd. make) 175 g (0.9 mol), 5% Pt carbon powder (NE CHEMCAT Co., Ltd. make) 0.11g, and heated to 85°C using an oil bath. 93 g (0.3 mol) of dimethyldiphenyldivinyldisiloxane (manufactured by Beixing Chemical Industry Co., Ltd.) was dropped therein. After the dripping, it was stirred at 90-100°C for 5 hours. After the stirring, the temperature was returned to 25°C, and it was ^{confirmed by 1} H-NMR spectrum measurement that the peak of the vinyl group disappeared. Add 4.0g of activated carbon, stir for 1 hour, filter off Pt carbon powder and activated carbon, and remove the remaining 1,4-bis(dimethylsilyl)benzene by concentration to obtain component (A-3) 182g (colorless and transparent, viscosity at 23°C: 1.5Pa･s).

As a result of analyzing the reaction product by GPC (Figure 4), etc., the reaction product obtained is a mixture of compounds having the structure represented by the following formulas (a3) to (d3), and the ratio of each compound is (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、虛線表示鍵結部位)。

(n=4~10, the dotted line indicates the bonding position).

[Examples 1 to 6, Comparative Examples 1 and 2] The following components were mixed in the composition ratio shown in Table 1 (numerical values indicate parts by mass), and the molar ratio of the SiH group is relative to the alkenyl group in the composition. The curable composition was prepared so that the ratio ([SiH group]/[alkenyl group]) became 1.1. In the following examples, the symbols representing the structural units of organopolysiloxane are as follows. M ^Vi : (CH ₂ =CH)(CH ₃ ) ₂ SiO _1/2 M ^H : 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 Synthesis Example 1 above (A-2) The addition reaction product obtained in Synthesis Example 2 above (A-3) The addition reaction product obtained in Synthesis Example 3 above Comparative composition of reactants (A-4) Branched organopolysiloxane represented by ^{M H} ₃ T ^Φ ₁

(B) Component (B-1) M ^Vi ₂ D ^2Φ ₁ represented by linear organopolysiloxane (B-2) bisphenol diallyl ether (manufactured by Beixing Chemical Industry Co., Ltd.: product name "BPA -AE」)

(C) Ingredients Polysiloxane diluent 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 examples and comparative examples, the following methods were followed to evaluate the properties of the cured products. Furthermore, in Comparative Example 2, the crosslinking agent and the main agent (component (B)) were not compatible, and a cured product could not 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 cured product. According to ASTM D 2240, the hardness (Shore D or Type A) of each hardened product measured at 23°C is shown in Table 2. In addition, ShoreD hardness is measured with a 2mm thick hardened product, and D is added before the value. In addition, TypeA hardness is measured with a 6mm thick hardened product, and A is added before the value.

(2) Light transmittance With respect to the cured product of 2 mm thickness prepared in the same manner as in the above-mentioned 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) Resilience assessment In the same manner as the above-mentioned hardness measurement, in Examples 1, 3, and 5 and Comparative Example 1, hardened materials with a thickness of 2 mm were prepared, and in Examples 2, 4, and 6 hardened materials with a thickness of 0.3 mm were prepared. The state when the respective hardened products were bent at a right angle at 23°C along a metal rod with a diameter of 1 mm was evaluated by 0 (bending without breaking) and × (breaking).

(4) Elongation, tensile strength Regarding the 2 mm thick cured product prepared in the same manner as the above-mentioned hardness measurement, the elongation and tensile strength of each cured product were measured at 23°C in accordance with JIS-K-6249:2003. The measurement results are shown in Table 2. Furthermore, the hardened products of Examples 2, 4, and 6 had very high hardness, 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 has good compatibility between the components (A) and (B), and imparts a cured product with excellent hardness, toughness, and transparency.

On the other hand, the use ^{of organopolysiloxane represented by M H} ₃ T ^Φ ₁ to replace the component (A) of the present invention has poor toughness, elongation, and tensile strength (Comparative Example 1), and uses no silicon The compatibility of the oxane component (B) is insufficient (Comparative Example 2).

In addition, the present invention is not limited to the above-mentioned embodiment. The above-mentioned embodiments are just examples, and those having substantially the same constitution as the technical idea described in the scope of patent application of the present invention and exerting the same effects are all included in the technical scope of the present invention.

1: Semiconductor device 2: Silver-plated substrate 3: package 4: Semiconductor wafer 5: Bonding wires 6: Hardening of hardening composition

[FIG. 1] 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. [Figure 2] GPC chart of the addition reactant (A-1) obtained in Synthesis Example 1. [Figure 3] GPC chart of the addition reactant (A-2) obtained in Synthesis Example 2. [Figure 4] GPC chart of the addition reactant (A-3) obtained in Synthesis Example 3.

1: Semiconductor device

2: Silver-plated substrate

3: package

4: Semiconductor wafer

5: Bonding wires

6: Hardening of hardening composition

Claims (7)

A curable composition containing the following (A), (B) and (C): (A) an organosilicon compound represented by the following formula (1), and a linear silicon compound represented by the following formula (2) The addition reactant of at least one of oxane and the cyclic siloxane represented by the following formula (3), and an addition reactant having two or more SiH groups in one molecule

(In the formula, R ¹ is a substituted or unsubstituted divalent hydrocarbon group with 1-12 carbon atoms);

(In the formula, R ² and R ⁴ are independently substituted or unsubstituted monovalent hydrocarbon groups with 1 to 12 carbon atoms, and 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, b is an integer from 0 to 100);

(In the formula, R ³ is as above, R ⁵ is independently methyl or phenyl, R ⁶ is independently a substituted or unsubstituted monovalent hydrocarbon group with 1 to 12 carbon atoms, c is 1 or 2, d is an integer from 2 to 10, e is an integer from 0 to 10; the arrangement of siloxane units can be arbitrary); (B) Compounds with more than 2 alkenyl groups in 1 molecule; (C) Hydrosilation reaction Media. The curable composition of 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 of claim 1 or 2, wherein the aforementioned (B) is a compound represented by the following formula (4);

(In the formula, R ⁷ is independently methyl or phenyl, R ⁸ is independently substituted or unsubstituted monovalent hydrocarbon group with 1-12 carbon atoms, f is an integer of 0-50, and g is 0~ An integer of 100; however, when f is 0, R ⁷ is a phenyl group, and g is an integer of 1 to 100; the arrangement of siloxane units in parentheses can be arbitrary). A hardened product characterized by hardening the hardenable composition according to any one of claims 1 to 3. Such as the hardened product of claim 4, wherein the light transmittance (25°C) at a wavelength of 400nm with a thickness of 2mm is more than 80%. Such as the hardened product of claim 4 or claim 5, wherein the hardness specified by ASTM D 2240 measured by rubber hardness meter A is 30 or more. A semiconductor device characterized by being coated with a semiconductor element by a hardened material as in any one of Claims 4 to 6.

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