JP6981938B2 - Additive curable silicone compositions and semiconductor devices - Google Patents

Description

The present invention relates to an addition-curable silicone composition and a semiconductor device in which a semiconductor element is coated with a cured product of the composition.

The addition-curable silicone composition that is cured by a hydrosilylation reaction is used as a protective coating agent for semiconductor devices in optical semiconductor devices such as photocouplers, light emitting diodes, and solid-state image pickup devices. The hardness and transparency of such a protective coating agent for a semiconductor element may change due to heat or light generated from the semiconductor element. In order to suppress this change, conventionally, Q units (SiO ₂ ) have been introduced into the molecule (Patent Documents 1 to 4), and soft segments have been introduced into the composition (Patent Document 5). However, such a method cannot cope with a permanent change in the hardness of the material. Further, since the peripheral element uses a heat-sensitive resin, there is a drawback that it is not economical because the amount of the curing catalyst is generally increased when curing at a low temperature such as 20 to 80 ° C.

Japanese Unexamined Patent Publication No. 7-252419 Japanese Unexamined Patent Publication No. 2011-252175 Japanese Unexamined Patent Publication No. 2013-067683 Japanese Unexamined Patent Publication No. 2009-052038 Japanese Unexamined Patent Publication No. 2007-63538

The present invention has been made in view of the above circumstances, and provides an addition-curable silicone composition that provides a cured product having fast curing, high light transmittance, and excellent high-temperature durability, and a semiconductor device using the same. With the goal.

In order to solve the above problems, in the present invention,
Additive-curing silicone composition
(A) Organopolysiloxane represented by the following average unit formula (1),
[O _{{(3-k) / 2)}} Si (R ¹ ) _k −R ² − (R ¹ ) _k SiO _{{(3-k) / 2)}} ] _a (R ¹ ₃ SiO _1/2 ) _b (X ¹ O _1/2 ) _c ... (1)
(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, and ^{0.1 to 50% of all R 1} is an alkenyl group. R ² is a substituted or substituted group. It is an unsubstituted divalent hydrocarbon group, k is an integer of 0, 1, 2 which may be the same or different, X ¹ is a hydrogen atom or an alkyl group. A, b, c are 0.1 ≦ a. ≦ 1, 0 ≦ b ≦ 0.75, 0 ≦ c ≦ 0.1, and a + b + c = 1).
(B) Organohydrogenpolysiloxane having at least two Si—H bonds in one molecule represented by the following average composition formula (2): 1 to 200 mass with respect to 100 parts by mass of the component (A). Department,
R ³ _{d He e} SiO _{[(4-d-e) / 2]} ... (2)
(In the formula, R ³ is a substituted or unsubstituted monovalent hydrocarbon group excluding the aliphatic unsaturated hydrocarbon group, which may be the same or different. D and e are 0.7 ≦ d ≦ 2. It is a positive number that satisfies 1, 0.01 ≦ e ≦ 1.0 and 0.8 ≦ d + e ≦ 2.7.)
as well as,
(C) Hydrosilylation Reaction Catalyst: Provided is an addition-curable silicone composition characterized by containing an amount of 0.01 to 500 ppm in terms of mass of metal atoms with respect to the entire composition.

A cured product made of such an addition-curable silicone composition of the present invention cures quickly, has high light transmittance, and has excellent high-temperature durability. Therefore, it is a light-reflecting material, for example, for a light emitting device, particularly a light emitting diode. It is useful as a sealing material for.

Further, in the component (A), the number of carbon atoms of the divalent hydrocarbon group R ² in said average unit formula (1) is preferably 2 to 8.

In such a case, since it contains an organic group having excellent heat resistance, it is possible to give a cured product having more excellent heat resistance.

Further, in the component (A), of R ¹ in said average unit formula (1), it is preferable that the content of methyl groups is 20 mol% or more.

If it is such a thing, it is possible to give a cured product having more stable heat resistance.

Further, in the component (A), a, b, and c in the average unit formula (1) preferably have (b + c) / a of 0.4 to 4.

If it is such a thing, it can be suitably used as the component (A).

Further, in the present invention, in the component (A), c in the average unit formula (1) can be set to 0.

Such a substance can also be suitably used as the component (A).

Further, the present invention provides a semiconductor device characterized in that a semiconductor element is coated with a cured product of the addition-curable silicone composition.

Such a semiconductor device is a semiconductor device having excellent reliability because it is made of a cured product having high curing speed, high light transmittance, and excellent high temperature durability as described above.

The cured product made of the addition-curable silicone composition of the present invention cures quickly, has high light transmittance, and has excellent high-temperature durability. It is useful as.

It is a schematic sectional drawing which shows an example of the semiconductor device of this invention.

As a result of diligent studies on the above problems, the present inventors have found that an addition-curable silicone composition containing an organopolysiloxane having a specific structure provides a cured product having excellent curability, transparency, and heat resistance. And completed the present invention.

That is, the present invention
Additive-curing silicone composition
(A) Organopolysiloxane represented by the following average unit formula (1),
[O _{{(3-k) / 2)}} Si (R ¹ ) _k −R ² − (R ¹ ) _k SiO _{{(3-k) / 2)}} ] _a (R ¹ ₃ SiO _1/2 ) _b (X ¹ O _1/2 ) _c ... (1)
(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, and ^{0.1 to 50% of all R 1} is an alkenyl group. R ² is a substituted or substituted group. It is an unsubstituted divalent hydrocarbon group, k is an integer of 0, 1, 2 which may be the same or different, X ¹ is a hydrogen atom or an alkyl group. A, b, c are 0.1 ≦ a. ≦ 1, 0 ≦ b ≦ 0.75, 0 ≦ c ≦ 0.1, and a + b + c = 1).
(B) Organohydrogenpolysiloxane having at least two Si—H bonds in one molecule represented by the following average composition formula (2): 1 to 200 mass with respect to 100 parts by mass of the component (A). Department,
R ³ _{d He e} SiO _{[(4-d-e) / 2]} ... (2)
(In the formula, R ³ is a substituted or unsubstituted monovalent hydrocarbon group excluding the aliphatic unsaturated hydrocarbon group, which may be the same or different. D and e are 0.7 ≦ d ≦ 2. It is a positive number that satisfies 1, 0.01 ≦ e ≦ 1.0 and 0.8 ≦ d + e ≦ 2.7.)
as well as,
(C) Hydrosilylation reaction catalyst: An addition-curable silicone composition containing an amount of 0.01 to 500 ppm in terms of mass of metal atoms with respect to the entire composition.

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto. In this specification, the viscosity is a value measured by a rotational viscometer.

<Additional curable silicone composition>
The addition-curable silicone composition of the present invention contains the following components (A) to (C). Hereinafter, each component will be described in detail.

[(A) component]
The component (A) is an organopolysiloxane represented by the following average unit formula (1).
[O _{{(3-k) / 2)}} Si (R ¹ ) _k −R ² − (R ¹ ) _k SiO _{{(3-k) / 2)}} ] _a (R ¹ ₃ SiO _1/2 ) _b (X ¹ O _1/2 ) _c ... (1)
(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, and ^{0.1 to 50% of all R 1} is an alkenyl group. R ² is a substituted or substituted group. It is an unsubstituted divalent hydrocarbon group, k is an integer of 0, 1, 2 which may be the same or different, X ¹ is a hydrogen atom or an alkyl group. A, b, c are 0.1 ≦ a. ≦ 1, 0 ≦ b ≦ 0.75, 0 ≦ c ≦ 0.1, and a + b + c = 1).

Examples of the alkenyl group in R ¹ are preferably a vinyl group, an allyl group, a butenyl group, a pentenyl group and a hexenyl group, and a vinyl group is particularly preferable. The content of the alkenyl group in R ¹ is 0.1 to 50 mol%, preferably 0.1 to 30 mol%, and particularly preferably 0.3 to 20 mol%. If it is less than 0.1 mol%, the curability of the composition becomes insufficient, and if it exceeds 50 mol%, the cured product becomes brittle.

Examples of the silicon atom-bonded organic group other than the alkenyl group in R ¹ include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and heptyl group; phenyl group, naphthyl group and the like. Alaryl groups such as benzyl group and phenethyl group; alkyl halide-substituted or unsubstituted monovalent hydrocarbon groups such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group are exemplified. Of these, the methyl group is most preferable from the viewpoint of heat resistance. When ^{the content of the silicon atom-bonded organic group other than these alkenyl groups in R 1} is 20 mol% or more, it is preferable because stable heat resistance can be imparted, and more preferably 40 mol% or more.

R ² is a substituted or unsubstituted divalent hydrocarbon group, an ethylene group, a propylene group, a butylene group, pentene group, when the alkylene group is 2 to 8 carbon atoms, such as hexene group is excellent in heat resistance Therefore, it is preferable, and it is particularly preferable that it is an ethylene group.

X ¹ is a hydrogen atom or an alkyl group, and ^{examples of the alkyl group include the same groups as those exemplified as R 1} , and a methyl group or an ethyl group is particularly preferable.

a is 0.1 to 1, b is 0 to 0.75, c is 0 to 0.1, and a + b + c is 1. If a, b and c are out of the above range, the hardness and / or strength of the obtained cured product will be insufficient.

a is preferably 0.15 to 0.9, particularly preferably 0.2 to 0.8, b is preferably 0 to 0.5, particularly preferably 0 to 0.4, and c is preferably. It is 0 to 0.05.

For a, b, and c, (b + c) / a is preferably 0.4 to 4. If (b + c) / a is within such a range, it can be suitably used as the component (A).

Further, c can be set to 0. Even if c is 0, it can be suitably used as the component (A).

The molecular weight of the component (A) is not limited, but the weight average molecular weight (Mw) in terms of standard polystyrene as measured by gel permeation chromatography (GPC) using a THF solvent is preferably 500 to 20,000, more preferably. It is 700 to 15,000, particularly preferably 1,000 to 10,000.

[(B) component]
The component (B) is an organohydrogenpolysiloxane represented by the following average composition formula (2).
R ³ _{d He e} SiO _{[(4-d-e) / 2]} ... (2)
(In the formula, R ³ is a substituted or unsubstituted monovalent hydrocarbon group excluding the aliphatic unsaturated hydrocarbon group, which may be the same or different. D and e are 0.7 ≦ d ≦ 2. It is a positive number that satisfies 1, 0.01 ≦ e ≦ 1.0 and 0.8 ≦ d + e ≦ 2.7.)

The ^{monovalent hydrocarbon group represented by R 3} has preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and examples of such a hydrocarbon group include a methyl group, an ethyl group, and a propyl group. Alkyl groups such as isopropyl group, butyl group, tert-butyl group and hexyl group, saturated hydrocarbon groups such as cycloalkyl group such as cyclohexyl group, aryl groups such as phenyl group and trill group, benzyl group, phenylethyl group and the like. Examples thereof include a halogen-substituted hydrocarbon group such as an aralkyl group, a 3,3,3-trifluoropropyl group, a cyano-substituted hydrocarbon group, and the like, and a methyl group is preferable.

From the viewpoint of physical properties such as compatibility and the cured product of the component (A) preferably has at least 20 mol% of all R ³ and H bonded to a silicon atom (hydrogen atom) is a methyl group, 50 mol% It is more preferable that the above is a methyl group.

The component (B) has at least two, preferably three or more Si—H bonds (that is, hydrogen atoms bonded to silicon atoms) in one molecule, and the viscosity at 25 ° C. is preferably 0.5. It is ~ 1,000 mPa · s, more preferably 1 to 500 mPa · s.

The structure of the siloxane chain of the component (B) is not particularly limited, but is preferably a linear or cyclic organohydrogenpolysiloxane.

d and e are positive numbers satisfying 0.7 ≦ d ≦ 2.1, 0.01 ≦ e ≦ 1.0 and 0.8 ≦ d + e ≦ 2.7, and d and e are outside the above range. Then, the hardness and / or strength of the obtained cured product becomes insufficient.

d is preferably 1.0 ≦ d ≦ 1.8, e is preferably 0.02 ≦ e ≦ 1.0, more preferably 0.10 ≦ e ≦ 1.0, and d + e is preferably 1. It is a positive number that satisfies 01 ≦ d + e ≦ 2.4, more preferably 1.6 ≦ d + e ≦ 2.2.

The blending amount of the component (B) is 1 to 200 parts by mass, preferably 5 to 80 parts by mass with respect to 100 parts by mass of the component (A), and if the blending amount is less than 1 part by mass, the curability becomes insufficient. If it exceeds 200 parts by mass, sufficient hardness and / or strength cannot be obtained.

In the component (B), the molar ratio of the silicon atom-bonded hydrogen atom (that is, the SiH group) in the component (B) to the alkenyl group in the component (A) is 0.5 to 5 mol / mol, particularly 1 to 3. It is more preferable to mix in an amount of mol / mol.

[(C) component]
The hydrosilylation reaction catalyst of the component (C) is a catalyst for promoting the hydrosilylation reaction between the alkenyl group in the component (A) and the hydrogen atom bonded hydrogen atom in the component (B). Examples of such a component (C) include a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst, and platinum-based catalysts are preferable because they can significantly accelerate the curing of the composition of the present invention. Examples of the platinum-based catalyst include platinum fine powder, platinum chloride acid, an alcohol solution of platinum chloride acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex, and in particular, a platinum-alkenylsiloxane complex. Is preferable. Examples of the alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, and these. Examples thereof include alkenylsiloxanes in which a part of the methyl group of the alkenylsiloxane is substituted with a group such as an ethyl group or a phenyl group, and an alkenylsiloxane in which the vinyl group of these alkenylsiloxanes is substituted with a group such as an allyl group or a hexenyl group. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferable because the platinum-alkenylsiloxane complex has good stability.

Further, in order to improve the stability of this platinum-alkenylsiloxane complex, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1,3-diallyl-1,1,3,3- Tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane, 1,3,5 It is preferable to add an alkenylsiloxane such as 7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane or an organosiloxane oligomer such as a dimethylsiloxane oligomer, and it is particularly preferable to add an alkenylsiloxane.

The content of the component (C) may be any amount as long as it promotes the curing (hydrosilylation reaction) of the composition of the present invention, but specifically, the mass of the metal atom in the component with respect to the composition. In terms of conversion, the amount is in the range of 0.01 to 500 ppm, preferably in the range of 0.05 to 100 ppm, and particularly preferably in the range of 0.01 to 50 ppm. If the content of the component (C) is out of the above range, the composition may not be sufficiently cured, or the obtained cured product may have problems such as coloration due to metal, and it is not economical.

[Arbitrary ingredient]
In the composition of the present invention, as other optional components, ethynylcyclohexanol, 2-methyl-3-butyne-2-ol, 3,5-dimethyl-1-hexin-3-ol, 2-phenyl-3-ol Alkyne alcohols such as butin-2-ol; enein compounds such as 3-methyl-3-pentene-1-in, 3,5-dimethyl-3-hexene-1-in; 1,3,5,7-tetramethyl Contains reaction inhibitors such as -1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane and benzotriazole. May be. The content of this reaction inhibitor is not limited, but is preferably in the range of 0.0001 to 5 parts by mass with respect to 100 parts by mass of the total of the component (A) and the component (B).

Further, the composition of the present invention may contain an adhesive-imparting agent for improving the adhesiveness thereof. The adhesion-imparting agent is preferably an organosilicon compound having at least one, preferably two or more alkoxy groups bonded to a silicon atom in one molecule. Examples of this alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group, and a methoxy group is particularly preferable. As the groups other than alkoxy groups bonded to the silicon atom of the organosilicon compound, exemplified as R ¹ and the like, the alkyl group, the alkenyl group, the aryl group, the aralkyl group, such as the halogenated alkyl group Substituent or unsubstituted monovalent hydrocarbon group; glycidoxyalkyl group such as 3-glycidoxypropyl group, 4-glycidoxybutyl group; 2- (3,4-epoxycyclohexyl) ethyl group, 3- ( 3,4-Epoxycyclohexyl) Epoxycyclohexylalkyl group such as propyl group; Epoxy group-containing monovalent organic group such as oxylanylalkyl group such as 4-oxylanylbutyl group and 8-oxylanyloctyl group; 3- Acrylic group-containing monovalent organic groups such as methacryloxypropyl groups; hydrogen atoms are exemplified. Specific examples thereof include a silane coupling agent such as an epoxy group-containing silane coupling agent and a (meth) acrylic group-containing silane coupling agent, and a partially hydrolyzed condensate thereof (oligomer of the silane coupling agent).

More specifically, silane compounds such as 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxidecyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane; silicon atom in one molecule. Silicon atom-bonded hydroxy in one molecule with a siloxane compound having at least one bonded alkenyl group or silicon atom-bonded hydrogen atom and at least one silicon atom-bonded alkoxy group, and a silane compound or siloxane compound having at least one silicon atom-bonded alkoxy group. Examples thereof include a mixture of a siloxane compound having at least one group and at least one silicon atom-bonded alkenyl group, a methyl polysilicate, an ethyl polysilicate, and an epoxy group-containing ethyl polysilicate.

The adhesive is preferably a low-viscosity liquid, and its viscosity is not limited, but is preferably in the range of 1 to 500 mPa · s at 25 ° C.

Further, in the above composition, the content of the adhesive is not limited, but is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A).

Further, in the composition of the present invention, as any other component, an inorganic filler such as silica, glass, alumina, zinc oxide; an organic resin fine powder such as a polymethacrylate resin; a heat resistant agent, a dye, a pigment, and flame retardancy. It may contain an imparting agent, a solvent and the like.

Further, the composition of the present invention is preferably cured to form a cured product having a hardness specified in JIS of 10 or more with a durometer A, particularly 30 to 90.

Further, the composition of the present invention has a refractive index in visible light (589 nm) of the cured product obtained by curing in order to impart sufficient reliability to the semiconductor device having the semiconductor element coated with the cured product of the composition. It is preferable that (25 ° C.) is 1.4 or more and the light transmittance (25 ° C.) of the cured product is 80% or more.

The refractive index can be measured by, for example, an Abbe type refractive index meter. At this time, the refractive index at an arbitrary wavelength can be measured by changing the wavelength of the light source in the Abbe type refractive index meter. Further, this light transmittance can be obtained, for example, by measuring a cured product having an optical path length of 2.0 mm with a spectrophotometer.

Further, it is preferable that the ultraviolet transmittance (25 ° C.) at a wavelength of 200 nm to 250 nm of the cured product obtained by curing the composition of the present invention is 10% or less. This is to prevent deterioration of the material constituting the semiconductor device when the semiconductor device having the semiconductor element coated with the cured product of the composition of the present invention receives ultraviolet rays having a short wavelength of 200 nm to 250 nm. Is. This ultraviolet transmittance can be obtained, for example, by measuring a cured product having an optical path length of 2.0 mm with a spectrophotometer.

Curing of the composition of the present invention proceeds at room temperature or by heating, but heating is preferable for rapid curing. The heating temperature is preferably in the range of 50 to 200 ° C.

The cured product obtained by curing the composition of the present invention can be obtained in an elastomeric form, for example, a gel form, or a flexible rubber form to an elastic resin form. Such a composition of the present invention can be used as an adhesive for electric / electronic use, a potting agent, a protective coating agent, and an underfill agent. In particular, since it has a high light transmittance, it is a semiconductor device for optical applications. It is suitable as an adhesive, a potting agent, a protective coating agent, and an underfill agent.

A cured product made of the addition-curable silicone composition as described above has a high curing rate, a high light transmittance, and excellent high-temperature durability. It is useful as a sealing material.

The present invention further provides a semiconductor device using such an addition-curable silicone composition of the present invention.

Hereinafter, the semiconductor device of the present invention will be described with reference to the drawings, but the present invention is not limited thereto.

FIG. 1 is a schematic cross-sectional view showing an example of the semiconductor device of the present invention (in this case, an LED (light emitting diode)).

In the semiconductor device 1 of the present invention, a semiconductor chip 4 is die-bonded on a package 3 on which a silver-plated substrate 2 is formed, and the semiconductor chip 4 is wire-bonded by a bonding wire 5.

The semiconductor chip 4 is coated with the cured product 6 of the addition-curable silicone composition of the present invention described above.

The coating of the semiconductor chip 4 is performed by applying the above-mentioned addition-curable silicone composition 6 of the present invention and curing the addition-curable silicone composition 6 by heating. Of course, 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 the influence of external stress and suppressing the adhesion of dust and the like as much as possible, the addition-curable silicone composition 6 has a hardness specified in JIS of 30 by the durometer A by curing. It is preferable that the above cured product is formed.

The addition-curable silicone composition of the present invention forms a cured product having high light transmittance, high adhesion to a substrate, excellent crack resistance, and a small change in hardness after heat resistance. The semiconductor device of the present invention using the composition of the present invention has excellent reliability and is particularly suitable as a diode, an LED, or the like.

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

The viscosity in the examples is a value at 25 ° C. measured using a rotational viscometer, and the weight average molecular weight is a value in terms of standard polystyrene measured by gel permeation chromatography (GPC) using a THF solvent. The characteristics of the addition-curable silicone composition and the cured product thereof were evaluated as follows, and the results are shown in Table 1.

[Curability]
The addition-curable silicone composition was measured at 120 ° C. for 30 minutes using a rheometer MDR2000 manufactured by Alpha Technology, and the time when the torque reached 10% compared to the end time reached T10 and 90% torque. With time as T90, the speed at which the material reached the cured state was evaluated. The smaller the difference between T10 and T90, the faster the time to reach curing, that is, the better the curing property.

[Hardness]
A cured product was prepared by heating the addition-curable silicone composition at 150 ° C. for 3 hours using a hot air circulation oven. The hardness of this cured product was measured using a Durometer A hardness tester.

[Light transmittance]
The light transmittance of a cured product (optical path length 2.0 mm) prepared by heating the addition-curable silicone composition in a hot air circulation oven at 150 ° C. at a wavelength of 400 nm at 25 ° C. was measured.

[Crack resistance]
The package prepared as shown in FIG. 1 and cured by heating at 150 ° C. × 4 hours is placed in a thermal shock tester having {-40 ° C. (30 minutes), 100 ° C. (30 minutes)} as one cycle. The package after 100 cycles was observed with an optical microscope, and the case where cracks were found in the cured product was evaluated as x, the case where no cracks were observed was evaluated as ◯, and the case where the presence or absence of cracks was not clear was evaluated as Δ.

[Heat resistance (transparency)]
The cured product used in the above light transmittance measurement was further heated in a hot air circulation oven at 180 ° C. for 500 hours, and then the light transmittance at a wavelength of 400 nm at 25 ° C. was measured, and the light transmittance before heating was set to 100. It was evaluated by converting it into the value obtained.

[Heat resistance (hardness)]
The cured product used in the above hardness measurement is further heated in a hot air circulation oven at 180 ° C. for 500 hours, and then the hardness of the cured product is measured using a durometer A hardness meter to determine the hardness before heating. It was evaluated by converting it to a value of 100. When the measured value reached the measurement limit or more, it was considered to be above the limit.

[Example 1]
Branched chain organopolysiloxane represented by the following average unit formula (I) {property = solid state (25 ° C.), content of silicon atom-bonded vinyl group in all silicon atom-bonded organic groups = 3.9 mol%, Silicon atom-bonded content of silicon atom-bonded methyl group in all organic groups = 78 mol%, weight average molecular weight = 3,000} 50 parts by mass, molecular chain terminal dimethylvinylsiloxy group sealed dimethylpolysiloxane (viscosity 5,000 mPa. s, content of silicon atom-bonded vinyl group = 0.6 mol%) 50 parts by mass, organohydrogenpolysiloxane represented by the following formula (II) 5.0 parts by mass, platinum 1,3-Divinyl-1,1,3,3-tetramethyldisiloxane complex in an amount of 20 ppm in terms of mass of platinum metal with respect to the entire composition, 0.1 part by mass of ethynylcyclohexanol as a reaction inhibitor , 0.5 parts by mass of the compound represented by the following structural formula (III) was mixed as an adhesion-imparting agent to prepare an addition-curable silicone composition having a viscosity of 3,500 mPa · s.
_{(O 3/2 Si-C 2 H} 4 - (CH 3) SiO) 0.45 ((CH 2 = CH) (CH 3) 2 SiO 1/2) 0.1 ((CH 3) 3 SiO 1 / ₂ ) _0.45 (I)
(CH ₃ ) ₃ SiO ((H) (CH ₃ ) SiO) ₁₀ Si (CH ₃ ) ₃ (II)

[Example 2]
Branched chain organopolysiloxane represented by the following average unit formula (IV) {property = solid state (25 ° C.), content of silicon atom-bonded vinyl group in all silicon atom-bonded organic groups = 3.3 mol%, Silicon atom-bonded content of silicon atom-bonded methyl group in all organic groups = 82 mol%, weight average molecular weight = 5,000} 50 parts by mass, molecular chain terminal dimethylvinylsiloxy group-sealed dimethylpolysiloxane (viscosity 5,000 mPa. s, content of silicon atom-bonded vinyl group = 0.6 mol%) 50 parts by mass, 3.3 parts by mass of organohydrogenpolysiloxane represented by the above formula (II), 1,3-divinyl-1 of platinum , 1, 3,3-Tetramethyldisiloxane complex in an amount of 20 ppm in terms of mass of platinum metal with respect to the entire composition, 0.1 part by mass of ethynylcyclohexanol as a reaction inhibitor, and the following structural formula as an adhesion-imparting agent. 2.0 parts by mass of the compound represented by (V) was mixed to prepare an addition-curable silicone composition having a viscosity of 3,500 mPa · s.
_{(OSi (CH 3) -C 2} H 4 - (CH 3) SiO) 0.55 ((CH 2 = CH) (CH 3) 2 SiO 1/2) 0.1 ((CH 3) 3 SiO 1 / ₂ ) _0.35 (IV)

[Comparative Example 1]
Branched chain-shaped organopolysiloxane represented by the following average unit formula (VI) {property = solid state (25 ° C.), content of silicon atom-bonded vinyl group in all silicon atom-bonded organic groups = 7.4 mol% , Content of silicon atom-bonded methyl group in silicon atom-bonded total organic group = 92.6 mol%, weight average molecular weight = 3,600} 50 parts by mass, molecular chain terminal dimethylvinylsiloxy group sealed dimethylpolysiloxane (viscosity 5) 000 mPa · s, silicon atom-bonded vinyl group content = 0.6 mol%) 50 parts by mass, organohydrogenpolysiloxane represented by the above formula (II) 4.0 parts by mass, 1,3- of platinum The amount of divinyl-1,1,3,3-tetramethyldisiloxane complex to be 20 ppm in terms of mass of platinum metal with respect to the entire composition, 0.1 part by mass of ethynylcyclohexanol as a reaction inhibitor, and as an adhesion-imparting agent. 2.0 parts by mass of the compound represented by the structural formula (V) was mixed to prepare an addition-curable silicone composition having a viscosity of 6,500 mPa · s.
(SiO ₂ ) _0.55 [(CH ₂ = CH) (CH ₃ ) ₂ SiO _1/2 ] _0.1 ((CH ₃ ) ₃ SiO _1/2 ) _0.35 (VI)

[Comparative Example 2]
Branched chain-shaped organopolysiloxane represented by the following average unit formula (VII) {property = solid state (25 ° C.), content of silicon atom-bonded vinyl group in all silicon atom-bonded organic groups = 6.3 mol% , Silicon atom-bonded total organic group content of silicon atom-bonded methyl group = 93.8 mol%, weight average molecular weight = 5,600} 50 parts by mass, molecular chain terminal dimethylvinylsiloxy group sealed dimethylpolysiloxane (viscosity 5) 000 mPa · s, content of silicon atom-bonded vinyl group = 0.6 mol%) 50 parts by mass, 4.5 parts by mass of organohydrogenpolysiloxane represented by the above formula (II), 1,3- of platinum The amount of divinyl-1,1,3,3-tetramethyldisiloxane complex to be 20 ppm in terms of mass of platinum metal with respect to the entire composition, 0.1 part by mass of ethynylcyclohexanol as a reaction inhibitor, and as an adhesion-imparting agent. 2.0 parts by mass of the compound represented by the structural formula (V) was mixed to prepare an addition-curable silicone composition having a viscosity of 6,500 mPa · s.
(CH ₃ SiO _3/2 ) _0.70 [(CH ₂ = CH) (CH ₃ ) SiO] _0.1 ((CH ₃ ) ₃ SiO _1/2 ) _0.2 (VII)

[Comparative Example 3]
Branched chain organopolysiloxane represented by the following average unit formula (VIII) {property = solid (25 ° C), silicon atom-bonded vinyl group content in all organic groups = 20 mol%, silicon Atomic bond Content of silicon atom-bonded phenyl group in all organic groups = 60 mol%, weight average molecular weight = 1,600} 45 parts by mass, molecular chain terminal dimethylvinylsiloxy group sealed dimethylpolysiloxane (viscosity 3,500 mPa · s) , Silicon atom-bonded vinyl group content = 0.2 mol%, silicon atom-bonded phenyl group content in all silicon atom-bonded organic groups = 49 mol%) 55 parts by mass, represented by the following formula (IX) 24 parts by mass of methylphenylpolysiloxane, which is a dimethylhydrogensiloxy group-sealed methylphenylpolysiloxane at both ends of the molecular chain, and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum is added to the entire composition by the mass of platinum metal. An addition-curable silicone composition having a viscosity of 1,700 mPa · s is prepared by mixing 2.0 parts by mass of the compound represented by the above structural formula (V) as an adhesive-imparting agent in an amount of 2.5 ppm in terms of conversion. did.
(C ₆ H ₅ SiO _3/2 ) _0.75 [(CH ₂ = CH) (CH ₃ ) ₂ SiO _1/2 ] _0.25 (VIII)
H (CH ₃ ) ₂ SiO [CH ₃ (C ₆ H ₅ ) SiO] ₄ Si (CH ₃ ) ₂ H (IX)

[Comparative Example 4]
In Example 1, the branched organopolysiloxane represented by the above average unit formula (I) is represented by the following average unit formula (X) in a branched organopolysiloxane {property = solid state (25 ° C.). , Content of silicon atom-bonded vinyl group in all silicon atom-bonded organic groups = 16.7 mol%, content of silicon atom-bonded phenyl group in silicon atom-bonded all organic groups = 3.3 mol%, weight average molecular weight An addition-curable silicone composition having a viscosity of 2,300 mPa · s was prepared in the same manner as in Example 1 except that the setting was 2,100}.
(C ₆ H ₅ SiO _3/2 ) _0.05 (CH ₃ SiO _3/2 ) _0.70 [(CH ₂ = CH) (CH ₃ ) ₂ SiO _1/2 ] _0.25 (X)

As shown in Table 1, in Examples 1 and 2, the hardness of the cured product was sufficient, the curability, light transmittance and heat resistance of the cured product were also good, and no cracks were observed in the cured product. .. Furthermore, peeling due to catalytic poison did not occur, and the adhesion was high.

On the other hand, in Comparative Examples 1, 3 and 4, although the hardness was sufficient, cracks were observed, and Comparative Example 1 having _{2 units of SiO had poor curability.} Comparative Example 2 having no component (A) represented by the formula (1) also had no cracks, but was inferior in heat resistance. Further, Comparative Examples 3 and 4 also did not have the component (A) and were inferior in heat resistance. Furthermore, exfoliation due to catalytic poison has occurred.

From the above, the addition-curable silicone composition of the present invention has high light transmittance, high adhesion to the substrate, and various optics in order to form a cured product having excellent heat resistance and crack resistance. It was proved that it is suitable for applications.

In the above embodiment, the addition-curable silicone composition of the present invention was used as a potting agent for a semiconductor device. However, since the addition-curable silicone composition of the present invention has a particularly high light transmittance, other optics are used. It is suitable as an adhesive, a protective coating agent, an underfill agent, etc. for semiconductor elements of use, and can also be used as an adhesive for electric / electronic use, a potting agent, a protective coating agent, an underfill agent, and the like.

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

1 ... semiconductor device, 2 ... silver-plated substrate, 3 ... package, 4 ... semiconductor chip,
5 ... Bonding wire, 6 ... Additive curable silicone composition (cured product).

Claims (4)

Additive-curing silicone composition
(A) Organopolysiloxane represented by the following average unit formula (1),
[O _{{(3-k) / 2)}} Si (R ¹ ) _k −R ² − (R ¹ ) _k SiO _{{(3-k) / 2)}} ] _a (R ¹ ₃ SiO _1/2 ) _b (X ¹ O _1/2 ) _c ... (1)
(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, and ^{0.1 to 50% of all R 1} is an alkenyl group. R ² is a substituted or substituted group. It is an unsubstituted divalent hydrocarbon group, k is an integer of 0, 1, 2 which may be the same or different, X ¹ is a hydrogen atom or an alkyl group. A, b, c are 0.1 ≦ a. ≦ 1, 0 ≦ b ≦ 0.75, (b + c) / a is 0.4 to 4, c is 0 , and a + b + c = 1 is satisfied.)
(B) Organohydrogenpolysiloxane having at least two Si—H bonds in one molecule represented by the following average composition formula (2): 1 to 200 mass with respect to 100 parts by mass of the component (A). Department,
R ³ _{d He e} SiO _{[(4-d-e) / 2]} ... (2)
(In the formula, R ³ is a substituted or unsubstituted monovalent hydrocarbon group excluding the aliphatic unsaturated hydrocarbon group, which may be the same or different. D and e are 0.7 ≦ d ≦ 2. It is a positive number that satisfies 1, 0.01 ≦ e ≦ 1.0 and 0.8 ≦ d + e ≦ 2.7.)
as well as,
(C) Hydrosilylation reaction catalyst: An addition-curable silicone composition characterized by containing an amount of 0.01 to 500 ppm in terms of mass of metal atoms with respect to the entire composition. Wherein the component (A) addition-curable silicone composition of claim 1, number of carbon atoms of the divalent hydrocarbon group R ² in the average unit formula (1) is characterized in that it is a 2-8 thing. The addition-curable silicone according to claim 1 or 2, wherein in the component (A), ^{the content of a methyl group among R 1 in the average unit formula (1) is 20 mol% or more.} Composition. A semiconductor device comprising a semiconductor device coated with a cured product of the addition-curable silicone composition according to any one of claims 1 to 3.

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