TWI801654B - Addition hardening polysiloxane composition and semiconductor device - Google Patents

Abstract

(B)下述平均單位式(2)所示之有機聚矽氧烷，

(C)下述平均組成式(3)所示之1分子中至少具有2個Si-H鍵之有機氫聚矽氧烷，

及， (D)矽氫化反應觸媒。An object of the present invention is to provide an addition-curable polysiloxane composition that provides a cured product that cures rapidly, has high light transmittance, and is excellent in high-temperature durability, and a semiconductor device using the composition. The solution is an addition-hardening polysiloxane composition characterized by containing: (A) an organopolysiloxane represented by the following average unit formula (1),

(B) organopolysiloxane represented by the following average unit formula (2),

(C) An organohydrogenpolysiloxane having at least two Si-H bonds in one molecule represented by the following average composition formula (3),

And, (D) Hydrosilation reaction catalyst.

Description

Addition hardening polysiloxane composition and semiconductor device

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

Addition-curable polysiloxane compositions hardened by hydrosilylation reactions are used as protective coating agents for semiconductor devices in optical semiconductor devices such as optical couplers, light-emitting diodes, and solid-state imaging devices. Such a protective coating agent for a semiconductor element may change in hardness or transparency due to heat or light generated from the semiconductor element. In order to suppress this change, conventionally, Q units (SiO ₂ ) were introduced into the molecule (Patent Documents 1 to 4) and soft segments were introduced into the composition (Patent Document 5). However, this corresponding method is still unable to respond to changes in the hardness of permanent materials. In addition, since the peripheral components are made of resin that is easy to be heated, when it is cured at a low temperature such as 20-80°C, it is generally necessary to increase the amount of hardening catalyst to deal with it, so it has a disadvantage of being uneconomical. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 7-252419 [Patent Document 2] Japanese Unexamined Patent Publication No. 2011-252175 [Patent Document 3] Japanese Unexamined Patent Publication No. 2013-067683 [Patent Document 4] Japanese Unexamined Patent Publication No. 2009-052038 [Patent Document 5] Japanese Unexamined Patent Publication No. 2007-63538

[Problem to be Solved by the Invention]

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an addition-curable polysiloxane composition that provides a cured product that cures quickly, has high light transmittance, and is excellent in high-temperature durability, and a semiconductor device using the same . [Means to solve the problem]

(式中，R¹ 可為相同或相異之取代或未取代之脂肪族一價烴基，全部R¹ 之中0.1~50%為烯基。X¹ 為氫原子或烷基。a1、b1、c1為滿足0.1≦a1≦1、0≦b1≦0.75、0≦c1≦0.1，且a1+b1+c1=1之數。) (B)下述平均單位式(2)所示之有機聚矽氧烷：相對於(A)成分100質量份為0~5,000質量份，

(式中，R² 可為相同或相異之取代或未取代之脂肪族一價烴基，全部R² 之中0.01~25莫耳%為烯基。a2、b2為滿足0.33≦a2≦0.999、0.001≦b2≦0.67，且a2+b2=1之正數。) (C)下述平均組成式(3)所示之1分子中至少具有2個Si-H鍵之有機氫聚矽氧烷：相對於(A)成分與(B)成分之合計100質量份為1~200質量份，

(式中，R³ 為脂肪族不飽和烴基以外之可為相同或相異之取代或未取代之一價烴基。d、e為滿足0.7≦d≦2.1、0.01≦e≦1.0，且0.8≦d+e≦2.7之正數。)， 及， (D)矽氫化反應觸媒：相對於組成物全體並以金屬原子之質量換算成為0.01~500ppm之量。In order to solve the above problems, the present invention provides an addition-curable polysiloxane composition characterized by comprising: (A) an organopolysiloxane represented by the following average unit formula (1),

(In the formula, ^R1 can be the same or different substituted or unsubstituted aliphatic monovalent hydrocarbon groups, and 0.1~50% of all ^R1s are alkenyl groups. ^X1 is a hydrogen atom or an alkyl group. a1, b1, c1 is a number satisfying 0.1≦a1≦1, 0≦b1≦0.75, 0≦c1≦0.1, and a1+b1+c1=1.) (B) Organic polysilicon represented by the following average unit formula (2) Oxane: 0 to 5,000 parts by mass relative to 100 parts by mass of component (A),

(In the formula, ^R2 can be the same or different substituted or unsubstituted aliphatic monovalent hydrocarbon groups, and 0.01~25 mole% of all ^R2 are alkenyl groups. a2 and b2 satisfy 0.33≦a2≦0.999, 0.001≦b2≦0.67, and a2+b2=1 positive number.) (C) Organohydrogenpolysiloxane having at least 2 Si-H bonds in one molecule represented by the following average composition formula (3): relative 1 to 200 parts by mass for a total of 100 parts by mass of component (A) and component (B),

(In the formula, ^R3 is a substituted or unsubstituted monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon group, which may be the same or different. d and e satisfy 0.7≦d≦2.1, 0.01≦e≦1.0, and 0.8≦ A positive number of d+e≦2.7.), and, (D) Hydrosilylation reaction catalyst: an amount of 0.01 to 500 ppm in terms of the mass of metal atoms relative to the entire composition.

The cured product composed of the addition-curable polysiloxane composition of the present invention is useful as a light-reflecting material, for example, for light-emitting devices, especially for Useful as a sealing material for light-emitting diodes.

Also, in the aforementioned (A) component, ^R in the aforementioned average unit formula (1) is preferably one that includes an alkyl group having 1 to 3 carbon atoms.

In such a case, a cured product having more excellent heat resistance and curability can be obtained.

Also, in the above-mentioned component (A), among ^R1 in the above-mentioned average unit formula (1), the content of methyl group is 80 mol% or more, and the remainder is preferably vinyl group.

In such a case, a cured product having more excellent heat resistance and curability can be obtained.

Also, with respect to the total of 100 parts by mass of the components (A) and (B), further contain (E) an epoxy group-containing organosilane compound, and either one or both of the organopolysiloxane by 0.01 ~3 parts by mass is better.

Adhesiveness can be improved by making it contain (E)component in this way.

Furthermore, the present invention provides a semiconductor device characterized in that a semiconductor element is coated with a cured product of the above-mentioned addition-curable polysiloxane composition.

Such a semiconductor device can be a highly reliable semiconductor device because it is composed of a cured product that hardens quickly, has high light transmittance, and is excellent in high-temperature durability as described above. [Effect of Invention]

The cured product composed of the addition-curable polysiloxane composition of the present invention is useful as a light-reflecting material, for example, for light-emitting devices, especially for light-emitting diodes, due to its rapid curing, high light transmittance, and excellent high-temperature durability. Sealing material for polar bodies.

As a result of repeated studies on the above-mentioned problems, the inventors of the present invention have found that an addition-curable polysiloxane composition containing an organopolysiloxane having a specific structure can provide a cured product having excellent curability, transparency, and heat resistance. , and then complete the present invention.

(式中，R¹ 可為相同或相異之取代或未取代之脂肪族一價烴基，全部R¹ 之中0.1~50%為烯基。X¹ 為氫原子或烷基。a1、b1、c1為滿足0.1≦a1≦1、0≦b1≦0.75、0≦c1≦0.1，且a1+b1+c1=1之數。) (B)下述平均單位式(2)所示之有機聚矽氧烷：相對於(A)成分100質量份為0~5,000質量份，

(式中，R² 可為相同或相異之取代或未取代之脂肪族一價烴基，全部R² 之中0.01~25莫耳%為烯基。a2、b2為滿足0.33≦a2≦0.999、0.001≦b2≦0.67，且a2+b2=1之正數。) (C)下述平均組成式(3)所示之1分子中至少具有2個Si-H鍵之有機氫聚矽氧烷：相對於(A)成分與(B)成分之合計100質量份為1~200質量份，

(式中，R³ 為脂肪族不飽和烴基以外之可為相同或相異之取代或未取代之一價烴基。d、e為滿足0.7≦d≦2.1、0.01≦e≦1.0，且0.8≦d+e≦2.7之正數。)， 及， (D)矽氫化反應觸媒：相對於組成物全體並以金屬原子之質量換算成為0.01~500ppm之量。That is, the present invention is an addition-curable polysiloxane composition characterized by containing: (A) an organopolysiloxane represented by the following average unit formula (1),

(In the formula, ^R1 can be the same or different substituted or unsubstituted aliphatic monovalent hydrocarbon groups, and 0.1~50% of all ^R1s are alkenyl groups. ^X1 is a hydrogen atom or an alkyl group. a1, b1, c1 is a number satisfying 0.1≦a1≦1, 0≦b1≦0.75, 0≦c1≦0.1, and a1+b1+c1=1.) (B) Organic polysilicon represented by the following average unit formula (2) Oxane: 0 to 5,000 parts by mass relative to 100 parts by mass of component (A),

(In the formula, ^R2 can be the same or different substituted or unsubstituted aliphatic monovalent hydrocarbon groups, and 0.01~25 mole% of all ^R2 are alkenyl groups. a2 and b2 satisfy 0.33≦a2≦0.999, 0.001≦b2≦0.67, and a2+b2=1 positive number.) (C) Organohydrogenpolysiloxane having at least 2 Si-H bonds in one molecule represented by the following average composition formula (3): relative 1 to 200 parts by mass for a total of 100 parts by mass of component (A) and component (B),

(In the formula, ^R3 is a substituted or unsubstituted monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon group, which may be the same or different. d and e satisfy 0.7≦d≦2.1, 0.01≦e≦1.0, and 0.8≦ A positive number of d+e≦2.7.), and, (D) Hydrosilylation reaction catalyst: an amount of 0.01 to 500 ppm in terms of the mass of metal atoms relative to the entire composition.

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

＜Addition hardening polysiloxane composition＞ The addition-curable polysiloxane composition of the present invention contains the following components (A)~(D). Hereinafter, each component will be described in detail.

(式中，R¹ 可為相同或相異之取代或未取代之脂肪族一價烴基，全部R¹ 之中0.1~50%為烯基。X¹ 為氫原子或烷基。a1、b1、c1為滿足0.1≦a1≦1、0≦b1≦0.75、0≦c1≦0.1，且a1+b1+c1=1之數。)[Component (A)] Component (A) is an organopolysiloxane represented by the following average unit formula (1).

(In the formula, ^R1 can be the same or different substituted or unsubstituted aliphatic monovalent hydrocarbon groups, and 0.1~50% of all ^R1s are alkenyl groups. ^X1 is a hydrogen atom or an alkyl group. a1, b1, c1 is a number satisfying 0.1≦a1≦1, 0≦b1≦0.75, 0≦c1≦0.1, and a1+b1+c1=1.)

The alkenyl in R ¹ is preferably exemplified by vinyl, allyl, butenyl, pentenyl, and hexenyl, and vinyl is particularly preferred. In R ¹ , the alkenyl group content is 0.1-50 mol%, preferably 0.1-30 mol%, particularly preferably 0.3-20 mol%. If it is less than 0.1 mol %, the curability of the composition will be insufficient, and if it exceeds 50 mol %, the cured product will become brittle.

Also, as an organic group bonded to a silicon atom other than an alkenyl group ⁱⁿ R, examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, etc.; chloromethyl , 3-chloropropyl, 3,3,3-trifluoropropyl and other halogenated alkyl-substituted or unsubstituted aliphatic monovalent hydrocarbon groups, among which methyl is the best in terms of heat resistance. In R ¹ , as the content rate of the organic group bonded to the silicon atom other than the alkenyl group, if it is 20 mole % or more, since it can impart stable heat resistance, it is preferable, and it is more preferably 40 mole. %above.

In the component (A), when R ¹ in the above-mentioned average unit formula (1) is an alkyl group having 1 to 3 carbon atoms, it is particularly preferable because a cured product having excellent heat resistance and curability can be obtained.

In addition, in the component (A), among ^R1 in the above-mentioned average unit formula (1), the content of the methyl group is 80 mol% or more, and when the remainder is a vinyl group, it is excellent in heat resistance and curability. The hardened product, so it is especially good.

X ¹ is a hydrogen atom or an alkyl group, and examples of the alkyl group include the same groups as exemplified for R ¹ , particularly preferably a methyl group or an ethyl group.

a1 is 0.1~1, b1 is 0~0.75, c1 is 0~0.1, and a1+b1+c1 is 1. When a1, b1, and c1 are outside the above-mentioned ranges, the hardness and/or strength of the cured product obtained will become insufficient.

Preferably a1 is 0.15-0.9, particularly preferably 0.2-0.8, b1 is preferably 0-0.5, particularly preferably 0-0.4, and c1 is preferably 0-0.05.

(A) The molecular weight of the component is not limited, and the weight average molecular weight (Mw) obtained by standard polystyrene conversion measured by gel permeation chromatography (GPC) using THF solvent is preferably 500~20,000. The best is 700~15,000, and the best is 1,000~10,000.

(式中，R² 可為相同或相異之取代或未取代之脂肪族一價烴基，全部R² 之中0.01~25莫耳%為烯基。a2、b2為滿足0.33≦a2≦0.999、0.001≦b2≦0.67，且a2+b2=1之正數。)[(B) Component] (B) Component is an organopolysiloxane represented by the following average unit formula (2).

(In the formula, ^R2 can be the same or different substituted or unsubstituted aliphatic monovalent hydrocarbon groups, and 0.01~25 mole% of all ^R2 are alkenyl groups. a2 and b2 satisfy 0.33≦a2≦0.999, 0.001≦b2≦0.67, and a2+b2=1 positive number.)

R ² can be exemplified as the same as R ¹ in the (A) component, as alkenyl in R ² , preferably vinyl, allyl, butenyl, pentenyl, hexenyl can be exemplified, Vinyl is especially preferred. In R ² , the alkenyl group content is 0.01-25 mol%, preferably 0.1-20 mol%, particularly preferably 0.3-20 mol%. If it is less than 0.01 mol%, the curability of the composition becomes insufficient, and if it exceeds 25 mol%, the cured product becomes brittle.

Also, as an organic group bonded to a silicon atom other than an alkenyl group in ^R , examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, etc.; Halogenated alkyl, 3-chloropropyl, 3,3,3-trifluoropropyl and other aliphatic monovalent hydrocarbon groups substituted or unsubstituted, among which methyl is the best in terms of heat resistance. In R ² , the content of the aliphatic monovalent hydrocarbon group is preferably at least 20 mol%, since stability and heat resistance can be imparted, and is preferably at least 40 mol%.

a2 is 0.33-0.999, preferably 0.90-0.998, more preferably 0.956-0.997. b2 is 0.001-0.67, preferably 0.002-0.10, more preferably 0.003-0.044. When a2 and b2 are outside the above-mentioned ranges, the hardness and/or strength of the obtained hardened product will become insufficient.

The compounding quantity of the said (B) component is 0-5,000 mass parts with respect to 100 mass parts of (A) components, Preferably it is 10-3000 mass parts, More preferably, it is 20-1,000 mass parts. When the compounding quantity exceeds 5,000 mass parts, sufficient hardness and/or intensity|strength cannot be acquired.

(式中，R³ 為脂肪族不飽和烴基以外之可為相同或相異之取代或未取代之一價烴基。d、e為滿足0.7≦d≦2.1、0.01≦e≦1.0，且0.8≦d+e≦2.7之正數。)[Component (C)] Component (C) is an organohydrogenpolysiloxane represented by the following average composition formula (3).

(In the formula, ^R3 is a substituted or unsubstituted monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon group, which may be the same or different. d and e satisfy 0.7≦d≦2.1, 0.01≦e≦1.0, and 0.8≦ A positive number of d+e≦2.7.)

The viscosity of component (C) at 25°C is preferably 0.5~1,000mPa·s, more preferably 1~500mPa·s.

The number of carbon atoms of the monovalent hydrocarbon group represented by ^R3 is preferably 1 to 20, preferably 1 to 10. Examples of such hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, etc. tert-butyl, alkyl such as hexyl, saturated hydrocarbon such as cyclohexyl, such as cyclohexyl, aryl such as phenyl, tolyl, aralkyl such as benzyl, phenylethyl, etc., 3, A halogen-substituted hydrocarbon group such as 3,3-trifluoropropyl, a cyano-substituted hydrocarbon group, etc., is preferably methyl.

From the viewpoint of the compatibility with component (A) and the physical properties of the hardened product, among all the R ³ and H (hydrogen atoms) bonded to the silicon atom, 20 mol% or more are methyl groups, and 50 More than mol% is methyl.

(C) Component has at least 2, preferably 3 or more Si-H bonds (that is, hydrogen atoms bonded to silicon atoms) in one molecule, and the viscosity at 25°C is 0.5~1,000mPa·s Preferably, 1~500mPa·s is the best.

The structure of the siloxane chain as the component (C) is not particularly limited, and linear or cyclic organohydrogenpolysiloxane is preferable.

d and e are positive numbers satisfying 0.7≦d≦2.1, 0.01≦e≦1.0, and 0.8≦d+e≦2.7. If d and e are outside the above range, the hardness and/or strength of the hardened product obtained will become insufficient adequate.

d preferably satisfies 1.0≦d≦1.8, e preferably satisfies 0.02≦e≦1.0, more preferably satisfies 0.10≦e≦1.0, d+e preferably satisfies 1.01≦d+e≦2.4, more preferably Satisfy the positive number of 1.6≦d+e≦2.2.

The compounding quantity of (C) component is 1-200 mass parts with respect to 100 mass parts of (A) component, Preferably it is 5-80 mass parts. At 200 parts by mass, sufficient hardness and/or strength cannot be obtained.

Among the components (C), the molar ratio of the silicon atom in the component (C) bonded to the hydrogen atom (that is, SiH group) to the total alkenyl group in the component (A) and the component (B) is 0.5~5 mol / Mole, especially the amount of 1~3 Mole/Mole is better.

[(D) ingredient] (D) The hydrosilylation reaction catalyst of the component is a catalyst for promoting the hydrosilylation reaction of the alkenyl group in the (A) component and (B) component, and the hydrogen atom bonded to the silicon atom in the (C) component. Such (D) component includes, for example, platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Platinum-based catalysts are preferred because they can remarkably accelerate the hardening of the present composition. Examples of the platinum catalyst include fine platinum powder, chloroplatinic acid, alcohol solution of chloroplatinic acid, platinum-alkenyl siloxane complex, platinum-olefin complex, platinum-carbonyl complex Compounds, especially platinum-alkenyl siloxane complexes are preferred. Examples of alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3, 5,7-Tetravinylcyclotetrasiloxane, alkenylsiloxanes in which part of the methyl group of these alkenylsiloxanes is replaced by ethyl, phenyl, etc. groups, these alkenylsiloxanes Alkenyl siloxane in which the vinyl group is substituted by allyl, hexenyl, etc. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred because the platinum-alkenylsiloxane complex has good stability.

Also, in order to improve the stability of the platinum-alkenylsiloxane complex, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl-1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane Oxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl Alkenyl siloxanes such as cyclotetrasiloxane or organosiloxane oligomers such as dimethyl siloxane oligomers are preferable, and it is especially preferable to add alkenyl siloxanes.

(D) The content of the component is sufficient as long as it promotes the hardening (hydrosilylation reaction) of the composition. Specifically, the metal atoms in the composition are in the range of 0.01 to 500 ppm by mass. The amount is preferable, more preferably in the range of 0.05 to 100 ppm, especially preferably in the range of 0.01 to 50 ppm. When the content of the component (D) is out of the above-mentioned range, not only sufficient curability cannot be obtained, but also problems such as coloring may be caused, and it is not economical.

[Component (E)] The addition-curable polysiloxane composition of the present invention may further include: an epoxy group-containing organosilane compound or organopolysiloxane as component (E). (E) The component is an adhesive aid for improving the adhesion of silver plating, aluminum, polyphthalamide, alumina ceramics, and polycyclohexyl dimethylene terephthalate, as an epoxy group, When specifically exemplified, glycidoxyalkyl groups such as 3-glycidoxypropyl, 4-glycidoxybutyl, etc.; 2-(3,4-epoxycyclohexyl) ) ethyl, 3-(3,4-epoxycyclohexyl) propyl, etc. epoxycyclohexylalkyl; 4-oxiranylbutyl, 8-oxiranyloctyl, etc. A valent organic group containing an epoxy group such as an oxiranyl alkyl group. These monovalent organic group-containing organopolysiloxane and organosilane compounds are exemplified below.

The content of component (E) is preferably 0.01 to 3 parts by mass, more preferably 0.03 to 2 parts by mass, more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the total of components (A) and (B) . If it exists in such a range, favorable adhesiveness can be acquired without affecting heat resistance.

[optional ingredient] In this composition, as other optional components, ethynylcyclohexanol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, Alkyne alcohols such as 2-phenyl-3-butyn-2-ol; alkenes such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne Alkyne compounds; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5, Reaction inhibitor of 7-tetrahexenylcyclotetrasiloxane, benzotriazole, etc. The content of this reaction inhibitor is not limited, but it is preferably in the range of 0.0001 to 5 parts by mass with respect to 100 parts by mass of the total of (A) component and (B) component.

In addition, this composition may contain an adhesive imparting agent for improving the adhesiveness. As the adhesive imparting agent, an organosilicon compound having at least one, preferably two or more, alkoxy groups bonded to a silicon atom in one molecule is preferable. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and methoxyethoxy, and methoxy is particularly preferred. In addition, examples of the group other than the ^alkoxy group bonded to the silicon atom of the organosilicon compound include the aforementioned alkyl group, the aforementioned alkenyl group, the aforementioned aryl group, the aforementioned aralkyl group, the aforementioned A substituted or unsubstituted valent hydrocarbon group such as a halogenated alkyl group; a valent organic group containing an acryl group such as a 3-methacryloxypropyl group; a hydrogen atom. Specifically, silane coupling agents such as (meth)acryloyl group-containing silane coupling agents or their partial hydrolyzed condensates (oligomers of silane coupling agents) and the like can be exemplified.

More specifically, for example, silane compounds such as 3-methacryloxypropyltrimethoxysilane; one molecule has at least one alkenyl group bonded to a silicon atom or an alkenyl group bonded to a silicon atom. A siloxane compound having a hydrogen atom and an alkoxy group bonded to a silicon atom, a silane compound having at least one alkoxy group bonded to a silicon atom, or a siloxane compound and a siloxane compound having at least 1 of each A mixture of siloxane compounds with a hydroxyl group bonded to a silicon atom and an alkenyl group bonded to a silicon atom, methyl polysilicate, ethyl polysilicate, epoxy-containing ethyl polysilicate .

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

In addition, in the above-mentioned composition, the content of the adhesive imparting agent is not limited, but it is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A).

In addition, this composition may also contain inorganic fillers such as silicon dioxide, glass, aluminum oxide, and zinc oxide; organic resin fine powder such as polymethacrylate resin; heat-resistant agents, dyes, etc., as other optional components. , pigments, flame retardancy imparting agents, solvents, etc.

In addition, this composition is preferably a hardened product with a hardness of 10 or more, especially 30 to 90, with a hardness specified by JIS after hardening.

In addition, in order to impart sufficient reliability to a semiconductor device having a semiconductor element covered with a cured product of the composition, the cured product obtained by curing has a refractive index (25°C) of 1.4 in visible light (589 nm). Above, the light transmittance (25°C) of the cured product is better than 80%.

Also, the refractive index can be measured by, for example, an Abbe type refractometer. At this time, the refractive index of any wavelength can be measured by changing the wavelength of the light source in the Abbe refractometer. In addition, this light transmittance can be obtained by measuring, for example, a cured product with an optical path length of 2.0 mm using a spectrophotometer.

In addition, the UV transmittance (25°C) of the cured product obtained by curing the composition is preferably 10% or less at a wavelength of 200nm to 250nm. This is to prevent the deterioration of the material constituting the semiconductor device when the semiconductor device formed by covering the semiconductor element with the cured product of this composition is exposed to short-wavelength ultraviolet rays of 200nm to 250nm. The ultraviolet transmittance can be obtained, for example, by measuring a cured product with an optical path length of 2.0 mm using a spectrophotometer.

This composition can be hardened at room temperature or by heating, but heating is preferred for rapid hardening. As this heating temperature, it is preferable to be in the range of 50-200 degreeC.

The hardened product obtained by hardening the composition can be in the form of an elastomer, such as a gel, or a soft rubber or even a resin with elasticity. This kind of composition can be used as adhesives, potting agents, protective coatings, and underfills for electrical and electronic applications, and is especially suitable for semiconductor components for optical applications because of its high light transmittance. Adhesives, encapsulants, protective coatings, and underfills.

The present invention further provides a semiconductor device using the addition-hardening polysiloxane composition of the present invention.

Hereinafter, a semiconductor device related to 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 a semiconductor device of the present invention (LED (light emitting diode) in this case).

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

And, the semiconductor wafer 4 is covered with the cured product 6 of the addition-curable polysiloxane composition of the present invention.

The semiconductor wafer 4 is coated by applying the above-mentioned addition-curable polysiloxane composition 6 of the present invention and curing the addition-curable polysiloxane composition 6 by heating. Also, of course, it can also be cured by a known curing method under other known curing conditions.

Also, in this case, from the standpoint of making it less susceptible to external stress and suppressing the adhesion of dust as much as possible, the addition-curable polysiloxane composition 6 is hardened to a hardness specified by JIS using a durometer A It is better to measure more than 30 hardened objects.

The addition-curable polysiloxane composition of the present invention can form a cured product with high light transmittance, high adhesion to the substrate, excellent crack resistance, and small change in hardness after heat resistance, so it is used The semiconductor device of the present invention having such a composition of the present invention is excellent in reliability, and is particularly suitable as a diode, LED, and the like. [Example]

Hereinafter, although an Example and a comparative example are shown and this invention is concretely demonstrated, this invention is not limited by the following Examples etc.

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

[hardening] Use the rheometer MDR2000 made by Alpha Technology Co., Ltd. to measure the addition hardening polysiloxane composition at 120°C for 30 minutes. Compared with the end time, set the time to reach 10% torque as T10, and reach 90% torque The time is set as T90, and the speed at which the material reaches the hardened state is evaluated. The smaller the difference between T10 and T90, the faster the time to harden, which means good hardenability.

[hardness] The cured product was produced by heating the addition-curable polysiloxane composition at 150° C. for 3 hours using a hot-air circulation oven. The hardness of this hardened product was measured using a durometer A durometer.

[Transmittance] The light transmittance at 400nm wavelength at 25°C of the cured product (optical path length 2.0mm) produced by heating the addition-curable polysiloxane composition in a hot air circulation oven at 150°C for 3 hours to harden was measured.

[crack resistance] Put the package made as shown in Figure 1 and heat hardened at 150°C x 4 hours into a thermal shock tester that uses {-40°C (30 minutes), 100°C (30 minutes)} as a cycle, and The package after 100 cycles was observed with an optical microscope. When cracks were found on the cured product, it was rated as ×, when no cracks were found, it was rated as ○, and when the presence or absence of cracks was not obvious, it was rated as △.

[heat resistance (transparency)] After heating the cured product used in the above measurement of light transmittance in a hot air circulation oven at 180°C for 500 hours, measure the light transmittance at 400nm wavelength at 25°C, and convert the light transmittance before heating to A value of 100 is used for evaluation.

[heat resistance (hardness)]

After heating the hardened object used for the above hardness measurement in a hot air circulation oven at 180°C for 500 hours, measure the hardness of the hardened object with a hardness meter A hardness meter, and convert it into a value with the hardness before heating as 100 to evaluate. When the measured value exceeds the measurement limit, it is deemed to be above the limit.

[Example 1]

Mix the branched chain organopolysiloxane represented by the following average unit formula (I) as the component (A) {property = solid (25°C), bonded to the silicon atom in the whole organic group Vinyl group content of silicon atoms = 4.0 mole %, methyl group content of silicon atoms bonded to silicon atoms in all organic groups bonded to silicon atoms = 96 mole %, weight average molecular weight in terms of standard polystyrene = 13,000}50 parts by mass, molecular chain terminal dimethylvinylsiloxy-blocked chain dimethyl polysiloxane as component (B) (content rate of vinyl groups bonded to silicon atoms = 0.6 mol%) 50 parts by mass, organohydrogenpolysiloxane (viscosity 5,000mPa‧s) represented by the following formula (II) as component (C) 4.5 parts by mass, platinum 1,3-diethylene as component (D) Radixyl-1,1,3,3-tetramethyldisiloxane complex: 0.1 mass of ethynylcyclohexanol as a reaction inhibitor in an amount of 20 ppm based on the mass of platinum metal relative to the entire composition parts, and 0.5 parts by mass of a compound represented by the following structural formula (III) as an adhesive imparting agent to prepare an addition-curable polysiloxane composition with a viscosity of 3,500 mPa‧s.

(CH ₃ SiO _3/2 ) _0.7 ((CH ₃ ) ₃ SiO _1/2 ) _0.236 ((CH ₂ =CH)(CH ₃ ) ₂ SiO _1/2 ) _0.064 (I)

(CH ₃ ) ₃ SiO((H)(CH ₃ )SiO) ₁₀ Si(CH ₃ ) ₃ (II)

[Example 2]

Mix the branched chain organopolysiloxane represented by the following average unit formula (IV) as the component (A) {property = solid (25°C), bonded to the silicon atom in the whole organic group Vinyl group content of silicon atoms = 4.0 mol %, methyl content rate of silicon atoms bonded to silicon atoms in all organic groups bonded to silicon atoms = 96 mol %, weight average molecular weight = 15,000} 50 parts by mass, as (B) Molecular chain terminal dimethylvinylsiloxy-blocked chain dimethyl polysiloxane (viscosity 5,000mPa‧s, content of vinyl groups bonded to silicon atoms = 0.6 mol%) 50 mass Parts, 5.0 parts by mass of organohydrogenpolysiloxane represented by the above formula (II) as component (C), 1,3-divinyl-1,1,3,3-platinum as component (D) Tetramethyldisiloxane complex: an amount of 20 ppm based on the mass of platinum metal relative to the entire composition, 0.1 parts by mass of ethynylcyclohexanol as a reaction inhibitor, and the following structure as an adhesive agent 1.0 parts by mass of the compound represented by formula (V) was used to prepare an addition-hardening polysiloxane composition with a viscosity of 3,500 mPa‧s.

(CH ₃ SiO _3/2 ) _0.65 ((CH ₃ ) ₃ SiO _1/2 ) _0.286 ((CH ₂ = CH)(CH ₃ ) ₂ SiO _1/2 ) _0.064 (IV)

[Comparative Example 1] A branched chain organopolysiloxane represented by the following average unit formula (VI) was mixed {properties = solid (25°C), bonded to silicon atoms in all organic groups Vinyl content of silicon atoms = 7.4 mol%, content of methyl groups bonded to silicon atoms in all organic groups bonded to silicon atoms = 92.6 mol%, weight average molecular weight = 3,600} 50 parts by mass, molecule 50 parts by mass of chain-end dimethylvinylsiloxy-blocked chain dimethyl polysiloxane (viscosity 5,000 mPa·s, vinyl group content rate bonded to silicon atoms = 0.6 mol%), the above formula (II ) 4.0 parts by mass of organohydrogenpolysiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum: The mass conversion of platinum metal is 20ppm, 0.1 mass part of ethynyl cyclohexanol as a reaction inhibitor, and 2.0 mass parts of the compound represented by the above structural formula (V) as a bonding agent to prepare a viscosity of 6,500mPa・s addition hardening polysiloxane composition.

[Comparative Example 2] A branched chain organopolysiloxane represented by the following average unit formula (VII) was mixed {property = solid (25°C), bonded to silicon atoms in all organic groups Vinyl content of silicon atoms = 6.3 mol%, content of methyl groups bonded to silicon atoms in all organic groups bonded to silicon atoms = 93.8 mol%, weight average molecular weight = 5,600} 50 parts by mass, molecule 50 parts by mass of chain-end dimethylvinylsiloxy-blocked chain dimethyl polysiloxane (viscosity 5,000 mPa·s, vinyl group content rate bonded to silicon atoms = 0.6 mol%), the above formula (II ) 4.0 parts by mass of organohydrogenpolysiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum: The mass conversion of platinum metal is 20ppm, 0.1 mass part of ethynyl cyclohexanol as a reaction inhibitor, and 2.0 mass parts of the compound represented by the above structural formula (V) as an adhesive agent to prepare a viscosity of 6,500mPa・s addition hardening polysiloxane composition.

[Comparative Example 3] A branched chain organopolysiloxane represented by the following average unit formula (VIII) was mixed {property = solid (25°C), bonded to silicon atoms in all organic groups Vinyl content of silicon atoms = 20 mol%, content of phenyl groups bonded to silicon atoms in all organic groups bonded to silicon atoms = 60 mol%, weight average molecular weight = 1,600} 45 parts by mass, molecule Dimethylvinylsiloxy-blocked chain methylphenylpolysiloxane at both ends of the chain (viscosity 3,500mPa·s, content of vinyl groups bonded to silicon atoms = 0.20 mole %, vinyl groups bonded to silicon atoms The content of phenyl groups bonded to silicon atoms in the total organic group = 49 mole %) 55 parts by mass, the two ends of the molecular chain shown in the following formula (IX) dimethyl hydrogen siloxy blocked chain methyl phenyl 24 parts by mass of polysiloxane, platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex: relative to the entire composition and in terms of mass of platinum metal The amount of 2.5ppm, 0.1 mass part of ethynylcyclohexanol as a reaction inhibitor, 2.0 mass parts of the compound represented by the above structural formula (V) as an adhesive imparting agent, and prepared addition hardening with a viscosity of 1,700mPa·s type polysiloxane composition.

[Comparative Example 4] Except in Example 1, the branched chain organopolysiloxane represented by the above average unit formula (I) was replaced with the branched chain organopolysiloxane represented by the following average unit formula (X) Organopolysiloxane {properties = solid (25°C), among all organic groups bonded to silicon atoms, content of vinyl groups bonded to silicon atoms = 16.7 mol%, all organic groups bonded to silicon atoms Except for the content of phenyl groups bonded to silicon atoms = 3.3 mol%, and the weight average molecular weight of 2,100}, the addition-hardening polysiloxane composition with a viscosity of 2,300mPa·s was prepared in the same manner as in Example 1. thing.

As shown in Table 1, the hardness of the cured products in Examples 1 and 2 is sufficient, and the cured products have good curability, light transmittance and heat resistance, and no cracks are found on the cured products. In addition, no peeling due to catalyst poison occurred, and the adhesiveness 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 SiO ₂ units had poor hardenability. Also, in Comparative Example 2 having SiO units, no cracks occurred, but the heat resistance was inferior. In addition, Comparative Examples 3 and 4 containing organopolysiloxanes having a phenyl group were also inferior in heat resistance. Also, peeling caused by catalyst poison has occurred.

Based on the above, it can be proved that the addition-curable polysiloxane composition according to the present invention forms a cured product with high light transmittance, high adhesion to the substrate, and excellent heat resistance and crack resistance. , so it is suitable for various optical applications.

In the above-mentioned embodiments, the addition-curable polysiloxane composition of the present invention is used as an encapsulant for semiconductor elements, but the addition-curable polysiloxane composition of the present invention is particularly high in light transmittance, so others can also be used. Suitable for use as adhesives, protective coatings, underfills, etc. for semiconductor elements for optical applications, and also as adhesives, encapsulants, protective coatings, underfills, etc. for electrical and electronic applications.

In addition, the present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and those having substantially the same configuration as the technical idea described in the claims of the present invention, and having the same function and effect, are included in the technical scope of the present invention regardless of the type.

1: Semiconductor device 2: Silver plated substrate 3: Encapsulation 4: Semiconductor wafer 5: Bonding wire 6: Addition hardening polysiloxane composition (hardened product)

[ Fig. 1 ] A schematic cross-sectional view showing an example of a semiconductor device of the present invention.

1: Semiconductor device

2: Silver plated substrate

3: Encapsulation

4: Semiconductor wafer

5: Bonding wire

6: Addition hardening polysiloxane composition (hardened product)

Claims (3)

An addition-hardening polysiloxane composition characterized by containing: (A) an organopolysiloxane represented by the following average unit formula (1), (R ¹ SiO _3/2 ) _a1 (R ¹ ₃ SiO _1/2 ) _b1 (X ¹ O _1/2 ) _c1 ...(1) In the formula, R ¹ is a substituted or unsubstituted aliphatic monovalent hydrocarbon group and can be the same or different, and ^0.1 ~ 20% is alkenyl, and the content of methyl group is more than 80 mole%, ^X1 is a hydrogen atom or an alkyl group, and a1, b1, c1 satisfy 0.1≦a1≦1, 0≦b1≦0.75, 0≦c1 ≦0.1, and the number of a1+b1+c1=1; (B) organopolysiloxane represented by the following average unit formula (2): 10 to 5,000 parts by mass relative to 100 parts by mass of component (A), (R ² ₂ SiO) _a2 (R ² ₃ SiO _1/2 ) _b2 ... (2) In the formula, R ² is a substituted or unsubstituted aliphatic monovalent hydrocarbon group and can be the same or different, all R ² 0.01~25 mole% of them are alkenyl groups, a2 and b2 are positive numbers satisfying 0.33≦a2≦0.999, 0.001≦b2≦0.67, and a2+b2=1; (C) the following average composition formula (3) Organohydrogenpolysiloxane having at least two Si-H bonds in one molecule: 1 to 200 parts by mass relative to 100 parts by mass of the total of components (A) and (B), R ³ _d H _e SiO _{[ (4-de)/2]} ... (3) In the formula, R ³ is a substituted or unsubstituted monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon group and can be the same or different, and d and e satisfy 0.7≦d ≦2.1, 0.01≦e≦1.0, and a positive number of 0.8≦d+e≦2.7; and, (D) Hydrosilation reaction catalyst: an amount of 0.01-500 ppm in terms of the mass of metal atoms relative to the entire composition. The addition-curable polysiloxane composition according to claim 1, which further contains (E) an epoxy group-containing organosilane compound relative to 100 parts by mass of the total of (A) component and (B) component, and organic 0.01 to 3 parts by mass of either polysiloxane or both. A semiconductor device characterized in that a semiconductor element is coated with a hardened product of the addition-curable polysiloxane composition as claimed in claim 1 or 2.

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