JP2013057001A - Thermosetting resin composition, member for semiconductor device, and semiconductor device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a member for a semiconductor device in which there is no generation of a crack and a release at a long period of time of use, and which is excellent in gas barrier property and adhesion.SOLUTION: A thermosetting resin composition contains (A) a polysiloxane having an epoxy equivalent of 800 to 2,000 g/eq. and represented by formula (1): (RRRSiO)(RRSiO)(RSiO)(SiO)(OR), (B) an epoxy compound, (C) a curing agent, and (D) a curing catalyst, wherein the total of the epoxy equivalent of (A) the polysiloxane and (B) the epoxy compound contained in the thermosetting resin composition is 600 to 1,500 g/eq.; and the storage elastic modulus at 150°C of a cured material formed by a thermal treatment of the thermosetting resin composition as measured by a dynamic viscoelasticity measurement is 5.00×10to 1.50×10Pa.

Description

  The present invention relates to a novel thermosetting resin composition, a semiconductor device member, and a semiconductor device using the same. In detail, it is related with the thermosetting resin composition excellent in adhesiveness, heat resistance, light resistance, and film formability, the member for semiconductor devices, and a semiconductor device using the same.

2. Description of the Related Art In semiconductor devices, particularly light emitting diodes (hereinafter abbreviated as “LEDs” where appropriate) and semiconductor light emitting devices such as semiconductor lasers, the semiconductor light emitting elements are sealed with a member such as a transparent resin (semiconductor device member). What stopped is common.
As the semiconductor device member, for example, an epoxy resin is used. Moreover, what converts the light emission wavelength from a semiconductor light-emitting element by containing wavelength conversion substances, such as fluorescent substance, in this sealing resin is known.

  However, epoxy resin is corroded by contact with oxygen and sulfur compounds in the atmosphere in metals used for devices and electrodes because it has excellent gas barrier properties because its cured product has a high crosslinking density. Although the phenomenon of discoloration can be avoided, many of them are poorly flexible and generally have high hygroscopicity, so that cracks are generated due to thermal stress from the semiconductor light emitting element that occurs when the semiconductor device is used for a long time. Or the phosphor or the light emitting element deteriorates due to peeling from the semiconductor container or intrusion of moisture.

In recent years, the epoxy resin deteriorates and becomes colored with the shortening of the emission wavelength, so that there is a problem that the brightness of the semiconductor device is remarkably lowered when used for a long time and at a high output (Patent Document). 1).
In response to these problems, it has been proposed to use an epoxy silicone resin having an epoxy group and a silicone unit having excellent heat resistance, ultraviolet light resistance, and flexibility in the molecule as an alternative or combined item of epoxy resin. However, epoxy silicone resin, especially for semiconductor light emitting device package members, is diversified in structure. Increasing the amount of epoxy groups in the molecule improves gas barrier properties but reduces flexibility. , Reliability such as wrinkles and poor appearance cannot be avoided. On the other hand, when the amount of epoxy is reduced, cracking and peeling from the container are improved, but because of the trade-off relationship that the gas barrier property is lowered, the compatibility is still insufficient (Patent Document 2).

  In addition, for the purpose of reducing stress, a method of combining an epoxy resin not having Si with a silicone resin having an aromatic group not having a reactive functional group has been disclosed. However, gas barrier properties, cracks, peeling, wrinkles are also disclosed. The effect of improving reliability and appearance defects such as these was still insufficient (Patent Document 3).

Japanese Patent Application Laid-Open No. 07-309927 WO2007 / 125756 International Publication Pamphlet JP 2006-274249 A

From the above background, it has excellent adhesion, gas barrier properties, heat resistance, light resistance, and film formability to semiconductor light emitting device packages made of various constituent materials, and does not cause cracking, peeling, or coloring even after long-term use. There is a need for a semiconductor device member capable of sealing a semiconductor device and holding a phosphor. Further, when the thermosetting resin composition is used as a member for a semiconductor device, it is necessary to improve the hardness from the viewpoint of handleability.
The present invention has been made in view of the above-described problems. That is, the object of the present invention is excellent in adhesion, gas barrier properties, heat resistance, light resistance, and film formability to a package for a semiconductor light emitting device made of various constituent materials. A semiconductor device can be sealed without being generated, and a phosphor can be retained as necessary. Further, a novel thermosetting resin composition excellent in handleability and the thermosetting resin composition are cured. It is providing the member for semiconductor devices, and the semiconductor device using these.

  As a result of intensive studies to achieve the above object, the inventors of the present invention pay attention to the physical properties of the cured product, which is the actual use form, together with the epoxy amount of the thermosetting resin composition, and measure the dynamic viscoelasticity. It was found that the storage elastic modulus in the film has a high correlation between the gas barrier property and the adhesion, which are problems. That is, a thermosetting resin composition in which the total epoxy amount of (A) polysiloxane having a specific amount of epoxy group and aromatic group and the above-mentioned (A) polysiloxane and (B) epoxy compound is adjusted to a specific range. Therefore, by adjusting the storage elastic modulus in the dynamic viscoelasticity measurement of the cured product within a certain range, it is possible to achieve both gas barrier properties and adhesion for the first time, and the hardness becomes easy to handle. As a result, the present invention was completed.

That is, the gist of the present invention resides in the following [1] to [6].
[1] A thermosetting resin composition comprising the following (A) to (D), wherein the total of epoxy equivalents of (A) polysiloxane and (B) epoxy compound contained in the thermosetting resin composition is 600. The storage elastic modulus at 150 ° C. by dynamic viscoelasticity measurement of the cured product formed by heat-treating the thermosetting resin composition is 5.00 × 10 ⁵ −1. A thermosetting resin composition, which is 50 × 10 ⁷ Pa.
(A) Polysiloxane having an epoxy equivalent of 800 to 2000 g / equivalent to polysiloxane and represented by the following formula (1)
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (O _1/2 R ⁷ ) _e. (1)
[In the formula (1), at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is an epoxy-containing group, and the functional groups other than the epoxy-containing group are independent of each other. A monovalent oxygen atom and a C1-C10 hydrocarbon group which may contain a sulfur atom, and 10 mol% or more of them may be a C1-C8 substituted aromatic group It is a group. a is 0 to 0.3, b is 0.2 to 1.0, c is 0.1 to 0.7, d is 0 to 0.2, e is a number of e> 0, and a + b + c + d = 1. 0. ]
(B) Epoxy compound (C) Curing agent (D) Curing catalyst [2] The ShoreD hardness when cured by heat-treating the thermosetting resin composition is 10 to 45 [1] The thermosetting resin composition described in 1.
[3] The (R ⁴ R ⁵ SiO _2/2 ) component in the formula (A) polysiloxane represented by the formula (1) has a structure represented by the following formula (2). The thermosetting resin composition according to [1] or [2].
(R ⁸ R ⁹ SiO _2/2 ) _n (R ¹⁰ R ¹¹ SiO _2/2 ) _m (2)
In (Equation ^(2), at least one of R 8, ^{R 9} is an optionally substituted aromatic group having 1 to 8 carbon atoms, and the other ^{R 8,} R ^9, R ^{10, R 11} Each independently represents a monovalent oxygen atom or a hydrocarbon group having 1 to 10 carbon atoms which may contain a sulfur atom, where n is n ≧ 1 and m is m ≧ 0.
[4] The thermosetting resin composition according to [3], wherein the formula (2) is an oligomer having a weight average molecular weight of 500 or more.
[5] A semiconductor device member comprising a cured product obtained by curing the thermosetting resin composition according to any one of [1] to [4].
[6] A semiconductor light-emitting device comprising at least the semiconductor device member according to [5].

The thermosetting resin composition of the present invention is excellent in adhesion to a semiconductor device container, gas barrier properties, heat resistance, and light resistance. Furthermore, the film formability is also good, and the handleability when used as a semiconductor device member is also excellent.
In addition, since the semiconductor light emitting device of the present invention uses the above-described member for a semiconductor device of the present invention, even if it is used for a long period of time, it does not cause cracking, peeling or coloring in the sealing material, etc. Can be maintained.

It is a conceptual diagram showing the one aspect | mode of the semiconductor light-emitting device of this invention.

Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made without departing from the scope of the invention. The thermosetting resin composition of the present invention includes the following (A) to (D), and the epoxy equivalent of (A) polysiloxane and (B) epoxy compound contained in the thermosetting resin composition. The storage elastic modulus at 150 ° C. by dynamic viscoelasticity measurement of the cured product having a total of 600 to 1500 g / equivalent and heat-treating the thermosetting resin composition is 5.00 × 10 ^{5 to} 1.50 × 10 ⁷ .
(A) Polysiloxane (R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO ₂ ) having an epoxy equivalent of 800 to 2000 g / equivalent to polysiloxane and represented by the following formula (1) _{^{/ 2) b (R 6 SiO}} 3/2) c (SiO 4/2) d (O 1/2 R 7) e ··· (1)
[In the formula (1), at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is an epoxy-containing group, and the functional groups other than the epoxy-containing group are independent of each other. And a monovalent oxygen atom, a C1-C10 hydrocarbon group that may contain a sulfur atom, and 10 mol% or more of them may be a substituted C1-C8 aromatic group It is. a is 0 to 0.3, b is 0.2 to 1.0, c is 0.1 to 0.7, d is 0 to 0.2, e is a number of e> 0, and a + b + c + d = 1. 0. ]
(B) Epoxy compound (C) Curing agent (D) Curing catalyst The thermosetting resin composition of this invention can contain another component according to the use. For example, when the semiconductor device member of the present invention obtained by curing the thermosetting resin composition of the present invention is used as a member for a semiconductor light emitting device, the thermosetting resin composition of the present invention is phosphor or inorganic. It is preferable to contain fine particles.
Hereinafter, each component of the thermosetting resin composition of the present invention will be described.
[(A) Polysiloxane]
The (A) polysiloxane (hereinafter sometimes referred to as “component (A)”) used in the thermosetting resin composition of the present invention is a polysiloxane having an epoxy group as an essential component. Hereinafter, the component (A) will be described in detail.

The component (A) includes a unit represented by the formula: R ³ ₃ SiO _1/2 (M unit), a unit represented by the formula: R ² ₂ SiO _2/2 (D unit), and a formula: R ¹ SiO _3/2. Among the units represented by the formula (T unit) and the unit represented by the formula: SiO _4/2 (Q unit) and (O _1/2 R ⁷ ), the D unit component and the T unit component are essential components. It is a polysiloxane having an epoxy group selected and is represented by the following formula (1).
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (O _1/2 R ⁷ ) _e. (1)
In the formula (1), at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ is an epoxy-containing group, and the functional groups other than the epoxy-containing group are respectively It is a C1-C10 hydrocarbon group which may contain the monovalent oxygen atom and the sulfur atom independently, and 10 mol% or more of functional groups other than an epoxy-containing group is C1-C8. It is an essential requirement that it is an aromatic group which may be substituted.

Here, it is preferable that 15 mol% or more of the functional groups other than the epoxy-containing group in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are aromatic groups, It is more preferable that 20 mol% or more thereof is an aromatic group. When the aromatic group is 10 mol% or less, the compatibility with the (B) epoxy compound is deteriorated, and the cured product tends to become cloudy, and there is a tendency that sufficient gas barrier properties cannot be imparted.
The “functional group other than the epoxy-containing group among the R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ ” refers to the R ¹ , R ² , R ³ , R ^4. , R ⁵ , R ⁶ , and R ⁷ are the ratio of the aromatic group to the functional group other than the epoxy group.

A to e in the formula (1) will be described.
a represents the number of moles of M units described later, and is usually 0 or more, preferably 0.1 or more, and usually 0.3 or less, preferably 0.2 or less.
b represents the number of moles of the D unit described later, and is usually 0.2 or more, preferably 0.3 or more, and usually 1.0 or less, preferably 0.8 or less.
c represents the number of moles of T units described later, and is usually 0.1 or more, preferably 0.2 or more, and usually 0.7 or less, preferably 0.6 or less.
d represents the number of moles of the Q unit described later, and is usually 0 or more, and usually 0.2 or less, preferably 0.1 or less.
Further, a + b + c + d = 1.0.
e is a part of each component (R ¹ R ² R ³ SiO _1/2 ), (R ⁴ R ⁵ SiO _2/2 ), (R ⁶ SiO _3/2 ), and (SiO _4/2 ). This is the molar ratio of hydroxyl group or alkoxy group unit (O _1/2 R ⁷ ) _e directly bonded to the silane atom, and e must be larger than 0, and is usually included in the polysiloxane in the formula (1). It is necessary to contain 0.001-3 wt%, preferably 0.01-2 wt%, more preferably 0.01-1.5 wt%.

If it is out of the above range, curability may be lowered or a gel-like compound may be obtained, and handling for a semiconductor light emitting device member may be difficult.
Further, in the formula (1), the (R ⁴ R ⁵ SiO _2/2 ) _b component and the (R ⁶ SiO _3/2 ) _c component are essential, thereby impairing handling properties such as gelation. In addition, there is an effect that the adhesion and gas barrier properties necessary for a semiconductor light emitting device member can be imparted.

  In the formula (1), examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; a vinyl group, Alkenyl groups such as allyl group, butenyl group, pentenyl group, hexenyl group; aryl groups such as phenyl group, tolyl group and xylyl group; aralkyl groups such as benzyl group and phenethyl group; chloromethyl group, 3-chloropropyl group, 3 , 3,3-trifluoropropyl group, substituted alkyl group such as nonafluorobutylethyl group. Among these, a monovalent hydrocarbon group having 1 to 8 carbon atoms is preferable, and a methyl group and a phenyl group are particularly preferable.

  In the formula (1), the epoxy group-containing group is an epoxyalkyl group such as 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group; 2-glycidoxy Glycidoxyalkyl groups such as ethyl group, 3-glycidoxypropyl group, 4-glycidoxybutyl group; β- (or 2-) (3,4-epoxycyclohexyl) ethyl group, γ- (or 3- ) Epoxycyclohexylalkyl groups such as (3,4-epoxycyclohexyl) propyl group. Among these, a β- (or 2-) (3,4-epoxycyclohexyl) ethyl group is preferable.

Further, from the viewpoint of ensuring compatibility with the epoxy compound of (B) and ensuring a viscosity that is easy to handle, (R ⁴ R ⁵ in the formula of (A) polysiloxane represented by the above formula (1) The SiO _2/2 component preferably has a structure represented by the following formula (2).
(R ⁸ R ⁹ SiO _2/2 ) _n (R ¹⁰ R ¹¹ SiO _2/2 ) _m (2)
In (Equation ^(2), at least one of R 8, ^{R 9} is an optionally substituted aromatic group having 1 to 8 carbon atoms, and the other ^{R 8,} R ^9, R ^{10, R 11} Each independently represents a monovalent oxygen atom or a hydrocarbon group having 1 to 10 carbon atoms which may contain a sulfur atom, where n is n ≧ 1 and m is m ≧ 0.
Furthermore, about the weight average molecular weight of the structure represented by said Formula (2), there exists a possibility of increasing the contamination of a semiconductor light-emitting device or the stress of sealing hardened | cured material by volatilizing out from sealing hardened | cured material. It is preferably 500 or more, more preferably 700 or more, from the viewpoint of suppressing new generation of the annular body.

(Epoxy equivalent of polysiloxane (A))
The polysiloxane having an epoxy group (A) used in the present invention has an essential requirement that an epoxy equivalent has an epoxy equivalent in the range of 800 to 2000 g / equivalent in a part of the substituents. Thereby, while providing the adhesiveness with respect to the package for semiconductor light-emitting devices, the effect of promoting compatibilization at the time of addition of the epoxy compound of (B) is acquired. (A) The epoxy equivalent of polysiloxane is more preferably 900 to 1900 g / equivalent, further preferably 1000 to 1800 g / equivalent, and particularly preferably 1100 to 1800 g / equivalent. When the epoxy equivalent is 800 g / equivalent or less, when the thermosetting composition containing a polysiloxane having an epoxy group is cured by heat treatment as a member for a semiconductor light-emitting device, the cured product is too hard and heated. Since it becomes insufficient to relieve the stress generated during cooling, there is a possibility that the wiring provided in the semiconductor light emitting device is cut and the function as the semiconductor light emitting device is lost. Further, when the epoxy equivalent is 2000 g / equivalent or more, it becomes difficult for the cured product to barrier the metal electrode in the semiconductor light-emitting device from oxygen and sulfur-based gas in the atmosphere, so that the corrosion of the metal electrode proceeds. As a result, the function as a semiconductor device may be lost.

[(A) Production method of polysiloxane]
The polysiloxane having an epoxy group (A) used in the present invention is required to have an epoxy group in a part of the substituents, but the method for introducing the epoxy group is not particularly limited. A method is mentioned.
(1) A method of co-hydrolyzing and condensing a silane compound having an epoxy group with a silane compound not having an epoxy group and / or an oligomer thereof using a polysiloxane production raw material.
(2) A method of adding a compound having an epoxy group and a double bond group to polysiloxane containing a hydrosilane structure.
(3) A method of converting an epoxy group by oxidizing a double bond portion of a polysiloxane having a double bond.

The method for producing the polysiloxane having an epoxy group is not particularly limited. For example, the following method can be used.
Formula: unit represented by R ³ ₃ SiO _1/2 (M unit), formula: unit represented by R ² ₂ SiO _2/2 (D unit), unit represented by formula: R ¹ SiO _3/2 (T Unit) and a silane compound and / or a silane compound containing at least one selected from the group consisting of units represented by the formula: SiO _4/2 (Q unit) and / or a polycondensation reaction. A method may be employed in which an oligomer and an alkoxysilane containing an epoxy group or a partial hydrolyzate thereof are reacted in the presence of an acidic and / or basic catalyst. Here, it is preferable that 10 mol% or more of the functional groups other than the epoxy-containing group in each R is an aromatic group having 1 to 8 carbon atoms which may be substituted.

(material)
Examples of the silane compound raw material used for introducing the unit (M unit) represented by R ³ ₃ SiO _1/2 include trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane, and triphenylsilanol. .
_Examples of the silane compound raw material used for introducing the unit represented by R ² ₂ SiO _2/2 (D unit) include dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, diphenyldimethoxysilane, and dimethyldiethoxy. Examples include silane and methylphenyldiethoxysilane.

^As the hydrolysis-condensation product oligomers used to introduce the unit (D unit) represented by _{R 2} 2 SiO _2/2, the GE Toshiba Silicone Co., Ltd. hydroxy-terminated dimethylpolysiloxane, for example, XC96-723 XF3905, YF3057, YF3800, YF3802, YF3807, YF3897 and the like.
Further, hydroxy-terminated methylphenyl polysiloxane and hydroxy-terminated polydimethyldiphenylsiloxane are also preferably used.
Examples of the hydroxy-terminated polydimethyldiphenylsiloxane manufactured by GE Toshiba Silicone include YF3804.

Examples of both-end silanol polydimethylsiloxane manufactured by Gelest include DMSS12 and DMS-S14.
An example of the double-ended silanol diphenylsiloxane-dimethylsiloxane copolymer manufactured by Gelest is PDS-1615.
An example of both-end silanol polydiphenylsiloxane manufactured by Gelest is PDS-9931.

Although the weight average molecular weight of the hydrolysis-condensation product oligomer is arbitrary as long as the member for semiconductor light-emitting devices of this invention can be obtained, it is desirable that it is 500 or more normally.
The method for introducing the unit (D unit) represented by R ² ₂ SiO _2/2 is not particularly limited, but it is preferable to use a hydrolytic condensation oligomer as a raw material rather than a silane compound. If a silane compound is used frequently, the low-boiling ring in the polycondensate may increase, and the low-boiling ring will volatilize when a cured product is obtained as a semiconductor device member. This is because it may cause a decrease or generation of stress. Furthermore, the heat resistance of a semiconductor device member containing a large amount of low-boiling annular bodies may be lowered.
It is particularly preferable to use methylphenyl polysiloxane having a phenyl group, diphenyl-dimethylsiloxane copolymer, or polydiphenylsiloxane as a raw material.

Examples of the silane compound raw material used for introducing the unit represented by R ¹ SiO _3/2 (T unit) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethylsilane. Examples include methoxysilane, phenyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, and hydrolytic condensates thereof.

Examples of the silane compound raw material used for introducing the unit represented by SiO _4/2 (Q unit) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and hydrolytic condensates thereof.
As silane compound raw materials used for introducing epoxy groups, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, (γ-glycidoxypropyl) (methyl) dimethoxysilane, (γ-glycidoxypropyl) (ethyl) dimethoxysilane, (γ-glycidoxy Propyl) (methyl) diethoxysilane, (γ-glycidoxypropyl) (ethyl) diethoxysilane, [2- (3,4-epoxycyclohexylethyl] (methyl) dimethoxysilane, [2- (3,4- Epoxycyclohexyl) ethyl] (ethyl) dimethoxysilane, [2- (3,4-ethylene (Poxycyclohexyl) ethyl] (methyl) diethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethyl) diethoxysilane, (γ-glycidoxypropyl) (methoxy) dimethylsilane, (γ-glycyl Sidoxypropyl) (methoxy) diethylsilane, (γ-glycidoxypropyl) (ethoxy) dimethylsilane, (γ-glycidoxypropyl) (ethoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl ] (Methoxy) dimethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (methoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethoxy) dimethylsilane, [2- (3 , 4-epoxycyclohexyl) ethyl] (ethoxy) diethylsilane, [2- Examples include (3,4-epoxycyclohexyl) ethyl] (dimethyl) disiloxane, 3-epoxypropyl (phenyl) dimethoxysilane, etc. Among them, 2- (3,4-epoxycyclohexyl) ethyl is particularly used. Examples include trimethoxysilane and γ-glycidoxypropyltrimethoxysilane.

(catalyst)
(A) In the method for producing an epoxy group-containing polysiloxane, the above-described compound and / or oligomer thereof is reacted in the presence of an acidic and / or basic catalyst.
The acidic catalyst is a catalyst for causing a hydrolysis reaction of the alkoxysilane raw material, and examples of the acidic catalyst include inorganic acids, organic acids, acid anhydrides or derivatives thereof, and the like.
Examples of the inorganic acid include hydrochloric acid, phosphoric acid, boric acid, and carbonic acid.
Examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, lactic acid, malic acid, tartaric acid, citric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, Examples include oleic acid.

  The basic catalyst is a catalyst for co-hydrolysis / condensation reaction, for example, alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, cesium hydroxide; sodium-t-butoxide, potassium-t- Examples include alkali metal alkoxides such as butoxide and cesium-t-butoxide; alkali metal silanol compounds such as sodium silanolate compounds, potassium silanolate compounds and cesium silanolate compounds.

The cohydrolysis / condensation reaction can be stopped by neutralizing the catalyst. For neutralization, it is preferable to add weak acids such as carbon dioxide, carboxylic acid, hydrogen carbonate, hydrogen phosphate, and weak bases such as aqueous ammonia. The salt produced by neutralization can be easily removed by filtration or washing with water.
(Reaction temperature)
In the co-hydrolysis / condensation reaction using an acidic and / or basic catalyst, the reaction temperature is preferably 10 ° C. to 200 ° C., particularly preferably 30 ° C. to 150 ° C. at normal pressure. If the reaction temperature is too low, the reaction may not proceed sufficiently. If the reaction temperature is too high, the silicon-bonded organic group may be thermally decomposed. Moreover, you may make it react further, adjusting the solid content concentration in a reaction system with an organic solvent as needed.

(solvent)
In order to carry out the cohydrolysis / condensation reaction, water may be added as necessary. The amount of water used for carrying out the cohydrolysis / condensation reaction is usually 80% by weight or more, especially 100% by weight, based on the amount of water required for conversion of all alkoxy groups in the raw material as 100%. The above range is preferable. When the hydrolysis rate is less than this range, the co-hydrolysis / condensation reaction is insufficient, so that the raw material may volatilize during curing or the strength of the cured product may be insufficient.

Moreover, in order to carry out a cohydrolysis and a condensation reaction, you may add an organic solvent as needed.
By selecting an organic solvent having a boiling point of 80 ° C. to 200 ° C., a cohydrolysis / condensation reaction can be easily performed at the reflux temperature. As the organic solvent, for example, lower alcohols having 1 to 3 carbon atoms, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, toluene and the like can be arbitrarily used. Among them, those which do not show strong acidity or basicity are preferable because they do not adversely affect the cohydrolysis / condensation reaction. The organic solvent may be used alone or in combination of two or more in any combination and ratio.

  A solvent may be used when the inside of the system is separated and becomes non-uniform during the co-hydrolysis / condensation reaction. As the solvent, for example, lower alcohols having 1 to 3 carbon atoms, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, toluene, water and the like can be arbitrarily used. Of these, those that do not exhibit strong acidity or basicity are preferred because they do not adversely affect cohydrolysis / condensation. The solvent may be used alone or in combination of two or more in any combination and ratio.

  The amount of solvent used can be freely selected. However, since the solvent is often removed when applied to a semiconductor device, it is preferable to use the minimum amount. In order to facilitate the removal of the solvent, it is preferable to select a solvent having a boiling point of 100 ° C. or lower, more preferably 80 ° C. or lower. In addition, even if it does not add a solvent from the exterior, since solvents, such as alcohol, are produced | generated by a hydrolysis reaction, even if it is heterogeneous at the beginning of reaction, it may become uniform during reaction.

  When a solvent is used in the above-mentioned cohydrolysis / condensation reaction, it is usually preferable to distill off the solvent from the cohydrolysis / condensation product before curing. Thereby, the member formation liquid (liquid cohydrolysis and condensate) for semiconductor light emitting devices which does not contain a solvent can be obtained. By distilling off the solvent before drying, cracking, peeling, disconnection, and the like due to solvent removal shrinkage can be prevented.

  When a specific range of the temperature conditions when the solvent is distilled off is given, it is usually 60 ° C. or higher, preferably 80 ° C. or higher, under reduced pressure such that the main component of the cohydrolysis / condensation reaction product does not distill. More preferably, it is 100 ° C. or higher, usually 150 ° C. or lower, preferably 130 ° C. or lower, more preferably 120 ° C. or lower. If the lower limit of this range is not reached, the evaporation of the solvent may be insufficient, and if the upper limit is exceeded, the cohydrolysis / condensation reaction product may gel or the yield may be reduced.

(Weight average molecular weight)
(A) Although the weight average molecular weight of polysiloxane is not specifically limited, It is preferable that a weight average molecular weight is the range of 500-100,000, and it is especially preferable that it is the range of 1000-30,000.
[(B) Epoxy compound]
(B) Although there is no restriction | limiting in particular as an epoxy compound, Especially the aliphatic or alicyclic epoxy compound which is excellent in light resistance is preferable. Moreover, the (B) epoxy compound may be condensed.

  Particularly preferred epoxy compounds include compounds having a cyclohexyl epoxy group exemplified by the following formulas 1 and 2, alicyclic glycidyl ether compounds exemplified by formulas 3, 4, 5, 6, and 7, 9 and the disiloxane both-end epoxy compound exemplified in No. 9.

Also, for the purpose of improving the solder heat resistance of the cured product, a part of the alicyclic epoxy compound is phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, naphthalene type epoxy resin, aryl alkylene type It can be replaced with an epoxy resin or the like.
Here, the aryl alkylene type epoxy resin refers to an epoxy resin having one or more aryl alkylene groups in the repeating unit, and examples thereof include a xylylene type epoxy resin and a biphenyl dimethylene type epoxy resin.
Among these, a biphenyl dimethylene type epoxy resin is preferable. The biphenyl dimethylene type epoxy resin can be represented by, for example, the following general formula (II).

As the repeating unit n of the biphenyldimethylene type epoxy resin represented by the general formula (II), for example, those having 1 to 10 can be used, and those having 2 to 5 can be particularly preferably used. .
If the value of n is too small, it becomes easy to crystallize, so that the solubility in a general-purpose solvent tends to be small. On the other hand, if the value of n is too large, the fluidity tends to decrease. Handleability may be reduced.

  In addition to these, alicyclic epoxy compounds obtained by hydrogenating the following aromatic epoxy compounds may be used. Bisphenol type epoxy resin obtained by glycidylation of bisphenols such as bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrafluorobisphenol A, dihydroxynaphthalene, 9,9- Epoxy resin obtained by glycidylation of divalent phenols such as bis (4-hydroxyphenyl) fluorene, epoxy resin obtained by glycidylation of trisphenols such as 1,1,1-tris (4-hydroxyphenyl) methane, Epoxy resins obtained by glycidylating tetrakisphenols such as 1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, cresol novolac, bisphenol A And novolak epoxy resins obtained by glycidylating novolaks such as novolak and brominated bisphenol A novolak.

(Epoxy equivalent)
The (B) epoxy compound used in the present invention has an epoxy group in an epoxy equivalent of 600 to 1500 g / equivalent after mixing (A) and (B) including the polysiloxane (A). It is an essential requirement. About epoxy equivalent, 600-1300 g / equivalent is more preferable, and 600-1200 g / equivalent is further more preferable.

  When the epoxy equivalent after mixing (A) and (B) is 600 g / equivalent or less, when the thermosetting composition is cured by heat treatment as a member for a semiconductor light-emitting device, the cured product is too hard. Since it becomes insufficient to relieve the stress generated during heating and cooling, the wiring provided in the semiconductor device is stressed or partially peeled off, resulting in a decrease in the emission intensity of the semiconductor device. There is a possibility that. Further, when the epoxy equivalent after mixing (A) and (B) is 1500 g / equivalent or more, the mechanical strength of the cured product is remarkably lowered, and cracks are generated not only by an external force such as a slight impact, but also in the atmosphere. Since it becomes difficult to barrier the metal electrode in the semiconductor light-emitting device from oxygen and sulfur-based gas in the metal, corrosion of the metal electrode is likely to proceed, and yellowing due to deterioration of the heat-resistant coloring property of the cured product is likely to occur. The emission intensity of the semiconductor light emitting device may be reduced.

[(C) Curing agent]
Although there is no restriction | limiting in particular about (C) hardening | curing agent used by this invention, A carboxylic acid anhydride is preferable from a light-resistant viewpoint.
Examples of the alicyclic carboxylic acid anhydride include compounds represented by the following formulas (10) to (15), 4-methyltetrahydrophthalic acid anhydride, methylnadic acid anhydride, dodecenyl succinic acid anhydride, and the like. And Diels-Alder reaction products of alicyclic compounds having conjugated double bonds such as α-terpinene and alloocimene and maleic anhydride, and hydrogenated products thereof.

In addition, arbitrary structural isomers and arbitrary geometric isomers can be used as the Diels-Alder reaction product and hydrogenated products thereof.
In addition, the alicyclic carboxylic acid anhydride can be used after being appropriately chemically modified as long as the curing reaction is not substantially hindered.

Among these alicyclic carboxylic acid anhydrides, from the viewpoint of fluidity and transparency of the composition, compounds represented by formula (10), formula (11), formula (12), or formula (13), etc. The compound represented by formula (10) or formula (11) is particularly preferable.
In this invention, an alicyclic carboxylic acid anhydride can be used individually or in mixture of 2 or more types.

  The amount of the curing agent used is preferably 0.4 to 1.2 as an equivalent ratio of the carboxylic acid anhydride group to 1 mol of the epoxy group calculated from the epoxy equivalent after mixing (A) and (B). More preferably, it is 0.5 to 1.0. In this case, even if the corresponding amount ratio is less than 0.4 or more than 1.2, inconveniences such as a decrease in the glass transition point (Tg) of the obtained cured product and coloring may occur.

[(D) Curing catalyst]
The (D) curing catalyst used in the present invention is not particularly limited, and examples thereof include benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, and triethanolamine. Tertiary amines: 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-un Decylimidazole, 1- (2-cyanoethyl) -2-fe Nylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (hydroxymethyl) imidazole, 1 -(2-cyanoethyl) -2-phenyl-4,5-di [(2'-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl] -(1 ')] ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s- Liazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid of 2-phenylimidazole Adducts, imidazoles such as 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine isocyanuric acid adducts; diphenylphosphine, triphenylphosphine, phosphorous acid Organophosphorus compounds such as triphenyl; benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphospho Nitrobromide, tetraphenylphospho Phonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, methyltributylphosphonium dimethyl phosphate, tetrabutylphosphonium diethylphosphodithionate, tetra-n-butylphosphonium benzotriazolate, tetra- Quaternary phosphonium salts such as n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate;
Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof; organometallic compounds such as zinc octylate, tin actinate, aluminum acetylacetone complex; tetraethylammonium bromide, tetra -Quaternary ammonium salts such as n-butylammonium bromide; Boron compounds such as boron trifluoride and triphenyl borate; Metal halide compounds such as zinc chloride and stannic chloride, dicyandiamide and amines and epoxy resins High-melting point dispersion type latent curing accelerators such as amine addition type accelerators such as adducts; Microcapsules in which the surface of curing accelerators such as imidazoles, organophosphorus compounds and quaternary phosphonium salts are coated with a polymer Mold latent curing accelerator;
Amine salt type latent curing agent accelerators; latent curing accelerators such as high temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

Among these (D) curing catalysts, quaternary phosphonium salts, diazabicycloalkenes, organometallic compounds and quaternary ammonium salts are colorless and transparent, and a cured product which is difficult to discolor even when heated for a long time is obtained. This is preferable.
The (D) curing catalyst can be used alone or in admixture of two or more.
(D) The use amount of the curing catalyst is preferably 0.01 to 3 parts by weight with respect to a total of 100 parts by weight of (A) polysiloxane having an epoxy group, (B) epoxy compound and (C) curing agent, More preferably, it is 0.1-1.5 weight part. In this case, if the amount of the (D) curing catalyst used is less than 0.01 parts by weight, the effect of promoting the curing reaction tends to be reduced. Inconvenience may occur.

[Ratio of (A) to (D) components]
About the mixing ratio of each component of (A)-(D), the sum total of the epoxy equivalent of (A) polysiloxane and (B) epoxy compound contained in a thermosetting composition will be 600-1500 g / equivalent, and When the thermosetting composition is cured, there is no particular limitation as long as the storage elastic modulus at 150 ° C. becomes 5.00 × 10 ^{5 to} 1.50 × 10 ⁷ . As a preferable mixing ratio, when the total thermosetting composition is 100% by weight, (A) the polysiloxane is 50 to 90% by weight, (B) the epoxy compound is 1 to 50% by weight, and (C The curing agent is 1 to 50% by weight, and the (D) curing catalyst is 0.001 to 3% by weight.

[Other ingredients]
In addition to the components (A) to (D) described above, the thermosetting resin composition of the present invention can contain, for example, other components exemplified below.
The thermosetting resin composition of the present invention preferably contains an antioxidant from the viewpoint of suppressing yellowing under the use environment.
As said antioxidant, a phenolic antioxidant, phosphorus antioxidant, etc. are used suitably. Among these, a hindered phenol antioxidant having an alkyl group at one or both ortho positions of the phenol hydroxyl group is preferably used.
Examples of hindered phenol antioxidants include 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,4-di-tert-pentylphenol, 4,4′-thiobis (3 -Methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), bis- [3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) ) -Butanoic acid] -glycol ester, 2,4-di-tert-butylphenol, 2,4-di-tert-pentylphenol, 2- [1- (2-hydroxy-3,5-di-tert-) Pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, bis- [3,3-bis- (4′- Dorokishi-3'-tert-butylphenyl) - butanoate dichroic acid - glycol esters, and the like.

The trade names of the hindered phenol compounds include IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295 (all of which are manufactured by Ciba Specialty Chemicals), ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, ADK STAB AO-330 (all of which are manufactured by ADEKA), Sumilizer GA-80, SUMILZ MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP (above, all manufactured by Sumitomo Chemical Co., Ltd.), HOSTANOX O10, HOSTANOX O16, HOSTANOX O14, HOSTANOX O3 (above, both manufactured by Clariant), Antage BHT, Antage W-300, Antage W-400, Antage W500 (All as described above, manufactured by Kawaguchi Chemical Industry Co., Ltd.), SEENOX 224M, SEENOX 326M (all as described above, manufactured by Sipro Kasei Co., Ltd.), and the like.
The blending amount of the phenol compound is not particularly limited, but a preferable lower limit is 0.01 part by weight and a preferable upper limit is 1.0 part by weight with respect to 100 parts by weight of the thermosetting resin composition. When the blending amount of the phenolic compound is less than 0.01 parts by weight, the effect of adding the hindered phenolic compound may not be obtained. When the blending amount exceeds 1.0 part by weight, the light resistance decreases. Since it becomes remarkable, it is not preferable. The minimum with more preferable compounding quantity of the said phenolic compound is 0.05 weight part, and a more preferable upper limit is 0.7 weight part. In addition, in the thermosetting composition of this invention, the hindered phenol type compound mentioned above may be used independently, and 2 or more types may be used together.

The phosphorus compound is not particularly limited as long as it is a phosphorus compound having at least one skeleton selected from the group consisting of a phosphite skeleton, a phosphonite skeleton, a phosphate skeleton, and a phosphinate skeleton. For example, ADEASTAB PEP-4C, Adasterab PEP-8, Adasterab PEP-24G, Adasterab PEP-36, Adasterab HP-10, Adasterab 2112, Adasterab 260, Adasterab 522A, Adasterab 1178, Adasterab 1500, Adasterab C, Adasterab 135A, Adasterab 30TP, Adasterab 30TP, Adasterab 30TP Also made by ADEKA) Sand stub P-EPQ, Hostanox PAR24 (all are made by Clariant) JP-312L, JP-318-0, JP -308, JPM-313, JPP-613M, JPP-31, JPP-2000PT, JPH-3800 (above all are Johoku Chemical Co., Ltd.).
The blending amount of the phosphorus compound is not particularly limited, but a preferable lower limit is 0.005 parts by weight and a preferable upper limit is 1.0 part by weight with respect to 100 parts by weight of the thermosetting resin composition. When the compounding amount of the phosphorus compound is less than 0.005 parts by weight, the effect of adding the phosphorus compound may not be obtained. At this time, modification to a phosphoric acid-derived compound is not preferable because the possibility of accelerating the decomposition of the cured thermosetting resin is increased. The more preferable lower limit of the compounding amount of the phosphorus compound is 0.005 parts by weight, and the more preferable upper limit is 0.5 parts by weight. In addition, in the thermosetting composition of this invention, the phosphorus compound mentioned above may be used independently, and 2 or more types may be used together.
Moreover, the said hindered phenol type compound and phosphorus compound may be used together.
The thermosetting resin composition of the present invention preferably contains a coupling agent for imparting adhesion.

The coupling agent is not particularly limited. For example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ- Examples include silane coupling agents such as methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane.
These coupling agents may be used independently and 2 or more types may be used together.
As a compounding quantity of the said coupling agent, a preferable minimum is 0.1 weight part and a preferable upper limit is 3 weight part with respect to 100 weight part of the said thermosetting resin compositions. When the blending amount of the coupling agent is less than 0.1 parts by weight, the blending effect of the coupling agent may not be sufficiently exhibited. When the blending amount exceeds 3 parts by weight, the excess coupling agent is volatilized, and the present invention. When the thermosetting resin composition is cured, film loss may occur.

[Heat treatment method]
The member for a semiconductor device of the present invention is obtained by heat-treating a thermosetting resin composition containing the above-mentioned (A) polysiloxane, (B) epoxy compound, (C) curing agent, and (D) curing catalyst. Is.
The heating method for the heat treatment is not particularly limited, and conventionally known methods such as hot air circulation heating, infrared heating, and high frequency heating can be employed.
The heat treatment conditions are not particularly limited as long as the thermosetting resin composition can be brought into a desired cured state, but for example, 90 ° C. to 200 ° C. and preferably about 0.2 hours to 10 hours.
When it is intended to reduce the internal stress of the resulting cured product, for example, after pre-curing at 80 ° C. to 120 ° C. for about 0.5 hours to 3 hours, for example, at 120 ° C. to 180 ° C., 0 It is further preferable to perform post-curing under conditions of about 5 hours to 3 hours.

[Characteristics of semiconductor device members]
In this invention, the hardened | cured material obtained by heat-processing the thermosetting resin composition containing the above-mentioned (A) polysiloxane, (B) epoxy compound, (C) hardening | curing agent, and (D) hardening catalyst, The storage elastic modulus at 10 Hz at 150 ° C. by dynamic viscoelasticity measurement is usually 5.00 × 10 ⁵ Pa or more, preferably 8.00 × 10 ⁵ Pa or more, more preferably 1.00 × 10 ⁶ Pa or more. Moreover, it is 1.50 * 10 < ⁷ > Pa or less normally, Preferably it is 1.00 * 10 < ⁷ > Pa or less.

  Here, the storage elastic modulus is an index relating to retention of stress stored inside, and if the storage elastic modulus is in the above range, the shape can be maintained and excessive stress can be relaxed. An effect is obtained. The heat treatment is not particularly limited as long as the thermosetting resin composition can be brought into a desired cured state, and means that the heat treatment is performed at 90 ° C. to 200 ° C. for about 0.2 hours to 10 hours. . As the heat treatment, for example, heating at 150 ° C. for 2 hours may be performed.

When the storage elastic modulus is lower than 5.00 × 10 ⁵ Pa, it becomes difficult to maintain the shape when cured as a semiconductor device member, and tends to cause appearance defects such as wrinkles, and 1.50 × If it is higher than 10 ⁷ Pa, it becomes difficult to relieve stress, and cracks are likely to occur due to cutting of the wiring provided in the semiconductor device, heat treatment during curing, and changes in the environmental temperature during subsequent use. The function as a light emitting device may be lost.

In addition, a storage elastic modulus can be measured by the method as described in an Example. Moreover, in this invention, the hardened | cured material obtained by heat-processing the thermosetting resin composition containing the above-mentioned (A) polysiloxane, (B) epoxy compound, (C) hardening | curing agent, and (D) hardening catalyst. A durometer (Shore hardness) measurement described in ISO 7619 is an example of an index that easily represents an important flexibility in characteristics.
About the cured product obtained by heat-treating the thermosetting resin composition of the present invention, when measured with a type D in a durometer (Shore hardness) conforming to ISO7619, the Shore D hardness is in the range of 10 to 45, It is preferable to adjust the combination of the resin composition raw materials so that it is preferably in the range of 10-40.
When this Shore D hardness is 45 or more, stress relaxation becomes insufficient, and when used as a semiconductor device member, peeling due to stress may occur due to changes in environmental temperature or humidity, and cracks may easily occur. There is. On the other hand, if the Shore D hardness is less than 10, the surface may be easily damaged, and the shape as a semiconductor device member may be difficult to maintain.

[Applications for semiconductor device components]
The use of the member for a semiconductor device of the present invention is not particularly limited and can be used for various semiconductor devices, but is preferably used as a member for a semiconductor light emitting device. As a member for semiconductor light emitting device, for example, a member for sealing a semiconductor light emitting element (sealing material), a member for bonding a wire or the like to a lead frame or the like, a resin molding of a semiconductor light emitting device package It can be used for various applications such as a member (package material) constituting the body. Depending on the application, other components can be used in combination. For example, when used as a sealing material, it is preferable to use a phosphor, inorganic fine particles, etc., and when used as a die bond agent, a heat conductive agent, inorganic fine particles, etc. Are preferably used in combination, and when used as a packaging material, inorganic fine particles and the like are preferably used in combination.

  Hereinafter, the case where the member for semiconductor devices of this invention is used as a sealing material is demonstrated. The semiconductor device member of the present invention includes, for example, a phosphor, an inorganic substance, and a thermosetting resin composition containing the above-mentioned (A) polysiloxane, (B) epoxy compound, (C) curing agent, and (D) curing catalyst. A composition containing fine particles and the like, and after filling the composition into a cup of a semiconductor light emitting device package, it is cured or coated in a thin layer on an appropriate transparent support, for wavelength conversion. It can be used as a member.

In addition, a fluorescent substance, an inorganic fine particle, etc. may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios. In addition to the phosphor and inorganic fine particles, other components may be included as necessary.
(Phosphor)
The phosphor is not particularly limited as long as it is a substance that emits light of a different wavelength directly or indirectly excited by light emitted from a semiconductor light emitting element described later, and an organic phosphor even if it is an inorganic phosphor. Can be used. For example, one or more of blue phosphor, green phosphor, yellow phosphor, orange to red phosphor as exemplified below can be used.
It is preferable to appropriately adjust the type and content of the phosphor used so that a desired emission color can be obtained.

<Blue phosphor>
The blue phosphor preferably has an emission peak wavelength of usually 420 nm or more, particularly 430 nm or more, more preferably 440 nm or more, and usually 490 nm or less, especially 480 nm or less, and more preferably 470 nm or less.
Specifically, (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu, (Ba, Ca, Mg, Sr) ₂ SiO ₄ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu, (Ba, Ca, Sr) ₃ MgSi ₂ O ₈ : Eu are preferred, Ba, Sr) MgAl ₁₀ O ₁₇ : Eu, (Ca, Sr, Ba) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu, and Ba ₃ MgSi ₂ O ₈ : Eu are more preferable.

<Green phosphor>
As the green phosphor, those having an emission peak wavelength of usually 500 nm or more, particularly 510 nm or more, more preferably 515 nm or more, and usually 550 nm or less, especially 542 nm or less, further 535 nm or less are preferred.
_{Specifically, Y 3 (Al, Ga)} 5 O 12: Ce, CaSc 2 O 4: Ce, Ca 3 (Sc, Mg) 2 Si 3 O 12: Ce, (Sr, Ba) 2 SiO 4: Eu Β-sialon, (Ba, Sr) ₃ Si ₆ O ₁₂ : N ₂ : Eu, SrGa ₂ S ₄ : Eu, and BaMgAl ₁₀ O ₁₇ : Eu, Mn are preferable.

<Yellow phosphor>
As the yellow phosphor, those having an emission peak wavelength of usually 530 nm or more, particularly 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, particularly 600 nm or less, and further 580 nm or less are suitable.
The yellow _{phosphor, Y 3 Al 5 O 12:} Ce, (Y, Gd) 3 Al 5 O 12: Ce, (Sr, Ca, Ba, Mg) 2 SiO 4: Eu, (Ca, Sr) Si 2 N ₂ O ₂ : Eu, (La, Y, Gd, Lu) ₃ (Si, Ge) ₆ N ₁₁ : Ce are preferable.

<Orange to red phosphor>
As the orange to red phosphors, those having an emission peak wavelength of usually 570 nm or more, particularly 580 nm or more, more preferably 585 nm or more, and usually 780 nm or less, particularly 700 nm or less, and further 680 nm or less are preferable.
Specifically, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Ca, Sr, Ba) Si (N, O) ₂ : Eu, (Ca, Sr, Ba) AlSi ( _{N, O) 3: Eu,} (Sr, Ba) 3 SiO 5: Eu, (Ca, Sr) S: Eu, (La, Y) 2 O 2 S: Eu, Eu ( _{dibenzoylmethane)} 3 · 1, Β-diketone Eu complex such as 10-phenanthroline complex, carboxylic acid Eu complex, K ₂ SiF ₆ : Mn is preferable, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Sr, Ca) AlSi (N, O): Eu, (La, Y) ₂ O ₂ S: Eu, and K ₂ SiF ₆ : Mn are more preferable.
As the orange phosphor, (Sr, Ba) ₃ SiO ₅ : Eu, (Sr, Ba) ₂ SiO ₄ : Eu, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, ( Ca, Sr, Ba) AlSi (N, O) ₃ : Ce is preferred.

(Inorganic fine particles)
Examples of the inorganic fine particles (fillers) include inorganic oxide particles such as silica, barium titanate, titanium oxide, zirconium oxide, niobium oxide, aluminum oxide, cerium oxide, yttrium oxide, and diamond particles. Other materials can be selected accordingly, but are not limited thereto. By containing inorganic fine particles, optical characteristics and workability can be improved. What is necessary is just to select the kind of inorganic fine particle to mix according to the objective.

The form of the inorganic fine particles may be any form depending on the purpose, such as powder form, slurry form, etc., but when it is necessary to maintain transparency, the refractive index is made equal to the semiconductor light emitting device member of the present invention, It is preferable to add it as a solvent-based transparent sol to the member forming liquid for a semiconductor light emitting device.
The weight average median diameter (D50) of these inorganic fine particles (primary particles) is not particularly limited, but is preferably about 1/10 or less of the phosphor particles. Specifically, those having the following weight average median diameter (D50) are used according to the purpose.

  For example, if inorganic particles are used as the light scattering material, the weight average median diameter (D50) is preferably 0.1 to 10 μm. For example, if inorganic fine particles are used as the aggregate, the weight average median diameter (D50) is preferably 1 nm to 10 μm. For example, when inorganic fine particles are used as a thickener (thixotropic agent), the weight average median diameter (D50) is preferably 10 to 100 nm. For example, if inorganic particles are used as the refractive index adjuster, the weight average median diameter (D50) is preferably 1 to 10 nm.

Moreover, in order to improve dispersibility, it may be surface-treated with a surface treatment agent such as a silane coupling agent.
Although the content rate of the inorganic particle in the member for semiconductor light-emitting devices of the present invention is arbitrary as long as the effect of the present invention is not significantly impaired, it can be freely selected depending on the application form. For example, when inorganic particles are used as the light scattering agent, the content is preferably 0.01 to 10% by weight. For example, when inorganic particles are used as the aggregate, the content is preferably 1 to 50% by weight. For example, when using inorganic particles as a thickener (thixotropic agent), the content is preferably 0.1 to 20% by weight. Further, for example, when inorganic particles are used as the refractive index adjuster, the content is preferably 10 to 80% by weight. If the amount of inorganic particles is too small, the desired effect may not be obtained, and if it is too large, various properties such as adhesion, transparency and hardness of the cured product may be adversely affected.

[Semiconductor light-emitting device]
The light-emitting device of the present invention has a semiconductor light-emitting element and at least uses the member for a semiconductor light-emitting device of the present invention. It is possible. A specific example of the device configuration will be described later.
Although there is no restriction | limiting in particular in the usage method of the member for semiconductor light-emitting devices of this invention in the light-emitting body light-emitting device of this invention, As mentioned above, it can use as a sealing material, a die-bonding agent, etc. Since the thermosetting resin composition containing the above-mentioned (A) polysiloxane, (B) epoxy compound, (C) curing agent, and (D) curing catalyst is usually in a liquid state, it is cured as necessary. It is preferable to use it. The thermosetting resin composition may be cured in a state where it is put in a mold having a desired shape, or by curing in a state where the thermosetting resin composition is applied to a target portion, The member for a semiconductor light emitting device of the present invention can be formed directly on a target site.

The semiconductor light emitting device is not particularly limited, and a light emitting diode (LED), a laser diode (LD), or the like can be used.
The emission peak wavelength of the semiconductor light emitting device is not particularly limited as long as it overlaps with the absorption wavelength of the above-described light emitter, and a light emitter having a wide light emission wavelength region can be used. Usually, a light emitter having an emission wavelength from the ultraviolet region to the blue region is used.

The specific value of the emission peak wavelength of the semiconductor light emitting device is usually 300 nm or more, preferably 330 nm or more, more preferably 360 nm or more, and usually 510 nm or less, preferably 480 nm or less, more preferably 450 nm or less. It is possible to use a light emitter having a wavelength. The semiconductor light-emitting device member of the present invention introduces an organic functional group or an organic compound such as an epoxy group or a phenyl group in order to achieve both high gas barrier properties and adhesion to a package for a semiconductor light-emitting device. From the viewpoint, a combination with a semiconductor light emitting device having light emission in the blue region is preferable, and therefore a combination with a semiconductor light emitting device having a light emission peak in a wavelength range of 430 nm to 470 nm is particularly preferable.

Among these, GaN-based LEDs and LDs using GaN-based compound semiconductors are preferable as the semiconductor light emitting device. This is because GaN-based LEDs and LDs have significantly higher emission output and external quantum efficiency than SiC-based LEDs that emit light in this region, and emit very bright light with low power when combined with the phosphor. It is because it is obtained. For example, for a current load of 20 mA, GaN-based LEDs and LDs usually have a light emission intensity 100 times or more that of SiC-based. As the GaN-based LED and LD, those having an Al _X Ga _Y N light emitting layer, a GaN light emitting layer, or an In _X Ga _Y N light emitting layer are preferable. Among them, since the emission intensity is very high, the GaN-based LED is particularly preferably one having an In _X Ga _Y N light emitting layer, and more preferably a multiple quantum well structure having an In _X Ga _Y N layer and a GaN layer. preferable.

In the above, the value of X + Y is usually a value in the range of 0.8 to 1.2. In the GaN-based LED, those in which the light emitting layer is doped with Zn or Si or those without a dopant are preferable for adjusting the light emission characteristics.
A GaN-based LED has these light-emitting layer, p-layer, n-layer, electrode, and substrate as basic components, and the light-emitting layer is an n-type and p-type Al _X Ga _Y N layer, GaN layer, or In _X Those having a heterostructure sandwiched between Ga _Y N layers and the like are preferable because of high light emission efficiency, and those having a heterostructure having a quantum well structure are more preferable because of high light emission efficiency.

Only one semiconductor light emitting element may be used, or two or more semiconductor light emitting elements may be used in any combination and ratio.
[Embodiment of Semiconductor Light-Emitting Device]
For example, as shown in FIG. 1, the semiconductor light emitting device includes a semiconductor light emitting element 1, a resin molded body 2, a bonding wire 3, a phosphor containing portion (wavelength converting portion) 4, a lead frame 5, and the like.
In the present specification, a material made of a conductive material such as the lead frame 5 and an insulating resin molding may be referred to as a package.

  The semiconductor light emitting device 1 uses a near ultraviolet semiconductor light emitting device that emits light having a wavelength in the near ultraviolet region, a purple semiconductor light emitting device that emits light in a purple region, a blue semiconductor light emitting device that emits light in a blue region, and the like. It emits light having a wavelength of 300 nm or more and 520 nm or less. Although only one semiconductor light emitting element is mounted in FIG. 1, a plurality of semiconductor light emitting elements can be arranged in a linear shape or a planar shape. By arranging the semiconductor light emitting element 1 in a planar shape, surface illumination can be obtained, and such an embodiment is suitable when it is desired to further increase the output.

  The resin molded body 2 constituting the package may be molded together with the lead frame 5. The shape of the package is not particularly limited, and may be a planar type or a cup type. The member for light emitting device of the present invention can also be used as the resin molded body 2. In addition, one of the surprising effects of the present invention is that, by using a polysiloxane having an epoxy group and an epoxy compound in combination, adhesion to polyphthalamide used as a material for a semiconductor light emitting device package for the first time is very high. It is mentioned that it was confirmed that it would be high. Therefore, in the case where the light emitting device member is used for the phosphor-containing portion, it is possible to express high adhesion by using polyphthalamide as the material of the resin molded body constituting the package, and to ensure long-term reliability. preferable.

The lead frame 5 is made of a conductive metal, and plays a role of supplying power from outside the semiconductor light emitting device and energizing the semiconductor light emitting element 1.
The bonding wire 3 has a role of fixing the semiconductor light emitting element 1 to the package. Further, when the semiconductor light emitting element 1 is not in contact with the lead frame as an electrode, the conductive bonding wire 3 plays a role of supplying power to the semiconductor light emitting element 1. The bonding wire 3 is bonded to the lead frame 5 by applying pressure and applying heat and ultrasonic vibration. The member for light emitting device of the present invention can also be used as a die bond agent used for bonding of the bonding wires.

A resin molded body 2 constituting the package is mounted with a semiconductor light emitting element 1 and sealed with a phosphor-containing portion (wavelength converting portion) 4 in which phosphors are mixed.
The member for semiconductor light emitting device of the present invention can be suitably used for the phosphor-containing portion 4 as a sealing material. The phosphor-containing part 4 can be obtained, for example, by mixing phosphors, inorganic fine particles, and the like in a semiconductor light-emitting device member forming liquid and curing as necessary. When the semiconductor light-emitting device member of the present invention is not selected as a component contained in the phosphor-containing portion 4, a light-transmitting resin that is usually used for a sealing material may be appropriately selected. Specifically, an epoxy resin, a silicone resin, an acrylic resin, a polycarbonate resin, and the like can be given, and it is preferable to use a silicone resin. In addition, you may use together these translucent resin and the member for semiconductor light-emitting devices of this invention.

  The phosphor converts the excitation light from the semiconductor light emitting element 1 and emits visible light having a wavelength different from that of the excitation light. The phosphor contained in the phosphor-containing part 4 is appropriately selected according to the wavelength of the excitation light of the semiconductor light emitting device 1. In a semiconductor light emitting device (white LED) that emits white light, when a semiconductor light emitting element that emits blue light is used as an excitation light source, white light is generated by including green and red phosphors in the phosphor layer. Can do. In the case of a semiconductor light emitting device that emits violet light, white light is generated by including blue and yellow phosphors in the phosphor layer, or by including blue, green, and red phosphors in the phosphor layer. be able to.

[Applications of semiconductor light-emitting devices]
The use of the light-emitting device of the present invention is not particularly limited, and can be used in various fields in which ordinary light-emitting devices are used. However, since the color rendering property is high and the color reproduction range is wide, the illumination device is particularly preferable. And as a light source for image display devices.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, they are for the purpose of explaining the present invention, and are not intended to limit the present invention to these embodiments.
[1] Measurement method [1-1] Measurement of gel permeation chromatography (GPC) The weight average molecular weight Mw and number average molecular weight Mn of the curable composition were measured by gel permeation chromatography under the following conditions, and converted into standard polystyrene. Shown as value. A 1.0 mass% tetrahydrofuran (THF) solution of polysiloxane was prepared, and then filtered through a 0.45 μm filter to obtain a measurement sample solution. Apparatus: 2695 (main body) -2410 (RI unit) (manufactured by Waters)
Column: KF-G + KF-602.5 + KF-603 + KF-604 (Showa Denko)
Eluent: THF, flow rate 0.7 mL / min, sample concentration 1.0%, injection volume 10 μL

[1-2] Epoxy equivalent It was determined by the following operation and calculation method.
About 0.5 g of (A) polysiloxane used in each example and comparative example was dissolved in 50 ml of 2-propanol. To this solution, 25 ml of hydrochloric acid / 2-propanol mixed solution (volume ratio 1: 4) and cresol red were added, and titrated with 0.2 N sodium hydroxide. The reaction system turned from red to yellow, and purple. The point that changed to was defined as the equivalent point. From the equivalent point, the epoxy equivalent of (A) polysiloxane was calculated according to the following formula.

Epoxy equivalent (g / equivalent) = (W / (Vr−V)) × (1000 / 0.2)

W: Weight of sample (g)
Vr: The amount of 0.2N sodium hydroxide solution required for titration of 25 ml of hydrochloric acid / 2-propyl alcohol mixed solution (mL)
V: Titration volume (mL) [1-3] Durometer (Shore D hardness) measurement The semiconductor device members (thermosetting compositions) of Examples and Comparative Examples were heat-treated at 80 ° C. for 1 hour and further at 150 ° C. for 1 hour. The cured product thus cured was subjected to hardness measurement using an Asker rubber hardness meter type D manufactured by Kobunshi Keiki Co., Ltd.

[1-4] Adhesion Evaluation Method Adhesion Evaluation Method (1) The hydrolysis / polycondensation liquid (thermosetting resin composition) before curing of the semiconductor device members of Examples and Comparative Examples was 9 mm in diameter The one dropped into a polyphthalamide cup on the Ag plating surface with a depth of 1 mm should be left in a hot air dryer set at 100 ° C. for 0.5 hour, then heated to 150 ° C. and then left for another 2 hours. The sample for measurement (member for semiconductor devices) was produced by curing with the above.

(2) A thin heat-dissipating silicone grease is applied to an aluminum plate having a thickness of 1 mm, a length of 25 mm, and a width of 70 mm. For 20 hours.
(3) The moisture-absorbing measurement sample was taken out from the moisture-absorbing environment (2) and cooled to room temperature (20 to 25 ° C.). The sample for measurement which was absorbed and cooled was placed on a hot plate set at 260 ° C. together with the aluminum plate, and held for 1 minute. Under this condition, the actual temperature of the measurement sample reaches 260 ° C. in about 50 seconds, and is then maintained at 260 ° C. for 10 seconds.

(4) The heated sample was placed together with the aluminum plate on a stainless steel, room temperature cooling plate and allowed to cool to room temperature. A sample that was observed to be peeled off, wrinkled, or turbid from the polyphthalamide cup by visual observation or microscopic observation was defined as “exterior appearance”.
[1-5] Evaluation of water vapor permeability The obtained curable composition was charged into an aluminum cup so that the dry film thickness was 1 mm, and held at 100 ° C. for 1 hour and at 150 ° C. for 3 hours. Produced. With reference to JISZ0208, 2.0 g of calcium chloride was weighed in a container having a volume of 20 cm ³ , and the container was sealed with a sample having a radius of 5.5 mm. This container was stored at a temperature of 60 ° C. and a humidity of 95% RH, and after 24 hours or 48 hours, the test sample was weighed and evaluated by weight increase.

Calculation formula (defined so that the transmission amount of Comparative Example 2 is 100):
(Water vapor transmission amount) = 100 × (Ws × Ds) / (Wr × Dr)
Ws: Weight change due to moisture permeation of sample Wr: Weight change due to moisture permeation of Comparative Example 2 Ds: Film thickness of sample Dr: Film thickness of Comparative Example 2 Note that this water vapor permeation amount (relative ratio) is preferably lower. .

[1-6] Dynamic viscoelasticity test About the thermosetting resin composition of each Example and each Comparative Example, about 2.0 g dropped on an aluminum cup having an inner diameter of 50 mm, inside a hot air dryer set at 100 ° C. After standing for 0.5 hour, the temperature was raised to 150 ° C., and then allowed to stand for 2 hours to obtain a cured product. About the cured product, a film having a width of 5 to 10 mm, a length of 15 to 30 mm, and a thickness of 0.5 to 1 mm was prepared as a test sample, and a dynamic viscoelasticity test at −150 ° C. to 260 ° C. was performed under the following conditions. . The conditions are as follows.
Measurement conditions
Distance between chucks: 5-20mm
Temperature increase rate: −150 ° C. to 260 ° C. within a temperature range of 3 ° C./min Measurement frequency: 10 Hz
Measuring device: EXSTAR6000 DMS6100

[2] (A) Synthesis of polysiloxane (Synthesis Example 1)
47.4 g of hydroxy-terminated methylphenylpolysiloxane having Mw = 740, 13.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as an epoxy group-containing alkoxysilane, and 3.85 g of a 1 mol / L aqueous hydrochloric acid solution were mixed. 2-propyl alcohol 32.5g was added and it was made to react at 25 degreeC for 3 hours.
To the obtained reaction solution, 102 g of 2-propyl alcohol and 0.443 g of potassium hydroxide were added, followed by heating and refluxing for 8 hours. Then, after neutralizing the reaction solution with an aqueous solution of sodium dihydrogen phosphate (10% by mass), volatile components were removed under reduced pressure, and the resulting polymer was dissolved in an aqueous solution of toluene / sodium dihydrogen phosphate (10% by mass). After washing with water using a toluene / water layer until the water after washing became neutral, volatile components were removed under reduced pressure to obtain polysiloxane (A) -1 having Mw = 1380.
When the epoxy equivalent of this polysiloxane (A) -1 was evaluated, it was 1245 g / equivalent.

(Synthesis Example 2)
30.0 g of hydroxy-terminated polydiphenyldimethylsiloxane (product name: YF3804, manufactured by Momentive Co., Ltd.) having Mw = 3000, 3.70 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as an epoxy group-containing alkoxysilane, 10 % Tetramethylammonium hydroxide aqueous solution 1.17g was mixed, 2-propyl alcohol 33.7g was added, and it heated and refluxed for 7 hours.
Thereafter, the obtained reaction solution was neutralized, removed of volatile components under reduced pressure, and washed in the same manner as in Synthesis Example 1 to obtain polysiloxane (A) -2 having Mw = 3280.
When the epoxy equivalent of this polysiloxane (A) -2 was evaluated, it was 2226 g / equivalent.
(Synthesis Example 3)
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 20.1 g, dimethyldimethoxysilane 1.36 g, diphenyldimethoxysilane 2.80 g , 75.0 g of methyl isobutyl ketone and 2.60 g of triethylamine were added and mixed at room temperature. Next, 20.2 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 8 hours while mixing under reflux.
After completion of the reaction, the organic layer is taken out from the obtained reaction solution, washed with an aqueous sodium dihydrogen phosphate solution (10% by mass) until the washed water becomes neutral, and then volatile components are removed under reduced pressure. Thus, polysiloxane (A) -3 having Mw = 1850 was obtained.
When the epoxy equivalent of this polysiloxane (A) -3 was evaluated, it was 247 g / equivalent.
The polysiloxanes synthesized in Synthesis Examples 1 to 3 were designated as polysiloxanes (A) -1 to (A) -3, respectively, and used in the examples. The raw materials used are summarized in the table below.

[3] Examples and Comparative Examples (Manufacture of members for semiconductor devices)
(Examples 1-3, Comparative Examples 1-3)
Each component shown below was mix | blended in the ratio shown in Table 2, and the thermosetting resin composition was prepared according to the method shown below.

(A) Polysiloxane, (B) epoxy compound, (E) additive (used only in Example 1 and Example 3), (G) inorganic fine particles (filler) (not used in Comparative Example 3) Were weighed, mixed, and then degassed.
Subsequently, (C) a curing agent (acid anhydride), (F) an antioxidant, and (D) a curing catalyst were further added, and stirring and defoaming were further performed.
(Details of each component)
(A) Polysiloxane (A) -1 Polysiloxane prepared in Synthesis Example 1 (A) -2 Polysiloxane prepared in Synthesis Example 2 (A) -3 Polysiloxane prepared in Synthesis Example 3 (B) Epoxy compound ( B) -1 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (B) -2 Epoxy NC-3000 manufactured by Nippon Kayaku Co., Ltd.
(B) -3 2,2-bis [4- (glycidyloxy) cyclohexyl] propane (jER YX8000 manufactured by Mitsubishi Chemical Corporation)
(C) Curing agent
4-Methylhexahydrophthalic anhydride / hexahydrophthalic anhydride mixture (Shin Nippon Rika Co., Ltd. Rikacid MH-700)
(D) Curing catalyst Methyltributylphosphonium dimethyl phosphate (Hishicolin PX-4MP manufactured by Nippon Chemical Industry Co., Ltd.)
The components (E) to (G) are as described in Table 2.

[4] Evaluation The thermosetting resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3 obtained as described in [3] above, and the evaluation method shown in [1] using the cured product thereof The physical properties were evaluated. The obtained physical property evaluation results are shown in Table 3. The epoxy equivalent is also shown in Table 3.

(A) The epoxy equivalent of the polysiloxane having an epoxy group and the sum of the epoxy equivalents of (A) and (B) the epoxy compound and the storage elastic modulus at 150 ° C. of 5.00 × 10 ^{5 to} 1.50 × 10 ⁷ Examples 1, 2, and 3 within the range of Pa are members for semiconductor devices that have a good appearance and a low water vapor transmission amount that is an indicator of gas permeability and are excellent in gas barrier properties. On the other hand, in Comparative Example 1, since the epoxy equivalent of (A) the polysiloxane having an epoxy group is too large, the appearance is poor, the water vapor transmission amount that is an index of gas permeability is high, and the gas barrier property is also inferior. Moreover, about the comparative example 2, since the epoxy equivalent of (A) the polysiloxane which has an epoxy group is too small and the storage elastic modulus in 150 degreeC is too high, stress cannot be relieve | moderated and an external appearance is unsatisfactory. Further, Comparative Example 3 does not contain polysiloxane having an epoxy group, and the storage elastic modulus at 150 ° C. is too high, so the stress cannot be relaxed and the appearance is poor.
In Examples 1 to 3 in which the Shore D hardness is in the range of 10 to 45, since stress can be relaxed, the adhesion to the substrate is good and the appearance is good, but Comparative Examples 1 to 3 in which the Shore D hardness is greater than 45. Then, it is difficult to relieve stress.
Moreover, the heat cycle test was done as follows. The thermosetting resin composition (sealing material) obtained in Examples 1 to 3 and Comparative Example 2 was potted on a commercially available polyphthalamide-type package, left at 100 ° C. for 0.5 hour, and then 150 ° C. And cured by standing for 2 hours.
The package coated with the sealing material liquid thus obtained was put into a small environmental tester SH-241 manufactured by Tabai Espec Co., Ltd., and “held at −40 ° C. for 30 minutes and taken from −40 ° C. to 100 ° C. for 1 hour. The temperature was cycled up and held at 100 ° C. for 30 minutes, and the temperature was decreased from 100 ° C. to −40 ° C. over 1 hour. The sample was taken out after 100 cycles, and the presence or absence of peeling of the contact portion between the cup and the sealant liquid was observed using a microscope.
As a result, in Examples 1 to 3, there was no crack and the adhesion to polyphthalamide and the metal surface was good. On the other hand, in Comparative Example 2, cracks occurred in the cured sealing material (sealing material layer), and peeling from the substrate was observed.

[5] Example (creation of semiconductor device)
A semiconductor device was produced using the thermosetting resin composition obtained in Example 2 and evaluated as follows.
(Semiconductor light emitting device and package)
As a semiconductor light-emitting device, one 350-μm square InGaN-based LED chip formed using a sapphire substrate and a main emission peak wavelength of 450 nm is used on a cavity bottom surface of a 3528 SMD type PPA resin package using a silicone resin-based transparent die bond paste. Glued to. After bonding, the die bond paste was cured by heating at 150 ° C. for 2 hours, and then the LED chip-side electrode and the package-side electrode were connected using an Au wire having a diameter of 25 μm. Two bonding wires were used.

(Sealing material forming liquid)
CaAlSi (ON) ₃ : Eu (manufactured by Mitsubishi Chemical Corporation, BR) as a red phosphor with respect to 1 part by weight of the thermosetting resin composition obtained in Examples 1 to 3 as a member for semiconductor device (encapsulant) -102C) 0.00650 parts by weight and 0.0605 parts by weight of β-type sialon (manufactured by Mitsubishi Chemical Co., Ltd., BG-601B) as a green phosphor were added and stirred until the whole became uniform. Next, (D) 0.002 part by weight of methyltributylphosphonium dimethyl phosphate was further added as a curing catalyst and stirred to obtain a sealing material forming liquid.

(Production of semiconductor light-emitting devices)
Using an air dispenser, 4 μL of the sealing material forming solution is injected into a semiconductor light emitting device provided with the semiconductor light emitting element, held at 100 ° C. for 0.5 hours, and then held at 150 ° C. for 2 hours to seal the sealing material. The stopping material forming liquid was cured to obtain a semiconductor light emitting device (white LED).

(Evaluation of semiconductor light emitting devices)
When a current of 20 mA was passed through the semiconductor light emitting device, white light was obtained.

DESCRIPTION OF SYMBOLS 1 Semiconductor light-emitting device 2 Resin molding 3 Bonding wire 4 Sealing material layer (phosphor layer) containing phosphor
5 Lead frame

Claims (6)

It is a thermosetting resin composition containing the following (A) to (D),
The total of epoxy equivalents of (A) polysiloxane and (B) epoxy compound contained in the thermosetting resin composition is 600 to 1500 g / equivalent,
And the storage elastic modulus in 150 degreeC by the dynamic viscoelasticity measurement of the hardened | cured material formed by heat-processing this thermosetting resin composition is 5.00 * 10 < ⁵ > -1.50 * 10 < ⁷ > Pa. There is a thermosetting resin composition.
(A) Polysiloxane having an epoxy equivalent of 800 to 2000 g / equivalent to polysiloxane and represented by the following formula (1)
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (O _1/2 R ⁷ ) _e. (1)
[In the formula (1), at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is an epoxy-containing group, and the functional groups other than the epoxy-containing group are independent of each other. A monovalent oxygen atom and a C1-C10 hydrocarbon group which may contain a sulfur atom, and 10 mol% or more of them may be a C1-C8 substituted aromatic group It is a group. a is 0 to 0.3, b is 0.2 to 1.0, c is 0.1 to 0.7, d is 0 to 0.2, e is a number of e> 0, and a + b + c + d = 1. 0. ]
(B) Epoxy compound (C) Curing agent (D) Curing catalyst 2. The thermosetting resin composition according to claim 1, wherein a Shore D hardness when the thermosetting resin composition is cured by heat treatment is 10 to 45. 3. The (R ⁴ R ⁵ SiO _2/2 ) component in the formula (A) polysiloxane represented by the formula (1) has a structure represented by the following formula (2). Or the thermosetting resin composition of Claim 2.
(R ⁸ R ⁹ SiO _2/2 ) _n (R ¹⁰ R ¹¹ SiO _2/2 ) _m (2)
In (Equation ^(2), at least one of R 8, ^{R 9} is an optionally substituted aromatic group having 1 to 8 carbon atoms, and the other ^{R 8,} R ^9, R ^{10, R 11} Each independently represents a monovalent oxygen atom or a hydrocarbon group having 1 to 10 carbon atoms which may contain a sulfur atom, where n is n ≧ 1 and m is m ≧ 0. The thermosetting resin composition according to claim 3, wherein the formula (2) is an oligomer having a weight average molecular weight of 500 or more. A member for a semiconductor device, comprising a cured product obtained by curing the thermosetting resin composition according to any one of claims 1 to 4. A semiconductor light-emitting device comprising at least the semiconductor device member according to claim 5.

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