WO2013035736A1

WO2013035736A1 - Curable composition for optical semiconductor device

Info

Publication number: WO2013035736A1
Application number: PCT/JP2012/072603
Authority: WO
Inventors: 穣末▲崎▼; 康成日下; 秀文保井; 亮介山▲崎▼; 良隆国広; 満谷川; 貴志渡邉; 靖乾; 千鶴金; 佑山田; 小林　祐輔
Original assignee: 積水化学工業株式会社
Priority date: 2011-09-08
Filing date: 2012-09-05
Publication date: 2013-03-14
Also published as: TW201319169A; JPWO2013035736A1; KR20140071961A

Abstract

Provided is a curable composition for an optical semiconductor device with which it is possible to cure the curable composition and obtain a cured product that will not peel when bonded to another object, even when the optical semiconductor device is used in a harsh environment under high temperatures and high humidity, and with which pot life of the curable composition for an optical semiconductor device is good. The curable composition for an optical semiconductor device relating to the present invention comprises a first organopolysiloxane having two or more alkenyl groups, a second organopolysiloxane having two or more hydrogen atoms bonded to silicon atoms, a hydrosilylation catalyst, and a first silane compound having ureido groups or isocyanate groups.

Description

Curable composition for optical semiconductor device

The present invention relates to a curable composition for an optical semiconductor device used for sealing an optical semiconductor element or forming a lens above the optical semiconductor element in an optical semiconductor device. The present invention also relates to an optical semiconductor device using the curable composition for optical semiconductor devices.

An optical semiconductor device such as a light emitting diode (LED) device has low power consumption and long life. Moreover, the optical semiconductor device can be used even in a harsh environment. Accordingly, optical semiconductor devices are used in a wide range of applications such as mobile phone backlights, liquid crystal television backlights, automobile lamps, lighting fixtures, and signboards.

When an optical semiconductor element (for example, LED), which is a light emitting element used in an optical semiconductor device, is in direct contact with the atmosphere, the light emission characteristics of the optical semiconductor element rapidly deteriorate due to moisture in the atmosphere or floating dust. For this reason, the said optical semiconductor element is normally sealed with the sealing compound for optical semiconductor devices.

The following Patent Document 1 discloses an epoxy resin material containing hydrogenated bisphenol A glycidyl ether, an alicyclic epoxy monomer, and a latent catalyst as a sealant for an optical semiconductor device. This epoxy resin material is cured by thermal cationic polymerization.

Also, in an optical semiconductor device, a lens may be formed using a lens material for an optical semiconductor device in order to control the light emission direction or to prevent the front luminance from becoming too high. The lens is disposed on the surface of the sealant, for example. The lens may be disposed on the optical semiconductor element or so as to cover the optical semiconductor element.

Patent Document 2 below includes (A) an organopolysiloxane having two or more aliphatic unsaturated bonds and (B) two or more hydrogen atoms bonded to silicon atoms as the lens material for an optical semiconductor device. A lens material including an organohydrogenpolysiloxane, (C) a platinum group metal catalyst, and (D) a release agent is disclosed.

In the following Patent Document 3, (1) optical transparency that is 90% or higher transmittance for light having a wavelength of 400 nm with an optical path length of 1.0 cm, and (2) after being exposed to 150 ° C. for 6 hours. , Thermal stability retaining 90% or higher transmission for light of 400 nm wavelength with 1.0 cm path length, and (3) thermal stability having a refractive index of 1.545 or higher at 589 nm A polysiloxane composition is disclosed.

Patent Document 4 listed below discloses an LED encapsulant composition comprising (1) at least one polyorganosiloxane and an effective amount of (2) an addition reaction catalyst, which is cured to form a resin. Has been. The average composition formula of the mixture of (1) at least one polyorganosiloxane is (R ¹ R ² R ³ SiO _1/2 ) _M · (R ⁴ R ⁵ SiO _2/2 ) _D · (R ⁶ SiO _{3 / 2} ) _T · (SiO _4/2 ) _Q Provided that R ¹ to R ⁶ are each selected from the same or different organic groups, hydroxyl groups or hydrogen atoms, and at least one of R ¹ to R ⁶ is a hydrocarbon group having a multiple bond and Alternatively, a hydrogen atom is included, M, D, T, and Q are numbers from 0 to less than 1, and M + D + T + Q = 1 and Q + T> 0.

JP 2003-073452 A JP 2006-328103 A JP 2006-519896 Gazette JP 2004-359756 A

In the conventional compositions for optical semiconductor devices as described in Patent Documents 1 to 4, there is a problem that the adhesiveness of the cured product obtained by curing the composition as the sealant and the lens material to the object to be bonded is low. For this reason, when the hardened | cured material of the conventional sealing agent for optical semiconductor devices is used in the severe environment under high temperature and high humidity, a sealing agent may peel from a housing material etc. In addition, when a cured product of a conventional lens material for an optical semiconductor device is used in a harsh environment under high temperature and high humidity, the lens is easily peeled off from a sealing agent, an optical semiconductor element, a housing, or a substrate. There is.

Also, when the sealant or the lens is peeled off, the light intensity (brightness) emitted from the optical semiconductor device may gradually decrease.

Even if the optical semiconductor device is used in a harsh environment under high temperature and high humidity, it is possible to suppress peeling of the cured product obtained by curing the curable composition from the object to be bonded, and further, curable for an optical semiconductor device. An object of the present invention is to provide a curable composition for an optical semiconductor device capable of improving the pot life of the composition, and an optical semiconductor device using the curable composition for an optical semiconductor device.

According to a wide aspect of the present invention, a first organopolysiloxane having two or more alkenyl groups, a second organopolysiloxane having two or more hydrogen atoms bonded to a silicon atom, a hydrosilylation reaction catalyst, And a first silane compound having a ureido group or an isocyanate group, and a curable composition for an optical semiconductor device.

The curable composition for optical semiconductor devices according to the present invention is preferably an encapsulant for optical semiconductor devices or a lens material for optical semiconductor devices.

In a specific aspect of the curable composition for optical semiconductor devices according to the present invention, the first silane compound has a ureido group.

In a specific aspect of the curable composition for optical semiconductor devices according to the present invention, the first silane compound is a first silane compound represented by the following formula (S1) or the following formula (S2).

In the above formula (S1), X1 represents an alkoxy group, X2 and X3 each represents an alkoxy group or a hydrocarbon group having 1 to 8 carbon atoms, and R4 is a single bond directly bonding a nitrogen atom and a silicon atom. Or a hydrocarbon group having 1 to 8 carbon atoms.

In the above formula (S2), X1 represents an alkoxy group, X2 and X3 each represents an alkoxy group or a hydrocarbon group having 1 to 8 carbon atoms, and R4 represents a single bond directly connecting a nitrogen atom and a silicon atom. It represents a bond or a hydrocarbon group having 1 to 8 carbon atoms.

In another specific aspect of the curable composition for optical semiconductor devices according to the present invention, the first silane compound is a first silane compound represented by the above formula (S1).

In another specific aspect of the curable composition for optical semiconductor devices according to the present invention, the first silane compound represented by the above formula (S1) is a first silane compound represented by the following formula (S1-1). Silane compound.

In the above formula (S1-1), R1 to R3 each represent a hydrocarbon group having 1 to 8 carbon atoms, and R4 represents a single bond directly bonding a nitrogen atom and a silicon atom, or 1 to 8 hydrocarbon groups are represented.

In a specific aspect of the curable composition for optical semiconductor devices according to the present invention, the number average molecular weight of the first organopolysiloxane is 500 or more and 200,000 or less, and the number average of the second organopolysiloxane. The molecular weight is 500 or more and 20000 or less.

In another specific aspect of the curable composition for an optical semiconductor device according to the present invention, a second silane compound having an epoxy group, a vinyl group, or a (meth) acryloyl group is further included.

In still another specific aspect of the curable composition for optical semiconductor devices according to the present invention, the second silane compound is 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl. Trimethoxysilane, vinyltrimethoxysilane or 3- (meth) acryloxypropyltrimethoxysilane.

In another specific aspect of the curable composition for optical semiconductor devices according to the present invention, the content of the second silane compound is 0 with respect to a total of 100 parts by weight of the first and second organopolysiloxanes. 0.01 parts by weight or more and 5 parts by weight or less.

In another specific aspect of the curable composition for optical semiconductor devices according to the present invention, the first organopolysiloxane does not have a hydrogen atom bonded to a silicon atom, and the second organopolysiloxane is alkenyl. Has a group.

In another specific aspect of the curable composition for optical semiconductor devices according to the present invention, the first organopolysiloxane has a methyl group represented by the following formula (1A) and bonded to an alkenyl group and a silicon atom. A second organopolysiloxane which is a first organopolysiloxane and the second organopolysiloxane is represented by the following formula (51A) and has a hydrogen atom bonded to a silicon atom and a methyl group bonded to a silicon atom. It is siloxane, or the first organopolysiloxane is represented by the following formula (1B), is a first organopolysiloxane having an aryl group and an alkenyl group, and the second organopolysiloxane is A second organopolysiloxane represented by the following formula (51B) and having a hydrogen atom bonded to an aryl group and a silicon atom.

In the above formula (1A), a, b and c are a / (a + b + c) = 0 to 0.30, b / (a + b + c) = 0.70 to 1.0 and c / (a + b + c) = 0 to 0. 10, R1 to R6 each represents at least one alkenyl group, at least one represents a methyl group, and R1 to R6 other than the alkenyl group and the methyl group represent a hydrocarbon group having 2 to 8 carbon atoms. .

In the above formula (51A), p, q and r are p / (p + q + r) = 0.10 to 0.50, q / (p + q + r) = 0 to 0.40 and r / (p + q + r) = 0.40 to 0.90 is satisfied, R51 to R56 each represents at least one hydrogen atom, at least one represents a methyl group, and R51 to R56 other than the hydrogen atom and the methyl group are hydrocarbon groups having 2 to 8 carbon atoms. Represents.

In the above formula (1B), a, b and c are a / (a + b + c) = 0 to 0.50, b / (a + b + c) = 0.40 to 1.0 and c / (a + b + c) = 0 to 0. 50, R1 to R6 each represents at least one aryl group, at least one represents an alkenyl group, and R1 to R6 other than the aryl group and the alkenyl group represent a hydrocarbon group having 1 to 8 carbon atoms. .

In the above formula (51B), p, q and r are p / (p + q + r) = 0.05 to 0.50, q / (p + q + r) = 0.05 to 0.50 and r / (p + q + r) = 0. 20 to 0.80 are satisfied, at least one of R51 to R56 represents an aryl group, at least one represents a hydrogen atom, and R51 to R56 other than the aryl group and the hydrogen atom are carbon atoms having 1 to 8 carbon atoms. Represents a hydrogen group.

In another specific aspect of the curable composition for optical semiconductor devices according to the present invention, the first organopolysiloxane represented by the above formula (1A) or the above formula (1B) is a hydrogen atom bonded to a silicon atom. And the second organopolysiloxane represented by the formula (51A) or the formula (51B) has an alkenyl group, and in the formula (51A), at least one of R51 to R56 is Represents a hydrogen atom, at least one represents a methyl group, at least one represents an alkenyl group, R51 to R56 other than a hydrogen atom, a methyl group and an alkenyl group represent a hydrocarbon group having 2 to 8 carbon atoms; In the above formula (51B), at least one of R51 to R56 represents an aryl group, at least one represents a hydrogen atom, at least one represents an alkenyl group, an aryl group, a hydrogen atom and an alkyl group. R51 ~ other than alkenyl groups R56 represents a hydrocarbon group having 1 to 8 carbon atoms.

In still another specific aspect of the curable composition for optical semiconductor devices according to the present invention, the second organopolysiloxane represented by the above formula (51A) or the above formula (51B) is represented by the following formula (51-a). ).

In the above formula (51-a), R52 and R53 each represent a hydrocarbon group having 1 to 8 carbon atoms.

It is preferable that the first organopolysiloxane is represented by the above formula (1A) and the second organopolysiloxane is represented by the above formula (51A). It is also preferred that the first organopolysiloxane is represented by the formula (1B) and the second organopolysiloxane is represented by the formula (51B).

In another specific aspect of the curable composition for optical semiconductor devices according to the present invention, the content of the second organopolysiloxane is 10 parts by weight or more with respect to 100 parts by weight of the first organopolysiloxane. 400 parts by weight or less, and the content of the catalyst for hydrosilylation reaction in the curable composition is 0.01 ppm or more and 1000 ppm or less by weight unit of metal atom, The content of the first silane compound is 0.01 parts by weight or more and 5 parts by weight or less with respect to a total of 100 parts by weight of siloxane.

The curable composition for optical semiconductor devices according to the present invention includes a first organopolysiloxane having an alkenyl group, a second organopolysiloxane having a hydrogen atom bonded to a silicon atom, a hydrosilylation reaction catalyst, Even if the optical semiconductor device using the curable composition for optical semiconductor devices is used in a harsh environment under high temperature and high humidity, since it contains the first silane compound having a ureido group or an isocyanate group The peeling from the adhesion target object of the hardened | cured material which the substance hardened | cured can be suppressed. Furthermore, since the curable composition for optical semiconductor devices which concerns on this invention has the composition mentioned above, the pot life of the curable composition for optical semiconductor devices can be made favorable.

FIG. 1 is a front sectional view showing an optical semiconductor device according to the first embodiment of the present invention. FIG. 2 is a front sectional view showing an optical semiconductor device according to the second embodiment of the present invention. FIG. 3 is a front sectional view showing an optical semiconductor device according to the third embodiment of the present invention.

Hereinafter, the details of the present invention will be described.

The curable composition for optical semiconductor devices according to the present invention includes a first organopolysiloxane having an alkenyl group, a second organopolysiloxane having a hydrogen atom bonded to a silicon atom, a hydrosilylation reaction catalyst, And a first silane compound having a ureido group or an isocyanate group.

By adopting the above composition in the curable composition for optical semiconductor devices according to the present invention, the optical semiconductor device using the curable composition for optical semiconductor devices is cured even when used in harsh environments under high temperature and high humidity. The peeling from the adhesion target object of the hardened | cured material which the property composition hardened | cured can be suppressed.

For example, when the optical semiconductor device is sealed using the curable composition for optical semiconductor devices according to the present invention or a lens is formed above the optical semiconductor device, the curable composition is cured. It becomes difficult for the object to peel from the object to be bonded. For example, the material of a package such as a sealant or a housing material in contact with a lens may be polyphthalamide (PPA). Moreover, in order to reflect the light which reached the back surface side of the light emitting element, an electrode plated with silver may be formed on the back surface of the light emitting element. There is a strong demand for the adhesiveness of the cured product to such a package formed by PPA or silver plating. When the cured product is peeled off from the package or silver plating, the amount of light (luminous intensity) emitted from the optical semiconductor device decreases.

In the case where only the silane coupling agent having no ureido group or isocyanate group is used in the curable composition for an optical semiconductor device, the present inventors do not sufficiently increase the adhesiveness of the cured product to the object to be bonded. I found out. In particular, in the optical semiconductor device used for the curable composition for optical semiconductor devices, it is difficult to sufficiently enhance the adhesion of the cured product to the object to be bonded. As a result of intensive studies, the inventor has a ureido group or an isocyanate group together with a first organopolysiloxane having an alkenyl group, a second organopolysiloxane having a hydrogen atom bonded to a silicon atom, and a catalyst for hydrosilylation reaction. It has been found that by adopting a composition further containing the first silane compound, the adhesion of the cured product to the object to be bonded can be sufficiently enhanced.

Furthermore, the present inventors use the first silane compound having a ureido group out of the first silane compound having a ureido group and the first silane compound having an isocyanate group, so that the cured product can be bonded. It has been found that the adhesion to objects is even higher.

Furthermore, the present inventors provide a ureido group in a composition comprising a first organopolysiloxane having an alkenyl group, a second organopolysiloxane having a hydrogen atom bonded to a silicon atom, and a catalyst for hydrosilylation reaction. Alternatively, it has also been found that if the first silane compound having an isocyanate group is used, the viscosity of the curable composition for optical semiconductor devices hardly changes, and the pot life of the curable composition for optical semiconductor devices is improved.

A curable composition for an optical semiconductor device comprising a first organopolysiloxane having an alkenyl group, a second organopolysiloxane having a hydrogen atom bonded to a silicon atom, and a hydrosilylation reaction catalyst is also obtained at room temperature. The polymerization reaction proceeds slowly. For this reason, the viscosity of the curable composition gradually increases even at room temperature. Therefore, the first organopolysiloxane having an alkenyl group and the second organopolysiloxane having a hydrogen atom bonded to a silicon atom are provided as two separate liquids (first and second liquids). There is. These two liquids are mixed and used immediately before use by the user. The hydrosilylation reaction catalyst is contained in at least one of the first liquid containing the first organopolysiloxane and the second liquid containing the second organopolysiloxane.

In such a kit having the first and second liquids, the reaction starts when the two liquids are mixed, so that the viscosity increases. When the viscosity suddenly increases after mixing the two liquids, the discharge amount when dispensing the curable composition changes, and it becomes difficult to maintain a certain shape. For example, the sealing agent may be insufficiently filled or the lens shape may be deteriorated.

In general, in consideration of the pot life when manufacturing an optical semiconductor device, two liquids having a viscosity η1 of the curable composition after mixing the two liquids and leaving them to stand at room temperature (23 ° C.) for 3 hours are mixed. The smaller the ratio (η1 / η2) to the viscosity η2 of the curable composition immediately after, the better.

Immediately after mixing the two liquids of the viscosity η1 of the curable composition after mixing the two liquids and leaving them at 23 ° C. for 3 hours (the curable composition after being left to stand at 23 ° C. for 3 hours immediately after the preparation) The ratio (η1 / η2) of the curable composition (the curable composition immediately after preparation) to the viscosity η2 is preferably 2 or less, more preferably 1.5 or less, and still more preferably 1.3 or less. The ratio (η1 / η2) is generally 1 or more, but may be 0.7 or more, for example, or 0.8 or more.

If the viscosity change of the curable composition is small, that is, if the pot life of the curable composition is good, it is easy to manufacture an optical semiconductor device of a certain quality under a certain production condition.

The first organopolysiloxane is represented by the formula (1A) and is a first organopolysiloxane having an alkenyl group and a methyl group bonded to a silicon atom, or represented by the formula (1B) and an aryl A first organopolysiloxane having a group and an alkenyl group is preferred. However, a first organopolysiloxane different from the first organopolysiloxane represented by the formula (1A) or the formula (1B) may be used. When the second organopolysiloxane has an alkenyl group, the first organopolysiloxane preferably does not have a hydrogen atom bonded to a silicon atom. The first organopolysiloxane preferably does not have a hydrogen atom bonded to a silicon atom.

The second organopolysiloxane is a second organopolysiloxane represented by the formula (51A) and having a hydrogen atom bonded to a silicon atom and a methyl group bonded to a silicon atom, or the formula (51B) And is preferably a second organopolysiloxane having an aryl group and a hydrogen atom bonded to a silicon atom. However, a second organopolysiloxane different from the second organopolysiloxane represented by the formula (51A) or the formula (51B) may be used.

From the viewpoint of improving the adhesiveness of the cured product to the object to be bonded, further improving the heat resistance and gas barrier properties of the cured product, and further improving the pot life of the curable composition, the above-mentioned first. The organopolysiloxane represented by the formula (1A) is a first organopolysiloxane having a methyl group bonded to an alkenyl group and a silicon atom, and the second organopolysiloxane is represented by the formula (51A) Or a second organopolysiloxane having a hydrogen atom bonded to a silicon atom and a methyl group bonded to a silicon atom, or the first organopolysiloxane is represented by the formula (1B) and is aryl The first organopolysiloxane having a group and an alkenyl group, and the second organopolysiloxane is represented by the formula (51B). It is preferred aryl group and a silicon atom is a second organopolysiloxane having hydrogen atoms bonded.

In addition, when a cured product of a conventional curable composition for optical semiconductor devices is used in a harsh environment such as a temperature cycle that repeatedly receives heating and cooling, the cured product is cracked or the cured product is a housing material. It may peel off from etc. In particular, a cured product of a conventional curable composition for optical semiconductor devices has a problem that heat resistance is low.

From the viewpoint of obtaining a cured product that is more excellent in heat resistance, the first organopolysiloxane is a first organopolysiloxane represented by the formula (1A) and having an alkenyl group and a methyl group bonded to a silicon atom. The second organopolysiloxane is preferably the second organopolysiloxane represented by the formula (51A) and having a hydrogen atom bonded to a silicon atom and a methyl group bonded to a silicon atom.

From the viewpoint of obtaining a cured product that is more excellent in heat resistance, the content ratios of methyl groups bonded to silicon atoms in the first organopolysiloxane and the second organopolysiloxane are each 80 mol% or more. preferable. The content ratio of the methyl group bonded to the silicon atom is represented by the following formula (X).

Content ratio (mol%) of methyl groups bonded to silicon atoms = {(Average number of methyl groups bonded to silicon atoms contained in one molecule of the first organopolysiloxane or the second organopolysiloxane × Molecular weight of methyl group) / (average number of functional groups bonded to silicon atoms contained in one molecule of the first organopolysiloxane or the second organopolysiloxane × average molecular weight of functional groups)} × 100 ... Formula (X)

In the above formula (X), the “functional group” means a group directly bonded to a silicon atom in the first organopolysiloxane or the second organopolysiloxane. When there are a plurality of types of the functional groups, “average molecular weight of functional groups” means the sum of “average number of functional groups × functional group molecular weight” of each functional group. The same applies to “functional group” and “average molecular weight of functional group” in the following formula (Y).

As described above, a silver-plated electrode may be formed on the back surface of the light emitting element in order to reflect the light reaching the back side of the light emitting element. If a crack occurs in the sealant or the lens, or the sealant is peeled off from the housing material, the silver-plated electrode is exposed to the atmosphere or easily exposed to the atmosphere. As a result, the silver plating may be discolored by a corrosive gas such as hydrogen sulfide gas or sulfurous acid gas present in the atmosphere. When the color of the electrode changes, the reflectance decreases, which causes a problem that the brightness of the light emitted from the light emitting element decreases. The sealant or lens formed by the cured product of the curable composition has a high gas barrier property against corrosive gas, thereby suppressing discoloration of silver plating and lowering the brightness of light emitted from the light emitting element. Can be suppressed.

From the viewpoint of obtaining a cured product that is more excellent in gas barrier properties, the first organopolysiloxane is the first organopolysiloxane represented by the formula (1B) and having an aryl group and an alkenyl group, and the first The second organopolysiloxane represented by the formula (51B) is preferably a second organopolysiloxane having an aryl group and a hydrogen atom bonded to a silicon atom.

From the viewpoint of obtaining a cured product that is more excellent in gas barrier properties, the content ratios of aryl groups in the first organopolysiloxane and the second organopolysiloxane are 30 mol% or more and 85 mol% or less, respectively. preferable. The content ratio of the aryl group is represented by the following formula (Y).

Content ratio of aryl group (mol%) = {(average number of aryl groups contained in one molecule of the first organopolysiloxane or the second organopolysiloxane × molecular weight of the aryl group) / (the first The average number of functional groups bonded to silicon atoms contained in one molecule of the second organopolysiloxane or the average molecular weight of the functional groups)} × 100 Formula (Y)

When the aryl group is a phenyl group, the content ratio of the aryl group indicates the content ratio of the phenyl group.

Further, according to a wide aspect of the present invention, an optical semiconductor device using the above-described curable composition for optical semiconductor devices is provided. That is, according to a broad aspect of the present invention, an optical semiconductor element and a sealing agent disposed so as to seal the optical semiconductor element or a lens disposed on the optical semiconductor element are provided, and the sealing is performed. An optical semiconductor device is provided in which the stopper or the lens is formed by curing a curable composition for an optical semiconductor device. The curable composition for an optical semiconductor device used in the optical semiconductor device includes a first organopolysiloxane having two or more alkenyl groups and a second organopolysiloxane having two or more hydrogen atoms bonded to silicon atoms. And a hydrosilylation reaction catalyst and a first silane compound having a ureido group or an isocyanate group.

In this specification, both the invention relating to the above-described curable composition for optical semiconductor devices and the invention relating to the above-described optical semiconductor device are disclosed.

In the optical semiconductor device according to the present invention, even when used in a harsh environment under high temperature and high humidity, the cured product obtained by curing the curable composition can be prevented from being peeled off from the adhesion target, and further cured for an optical semiconductor device. Since the pot life of the composition is good, a homogeneous optical semiconductor device can be provided.

Hereinafter, the detail of each component contained in the curable composition for optical semiconductor devices which concerns on this invention is demonstrated.

(First organopolysiloxane)
The first organopolysiloxane contained in the curable composition for optical semiconductor devices according to the present invention has two or more alkenyl groups. The alkenyl group is preferably directly bonded to the silicon atom. The carbon atom in the carbon-carbon double bond of the alkenyl group may be bonded to the silicon atom, and the carbon atom different from the carbon atom in the carbon-carbon double bond of the alkenyl group is bonded to the silicon atom. It may be bonded. As for said 1st organopolysiloxane, only 1 type may be used and 2 or more types may be used together.

From the viewpoint of obtaining a cured product that is more excellent in heat resistance, the first organopolysiloxane is represented by the following formula (1A), and includes a first organopolysiloxane having an alkenyl group and a methyl group bonded to a silicon atom. Siloxane (hereinafter sometimes referred to as first organopolysiloxane A) is preferred. The first organopolysiloxane A is preferably a first organopolysiloxane which does not have a hydrogen atom bonded to a silicon atom but has an alkenyl group and a methyl group bonded to a silicon atom.

From the viewpoint of obtaining a cured product that is more excellent in gas barrier properties, the first organopolysiloxane is represented by the following formula (1B) and has a first organopolysiloxane having an aryl group and an alkenyl group (hereinafter referred to as the first organopolysiloxane). 1 may be referred to as organopolysiloxane B). The first organopolysiloxane B is preferably a first organopolysiloxane which does not have a hydrogen atom bonded to a silicon atom and has an aryl group and an alkenyl group. Examples of the aryl group include an unsubstituted phenyl group and a substituted phenyl group.

In the above formula (1A) and the above formula (1B), the structural unit represented by (R4R5SiO _2/2 ) and the structural unit represented by (R6SiO _3/2 ) each have an alkoxy group. It may have a hydroxy group.

The above formula (1A) and the above formula (1B) show an average composition formula. The hydrocarbon group in the above formula (1A) and the above formula (1B) may be linear or branched. R1 to R6 in the above formula (1A) and the above formula (1B) may be the same or different.

In the formula (1A) and the formula (1B), the oxygen atom part in the structural unit represented by (R4R5SiO _2/2 ) and the oxygen atom part in the structural unit represented by (R6SiO _3/2 ) are respectively siloxane. An oxygen atom part forming a bond, an oxygen atom part of an alkoxy group, or an oxygen atom part of a hydroxy group is shown.

In general, in each structural unit of the above formula (1A) and the above formula (1B), the content of alkoxy groups is small, and the content of hydroxy groups is also small. Generally, when an organosilicon compound such as an alkoxysilane compound is hydrolyzed and polycondensed to obtain a first organopolysiloxane, most of the alkoxy groups and hydroxy groups are converted into a partial skeleton of siloxane bonds. It is to be done. That is, most of oxygen atoms of the alkoxy group and oxygen atoms of the hydroxy group are converted into oxygen atoms forming a siloxane bond. When each structural unit of the above formula (1A) and the above formula (1B) has an alkoxy group or a hydroxy group, an unreacted alkoxy group or hydroxy group that has not been converted into a partial skeleton of a siloxane bond remains slightly. Indicates that The same applies to the case where each structural unit of formula (51A) and formula (51B) described later has an alkoxy group or a hydroxy group.

Examples of the alkenyl group include vinyl group, allyl group, butenyl group, pentenyl group, and hexenyl group. From the viewpoint of further enhancing the gas barrier properties, the alkenyl group in the first organopolysiloxane and the alkenyl group in the above formula (1A) and the above formula (1B) are preferably vinyl groups or allyl groups. More preferably, it is a group. From the viewpoint of further improving the curability of the curable composition, the first organopolysiloxane preferably has a vinyl group.

The hydrocarbon group having 2 to 8 carbon atoms in the above formula (1A) is not particularly limited, and examples thereof include ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, and n-heptyl. Group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group, cyclohexyl group and aryl group. Examples of the hydrocarbon group having 1 to 8 carbon atoms in the above formula (1B) include the same groups as the hydrocarbon group having 2 to 8 carbon atoms in the above formula (1A), and further includes a methyl group.

From the viewpoint of enhancing the curability of the curable composition and further suppressing cracking and peeling during thermal cycling, the first organopolysiloxane contains one vinyl group and two carbon atoms per silicon atom. It preferably contains a structural unit bonded to a hydrocarbon group of 1 to 8 (methyl group or hydrocarbon group of 2 to 8 carbon atoms). In the above formula (1A) and the above formula (1B), (R1R2R3SiO _{1 / The} structural unit represented by ₂ ) includes a structural unit in which R1 represents a vinyl group, and R2 and R3 represent a hydrocarbon group having 1 to 8 carbon atoms (methyl group or hydrocarbon group having 2 to 8 carbon atoms). It is preferable. That is, the first organopolysiloxane is represented by (CH ₂ = CHSiR ₂ R 3 O _1/2 ) from the viewpoint of enhancing the curability of the curable composition and further suppressing cracking and peeling during thermal cycling. It preferably has a structural unit, that is, it preferably has a structural unit represented by the following formula (1-a). The structural unit represented by (R1R2R3SiO _1/2 ) may contain only the structural unit represented by the following formula (1-a), and the structural unit represented by the following formula (1-a) and And a structural unit other than the structural unit represented by the formula (1-a). The presence of the structural unit represented by the following formula (1-a) allows a vinyl group to be present at the terminal, and the presence of the vinyl group at the terminal increases the opportunity for reaction, and the curability of the curable composition. Can be further increased. In the structural unit represented by the following formula (1-a), the terminal oxygen atom generally forms a siloxane bond with an adjacent silicon atom, and shares an oxygen atom with the adjacent structural unit. Therefore, one oxygen atom at the terminal is defined as “O _1/2 ”.

In the above formula (1-a), R2 and R3 each represent a hydrocarbon group having 1 to 8 carbon atoms.

The content ratio of methyl groups bonded to silicon atoms in the first organopolysiloxane A is preferably 80 mol% or more. The content ratio of the methyl group bonded to the silicon atom is obtained from the following formula (X1). When the content ratio of the methyl group is 80 mol% or more, the heat resistance of the cured product becomes considerably high, and even if the optical semiconductor device is used in a harsh environment under high temperature and high humidity, Is difficult to decrease and discoloration of the cured product is difficult to occur. The content ratio of the methyl group bonded to the silicon atom in the first organopolysiloxane A is preferably 85 mol% or more, preferably 99.9 mol% or less, more preferably 99 mol% or less, and still more preferably 98 mol%. It is less than mol%. When the content ratio of the methyl group is not less than the above lower limit, the heat resistance of the cured product is further enhanced. When the content ratio of the methyl group is not more than the above upper limit, alkenyl groups can be sufficiently introduced, and it is easy to improve the curability of the curable composition.

Content ratio (mol%) of methyl groups bonded to silicon atoms = {(average number of methyl groups bonded to silicon atoms contained in one molecule of the first organopolysiloxane × molecular weight of methyl groups) / (above Average number of functional groups bonded to silicon atoms contained in one molecule of the first organopolysiloxane × average of molecular weight of functional groups)} × 100 Formula (X1)

The content ratio of the aryl group in the first organopolysiloxane B is preferably 30 mol% or more, and preferably 85 mol% or less. The content ratio of this aryl group is calculated | required from a following formula (Y1). When the content ratio of the aryl group is 30 mol% or more, the gas barrier property of the cured product is further enhanced, and cracks and peeling are less likely to occur in the cured product. When the content ratio of the aryl group is 85 mol% or less, peeling of the cured product is more difficult to occur. From the viewpoint of further enhancing the gas barrier properties, the content ratio of the aryl group in the first organopolysiloxane B is more preferably 35 mol% or more. From the viewpoint of making peeling more difficult, the content ratio of the aryl group in the first organopolysiloxane B is more preferably 80 mol% or less, still more preferably 75 mol% or less, and particularly preferably 70 mol%. Hereinafter, it is most preferably 65 mol% or less.

Content ratio of aryl group (mol%) = (average number of aryl groups contained in one molecule of the first organopolysiloxane × molecular weight of aryl group / contained in one molecule of the first organopolysiloxane) Average number of functional groups bonded to silicon atoms × average molecular weight of functional groups) × 100 Formula (Y1)

From the viewpoint of further improving the storage stability of the curable composition, the first organopolysiloxane A preferably has an aryl group. Examples of the aryl group include an unsubstituted phenyl group and a substituted phenyl group. The content ratio of the aryl group in the first organopolysiloxane A is preferably 0.5 mol% or more, preferably 10 mol% or less, more preferably 5 mol% or less. When the content ratio of the aryl group in the first organopolysiloxane A is not more than the above upper limit, the heat resistance of the cured product is further improved.

In the first organopolysiloxane represented by the above formula (1A) and the above formula (1B), the structural unit represented by (R4R5SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) has the following formula ( The structure represented by 1-2), that is, a structure in which one of the oxygen atoms bonded to the silicon atom in the bifunctional structural unit forms a hydroxy group or an alkoxy group may be included.

(R4R5SiXO _1/2 ) Formula (1-2)

The structural unit represented by (R4R5SiO _2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (1-b), and is further represented by the following formula (1-2-b). A portion surrounded by a broken line of the structural unit may be included. That is, a structural unit having a group represented by R4 and R5 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R4R5SiO _2/2 ). Specifically, when the alkoxy group is converted to a partial skeleton of a siloxane bond, the structural unit represented by (R4R5SiO _2/2 ) is a broken line of the structural unit represented by the following formula (1-b) The part enclosed by is shown. When an unreacted alkoxy group remains, or when the alkoxy group is converted to a hydroxy group, the structural unit represented by (R4R5SiO _2/2 ) having the remaining alkoxy group or hydroxy group has the following formula: A portion surrounded by a broken line in the structural unit represented by (1-2-b) is shown. In the structural unit represented by the following formula (1-b), the oxygen atom in the Si—O—Si bond forms a siloxane bond with the adjacent silicon atom, and the adjacent structural unit and oxygen atom Sharing. Accordingly, one oxygen atom in the Si—O—Si bond is defined as “O _1/2 ”.

In the above formulas (1-2) and (1-2-b), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. R4 and R5 in formula (1-b), formula (1-2), and formula (1-2-b) are the same groups as R4 and R5 in formula (1A) and formula (1B). It is.

In the first organopolysiloxane represented by the above formula (1A) and the above formula (1B), the structural unit represented by (R6SiO _3/2 ) (hereinafter also referred to as trifunctional structural unit) has the following formula ( 1-3) or a structure represented by formula (1-4), that is, a structure in which two oxygen atoms bonded to a silicon atom in a trifunctional structural unit each constitute a hydroxy group or an alkoxy group, or a trifunctional One of the oxygen atoms bonded to the silicon atom in the structural unit may include a structure constituting a hydroxy group or an alkoxy group.

(R6SiX ₂ O _1/2 ) Formula (1-3)

(R6SiXO _2/2 ) Formula (1-4)

The structural unit represented by (R6SiO _3/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (1-c), and further includes the following formula (1-3-c) or formula ( A portion surrounded by a broken line of the structural unit represented by 1-4-4-c) may be included. That is, a structural unit having a group represented by R6 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R6SiO _3/2 ).

In the above formula (1-3), formula (1-3-c), formula (1-4) and formula (1-4-c), X represents OH or OR, and OR represents a linear or A branched alkoxy group having 1 to 4 carbon atoms is represented. R6 in the above formula (1-c), formula (1-3), formula (1-3-c), formula (1-4) and formula (1-4-c) represents the above formula (1A) and It is the same group as R6 in the above formula (1B).

Formula (1-b) and Formula (1-c), Formulas (1-2) to (1-4), Formula (1-2-b), Formula (1-3-c) and Formula (1) In -4-c), the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited. For example, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, isopropoxy group , Isobutoxy group, sec-butoxy group and t-butoxy group.

In the above formula (1A), the lower limit of a / (a + b + c) is 0, and the upper limit is 0.30. When a / (a + b + c) is less than or equal to the above upper limit, the heat resistance of the cured product is further increased, and peeling of the cured product can be further suppressed. In said formula (1A), a / (a + b + c) becomes like this. Preferably it is 0.25 or less, More preferably, it is 0.20 or less. When a is 0 and a / (a + b + c) is 0, there is no structural unit (R1R2R3SiO _1/2 ) in the above formula (1A).

In the above formula (1A), the lower limit of b / (a + b + c) is 0.70, and the upper limit is 1.0. When b / (a + b + c) is not less than the above lower limit, the cured product does not become too hard, and cracks hardly occur in the cured product. In the above formula (1A), b / (a + b + c) is preferably 0.75 or more, more preferably 0.80 or more.

In the above formula (1A), the lower limit of c / (a + b + c) is 0, and the upper limit is 0.10. When c / (a + b + c) is not more than the above upper limit, it is easy to maintain an appropriate viscosity of the curable composition, and the adhesiveness of the cured product is further enhanced. In the above formula (1A), c / (a + b + c) is preferably 0.05 or less. In addition, when c is 0 and c / (a + b + c) is 0, the structural unit of (R6SiO _3/2 ) does not exist in the above formula (1A).

C / (a + b + c) in the above formula (1A) is preferably 0. That is, the first organopolysiloxane represented by the above formula (1A) is preferably the first organopolysiloxane represented by the following formula (1Aa). As a result, cracks are less likely to occur in the cured product, and the cured product is more difficult to peel from the housing material or the like.

In the above formula (1Aa), a and b satisfy a / (a + b) = 0 to 0.30 and b / (a + b) = 0.70 to 1.0, and at least one of R1 to R5 is alkenyl And at least one of them represents a methyl group, and R1 to R5 other than an alkenyl group and a methyl group represent a hydrocarbon group having 2 to 8 carbon atoms.

In the above formula (1Aa), a / (a + b) is preferably 0.25 or less, more preferably 0.20 or less, and still more preferably 0.15 or less. In the above formula (1Aa), b / (a + b) is preferably 0.75 or more, more preferably 0.80 or more, and further preferably 0.85 or more.

In the above formula (1B), a / (a + b + c) is 0 or more and 0.50 or less. When a / (a + b + c) is less than or equal to the above upper limit, the heat resistance of the cured product is further increased, and peeling of the cured product can be further suppressed. In the above formula (1B), a / (a + b + c) is preferably 0.45 or less, more preferably 0.40 or less. When a is 0 and a / (a + b + c) is 0, there is no structural unit of (R1R2R3SiO _1/2 ) in the above formula (1B).

In the above formula (1B), b / (a + b + c) is 0.40 or more and 1.0 or less. When b / (a + b + c) is not less than the above lower limit, the cured product does not become too hard, and cracks hardly occur in the cured product. In the above formula (1B), b / (a + b + c) is preferably 0.50 or more.

In the above formula (1B), c / (a + b + c) is 0 or more and 0.50 or less. When c / (a + b + c) is not more than the above upper limit, it is easy to maintain an appropriate viscosity of the curable composition, and the adhesiveness of the cured product is further enhanced. In the above formula (1B), c / (a + b + c) is preferably 0.45 or less, more preferably 0.40 or less, and still more preferably 0.35 or less. In addition, when c is 0 and c / (a + b + c) is 0, the structural unit of (R6SiO _3/2 ) does not exist in the above formula (1B).

C / (a + b + c) in the above formula (1B) is preferably 0. That is, the first organopolysiloxane represented by the above formula (1B) is preferably the first organopolysiloxane represented by the following formula (1Bb). As a result, cracks are less likely to occur in the cured product, and peeling of the cured product is further less likely to occur.

In the above formula (1Bb), a and b satisfy a / (a + b) = 0 to 0.50 and b / (a + b) = 0.50 to 1.0, and at least one of R1 to R5 is aryl And at least one represents an alkenyl group, and R1 to R5 other than the aryl group and alkenyl group represent a hydrocarbon group having 1 to 8 carbon atoms.

A / (a + b) in the above formula (1Bb) is preferably 0.45 or less, more preferably 0.40 or less. In the above formula (1Bb), b / (a + b) is preferably 0.55 or more, more preferably 0.60 or more.

When the first organopolysiloxane was subjected to ²⁹ Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) based on tetramethylsilane (hereinafter referred to as TMS), although some variation was observed depending on the type of substituent, A peak corresponding to the structural unit represented by (R1R2R3SiO _1/2 ) in the formula (1A) and the above formula (1B) appears in the vicinity of +10 to −5 ppm, and in the above formula (1A) and the above formula (1B) Each peak corresponding to the structural unit represented by (R4R5SiO _2/2 ) and the bifunctional structural unit of the above formula (1-2) appears in the vicinity of −10 to −50 ppm, and the above formula (1A) and the above formula (1B ), The peaks corresponding to the structural unit represented by (R6SiO _3/2 ) and the trifunctional structural units of the above formulas (1-3) and (1-4) appear in the vicinity of −50 to −80 ppm. .

Therefore, the ratio of each structural unit in the above formula (1A) and the above formula (1B) can be measured by measuring ²⁹ Si-NMR and comparing the peak areas of the respective signals.

However, in the case where the structural unit in the above formula (1A) and the above formula (1B) cannot be distinguished by the ²⁹ Si-NMR measurement based on the TMS, not only the ²⁹ Si-NMR measurement result but also ¹ By using the measurement results of H-NMR as necessary, the ratio of each structural unit in the above formula (1A) and the above formula (1B) can be distinguished.

(Second organopolysiloxane)
The second organopolysiloxane contained in the curable composition for optical semiconductor devices according to the present invention has two or more hydrogen atoms bonded to silicon atoms. The hydrogen atom is directly bonded to the silicon atom. As for said 2nd organopolysiloxane, only 1 type may be used and 2 or more types may be used together. The second organopolysiloxane may contain a structural unit in which three oxygen atoms are bonded to one silicon atom. In this case, one hydrogen atom may be bonded to the silicon atom to which three oxygen atoms are bonded, and one hydrocarbon group having 1 to 8 carbon atoms (methyl group or hydrocarbon having 2 to 8 carbon atoms). Group) may be bonded.

From the viewpoint of obtaining a cured product that is more excellent in heat resistance, the second organopolysiloxane is represented by the following formula (51A) and has a hydrogen atom bonded to a silicon atom and a methyl group bonded to the silicon atom. A second organopolysiloxane (hereinafter sometimes referred to as a second organopolysiloxane A) is preferred.

From the viewpoint of obtaining a cured product that is more excellent in gas barrier properties, the second organopolysiloxane is represented by the following formula (51B), and includes a second organopolysiloxane having an aryl group and a hydrogen atom bonded to a silicon atom. Siloxane (hereinafter sometimes referred to as second organopolysiloxane B) is preferred. Examples of the aryl group include an unsubstituted phenyl group and a substituted phenyl group.

In the above formula (51A) and the above formula (51B), the structural unit represented by (R54R55SiO _2/2 ) and the structural unit represented by (R56SiO _3/2 ) each have an alkoxy group. It may have a hydroxy group.

The above formula (51A) and the above formula (51B) show the average composition formula. The hydrocarbon group in the above formula (51A) and the above formula (51B) may be linear or branched. R51 to R56 in the above formula (51A) and the above formula (51B) may be the same or different.

In the formula (51A) and the formula (51B), the oxygen atom part in the structural unit represented by (R54R55SiO _2/2 ) and the oxygen atom part in the structural unit represented by (R56SiO _3/2 ) are respectively siloxane. An oxygen atom part forming a bond, an oxygen atom part of an alkoxy group, or an oxygen atom part of a hydroxy group is shown.

The hydrocarbon group having 2 to 8 carbon atoms in the formula (51A) is not particularly limited, and examples thereof include an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-heptyl group. Group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group, cyclohexyl group, vinyl group, allyl group and aryl group Is mentioned. Examples of the hydrocarbon group having 1 to 8 carbon atoms in the above formula (51B) include the same groups as the hydrocarbon group having 2 to 8 carbon atoms in the above formula (51A), and further includes a methyl group.

From the viewpoint of enhancing the curability of the curable composition and further suppressing cracking and peeling during thermal cycling, the second organopolysiloxane contains one hydrogen atom and two carbon atoms in one silicon atom. It preferably contains a structural unit bonded to a hydrocarbon group of 1 to 8 (methyl group or hydrocarbon group of 2 to 8 carbon atoms). In the above formula (51A) and the above formula (51B), (R51R52R53SiO _{1 / The} structural unit represented by ₂ ) includes a structural unit in which R51 represents a hydrogen atom, and R52 and R53 represent a hydrocarbon group having 1 to 8 carbon atoms (a methyl group or a hydrocarbon group having 2 to 8 carbon atoms). It is preferable. That is, from the viewpoint of enhancing the curability of the curable composition and further suppressing cracking and peeling in the thermal cycle, the second organopolysiloxane has a structural unit represented by (HR52R53SiO _1/2 ). In other words, it preferably has a structural unit represented by the following formula (51-a). The structural unit represented by (R51R52R53SiO _1/2 ) may contain only the structural unit represented by the following formula (51-a), and the structural unit represented by the following formula (51-a) And a structural unit other than the structural unit represented by the formula (51-a). Due to the presence of the structural unit represented by the following formula (51-a), a hydrogen atom can be present at the terminal. The presence of a hydrogen atom at the end increases the opportunity for reaction and can further enhance the curability of the curable composition. In the structural unit represented by the following formula (51-a), the terminal oxygen atom generally forms a siloxane bond with an adjacent silicon atom, and shares an oxygen atom with the adjacent structural unit. Therefore, one oxygen atom at the terminal is defined as “O _1/2 ”.

In the above formula (51-a), R52 and R53 each represent a methyl group or a hydrocarbon group having 2 to 8 carbon atoms.

From the viewpoint of further improving the curability of the curable composition and further suppressing cracking and peeling during thermal cycling, the first organopolysiloxane is a structural unit represented by the above formula (1-a). It is particularly preferable that the second organopolysiloxane has a structural unit represented by the above formula (51-a).

From the viewpoint of further improving the curability of the curable composition, the second organopolysiloxane preferably has an alkenyl group, and more preferably has a vinyl group. In this case, in the formula (51A), at least one of R51 to R56 represents a silicon atom, at least one represents a methyl group, at least one represents an alkenyl group, a hydrogen atom, a methyl group, and R51 to R56 other than the alkenyl group represent a hydrocarbon group having 2 to 8 carbon atoms. In the above formula (51B), at least one of R51 to R56 represents an aryl group, at least one represents a silicon atom, at least one represents an alkenyl group, and other than an aryl group, a hydrogen atom, and an alkenyl group R51 to R56 each represents a hydrocarbon group having 2 to 8 carbon atoms.

The content ratio of methyl groups bonded to silicon atoms in the second organopolysiloxane A is preferably 80 mol% or more. The content ratio of the methyl group bonded to the silicon atom is obtained from the following formula (X51). When the content ratio of the methyl group is 80 mol% or more, the heat resistance of the cured product becomes considerably high, and even if the optical semiconductor device is used in a harsh environment under high temperature and high humidity, Is difficult to decrease and discoloration of the cured product is difficult to occur. The content ratio of the methyl group bonded to the silicon atom in the second organopolysiloxane is preferably 85 mol% or more, preferably 99.9 mol% or less, more preferably 99 mol% or less, and still more preferably 98 mol%. % Or less. When the content ratio of the methyl group is not less than the preferable lower limit, the heat resistance of the cured product is further enhanced. When the content ratio of the methyl group is not more than the above upper limit, hydrogen atoms bonded to silicon atoms can be sufficiently introduced, and it is easy to improve the curability of the curable composition.

Content ratio (mol%) of methyl groups bonded to silicon atoms = {(average number of methyl groups bonded to silicon atoms contained in one molecule of the second organopolysiloxane × molecular weight of methyl groups) / (above Average number of functional groups bonded to silicon atoms contained in one molecule of the second organopolysiloxane × average molecular weight of functional groups)} × 100 Formula (X51)

The content ratio of the aryl group in the second organopolysiloxane B is preferably 30 mol% or more, and preferably 85 mol% or less. The content ratio of this aryl group is calculated | required from a following formula (Y51). When the content ratio of the aryl group is 30 mol% or more, the gas barrier property of the cured product is further enhanced, and cracks and peeling are less likely to occur in the cured product. When the content ratio of the aryl group is 85 mol% or less, peeling of the cured product is more difficult to occur. From the viewpoint of further enhancing the gas barrier properties, the content ratio of the aryl group in the second organopolysiloxane B is more preferably 35 mol% or more. From the viewpoint of making peeling more difficult, the content ratio of the aryl group in the second organopolysiloxane B is more preferably 80 mol% or less, still more preferably 75 mol% or less, and particularly preferably 70 mol%. Hereinafter, it is most preferably 65 mol% or less.

Aryl group content (mol%) = (average number of aryl groups contained in one molecule of the second organopolysiloxane × molecular weight of aryl group / included in one molecule of the second organopolysiloxane) Average number of functional groups bonded to silicon atoms × average molecular weight of functional groups) × 100 Formula (Y51)

From the viewpoint of further improving the storage stability of the curable composition, the second organopolysiloxane A preferably has an aryl group. Examples of the aryl group include an unsubstituted phenyl group and a substituted phenyl group. The content ratio of the aryl group in the second organopolysiloxane A is preferably 0.5 mol% or more, preferably 10 mol% or less, more preferably 5 mol% or less. When the content ratio of the aryl group in the second organopolysiloxane A is not more than the above upper limit, the heat resistance of the cured product is further improved.

In the second organopolysiloxane represented by the above formula (51A) and the above formula (51B), the structural unit represented by (R54R55SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) has the following formula ( 51-2), that is, a structure in which one of oxygen atoms bonded to a silicon atom in the bifunctional structural unit constitutes a hydroxy group or an alkoxy group may be included.

(R54R55SiXO _1/2 ) Formula (51-2)

The structural unit represented by (R54R55SiO _2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (51-b), and is further represented by the following formula (51-2-b). A portion surrounded by a broken line of the structural unit may be included. That is, a structural unit having a group represented by R54 and R55 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R54R55SiO _2/2 ).

In the above formulas (51-2) and (51-2-b), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. R54 and R55 in the formula (51-b), formula (51-2) and formula (51-2-b) are the same groups as R54 and R55 in the formula (51A) and the formula (51B). It is.

In the second organopolysiloxane represented by the above formula (51A) and the above formula (51B), the structural unit represented by (R56SiO _3/2 ) (hereinafter also referred to as trifunctional structural unit) has the following formula ( 51-3) or a structure represented by formula (51-4), that is, a structure in which two oxygen atoms bonded to a silicon atom in a trifunctional structural unit each constitute a hydroxy group or an alkoxy group, or a trifunctional One of the oxygen atoms bonded to the silicon atom in the structural unit may include a structure constituting a hydroxy group or an alkoxy group.

(R56SiX ₂ O _1/2 ) Formula (51-3)

(R56SiXO _2/2 ) Formula (51-4)

The structural unit represented by (R56SiO _3/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (51-c), and further includes the following formula (51-3-c) or formula ( A part surrounded by a broken line of the structural unit represented by 51-4-c) may be included. That is, a structural unit having a group represented by R56 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R56SiO _3/2 ).

In the above formula (51-3), formula (51-3-c), formula (51-4) and formula (51-4-c), X represents OH or OR, and OR represents a linear or A branched alkoxy group having 1 to 4 carbon atoms is represented. R56 in the above formula (51-c), formula (51-3), formula (51-3-c), formula (51-4) and formula (51-4-c) represents the above formula (51A) and It is the same group as R56 in the above formula (51B).

Formula (51-b) and Formula (51-c), Formulas (51-2) to (51-4), Formula (51-2-b), Formula (51-3-c) and Formula (51) In -4-c), the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited. For example, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, isopropoxy group , Isobutoxy group, sec-butoxy group and t-butoxy group.

In the above formula (51A), the lower limit of p / (p + q + r) is 0.10 and the upper limit is 0.50. When p / (p + q + r) is less than or equal to the above upper limit, the hardness of the cured product is increased, adhesion of scratches and dust can be prevented, the heat resistance of the cured product is further increased, and peeling of the cured product can be further suppressed. . In said formula (51A), p / (p + q + r) becomes like this. Preferably it is 0.45 or less, More preferably, it is 0.40 or less.

In the above formula (51A), the lower limit of q / (p + q + r) is 0, and the upper limit is 0.40. When q / (p + q + r) exceeds 0, the cured product does not become too hard and cracks are hardly generated in the cured product. In said formula (51A), q / (p + q + r) becomes like this. Preferably it is 0.10 or more, More preferably, it is 0.15 or more. In addition, when q is 0 and q / (p + q + r) is 0, the structural unit of (R54R55SiO _2/2 ) does not exist in the above formula (51A).

In the above formula (51A), the lower limit of r / (p + q + r) is 0.40, and the upper limit is 0.90. When r / (p + q + r) is not less than the above lower limit, the hardness of the cured product is increased, and scratches and dust can be prevented from adhering. When r / (p + q + r) is not more than the above upper limit, it is easy to maintain an appropriate viscosity of the curable composition, and the adhesiveness of the cured product is further enhanced.

In the above formula (51B), p / (p + q + r) is 0.05 or more and 0.50 or less. When p / (p + q + r) is less than or equal to the above upper limit, the heat resistance of the cured product is further increased, and peeling of the cured product can be further suppressed. In said formula (51B), p / (p + q + r) becomes like this. Preferably it is 0.10 or more, Preferably it is 0.45 or less.

In the above formula (51B), q / (p + q + r) is 0.05 or more and 0.50 or less. When q / (p + q + r) is not less than the above lower limit, the cured product does not become too hard and cracks are hardly generated in the cured product. When q / (p + q + r) is not more than the above upper limit, the gas barrier property of the cured product is further enhanced. In the above formula (51B), q / (p + q + r) is preferably 0.10 or more, and preferably 0.45 or less.

In the above formula (51B), r / (p + q + r) is 0.20 or more and 0.80 or less. When r / (p + q + r) is equal to or greater than the above lower limit, the hardness of the cured product is increased, scratches and dust can be prevented, the heat resistance of the cured product is increased, and the thickness of the cured product is less likely to decrease in a high temperature environment. Become. When r / (p + q + r) is not more than the above upper limit, it is easy to maintain an appropriate viscosity of the curable composition, and the adhesiveness of the cured product is further enhanced.

When the second organopolysiloxane was subjected to ²⁹ Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) based on tetramethylsilane (hereinafter referred to as TMS), although some variation was observed depending on the type of substituent, The peak corresponding to the structural unit represented by (R51R52R53SiO _1/2 ) in the formula (51A) and the above formula (51B) appears in the vicinity of +10 to −5 ppm, and in the above formula (51A) and the above formula (51B) Each peak corresponding to the structural unit represented by (R54R55SiO _2/2 ) and the bifunctional structural unit of the above formula (51-2) appears in the vicinity of −10 to −50 ppm, and the above formula (51A) and the above formula (51B ), The peak corresponding to the structural unit represented by (R56SiO _3/2 ) and the trifunctional structural unit of the above formulas (51-3) and (51-4) is −5 Appears around 0 to -80 ppm.

Therefore, the ratio of each structural unit in the above formula (51A) and the above formula (51B) can be measured by measuring ²⁹ Si-NMR and comparing the peak areas of the respective signals.

However, in the case where the structural unit in the formula (51A) and the formula (51B) cannot be distinguished by the ²⁹ Si-NMR measurement based on the TMS, not only the ²⁹ Si-NMR measurement result but also ¹ By using the measurement results of H-NMR as necessary, the ratio of each structural unit in the above formula (51A) and the above formula (51B) can be distinguished.

The content of the second organopolysiloxane is preferably 10 parts by weight or more, more preferably 15 parts by weight or more, still more preferably 20 parts by weight or more, preferably 100 parts by weight of the first organopolysiloxane. 400 parts by weight or less, more preferably 300 parts by weight or less, still more preferably 200 parts by weight or less. When the content of the first and second organopolysiloxanes is not less than the above lower limit and not more than the above upper limit, a curable composition more excellent in curability can be obtained.

(Other properties of the first and second organopolysiloxanes and synthesis methods thereof)
The number average molecular weight (Mn) of the first organopolysiloxane is preferably 500 or more, more preferably 1000 or more, still more preferably 5000 or more, preferably 200000 or less, more preferably 100000 or less, still more preferably 60000 or less, Particularly preferred is 10,000 or less, and most preferred is 8000 or less. The number average molecular weight (Mn) of the first organopolysiloxane represented by the above formula (1A) is preferably 500 or more, more preferably 1000 or more, further preferably 5000 or more, preferably 200000 or less, more preferably 100000. Hereinafter, it is more preferably 60000 or less. The number average molecular weight (Mn) of the first organopolysiloxane represented by the above formula (1B) is preferably 500 or more, more preferably 1000 or more, preferably 10,000 or less, more preferably 8000 or less. The number average molecular weights (Mn) of the second organopolysiloxane, the second organopolysiloxane represented by the formula (51A), and the second organopolysiloxane represented by the formula (51B) are each preferably Is 500 or more, more preferably 1000 or more, preferably 20000 or less, more preferably 10,000 or less. When the number average molecular weight is not less than the above lower limit, the volatile components are reduced at the time of thermosetting, and the thickness of the cured product is hardly reduced under a high temperature environment. When the number average molecular weight is not more than the above upper limit, viscosity adjustment is easy.

The number average molecular weight (Mn) is a value obtained by using polystyrene as a standard substance using gel permeation chromatography (GPC). The number average molecular weight (Mn) is determined by two measuring devices manufactured by Waters (column: Shodex GPC LF-804 (length: 300 mm) manufactured by Showa Denko KK), measuring temperature: 40 ° C., flow rate: 1 mL / min, solvent: Tetrahydrofuran, standard substance: polystyrene) means a value measured.

The method for synthesizing the first and second organopolysiloxanes is not particularly limited, and examples thereof include a method in which an alkoxysilane compound is hydrolyzed and subjected to a condensation reaction, and a method in which a chlorosilane compound is hydrolyzed and condensed. Especially, the method of hydrolyzing and condensing an alkoxysilane compound from a viewpoint of reaction control is preferable.

Examples of the method of hydrolyzing and condensing the alkoxysilane compound include a method of reacting an alkoxysilane compound in the presence of water and an acidic catalyst or a basic catalyst. Further, the disiloxane compound may be hydrolyzed and used.

Examples of the organosilicon compound for introducing an alkenyl group into the first organopolysiloxane include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, methoxydimethylvinylsilane, vinyldimethylethoxysilane, and 1,3-divinyl. -1,1,3,3-tetramethyldisiloxane and the like.

Examples of the organosilicon compound for introducing a hydrogen atom bonded to a silicon atom into the second organopolysiloxane include trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyldiethoxysilane, and 1,1,3, Examples include 3-tetramethyldisiloxane.

Examples of the organosilicon compound for introducing an aryl group into the first and second organopolysiloxanes as necessary include triphenylmethoxysilane, triphenylethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methyl (phenyl) ) Dimethoxysilane, phenyltrimethoxysilane and the like.

Examples of other organosilicon compounds that can be used to obtain the first and second organopolysiloxanes include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and isopropyl (methyl) dimethoxy. Examples include silane, cyclohexyl (methyl) dimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, and octyltrimethoxysilane.

Examples of the acidic catalyst include inorganic acids, organic acids, acid anhydrides of inorganic acids and derivatives thereof, and acid anhydrides of organic acids and derivatives thereof.

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 and oleic acid. Is mentioned.

Examples of the basic catalyst include alkali metal hydroxides, alkali metal alkoxides, and alkali metal silanol compounds.

Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide and cesium hydroxide. Examples of the alkali metal alkoxide include sodium-t-butoxide, potassium-t-butoxide, and cesium-t-butoxide.

Examples of the alkali metal silanol compound include a sodium silanolate compound, a potassium silanolate compound, and a cesium silanolate compound. Among these, a potassium catalyst or a cesium catalyst is preferable.

(Catalyst for hydrosilylation reaction)
The hydrosilylation reaction catalyst contained in the curable composition for optical semiconductor devices according to the present invention is bonded to an alkenyl group in the first organopolysiloxane and a silicon atom in the second organopolysiloxane. It is a catalyst for the hydrosilylation reaction between the hydrogen atom.

As the hydrosilylation reaction catalyst, various catalysts that cause the hydrosilylation reaction to proceed can be used. As for the said catalyst for hydrosilylation reaction, only 1 type may be used and 2 or more types may be used together.

Examples of the hydrosilylation reaction catalyst include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Since the transparency of the cured product is increased, a platinum-based catalyst is preferable.

Examples of the platinum-based catalyst include platinum powder, chloroplatinic acid, platinum-alkenylsiloxane complex, platinum-olefin complex, and platinum-carbonyl complex. In particular, a platinum-alkenylsiloxane complex or a platinum-olefin complex is preferred.

Examples of the alkenylsiloxane in the platinum-alkenylsiloxane complex include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1,3,5,7-tetramethyl-1,3,5. , 7-tetravinylcyclotetrasiloxane and the like. Examples of the olefin in the platinum-olefin complex include allyl ether and 1,6-heptadiene.

In order to improve the stability of the platinum-alkenylsiloxane complex and the platinum-olefin complex, it is preferable to add alkenylsiloxane, organosiloxane oligomer, allyl ether or olefin to the platinum-alkenylsiloxane complex or platinum-olefin complex. The alkenylsiloxane is preferably 1,3-divinyl-1,1,3,3-tetramethyldisiloxane. The organosiloxane oligomer is preferably a dimethylsiloxane oligomer. The olefin is preferably 1,6-heptadiene.

In the curable composition, the content of the catalyst for hydrosilylation reaction is preferably 0.01 ppm or more, more preferably 1 ppm or more, preferably in terms of weight units of metal atoms (platinum atoms in the case of platinum alkenyl complexes). Is 1000 ppm or less, more preferably 500 ppm or less. When the content of the hydrosilylation reaction catalyst is not less than the above lower limit, it is easy to sufficiently cure the curable composition. When the content of the catalyst for hydrosilylation reaction is not more than the above upper limit, the problem of coloring of the cured product hardly occurs.

(First silane compound)
The curable composition for optical semiconductor devices according to the present invention includes a first silane compound having a ureido group or an isocyanate group. By using the first silane compound having this specific group, even if the optical semiconductor device is used in a harsh environment under high temperature and high humidity, the curable composition is cured from the bonded object of the cured product. Peeling is less likely to occur. The first silane compound may have a ureido group or an isocyanate group.

Further, in the composition comprising the first organopolysiloxane having an alkenyl group, the second organopolysiloxane having a hydrogen atom bonded to a silicon atom, and a catalyst for hydrosilylation reaction, the second organopolysiloxane having an ureido group or an isocyanate group. By using 1 silane compound, the viscosity of the curable composition for optical semiconductor devices hardly changes, and the pot life of the curable composition for optical semiconductor devices is improved.

The first silane compound may have a ureido group or an isocyanate group. From the viewpoint of further increasing the adhesiveness of the cured product to the object to be bonded, the first silane compound preferably has a ureido group. In addition, the use of the first silane compound having a ureido group can further suppress electrode discoloration due to sulfur-containing gas in the atmosphere in the optical semiconductor device.

From the viewpoint of further suppressing the peeling of the cured product from the object to be bonded, the first silane compound is a first silane compound represented by the following formula (S1) or the following formula (S2). preferable. From the viewpoint of further improving the adhesion of the cured product to the object to be bonded and further suppressing electrode discoloration due to sulfur-containing gas in the atmosphere in the optical semiconductor device, the first silane compound is represented by the following formula (S1). It is preferable that it is the 1st silane compound represented.

In the above formula (S2), X1 represents an alkoxy group, X2 and X3 each represents an alkoxy group or a hydrocarbon group having 1 to 8 carbon atoms, and R4 represents a single bond directly connecting a nitrogen atom and a silicon atom. It represents a bond or a hydrocarbon group having 1 to 8 carbon atoms. The number of carbon atoms of the alkoxy group in X1 in the formula (S1) and the formula (S2) is preferably 1-8. When X2 and X3 in the formula (S1) and the formula (S2) are alkoxy groups, the alkoxy group in X2 and X3 preferably has 1 to 8 carbon atoms.

The first silane compound represented by the above formula (S1) is preferably the first silane compound represented by the following formula (S1-1). By using the first silane compound represented by the following formula (S1-1), the adhesion of the cured product to the object to be bonded is further enhanced.

The first silane compound represented by the above formula (S2) is preferably the first silane compound represented by the following formula (S2-1). By using the first silane compound represented by the following formula (S2-1), the adhesion of the cured product to the object to be bonded is further enhanced.

In the above formula (S2-1), R1 to R3 each represent a hydrocarbon group having 1 to 8 carbon atoms, and R4 represents a single bond directly bonding a nitrogen atom and a silicon atom, or 1 carbon atom. Represents 8 to 8 hydrocarbon groups.

The content of the first silane compound is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 100 parts by weight in total for the first and second organopolysiloxanes. 5 parts by weight or less, more preferably 3 parts by weight or less. When the content of the first silane compound is equal to or higher than the lower limit, peeling of the cured product from the adhesion target can be further suppressed. When the content of the first silane compound is not more than the above upper limit, it is possible to prevent the surface stickiness of the sealing agent from being deteriorated due to the excessive first silane coupling agent.

(Second silane compound)
The curable composition for optical semiconductor devices according to the present invention preferably contains a second silane compound different from the first silane compound having a ureido group or an isocyanate group. The second silane compound does not have a ureido group and an isocyanate group. By using the second silane compound together with the first silane compound, peeling of the cured product from the object to be bonded can be further suppressed. As for the said 2nd silane compound, only 1 type may be used and 2 or more types may be used together.

The second silane compound is not particularly limited, and examples thereof include vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Examples include 3- (meth) acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane.

The above “(meth) acryloyl” indicates acryloyl and methacryloyl. The “(meth) acryloxy” refers to acryloxy and methacryloxy.

From the viewpoint of further suppressing peeling of the cured product from the object to be bonded, the second silane compound preferably has an epoxy group, a vinyl group or a (meth) acryloyl group.

From the viewpoint of further suppressing peeling of the cured product from the object to be bonded, the second silane compound is 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Vinyltrimethoxysilane or 3- (meth) acryloxypropyltrimethoxysilane is preferable.

The content of the second silane compound is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 100 parts by weight based on the total of the first and second organopolysiloxanes. 5 parts by weight or less, more preferably 3 parts by weight or less. When the content of the second silane compound is equal to or more than the lower limit, peeling of the cured product from the adhesion target can be further suppressed. When the content of the second silane compound is not more than the above upper limit, it is possible to prevent the surface stickiness of the sealing agent from being deteriorated due to an excessive second silane coupling agent.

(Silicon oxide particles)
The curable composition for optical semiconductor devices according to the present invention preferably further contains silicon oxide particles. When the curable composition for optical semiconductor devices according to the present invention is an encapsulant for optical semiconductor devices, the encapsulant preferably further contains silicon oxide particles. By using the silicon oxide particles, the viscosity of the curable composition can be adjusted to an appropriate range without impairing the heat resistance and light resistance of the cured product. Therefore, the handleability of the curable composition can be improved.

The primary particle diameter of the silicon oxide particles is preferably 5 nm or more, more preferably 8 nm or more, preferably 200 nm or less, more preferably 150 nm or less. When the primary particle diameter of the silicon oxide particles is not less than the above lower limit, the dispersibility of the silicon oxide particles is further increased, and the transparency of the cured product is further increased. When the primary particle diameter of the silicon oxide particles is not more than the above upper limit, it is possible to sufficiently obtain the effect of increasing the viscosity at 25 ° C. and to suppress the decrease in the viscosity due to the temperature increase.

The primary particle diameter of the silicon oxide particles is measured as follows. The cured product of the curable composition for optical semiconductor devices is observed using a transmission electron microscope (“JEM-2100” manufactured by JEOL Ltd.). The size of the primary particles of 100 silicon oxide particles in the visual field is measured, and the average value of the measured values is defined as the primary particle diameter. The primary particle diameter means an average value of the diameters of the silicon oxide particles when the silicon oxide particles are spherical, and an average value of the major diameters of the silicon oxide particles when the silicon oxide particles are non-spherical.

The BET specific surface area of the silicon oxide particles is preferably 30 m ² / g or more, and preferably 400 m ² / g or less. When the BET specific surface area of the silicon oxide particles is 30 m ² / g or more, the viscosity at 25 ° C. of the curable composition can be controlled within a suitable range, and the decrease in the viscosity due to a temperature rise can be suppressed. When the BET specific surface area of the silicon oxide particles is 400 m ² / g or less, the aggregation of the silicon oxide particles hardly occurs, the dispersibility can be increased, and the transparency of the cured product can be further increased. it can.

The silicon oxide particles are not particularly limited, and examples thereof include silica produced by a dry method such as fumed silica and fused silica, and silica produced by a wet method such as colloidal silica, sol-gel silica and precipitated silica. It is done. Among these, fumed silica is suitably used as the silicon oxide particles from the viewpoint of obtaining a cured product with less volatile components and higher transparency.

Examples of the fumed silica include Aerosil 50 (specific surface area: 50 m ² / g), Aerosil 90 (specific surface area: 90 m ² / g), Aerosil 130 (specific surface area: 130 m ² / g), Aerosil 200 (specific surface area). : 200 m ² / g), Aerosil 300 (specific surface area: 300 m ² / g), Aerosil 380 (specific surface area: 380 m ² / g) (all manufactured by Nippon Aerosil Co., Ltd.) and the like.

The silicon oxide particles are preferably surface-treated with an organosilicon compound. By this surface treatment, the dispersibility of the silicon oxide particles becomes very high, and it is possible to further suppress the decrease in the viscosity due to the temperature rise of the curable composition.

The content of the silicon oxide particles is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight with respect to a total of 100 parts by weight of the first organopolysiloxane and the second organopolysiloxane. More preferably, it is 1 part by weight or more, preferably 40 parts by weight or less, more preferably 35 parts by weight or less, and still more preferably 20 parts by weight or less. When the content of the silicon oxide particles is equal to or higher than the lower limit, it is possible to suppress a decrease in viscosity at the time of curing. When the content of the silicon oxide particles is not more than the above upper limit, the viscosity of the curable composition can be controlled to a more appropriate range, and the transparency of the cured product is further enhanced.

(Phosphor)
The curable composition for optical semiconductor devices according to the present invention may further contain a phosphor. When the curable composition for optical semiconductor devices according to the present invention is an encapsulant for optical semiconductor devices, the encapsulant preferably further contains a phosphor. Moreover, the curable composition for optical semiconductor devices which concerns on this invention does not need to contain fluorescent substance. In this case, a phosphor may be added when the curable composition is used.

For example, the phosphor absorbs light emitted from a light-emitting element that is sealed using the curable composition for optical semiconductor devices, and generates fluorescence to finally obtain light of a desired color. Acts as follows. The phosphor is excited by light emitted from the light emitting element to emit fluorescence, and light of a desired color is obtained by a combination of light emitted from the light emitting element and fluorescence emitted from the phosphor.

For example, when it is intended to finally obtain white light using an ultraviolet LED chip as a light emitting element, it is preferable to use a combination of a blue phosphor, a red phosphor and a green phosphor. When it is intended to finally obtain white light using a blue LED chip as a light emitting element, it is preferable to use a combination of a green phosphor and a red phosphor, or a yellow phosphor. As for the said fluorescent substance, only 1 type may be used and 2 or more types may be used together.

The content of the phosphor can be adjusted as appropriate so as to obtain light of a desired color, and is not particularly limited. The content of the phosphor is preferably 0.1 parts by weight or more and preferably 40 parts by weight or less with respect to 100 parts by weight of the curable composition for optical semiconductor devices according to the present invention. The content of the phosphor is preferably 0.1 parts by weight or more and preferably 40 parts by weight or less with respect to 100 parts by weight of all components excluding the phosphor of the curable composition for optical semiconductor devices.

(Other ingredients)
The curable composition for an optical semiconductor device according to the present invention includes a dispersant, an antioxidant, an antifoaming agent, a colorant, a modifier, a leveling agent, a light diffusing agent, a heat conductive filler, or a flame retardant as necessary. Etc. may further be included.

In addition, said 1st organopolysiloxane, said 2nd organopolysiloxane, said hydrosilylation reaction catalyst, and said 1st silane compound are the liquids containing these 1 type, or 2 or more types separately. The curable composition for optical semiconductor devices according to the present invention may be prepared by preparing and mixing a plurality of liquids immediately before use. For example, the first liquid containing the first organopolysiloxane and the second liquid containing the second organopolysiloxane are prepared separately, and the first liquid and the second liquid are prepared just before use. The curable composition for optical semiconductor devices according to the present invention may be prepared by mixing with a liquid. At least one of the first liquid and the second liquid contains the hydrosilylation reaction catalyst. The first liquid preferably contains a hydrosilylation reaction catalyst. The first silane compound may be added to the first liquid or may be added to the second liquid. At least one of the first liquid and the second liquid contains the first silane compound. When the second silane compound, the silicon oxide particles, or the phosphor is used, the second silane compound, the silicon oxide particles, or the phosphor may be added to the first liquid, respectively. It may be added to the second liquid. It is preferable that at least one of the first liquid and the second liquid contains the second silane compound. Thus, storage stability improves by making said 1st organopolysiloxane and said 2nd organopolysiloxane into 2 liquids of a 1st liquid and a 2nd liquid separately.

(Details and applications of curable composition for optical semiconductor devices)
The curing temperature of the curable composition for optical semiconductor devices according to the present invention is not particularly limited. The curing temperature of the curable composition for optical semiconductor devices is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, preferably 180 ° C. or lower, more preferably 150 ° C. or lower. When the curing temperature is not less than the above lower limit, curing of the curable composition proceeds sufficiently. When the curing temperature is not more than the above upper limit, the package is unlikely to be thermally deteriorated.

The curing method is not particularly limited, but it is preferable to use a step cure method. The step cure method is a method in which the resin is temporarily cured at a low temperature and then cured at a high temperature. By using the step cure method, curing shrinkage of the cured product can be suppressed.

It does not specifically limit as a manufacturing method of the curable composition for optical semiconductor devices which concerns on this invention, For example, using mixers, such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, a triple roll, or a bead mill. Mixing the first organopolysiloxane, the second organopolysiloxane, the hydrosilylation catalyst, the first silane compound, and other components blended as necessary at room temperature or under heating And the like.

The light-emitting element is not particularly limited as long as it is a light-emitting element using a semiconductor. For example, when the light-emitting element is a light-emitting diode, a structure in which an LED-type semiconductor material is stacked on a substrate is exemplified. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.

Examples of the material of the substrate include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. Further, a buffer layer may be formed between the substrate and the semiconductor material as necessary. Examples of the material of the buffer layer include GaN and AlN.

Specific examples of the optical semiconductor device according to the present invention include a light emitting diode device, a semiconductor laser device, and a photocoupler. Such optical semiconductor devices include, for example, backlights such as liquid crystal displays, illumination, various sensors, light sources such as printers and copiers, vehicle measuring instrument light sources, signal lights, indicator lights, display devices, and light sources for planar light emitters. It is suitably used for displays, decorations, various lights and switching elements.

The curable composition for optical semiconductor devices according to the present invention is preferably an encapsulant for optical semiconductor devices or a lens material for optical semiconductor devices. The curable composition for optical semiconductor devices according to the present invention may be an encapsulant for optical semiconductor devices or a lens material for optical semiconductor devices. The curable composition for optical semiconductor devices according to the present invention is also used as a coating material for optical semiconductor devices for forming a coating layer on the surface of an optical semiconductor element.

An optical semiconductor device according to the present invention includes an optical semiconductor element and a sealing agent disposed so as to seal the optical semiconductor element or a lens disposed on the optical semiconductor element. The sealing agent or the lens is formed by curing the above-described curable composition for optical semiconductor devices. When a cured product of the curable composition for an optical semiconductor device is disposed so as to seal a light emitting element formed of an optical semiconductor such as an LED, the cured product is effectively peeled from the housing or the like. Can be suppressed. The lens may be directly laminated on the optical semiconductor element, or may be disposed on the optical semiconductor element via a sealant or the like disposed so as to seal the optical semiconductor element. That is, the lens may be disposed on the surface of the sealant.

The shape of the lens is not particularly limited. From the viewpoint of controlling the light emission direction in the optical semiconductor device and further suppressing the front luminance from becoming too high, the shape of the lens may be a part of a sphere or a part of a spheroid. preferable.

(Embodiment of optical semiconductor device)
FIG. 1 is a front sectional view showing an optical semiconductor device according to the first embodiment of the present invention.

The optical semiconductor device 1 of this embodiment has a housing 2. An optical semiconductor element 3 is disposed in the housing 2. The optical semiconductor element 3 is surrounded by an inner surface 2 a having light reflectivity of the housing 2. The optical semiconductor element 3 is a light emitting element such as an LED.

The inner surface 2a is formed such that the diameter of the inner surface 2a increases toward the opening end. Therefore, of the light emitted from the optical semiconductor element 3, the light that has reached the inner surface 2 a is reflected by the inner surface 2 a and travels forward of the optical semiconductor element 3. In a region surrounded by the inner surface 2 a so as to seal the optical semiconductor element 3, a sealing agent 4 that is a cured product of the curable composition for optical semiconductor devices is filled. The sealant 4 is formed by curing the sealant that is the curable composition for optical semiconductor devices according to the present invention, and is a cured product of the sealant.

FIG. 2 is a front sectional view showing an optical semiconductor device according to the second embodiment of the present invention.

The optical semiconductor device 11 shown in FIG. An optical semiconductor element 3 is disposed in the housing 2. A sealing agent 12 is filled in a region surrounded by the inner surface 2 a of the housing 2 so as to seal the optical semiconductor element 3. That is, the optical semiconductor element 3 is sealed with the sealant 12 in the housing 2. In the optical semiconductor device 11, a sealing agent 12 is disposed so as to seal the optical semiconductor element 3.

Furthermore, in the optical semiconductor device 11, a lens 13 is disposed on the surface 12 a of the sealant 12. The lens 13 is formed by curing a lens material that is a curable composition for optical semiconductor devices according to the present invention, and is a cured product of the lens material.

FIG. 3 is a front sectional view showing an optical semiconductor device according to the third embodiment of the present invention.

In the optical semiconductor device 21 shown in FIG. 3, an optical semiconductor element 23 is arranged on a substrate 22 on which a terminal 22a is provided. An electrode 23 a provided on the upper surface of the optical semiconductor element 23 and a terminal 22 a provided on the upper surface of the substrate 22 are electrically connected by a bonding wire 24. Further, in the optical semiconductor device 21, a lens 25 is disposed on the optical semiconductor element 23. The lens 25 covers the surface of the optical semiconductor element 23 and the bonding wire 24. The lens 25 is formed by curing a lens material that is a curable composition for optical semiconductor devices according to the present invention, and is a cured product of the lens material.

The structures shown in FIGS. 1 to 3 are merely examples of the optical semiconductor device according to the present invention, and the mounting structure of the optical semiconductor device can be modified as appropriate.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples.

(Synthesis Example 1) Synthesis of first organopolysiloxane In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 486 g of dimethyldimethoxysilane and 1,3-divinyl-1,1,3,3- 2.7 g of tetramethyldisiloxane was added and stirred at 50 ° C. A solution prepared by dissolving 2.2 g of potassium hydroxide in 144 g of water was slowly added dropwise thereto, and after the addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, volatile components were removed under reduced pressure, 2.4 g of acetic acid was added to the reaction solution, and the mixture was heated under reduced pressure. Thereafter, potassium acetate was removed by filtration to obtain a polymer (A).

The number average molecular weight of the obtained polymer (A) was 37400. As a result of identifying the chemical structure by ²⁹ Si-NMR, the polymer (A) had the following average composition formula (A1).

(Me ₂ SiO _2/2 ) _0.992 (ViMe ₂ SiO _1/2 ) _0.008 Formula (A1)

In the above formula (A1), Me represents a methyl group, and Vi represents a vinyl group. The content ratio of the methyl group of the obtained polymer (A) was 99 mol%.

The molecular weight of each polymer obtained in Synthesis Example 1 and Synthesis Examples 2 to 6 was measured by GPC measurement by adding 1 mL of tetrahydrofuran to 10 mg, stirring until dissolved. For GPC measurement, a measuring device manufactured by Waters (column: Shodex GPC LF-804 (length: 300 mm) x 2 manufactured by Showa Denko KK), measuring temperature: 40 ° C., flow rate: 1 mL / min, solvent: tetrahydrofuran, standard substance: Polystyrene) was used.

(Synthesis Example 2) Synthesis of First Organopolysiloxane In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 56 g of divinyltetramethyldisiloxane, 122 g of dimethyldimethoxysilane, and 366 g of diphenyldimethoxysilane were added, and 50 Stir at ° C. A solution obtained by dissolving 0.8 g of potassium hydroxide in 114 g of water was slowly dropped therein, and after the dropwise addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, 0.9 g of acetic acid was added to the reaction solution, the pressure was reduced to remove volatile components, and potassium acetate was removed by filtration to obtain a polymer (B).

The number average molecular weight (Mn) of the obtained polymer (B) was 1700. As a result of identifying the chemical structure by ²⁹ Si-NMR, the polymer (B) had the following average composition formula (B1).

(ViMe ₂ SiO _1/2 ) _0.07 (Me ₂ SiO _2/2 ) _0.45 (Ph ₂ SiO _2/2 ) _0.48 ... Formula (B1)

In the above formula (B1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group. The content ratio of the phenyl group of the obtained polymer (B) was 80.8 mol%.

(Synthesis Example 3) Synthesis of Second Organopolysiloxane In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 90.2 g of dimethyldimethoxysilane, 217 g of methyltrimethoxysilane, 31 g of vinyltrimethoxysilane, 1 , 1,3,3-tetramethyldisiloxane and 16 g of trimethylmethoxysilane were added and stirred at 50 ° C. Into this, a solution of 2.0 g of hydrochloric acid and 134 g of water was slowly added dropwise. After the addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by removing the volatile component under reduced pressure. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (C) was obtained.

The number average molecular weight of the obtained polymer (C) was 3420. As a result of identifying the chemical structure by ²⁹ Si-NMR, the polymer (C) had the following average composition formula (C1).

(Me ₂ SiO _2/2 ) _0.25 (MeSiO _3/2 ) _0.52 (ViSiO _3/2 ) _0.07 (HMe ₂ SiO _1/2 ) _0.10 (Me ₃ SiO _1/2 ) _{0. 06} Formula (C1)

In the above formula (C1), Me represents a methyl group, and Vi represents a vinyl group. The content ratio of methyl groups of the obtained polymer (C) was 90 mol%.

Synthesis Example 4 Synthesis of Second Organopolysiloxane A 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer was charged with 31 g of trimethylmethoxysilane, 40 g of 1,1,3,3-tetramethyldisiloxane, diphenyl. 110 g of dimethoxysilane, 268 g of phenyltrimethoxysilane, and 45 g of vinyltrimethoxysilane were added and stirred at 50 ° C. Into this, a solution of 1.4 g of hydrochloric acid and 116 g of water was slowly added dropwise, and after the addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by removing the volatile component under reduced pressure. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (D) was obtained.

The number average molecular weight (Mn) of the obtained polymer (D) was 1100. As a result of identifying the chemical structure by ²⁹ Si-NMR, the polymer (D) had the following average composition formula (D1).

(Me ₃ SiO _1/2 ) _0.09 (HMe ₂ SiO _1/2 ) _0.19 (Ph ₂ SiO _2/2 ) _0.16 (PhSiO _3/2 ) _0.46 (ViSiO _3/2 ) _{0. 10} : Formula (D1)

In the above formula (D1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group. The content ratio of the phenyl group of the obtained polymer (D) was 82.5 mol%.

Synthesis Example 5 Synthesis of First Organopolysiloxane A 1 L separable flask equipped with a thermometer, a dropping device and a stirrer was charged with 474 g of dimethyldimethoxysilane, 10 g of diphenyldimethoxysilane, 1,3-divinyl-1,1, 1.2 g of 3,3-tetramethyldisiloxane and 200 g of dimethylformamide were added and stirred at 50 ° C. A solution prepared by dissolving 2.2 g of potassium hydroxide in 144 g of water was slowly added dropwise thereto, and after the dropwise addition, the mixture was stirred at 50 ° C. for 2 hours to react, further heated to 85 ° C. and heated to 105 ° C. for 2 hours. The reaction was carried out while raising the temperature and raising the reaction temperature for 2 hours to obtain a reaction solution. Next, volatile components were removed under reduced pressure, 2.4 g of acetic acid was added to the reaction solution, and the mixture was heated under reduced pressure. Thereafter, potassium acetate was removed by filtration to obtain a polymer (E).

The number average molecular weight of the obtained polymer (E) was 52300. As a result of identifying the chemical structure by ²⁹ Si-NMR, the polymer (E) had the following average composition formula (E1).

(Me ₂ SiO _2/2 ) _0.987 (Ph ₂ SiO _2/2 ) _0.010 (ViMe ₂ SiO _1/2 ) _0.003 Formula (E1)

In the above formula (E1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group. The content ratio of the methyl group of the obtained polymer (E) was 99 mol%.

(Synthesis Example 6) Synthesis of Second Organopolysiloxane Into a 1 L separable flask equipped with a thermometer, a dropping device and a stirrer, 150 g of dimethyldimethoxysilane, 360 g of methyltrimethoxysilane, 52 g of vinyltrimethoxysilane, 1,1 , 3,3-tetramethyldisiloxane (67 g) and trimethylmethoxysilane (21 g) were added and stirred at 50 ° C. Into this, a solution of 2.6 g of hydrochloric acid and 220 g of water was slowly added dropwise. After the addition, the solution was stirred at 50 ° C. for 8 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by removing the volatile component under reduced pressure. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (F) was obtained.

The number average molecular weight of the obtained polymer (F) was 5480. As a result of identifying the chemical structure by ²⁹ Si-NMR, the polymer (F) had the following average composition formula (F1).

(Me ₂ SiO _2/2 ) _0.20 (MeSiO _3/2 ) _0.59 (ViSiO _3/2 ) _0.07 (HMe ₂ SiO _1/2 ) _0.10 (Me ₃ SiO _1/2 ) _{0. 04} ... Formula (F1)

In the above formula (F1), Me represents a methyl group, and Vi represents a vinyl group. The content ratio of the methyl group of the obtained polymer (F) was 90 mol%.

Example 1
Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) And 3-ureidopropyltriethoxysilane (0.2 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Example 2)
Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) And 3-isocyanatopropyltriethoxysilane (0.2 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Example 3)
Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) 2), 3-ureidopropyltriethoxysilane (0.15 g), and 3-glycidoxypropyltrimethoxysilane (0.15 g) are mixed and defoamed to obtain a curable composition for optical semiconductor devices. Obtained.

(Example 4)
Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) ), 3-ureidopropyltriethoxysilane (0.15 g), and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (0.15 g) are mixed and degassed for use in an optical semiconductor device. A curable composition was obtained.

(Example 5)
Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) ), 3-ureidopropyltriethoxysilane (0.15 g), and vinyltrimethoxysilane (0.15 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Example 6)
Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) 2), 3-ureidopropyltriethoxysilane (0.15 g), and 3-methacryloxypropyltrimethoxysilane (0.15 g) are mixed and degassed to obtain a curable composition for an optical semiconductor device. It was.

(Example 7)
Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) 3), 3-ureidopropyltriethoxysilane (0.10 g), 3-glycidoxypropyltrimethoxysilane (0.10 g), and vinyltrimethoxysilane (0.10 g) are mixed and defoamed. A curable composition for an optical semiconductor device was obtained.

(Example 8)
Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) ), 3-isocyanatopropyltriethoxysilane (0.15 g), and 3-glycidoxypropyltrimethoxysilane (0.15 g) are mixed and degassed to obtain a curable composition for optical semiconductor devices. Obtained.

Example 9
Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) ), 3-isocyanatopropyltriethoxysilane (0.15 g), and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (0.15 g) are mixed and degassed for use in an optical semiconductor device. A curable composition was obtained.

(Example 10)
Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) ), 3-isocyanatopropyltriethoxysilane (0.15 g), and vinyltrimethoxysilane (0.15 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Example 11)
Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) 2), 3-isocyanatopropyltriethoxysilane (0.15 g), and 3-methacryloxypropyltrimethoxysilane (0.15 g) are mixed and defoamed to obtain a curable composition for optical semiconductor devices. It was.

Example 12
Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) 3), 3-isocyanatopropyltriethoxysilane (0.10 g), 3-glycidoxypropyltrimethoxysilane (0.10 g), and vinyltrimethoxysilane (0.10 g) are mixed and defoamed. A curable composition for an optical semiconductor device was obtained.

(Example 13)
Polymer B (10 g), Polymer D (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) And 3-ureidopropyltriethoxysilane (0.2 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Example 14)
Polymer B (10 g), Polymer D (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) And 3-isocyanatopropyltriethoxysilane (0.2 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Example 15)
Polymer B (10 g), Polymer D (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) 2), 3-ureidopropyltriethoxysilane (0.15 g), and 3-glycidoxypropyltrimethoxysilane (0.15 g) are mixed and defoamed to obtain a curable composition for optical semiconductor devices. Obtained.

(Example 16)
Polymer B (10 g), Polymer D (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) ), 3-ureidopropyltriethoxysilane (0.15 g), and vinyltrimethoxysilane (0.15 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Example 17)
Polymer B (10 g), Polymer D (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) 3), 3-ureidopropyltriethoxysilane (0.10 g), 3-glycidoxypropyltrimethoxysilane (0.10 g), and vinyltrimethoxysilane (0.10 g) are mixed and defoamed. A curable composition for an optical semiconductor device was obtained.

(Example 18)
Polymer B (10 g), Polymer D (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) ), 3-isocyanatopropyltriethoxysilane (0.15 g), and 3-glycidoxypropyltrimethoxysilane (0.15 g) are mixed and degassed to obtain a curable composition for optical semiconductor devices. Obtained.

(Example 19)
Polymer B (10 g), Polymer D (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) ), 3-isocyanatopropyltriethoxysilane (0.15 g), and vinyltrimethoxysilane (0.15 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Example 20)
Polymer B (10 g), Polymer D (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) 3), 3-isocyanatopropyltriethoxysilane (0.10 g), 3-glycidoxypropyltrimethoxysilane (0.10 g), and vinyltrimethoxysilane (0.10 g) are mixed and defoamed. A curable composition for an optical semiconductor device was obtained.

(Comparative Example 1)
Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) And 3-glycidoxypropyltrimethoxysilane (0.2 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Comparative Example 2)
Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) And 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (0.2 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Comparative Example 3)
Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) And vinyltrimethoxysilane (0.2 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Comparative Example 4)
Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) And 3-methacryloxypropyltrimethoxysilane (0.2 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Comparative Example 5)
Polymer B (10 g), Polymer D (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) And 3-glycidoxypropyltrimethoxysilane (0.2 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Comparative Example 6)
Polymer B (10 g), Polymer D (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) And vinyltrimethoxysilane (0.2 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Example 21)
Polymer E (10 g), Polymer F (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) And 3-ureidopropyltriethoxysilane (0.2 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Example 22)
Polymer E (10 g), Polymer F (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) And 3-isocyanatopropyltriethoxysilane (0.2 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Example 23)
Polymer E (10 g), Polymer F (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) 2), 3-ureidopropyltriethoxysilane (0.15 g), and 3-glycidoxypropyltrimethoxysilane (0.15 g) are mixed and defoamed to obtain a curable composition for optical semiconductor devices. Obtained.

(Example 24)
Polymer E (10 g), Polymer F (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) ), 3-ureidopropyltriethoxysilane (0.15 g), and vinyltrimethoxysilane (0.15 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Example 25)
Polymer E (10 g), Polymer F (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) 3), 3-ureidopropyltriethoxysilane (0.10 g), 3-glycidoxypropyltrimethoxysilane (0.10 g), and vinyltrimethoxysilane (0.10 g) are mixed and defoamed. A curable composition for an optical semiconductor device was obtained.

(Example 26)
Polymer E (10 g), Polymer F (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) ), 3-isocyanatopropyltriethoxysilane (0.15 g), and 3-glycidoxypropyltrimethoxysilane (0.15 g) are mixed and degassed to obtain a curable composition for optical semiconductor devices. Obtained.

(Example 27)
Polymer E (10 g), Polymer F (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) ), 3-isocyanatopropyltriethoxysilane (0.15 g), and vinyltrimethoxysilane (0.15 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Example 28)
Polymer E (10 g), Polymer F (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) 3), 3-isocyanatopropyltriethoxysilane (0.10 g), 3-glycidoxypropyltrimethoxysilane (0.10 g), and vinyltrimethoxysilane (0.10 g) are mixed and defoamed. A curable composition for an optical semiconductor device was obtained.

(Comparative Example 7)
Polymer E (10 g), Polymer F (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) And 3-glycidoxypropyltrimethoxysilane (0.2 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Comparative Example 8)
Polymer E (10 g), Polymer F (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) And vinyltrimethoxysilane (0.2 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Evaluation)
In a structure in which a light emitting element having a main emission peak of 460 nm is mounted on a silver-plated polyphthalamide housing material with a lead electrode by a die bond material, and the light emitting element and the lead electrode are connected by a gold wire. The obtained curable composition for optical semiconductor devices was poured and cured by heating at 150 ° C. for 2 hours to produce an optical semiconductor device. Using this optical semiconductor device, the following gas corrosion test, thermal shock test and energization test were carried out.

(Gas corrosion test 1)
The obtained optical semiconductor device was placed in a chamber at 40 ° C. and a relative humidity of 90% RH, and the chamber was filled with gas so that the concentration of hydrogen sulfide gas was 5 ppm and the concentration of sulfur dioxide gas was 15 ppm. . From the gas filling, the lead electrodes plated with silver were visually observed after 24 hours, 48 hours, 96 hours, 168 hours and 500 hours.

“○○” indicates no discoloration in the silver plating, “○” indicates that the silver plating is slightly browned, “△” indicates that almost all of the silver plating has changed to brown, The case where almost all of the plating changed to black was judged as “x”.

(Thermal shock test)
Using the obtained optical semiconductor device and using a liquid bath thermal shock tester (“TSB-51” manufactured by ESPEC), the temperature was maintained at −50 ° C. for 5 minutes, and then the temperature was increased to 135 ° C. A cold cycle test was conducted in which the process of holding at 5 ° C. for 5 minutes and then lowering the temperature to −50 ° C. was 1 cycle. 20 samples were taken out after 500 cycles, 1000 cycles, 1500 cycles, 2000 cycles and 3000 cycles, respectively.

The sample was observed with a stereomicroscope ("SMZ-10" manufactured by Nikon Corporation). It is observed whether cracks are generated in the cured products obtained by curing 20 samples of the curable composition for optical semiconductor devices, or whether the cured products are separated from the package or the electrode. The number of samples produced (NG number) was counted.

(Viscosity ratio)
A curable composition for optical semiconductor devices immediately after fabrication (a curable composition immediately after fabrication) was prepared. Furthermore, the curable composition immediately after preparation was allowed to stand at room temperature (23 ° C.) for 3 hours to prepare a curable composition after 3 hours. Using a viscosity measuring device (“VISCOMETER TV-22” manufactured by Toki Sangyo Co., Ltd.), the viscosity of the curable composition immediately after preparation at 23 ° C. and 10 rpm, and the temperature of the curable composition after 3 hours at 23 ° C. and 10 rpm And the viscosity was measured. The viscosity ratio (viscosity value after 3 hours / initial viscosity value) to the viscosity value in the curable composition immediately after production of the viscosity value in the curable composition after 3 hours was determined.

(High temperature and high humidity energization test)
About the obtained optical semiconductor device, the luminous intensity when a current of 20 mA was passed through the light emitting element was measured using a photometric measuring device (“OL770” manufactured by Optronic Laboratories) at a temperature of 23 ° C. (hereinafter, “initial” Called “luminosity”).

Next, the optical semiconductor device was placed in a chamber under an atmosphere of 85 ° C. and a relative humidity of 85 RH% with a current of 20 mA flowing through the light emitting element, and left for 1000 hours. After 1000 hours, at a temperature of 23 ° C., the light intensity when a current of 20 mA was passed through the light emitting element was measured using a light intensity measuring device (“OL770” manufactured by Optronic Laboratories), and the rate of decrease in light intensity relative to the initial light intensity Calculated. When the rate of decrease in luminous intensity is less than 5%, it is “◯◯”, when it is 5% or more and less than 10%, “◯”, when it is 10% or more and less than 20%, “△”, when it is 20% or more It was determined as “x”.

The results are shown in Tables 1 and 2 below.

(Gas corrosion test 2)
The obtained optical semiconductor device was fixed with a double-sided tape on a slide glass with the light emitting surface facing up. Next, 0.2 g of sulfur was placed in a glass container with a lid having a capacity of 120 mL, and a slide glass on which the optical semiconductor device was fixed was placed in the glass container so that the optical semiconductor device and sulfur were not in direct contact. Thereafter, the glass container was sealed and placed in an oven at 80 ° C. After being placed in the oven, changes in the silver-plated lead electrode were visually observed after 4 hours, 8 hours, 16 hours, 24 hours and 48 hours, respectively. The gas corrosion test 2 was determined according to the following criteria. In addition, when the adhesiveness with respect to the adhesion target object of hardened | cured material is low, a silver electrode will become easy to discolor.

[Criteria for gas corrosion test 2]
○○: No change in the silver electrode ○: About 10% of the area of the silver electrode changes to black, or the entire surface changes slightly △: About half of the area of the silver electrode changes to black, or the entire surface Changes to brown ×: almost the entire surface of the silver electrode changes to black

The results are shown in Table 3 below.

DESCRIPTION OF SYMBOLS 1 ... Optical semiconductor device 2 ... Housing 2a ... Inner surface 3 ... Optical semiconductor element 4 ... Sealing agent 11 ... Optical semiconductor device 12 ... Sealing agent 12a ... Surface 13 ... Lens 21 ... Optical semiconductor device 22 ... Substrate 22a ... Terminal 23 ... Optical semiconductor element 23a ... Electrode 24 ... Bonding wire 25 ... Lens

Claims

A first organopolysiloxane having two or more alkenyl groups;
A second organopolysiloxane having two or more hydrogen atoms bonded to silicon atoms;
A catalyst for hydrosilylation reaction;
A curable composition for optical semiconductor devices, comprising a first silane compound having a ureido group or an isocyanate group.
The curable composition for optical semiconductor devices according to claim 1, which is a sealant for optical semiconductor devices or a lens material for optical semiconductor devices.
The curable composition for optical semiconductor devices according to claim 1, wherein the first silane compound has a ureido group.
The curable composition for optical semiconductor devices according to claim 1 or 2, wherein the first silane compound is a first silane compound represented by the following formula (S1) or the following formula (S2).

In the formula (S1), X1 represents an alkoxy group, X2 and X3 each represents an alkoxy group or a hydrocarbon group having 1 to 8 carbon atoms, and R4 is a single bond directly bonding a nitrogen atom and a silicon atom. Or a hydrocarbon group having 1 to 8 carbon atoms.

In the formula (S2), X1 represents an alkoxy group, X2 and X3 each represents an alkoxy group or a hydrocarbon group having 1 to 8 carbon atoms, and R4 represents a single bond directly connecting a nitrogen atom and a silicon atom. It represents a bond or a hydrocarbon group having 1 to 8 carbon atoms.
The curable composition for optical semiconductor devices according to claim 4, wherein the first silane compound is a first silane compound represented by the formula (S1).
The curable composition for optical semiconductor devices according to claim 4 or 5, wherein the first silane compound represented by the formula (S1) is a first silane compound represented by the following formula (S1-1). object.

In the formula (S1-1), R1 to R3 each represent a hydrocarbon group having 1 to 8 carbon atoms, and R4 represents a single bond directly bonding a nitrogen atom and a silicon atom, or 1 to 8 hydrocarbon groups are represented.
The number average molecular weight of the first organopolysiloxane is 500 or more and 200000 or less,
The curable composition for optical semiconductor devices according to any one of claims 1 to 6, wherein the number average molecular weight of the second organopolysiloxane is 500 or more and 20000 or less.
The curable composition for optical semiconductor devices according to any one of claims 1 to 7, further comprising a second silane compound having an epoxy group, a vinyl group or a (meth) acryloyl group.
The second silane compound is 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane or 3- (meth) acryloxypropyltrimethoxysilane. The curable composition for optical semiconductor devices according to claim 8.
The content of the second silane compound is 0.01 parts by weight or more and 5 parts by weight or less with respect to a total of 100 parts by weight of the first and second organopolysiloxanes. Curable composition for optical semiconductor devices.
The first organopolysiloxane does not have a hydrogen atom bonded to a silicon atom;
The curable composition for optical semiconductor devices according to any one of claims 1 to 10, wherein the second organopolysiloxane has an alkenyl group.
The first organopolysiloxane is represented by the following formula (1A), is a first organopolysiloxane having an alkenyl group and a methyl group bonded to a silicon atom, and the second organopolysiloxane is: A second organopolysiloxane represented by formula (51A) and having a hydrogen atom bonded to a silicon atom and a methyl group bonded to the silicon atom, or
The first organopolysiloxane is represented by the following formula (1B), is a first organopolysiloxane having an aryl group and an alkenyl group, and the second organopolysiloxane is represented by the following formula (51B). The curable composition for optical semiconductor devices according to any one of claims 1 to 11, which is a second organopolysiloxane represented by an aryl group and having a hydrogen atom bonded to a silicon atom.

In the formula (1A), a, b and c are a / (a + b + c) = 0 to 0.30, b / (a + b + c) = 0.70 to 1.0 and c / (a + b + c) = 0 to 0. 10, R1 to R6 each represents at least one alkenyl group, at least one represents a methyl group, and R1 to R6 other than the alkenyl group and the methyl group represent a hydrocarbon group having 2 to 8 carbon atoms. .

In the formula (51A), p, q and r are p / (p + q + r) = 0.10 to 0.50, q / (p + q + r) = 0 to 0.40 and r / (p + q + r) = 0.40 to 0.90 is satisfied, R51 to R56 each represents at least one hydrogen atom, at least one represents a methyl group, and R51 to R56 other than the hydrogen atom and the methyl group are hydrocarbon groups having 2 to 8 carbon atoms. Represents.

In the formula (1B), a, b and c are a / (a + b + c) = 0 to 0.50, b / (a + b + c) = 0.40 to 1.0 and c / (a + b + c) = 0 to 0. 50, R1 to R6 each represents at least one aryl group, at least one represents an alkenyl group, and R1 to R6 other than the aryl group and the alkenyl group represent a hydrocarbon group having 1 to 8 carbon atoms. .

In the formula (51B), p, q and r are p / (p + q + r) = 0.05 to 0.50, q / (p + q + r) = 0.05 to 0.50 and r / (p + q + r) = 0. 20 to 0.80 are satisfied, at least one of R51 to R56 represents an aryl group, at least one represents a hydrogen atom, and R51 to R56 other than the aryl group and the hydrogen atom are carbon atoms having 1 to 8 carbon atoms. Represents a hydrogen group.
The first organopolysiloxane represented by the formula (1A) or the formula (1B) does not have a hydrogen atom bonded to a silicon atom,
The second organopolysiloxane represented by the formula (51A) or the formula (51B) has an alkenyl group,
In the formula (51A), at least one of R51 to R56 represents a hydrogen atom, at least one represents a methyl group, at least one represents an alkenyl group, and R51 other than a hydrogen atom, a methyl group, and an alkenyl group ~ R56 represents a hydrocarbon group having 2 to 8 carbon atoms,
In the formula (51B), at least one of R51 to R56 represents an aryl group, at least one represents a hydrogen atom, at least one represents an alkenyl group, and R51 other than an aryl group, a hydrogen atom and an alkenyl group 13. The curable composition for optical semiconductor devices according to claim 12, wherein -R56 represents a hydrocarbon group having 1 to 8 carbon atoms.
The optical semiconductor device according to claim 12 or 13, wherein the second organopolysiloxane represented by the formula (51A) or the formula (51B) has a structural unit represented by the following formula (51-a). Curable composition.

In the formula (51-a), R52 and R53 each represent a hydrocarbon group having 1 to 8 carbon atoms.
The light according to any one of claims 12 to 14, wherein the first organopolysiloxane is represented by the formula (1A), and the second organopolysiloxane is represented by the formula (51A). Curable composition for semiconductor devices.
The light according to any one of claims 12 to 14, wherein the first organopolysiloxane is represented by the formula (1B) and the second organopolysiloxane is represented by the formula (51B). Curable composition for semiconductor devices.
The content of the second organopolysiloxane is 10 parts by weight or more and 400 parts by weight or less with respect to 100 parts by weight of the first organopolysiloxane.
In the curable composition, the content of the hydrosilylation reaction catalyst is 0.01 ppm or more and 1000 ppm or less in terms of weight units of metal atoms,
The content of the first silane compound is 0.01 parts by weight or more and 5 parts by weight or less with respect to a total of 100 parts by weight of the first and second organopolysiloxanes. The curable composition for optical semiconductor devices of Claim 1.