JP2014156577A - Curable composition for optical semiconductor device, and optical semiconductor device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition for an optical semiconductor device, which can prevent an electrode from degrading due to sulfur-containing gas in the atmosphere, in the optical semiconductor device.SOLUTION: A 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 reaction catalyst, and an azole structure.

Description

  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. Moreover, this invention relates to the optical semiconductor device using the said 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, an 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.

  Patent Document 1 listed below 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.

  Further, 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 Including hydrogen atom, 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 Special table 2006-519896 gazette JP 2004-359756 A

  In the conventional composition for optical semiconductor devices as described in Patent Documents 1 to 4, luminous intensity (brightness) emitted from the optical semiconductor device may gradually decrease. This is because moisture in the atmosphere invades and deteriorates the optical semiconductor element, and the sulfur-containing gas such as sulfurous acid gas and hydrogen sulfide gas in the atmosphere causes the electrodes to be discolored and easily absorbs light. It is known that there is.

  Moreover, in the conventional composition 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 adhesion target object 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.

  The present invention provides a curable composition for an optical semiconductor device capable of suppressing electrode deterioration caused by sulfur-containing gas in the atmosphere in an optical semiconductor device, and an optical semiconductor device using the curable composition for an optical semiconductor device. The purpose is to do.

  A limited object of the present invention is that light that can make it difficult to peel a cured product obtained by curing a curable composition from an object to be bonded even when the optical semiconductor device is used in a harsh environment under high temperature and high humidity. It is providing the curable composition for semiconductor devices, and the optical semiconductor device using the curable composition for optical semiconductor devices.

  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 curable composition for optical semiconductor devices, comprising a compound having an azole structure.

  In a specific aspect of the curable composition for optical semiconductor devices according to the present invention, the compound having an azole structure is a silane compound, a compound having an imidazole structure, a compound having a triazole structure, or a compound having a tetrazole structure. .

  The compound having an azole structure is preferably a silane compound or a compound having a triazole structure. The compound having an azole structure is a silane compound, or 3- (N-salicyloyl) amino-1,2,4-triazole, 3-methyl-N- (4H-1,2,4-triazole-3- Yl) benzamide or N-cyclopentanyl-1H-1,2,4-triazole-3-carboxamide, or a compound having a benzotriazole structure. More preferably, the compound having the azole structure is a compound having the benzotriazole structure.

  The compound having an azole structure is a silane compound, or 3- (N-salicyloyl) amino-1,2,4-triazole, 3-methyl-N- (4H-1,2,4-triazole- 3-yl) benzamide or N-cyclopentanyl-1H-1,2,4-triazole-3-carboxamide is preferred. The compound having an azole structure is preferably a silane compound. The silane compound that is a compound having the azole structure is preferably a silane compound represented by the following formula (S).

  In said Formula (S), R4 represents an alkoxy group, R5 and R6 represent a C1-C8 alkyl group or an alkoxy group, respectively.

  The silane compound which is a compound having the azole structure is preferably a silane compound represented by any one of the following formulas (S1) to (S6).

  In the formulas (S1) to (S6), R1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R2 and R3 are each a hydrogen atom, a vinyl group, an amino group, or an alkyl group having 1 to 5 carbon atoms. R4 represents an alkoxy group, and R5 and R6 each represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group.

  The compound having the azole structure is 3- (N-salicyloyl) amino-1,2,4-triazole, 3-methyl-N- (4H-1,2,4-triazol-3-yl) benzamide or N- Cyclopentanyl-1H-1,2,4-triazole-3-carboxamide is preferred.

  The curable composition for optical semiconductor devices according to the present invention further includes an adhesion promoter, and the adhesion promoter is preferably a silane compound having an epoxy group, a vinyl group, or a (meth) acryloyl group. The adhesion-imparting agent is 3-glycidoxypropyltrialkoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane or 3- (meth) acryloxypropyltrialkoxysilane. Is preferred.

  In a specific aspect of the curable composition for optical semiconductor devices according to the present invention, among all the functional groups bonded to silicon atoms in the first organopolysiloxane, the number ratio of methyl groups is 80% or more. The ratio of the number of methyl groups in all functional groups bonded to silicon atoms in the second organopolysiloxane is 80% or more.

  In a specific aspect of the curable composition for optical semiconductor devices according to the present invention, the ratio of the number of aryl groups to all functional groups bonded to silicon atoms in the first organopolysiloxane is 30% or more, 70 % Of all functional groups bonded to silicon atoms in the second organopolysiloxane are 30% or more and 70% or less.

  In a 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 a specific aspect of the curable composition for optical semiconductor devices according to the present invention, the first organopolysiloxane is represented by the following formula (1A), and has a methyl group bonded to an alkenyl group and a silicon atom. 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 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: 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 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. 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 represent 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, R51 to R56 each represents at least one 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 a specific aspect of the curable composition for an optical semiconductor device according to the present invention, the first organopolysiloxane represented by the formula (1A) or the formula (1B) contains a hydrogen atom bonded to a silicon atom. 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 hydrogen. Represents an 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 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 alkenyl group. R51~R56 other than Le group represents a hydrocarbon group having 1 to 8 carbon atoms.

  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.

  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. Alternatively, the lens is formed by curing the curable composition for optical semiconductor devices described above.

  The curable composition for optical semiconductor devices according to the present invention includes a first organopolysiloxane having two or more alkenyl groups, a second organopolysiloxane having two or more hydrogen atoms bonded to silicon atoms, and hydrosilyl In the optical semiconductor device using the curable composition for optical semiconductor devices according to the present invention, the deterioration of the electrode due to sulfur-containing gas in the atmosphere is suppressed, because the catalyst for the oxidation reaction and the compound having an azole structure are included. be able to.

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.

  Details of the present invention will be described below.

  The curable composition for optical semiconductor devices according to the present invention includes a first organopolysiloxane having two or more alkenyl groups, a second organopolysiloxane having two or more hydrogen atoms bonded to silicon atoms, and hydrosilyl And a compound having an azole structure.

  The present inventors have an azole structure together with a first organopolysiloxane having two or more alkenyl groups, a second organopolysiloxane having two or more hydrogen atoms bonded to silicon atoms, and a catalyst for hydrosilylation reaction. When an optical semiconductor device is obtained by forming a sealant or a lens using a curable composition containing a compound, a cured product that does not contain a compound having an azole structure is used. It has been found that the resistance to sulfidation is enhanced and the discoloration deterioration of the electrode with respect to the sulfur-containing gas is greatly suppressed.

  Furthermore, by adopting the above composition in the curable composition for optical semiconductor devices according to the present invention, even if the optical semiconductor device using the curable composition for optical semiconductor devices is used in a severe environment under high temperature and high humidity. The cured product obtained by curing the curable composition is difficult to peel from the object to be bonded. As a result, the adhesion between the sealant or the lens and the housing or the substrate is improved, and it becomes difficult to enter from the interface between the cured product and the bonding target. Discoloration of the electrode can also be suppressed by making it difficult to enter from the interface between the cured product and the object to be bonded.

  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. It is strongly required that the cured product has high adhesion to a housing or electrode formed of such PPA. If the cured product is peeled off from the housing or the electrode or has poor adhesion, the amount of light (luminous intensity) emitted from the optical semiconductor device decreases. On the other hand, in the present invention, a decrease in the amount of light emitted from the optical semiconductor device can be suppressed.

  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. The first organopolysiloxane represented by the formula (1A) and the formula (1B) has two or more alkenyl groups. 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. The second organopolysiloxane represented by the formula (51A) and the formula (51B) has two or more hydrogen atoms bonded to silicon atoms. However, a second organopolysiloxane different from the second organopolysiloxane represented by the formula (51A) or the formula (51B) may be used.

  Improves the adhesion of the cured product to the object to be bonded, further enhances the sulfidation resistance of the cured product to further suppress the discoloration of the electrode, and the pot life of the cured product with heat resistance, gas barrier properties and curable composition From the viewpoint of further improving the quality, the first organopolysiloxane is the first organopolysiloxane represented by the formula (1A) and having an alkenyl group and a methyl group bonded to a silicon atom, and the above The second organopolysiloxane is 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, or the first organopolysiloxane The polysiloxane is a first organopolysiloxane represented by the formula (1B) and having an aryl group and an alkenyl group, and the second organopolysiloxane Sun, represented by the formula (51B), it is preferable that the second organopolysiloxane having a hydrogen atom bonded to an aryl group and a silicon atom.

  In addition, when a cured product of a conventional curable composition for an optical semiconductor device 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, etc. Or may peel off. 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, it is preferable that the number ratio of methyl groups in all functional groups bonded to silicon atoms in the first organopolysiloxane is 80% or more. From the viewpoint of obtaining a cured product that is more excellent in heat resistance, it is preferable that the number ratio of methyl groups is 80% or more among all functional groups bonded to silicon atoms of the second organopolysiloxane.

  Among all the functional groups bonded to silicon atoms in the first and second organopolysiloxanes, the number ratio of methyl groups is more preferably 85% or more, still more preferably 90% or more, and preferably 99.9. % Or less, more preferably 99% or less, and still more preferably 98% or less. When the number ratio of methyl groups is 80% or more, the heat resistance of the cured product is increased, and even if the optical semiconductor device is used in a harsh environment under high temperature and high humidity, the cured product can be used. Is less likely to occur and the luminous intensity is less reduced. Moreover, the heat resistance of hardened | cured material becomes still higher that the number ratio for which the said methyl group accounts is more than the said minimum. When the number ratio of the methyl groups is not more than the above upper limit, alkenyl groups can be sufficiently introduced into the first organopolysiloxane, and hydrogen atoms bonded to silicon atoms can be sufficiently introduced into the second organopolysiloxane, It is easy to improve the curability of the curable composition.

  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, among all the functional groups bonded to the silicon atom of the first organopolysiloxane, the number ratio of the aryl group is 30% or more and 70% or less. Is preferred. From the viewpoint of obtaining a cured product that is more excellent in gas barrier properties, the ratio of the number of aryl groups in the total functional groups bonded to silicon atoms of the second organopolysiloxane is 30% or more and 70% or less. Is preferred.

  Of all the functional groups bonded to silicon atoms in the first and second organopolysiloxanes, the number ratio of the aryl group is more preferably 35% or more, and more preferably 65% or less. When the number ratio of the aryl group is equal to or more than the above lower limit, 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 number ratio of the aryl group is less than or equal to the above upper limit, peeling of the cured product is more difficult to occur.

  In addition, when the aryl group is a phenyl group, the number ratio of the aryl group indicates the number ratio of the phenyl group.

  Moreover, according to the wide situation of this invention, the optical semiconductor device using the curable composition for optical semiconductor devices mentioned above 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 catalyst and a compound having an azole structure.

  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 object to be bonded, and further the electrode using sulfur-containing gas. Can be suppressed.

  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 in 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.

  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. .

  From the viewpoint of obtaining a cured product that is more excellent in suppressing the discoloration deterioration of the electrode due to sulfur-containing gas, the first organopolysiloxane is represented by the following formula (1B) and has an aryl group and an alkenyl group. 1 organopolysiloxane (hereinafter sometimes referred to as first 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 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 represent 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 (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 a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. From the standpoint of further improving the sulfidation resistance of the cured product to further suppress the discoloration of the electrode and further increase the gas barrier property, the alkenyl group in the first organopolysiloxane, the above formula (1A) and the above formula The alkenyl group in (1B) is preferably a vinyl group or an allyl group, and more preferably a vinyl group. From the viewpoint of further improving the curability of the curable composition, the first organopolysiloxane preferably has a vinyl group.

  It does not specifically limit as a C2-C8 hydrocarbon group in said formula (1A), For example, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, 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. As a C1-C8 hydrocarbon group in the said Formula (1B), the group similar to a C2-C8 hydrocarbon group in the said Formula (1A) is mentioned, Furthermore, a methyl group is mentioned.

  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. Among all the functional groups bonded to silicon atoms in the first organopolysiloxane A, the number ratio of the aryl group is preferably 0.5% or more, preferably 10% or less, more preferably 5% 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.

From the viewpoint of enhancing the curability of the sealant and further suppressing cracking and peeling during thermal cycling, the first organopolysiloxane contains one vinyl group, two vinyl atoms and one carbon atom. It preferably contains a structural unit bonded to a hydrocarbon group of ˜8 (methyl group or hydrocarbon group of 2 to 8 carbon atoms), and has a structural unit represented by (CH ₂ ═CHR ₂ R 3 SiO _1/2 ) Is preferred.

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, the structure in which one of the oxygen atoms bonded to the silicon atom in the bifunctional structural unit constitutes 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 (1-2b). 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 into 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: The part enclosed with the broken line of 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 (1-2b), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. R4 and R5 in the above formula (1-b), formula (1-2), and formula (1-2b) are the same groups as R4 and R5 in the above formula (1A) and the above 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 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 ( The part enclosed with the 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 is 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, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, and an 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 Represents at least one group, and R1 to R5 other than the alkenyl group and the 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. Represents at least one alkenyl group, and R1 to R5 other than an aryl group and an 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, The 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) Each peak corresponding to the structural unit represented by (R6SiO _3/2 ) and the trifunctional structural units of the above formulas (1-3) and (1-4) appears 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 a silicon atom to which three oxygen atoms are bonded, and one hydrocarbon group having 1 to 8 carbon atoms (methyl group or carbon atom having 2 to 8 carbon atoms). Hydrogen 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.

  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. 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.

  From the viewpoint of further improving the resistance to sulfidation of the cured product to further suppress discoloration of the electrode, and further obtaining a cured product with better gas barrier properties, the second organopolysiloxane is represented by the following formula (51B). It is preferably a second organopolysiloxane represented by an aryl group and a hydrogen atom bonded to a silicon atom (hereinafter sometimes referred to as a second organopolysiloxane B). Examples of the aryl group include an unsubstituted phenyl group and a substituted phenyl group.

  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, R51 to R56 each represents at least one 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 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.

  It does not specifically limit as a C2-C8 hydrocarbon group in said Formula (51A), The hydrocarbon group similar to C2-C8 in said Formula (1A) is mentioned. As a C1-C8 hydrocarbon group in the said Formula (51B), the group similar to a C2-C8 hydrocarbon group in the said Formula (1A) is mentioned, Furthermore, a methyl group is mentioned.

From the viewpoint of enhancing the curability of the sealant and further suppressing cracking and peeling during thermal cycling, the second organopolysiloxane contains one hydrogen atom and two carbon atoms of 1 in one silicon atom. It is preferable to include a structural unit bonded with ˜8 hydrocarbon groups (methyl group or hydrocarbon group having 2 to 8 carbon atoms), and it is preferable to have a structural unit represented by (HR52R53SiO _1/2 ).

  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 above 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 represent a hydrocarbon group having 2 to 8 carbon atoms.

  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. Among all the functional groups bonded to silicon atoms in the second organopolysiloxane A, the number ratio of the aryl group is preferably 0.5% or more, preferably 10% or less, more preferably 5% 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 ( The structure represented by 51-2), that is, the structure in which one of the oxygen atoms bonded to the 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 above formula (51-b), formula (51-2) and formula (51-2-b) are the same groups as R54 and R55 in the above formula (51A) and the above 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 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 ( The part enclosed by the 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 is 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, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, and an 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 less than or equal to the above upper limit, the sulfidation resistance of the cured product is further increased, discoloration of the electrode is further suppressed, and the gas barrier property of the cured product is further enhanced. In said formula (51B), q / (p + q + r) becomes like this. Preferably it is 0.10 or more, More preferably, it is 0.45 or less.

  In said 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 higher than the above lower limit, the hardness of the cured product is increased, and scratches and dust can be prevented from being attached. 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 formula (51-3) and formula (51-4) is −5 Appears near 0-80 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 above formula (51A) and the above formula (51B) cannot be distinguished by the ²⁹ Si-NMR measurement based on the above TMS, not only the ²⁹ Si-NMR measurement result but also ¹ By using the measurement result 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 weight (Mn) of the second organopolysiloxane is preferably 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) was measured using 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 for hydrolyzing and condensing the alkoxysilane compound include a method in which an alkoxysilane compound is reacted 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.

(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, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex. In particular, a platinum-alkenylsiloxane complex or a platinum-olefin complex is preferable.

  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.

(Compound having azole structure)
The curable composition for optical semiconductor devices according to the present invention includes a compound having an azole structure. By using the compound having this specific structure, even if the optical semiconductor device is used in a harsh environment under high temperature and high humidity, the cured product obtained by curing the curable composition is difficult to peel from the object to be bonded. Furthermore, in the optical semiconductor device, the intrusion from the interface between the cured object of corrosive gas such as sulfur-containing gas and the object to be bonded can be suppressed. It becomes difficult. In particular, the use of the compound having the azole structure imparts sulfur resistance of the silver electrode to the cured product, and can suppress a decrease in luminance of the optical semiconductor device due to sulfurous acid gas and hydrogen sulfide gas in the atmosphere.

  Examples of the azole structure include an imidazole structure (including a benzimidazole structure), a pyrazole structure, a triazole structure (including a benzotriazole structure), a thiazole structure, a tetrazole structure, an indazole structure, and a bendazole structure. Among these, from the viewpoint of effectively suppressing peeling and discoloration of the electrode, an imidazole structure, a triazole structure or a tetrazole structure is particularly preferable, and an imidazole structure or a triazole structure is also preferable. From the viewpoint of effectively suppressing peeling and discoloration of the electrode, an imidazole structure is preferable, a triazole structure is also preferable, and a tetrazole structure is also preferable. The compound having an azole structure is preferably a silane compound, a compound having an imidazole structure, a compound having a triazole structure, or a compound having a tetrazole structure.

  Examples of the compound having an imidazole structure include imidazole, 1-methylimidazole, benzimidazole, 1-methylbenzimidazole, 5-carboxybenzimidazole, 5-nitrobenzimidazole, and 5,6-dichloro-2-methylbenzimidazole. It is done.

  Examples of the compound having a triazole structure include triazole, benzotriazole, and benzotriazole derivatives. Examples of the benzotriazole derivatives include 1-aminobenzotriazole, 1-methylbenzotriazole, 5-methylbenzotriazole, 5-chlorobenzotriazole, 4-carboxybenzotriazole, 5-carboxybenzotriazole, 4-nitrobenzotriazole, and 5 -Nitrobenzotriazole and the like.

  Examples of the compound having a tetrazole structure include tetrazole, 1H-tetrazole, 1-methyltetrazole, 1-ethyltetrazole, 1-phenyltetrazole, 2-methyltetrazole, 2-ethyltetrazole, 5-methyltetrazole, 1,5-dimethyltetrazole. 1-methyl-5-ethyltetrazole, 5-methoxytetrazole, 1-methyl-5-methoxytetrazole, 2-ethyl-5-methoxytetrazole, 5-aminotetrazole, 5-amino-2-phenyltetrazole, 2-methyl -5-nitrotetrazole, 1-methyl-5-phenylaminotetrazole, 1-methyl-5-methylaminotetrazole, 2-phenyltetrazole, 5-phenyltetrazole, 1-oxytetrazole, 5-oxytetrazol 5-oxy-1-methyltetrazole, 5-oxy-2-methyltetrazole, 2-oxy-5-phenyltetrazole, 1-amino-5-phenyltetrazole, 5-amino-2-phenyltetrazole, 5-amino -1-methyltetrazole, 5-amino-2-methyltetrazole, 1-methyl-5-methoxytetrazole, 5- (3-aminophenyl) tetrazole, 5-tetrazolecarboxylic acid, 5-cyanotetrazole, 1-phenyl-5 Tetrazoles such as tetrazole carboxylic acid, 2-ethyl-5-tetrazole carboxylic acid, 2-phenyl-5-tetrazole carboxylic acid, and 5-tetrazole sulfonic acid, and 5,5′-bistetrazole, 5,5 ′ -Bistetrazole disodium salt, 5,5'-bistetra Diammonium salt, bistetrazoleamine monoammonium salt, 5,5′-azobistetrazole, 1,4-di (1H-tetrazol-5-yl) benzene, 1,4-di (1H-tetrazol-5-yl) ) Benzene sodium salt, and bistetrazole such as 4,4′-di (1H-tetrazol-5-yl) 1,1′-biphenyl.

  Examples of the compound having a thiazole structure include benzothiazole and benzothiazole derivatives. Examples of the benzothiazole derivative include 2-mercaptobenzothiazole, (2-benzothiazylthio) acetic acid, and 3- (2-benzothiazylthio) propionic acid.

  From the viewpoint of further suppressing peeling and discoloration of the electrode, the compound having the azole structure is preferably a silane compound or a compound having a triazole structure. The compound having the triazole structure is 3- (N-salicyloyl) amino-1,2,4-triazole, 3-methyl-N- (4H-1,2,4-triazol-3-yl) benzamide or N- It is preferably cyclopentanyl-1H-1,2,4-triazole-3-carboxamide or a compound having a benzotriazole structure. The compound having the benzotriazole structure is preferably a compound represented by the following formula (U). From the viewpoint of further suppressing peeling and discoloration of the electrode, the compound having the azole structure is a silane compound, or 3- (N-salicyloyl) amino-1,2,4-triazole, 3-methyl. -N- (4H-1,2,4-triazol-3-yl) benzamide or N-cyclopentanyl-1H-1,2,4-triazole-3-carboxamide is preferred. From the viewpoint of further improving the sulfidation resistance of the cured product and further suppressing the discoloration of the electrode, the compound having the azole structure is preferably a compound having a benzotriazole structure. More preferably, it is a compound represented. The compound having an azole structure is preferably a silane compound, preferably a compound having a triazole structure, preferably a compound having a benzotriazole structure, and a compound represented by the following formula (U). 3- (N-salicyloyl) amino-1,2,4-triazole (a compound represented by the following formula (T1)), 3-methyl-N- (4H-1,2,4-triazole -3-yl) benzamide (a compound represented by the following formula (T2)) or N-cyclopentanyl-1H-1,2,4-triazole-3-carboxamide (a compound represented by the following formula (T3)) ) Is also preferable. By using a compound having a benzotriazole structure or a compound represented by the following formula (U), the sulfidation resistance of the cured product is further enhanced.

  In the above formula (U), X represents a hydrogen atom, alkyl group, amino group, sodium atom or ammonium group, and Z represents an alkyl group, amino group, carboxyl group, carboxyl ester group, nitro group or halogen atom. . In addition, the coupling | bond part with respect to the benzene ring of Z group is not specifically limited. X in the above formula (U) is preferably a hydrogen atom. Z in the above formula (U) is preferably a carboxyl group, a carboxyl ester group or a nitro group. Z in the above formula (U) may be a carboxyl group, a nitro group or a carboxyl ester group.

  When the compound represented by the above formula (T1), formula (T2) or formula (T3) is used, the compound represented by the above formula (T1) may be used, and the above formula (T2) or the above formula ( A compound represented by T3) may be used.

  The compound represented by the above formula (U) is preferably a compound represented by the following formula (U1), the following formula (U2), the following formula (U3), or the following formula (U4). By using the compound represented by the formula (U1), the formula (U2), the formula (U3), or the formula (U4), the sulfidation resistance of the cured product is further increased. The compound represented by the above formula (U) may be a compound represented by the following formula (U1) or the following formula (U2), or a compound represented by the following formula (U3) or the following formula (U4). It may be. In addition, in the formula (U1), the formula (U2), the formula (U3), and the formula (U4), there are no particular limitations on the binding site of the carboxyl group, carboxyl ester group, and nitro group to the benzene ring.

  A silane compound having an azole structure can be obtained, for example, by a reaction between an azole structure-containing compound and a silane compound having an epoxy group. Silane compounds having an azole structure and methods for producing the silane compounds are known. For example, JP-A-6-256358 discloses a silane coupling agent obtained by a reaction between an imidazole compound and a silane compound having an epoxy group. Examples of the azole structure-containing compound for obtaining the silane compound having the azole structure include imidazole compounds, pyrazole compounds, triazole compounds, tetrazole compounds, benzimidazole compounds, indazole compounds, bendazole compounds, benzotriazole compounds, and derivatives thereof. . Moreover, as a silane compound which has an epoxy group made to react with the said azole structure containing compound, the silane compound which has a structural unit represented by a following formula (s-1-1) is mentioned. Examples of the silane compound having a structural unit represented by the following formula (s-1-1) include a silane compound represented by the following formula (s-1).

  In said formula (s-1-1), R4 represents an alkoxy group, R5 and R6 represent a C1-C8 alkyl group or an alkoxy group, respectively.

  In said formula (s-1), R4 represents an alkoxy group, R5 and R6 represent a C1-C8 alkyl group or an alkoxy group, respectively.

  The compound having an azole structure is preferably a reaction product of an azole structure-containing compound and a silane compound having a structural unit represented by the above formula (s-1-1).

  From the viewpoint of further suppressing peeling and discoloration of the electrode, the silane compound (silane compound having an azole structure), which is a compound having the azole structure, is a silane compound represented by the following formula (S). preferable. The compound having the azole structure is a silane compound represented by the following formula (S), or a compound represented by the above formula (T1), a compound represented by the above formula (T2), or the above formula ( A compound represented by T3) is preferred.

  In said formula (S), R4 represents an alkoxy group, R5 and R6 represent a C1-C8 alkyl group or an alkoxy group, respectively.

  From the viewpoint of further suppressing peeling and discoloration of the electrode, the silane compound that is a compound having the azole structure is preferably a silane compound represented by any one of the following formulas (S1) to (S6). .

  In said formula (S1), R1 represents a hydrogen atom or a C1-C20 alkyl group, R2 represents a hydrogen atom, a vinyl group, an amino group, or a C1-C5 alkyl group, R4 is alkoxy R5 and R6 each represent a C 1-8 alkyl group or alkoxy group.

  In the above formula (S2), R2 and R3 each represent a hydrogen atom, a vinyl group, an amino group, or an alkyl group having 1 to 5 carbon atoms, R4 represents an alkoxy group, and R5 and R6 each have 1 to 5 carbon atoms. 8 represents an alkyl group or an alkoxy group.

  In said formula (S3), R2 represents a hydrogen atom, a vinyl group, an amino group, or a C1-C5 alkyl group, R4 represents an alkoxy group, R5 and R6 are respectively a C1-C8 alkyl. Represents a group or an alkoxy group.

  In said formula (S4), R1 represents a hydrogen atom or a C1-C20 alkyl group, R2 and R3 respectively represent a hydrogen atom, a vinyl group, an amino group, or a C1-C5 alkyl group, R4 represents an alkoxy group, and R5 and R6 each represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group.

  In the above formula (S5), R2 represents a hydrogen atom, a vinyl group, an amino group or an alkyl group having 1 to 5 carbon atoms, R4 represents an alkoxy group, and R5 and R6 are each an alkyl having 1 to 8 carbon atoms. Represents a group or an alkoxy group.

  In the formula (S6), R2 and R3 each represent a hydrogen atom, a vinyl group, an amino group, or an alkyl group having 1 to 5 carbon atoms, R4 represents an alkoxy group, and R5 and R6 each have 1 to 5 carbon atoms. 8 represents an alkyl group or an alkoxy group.

  The compound having the azole structure may be an adhesion imparting agent (first adhesion imparting agent). The silane compound and 3- (N-salicyloyl) amino-1,2,4-triazole can be suitably used as an adhesion-imparting agent (first adhesion-imparting agent).

  The content of the compound having the azole structure is preferably 1 ppm or more, more preferably 100 ppm or more, still more preferably 1000 ppm or more, preferably 50000 ppm or less, more preferably based on the total of the first and second organopolysiloxanes. Is 30000 ppm or less, more preferably 5000 ppm or less. When the compound having an azole structure is a compound having a triazole structure, particularly when it is a benzotriazole compound and when it is a compound represented by the above formula (U), the effect can be expressed even in a smaller amount. The content of the compound having an azole structure is preferably 1 ppm or more and 5000 ppm or less with respect to the total of the first and second organopolysiloxanes. When the compound having the azole structure is other than the compound having a triazole structure, particularly when the compound is the silane compound, the compound having the azole structure with respect to the total of the first and second organopolysiloxanes. The content of is 1 ppm or more, more preferably 100 ppm or more, still more preferably 1000 ppm or more, preferably 50000 ppm or less, more preferably 30000 ppm or less. When the content of the compound having the azole structure is not less than the above lower limit, peeling of the cured product from the object to be bonded is further suppressed, and further, the sulfidation resistance of the cured product is further increased, resulting in more discoloration of the electrode. It is further suppressed. When the content of the compound having the azole structure is not more than the above upper limit, deterioration of the stickiness of the surface of the cured product and discoloration of the cured product due to the excessive compound having the azole structure are suppressed.

(Adhesive agent)
The curable composition for optical semiconductor devices according to the present invention may contain an adhesion-imparting agent (second adhesion-imparting agent) different from the compound having an azole structure. By using the adhesion-imparting agent together with the compound having the azole structure, peeling of the cured product from the object to be bonded can be further suppressed. As for the said adhesion imparting agent, only 1 type may be used and 2 or more types may be used together.

  The adhesion-imparting agent is not particularly limited, and examples thereof include vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (Meth) acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ- Examples include aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

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

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

  From the viewpoint of further suppressing the peeling of the cured product from the object to be bonded, the above-mentioned adhesion-imparting agent is 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyl. Trimethoxysilane or 3- (meth) acryloxypropyltrimethoxysilane is preferred.

  The content of the adhesion-imparting agent (second adhesion-imparting agent) is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight with respect to a total of 100 parts by weight of the first and second organopolysiloxanes. It is at least 5 parts by weight, preferably at most 5 parts by weight, more preferably at most 3 parts by weight. When the content of the adhesion imparting agent is equal to or more than the lower limit, peeling of the cured product from the object to be bonded is further suppressed. When the content of the adhesion-imparting agent is not more than the above upper limit, deterioration of the stickiness of the surface of the cured product due to an excess of the adhesion-imparting agent can be suppressed.

(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 is 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, the effect of increasing the viscosity at 25 ° C. can be sufficiently obtained, and the decrease in the viscosity due to the temperature increase can be suppressed.

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.

  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 or more, still more preferably 1 with respect to 100 parts by weight of the total of the first and second organopolysiloxanes. Part by weight or more, preferably 40 parts by weight or less, more preferably 35 parts by weight or less, 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 phosphor content 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.

  The first organopolysiloxane, the second organopolysiloxane, the hydrosilylation reaction catalyst, and the compound having the azole structure are separately included in a liquid containing one or more of these. 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 compound having an azole structure may be added to the first liquid or the second liquid. At least one of the first liquid and the second liquid contains the compound having the azole structure. When the adhesion imparting agent (second adhesion imparting agent), the silicon oxide particles, or the phosphor is used, the adhesion imparting agent, the silicon oxide particles, and the phosphor are each in the first liquid. It may be added or added to the second liquid. It is preferable that at least one of the first liquid and the second liquid contains the adhesion-imparting agent. 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 160 ° 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 total light transmittance at a wavelength of 400 nm of a cured product having a thickness of 1 mm obtained by curing the curable composition for optical semiconductor devices according to the present invention is preferably 80% or more.

  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 is preferably an encapsulant for optical semiconductor devices, and is also preferably 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 so 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, the 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 having terminals 22a provided on the upper surface. 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 and the like 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 1 L 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 from 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 number ratio of the methyl group in the obtained polymer (A) was 99.6%.

  In addition, 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. In 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 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 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 (B).

The number average molecular weight of the obtained polymer (B) was 38000. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (B) had the following average composition formula (B1).

(Me ₂ SiO _2/2 ) _0.987 (Ph ₂ SiO _2/2 ) _0.010 (ViMe ₂ SiO _1/2 ) _0.003 Formula (B1)

  In the above formula (B1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group. The number ratio of the methyl group in the obtained polymer (B) was 98.9%.

(Synthesis Example 3) Synthesis of First Organopolysiloxane A 1 L separable flask equipped with a thermometer, a dropping device and a stirrer was charged with 56 g of divinyltetramethyldisiloxane, 122 g of dimethyldimethoxysilane, and 366 g of diphenyldimethoxysilane, 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 (C).

The number average molecular weight (Mn) of the obtained polymer (C) was 1700. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (C) had the following average composition formula (C1).

(ViMe ₂ SiO _1/2 ) _0.07 (Me ₂ SiO _2/2 ) _0.45 (Ph ₂ SiO _2/2 ) _0.48 ... Formula (C1)

  In the above formula (C1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group. The number ratio of the phenyl groups in the obtained polymer (C) was 46.4 mol%.

Synthesis Example 4 Synthesis of Second Organopolysiloxane Into a 1 L 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 40 g and trimethylmethoxysilane 16 g 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 (D) was obtained.

The number average molecular weight of the obtained polymer (D) was 3420. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (D) had the following average composition formula (D1).

(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 (D1)

  In the above formula (D1), Me represents a methyl group, and Vi represents a vinyl group. The number ratio of the methyl groups in the obtained polymer (D) was 95.2%.

(Synthesis Example 5) 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 67g and trimethylmethoxysilane 21g 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 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 (E) was obtained.

The number average molecular weight of the obtained polymer (E) was 3480. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (E) had the following average composition formula (E1).

(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 (E1)

  In the above formula (E1), Me represents a methyl group, and Vi represents a vinyl group. The number ratio of the methyl group in the obtained polymer (E) was 94.9%.

Synthesis Example 6 Synthesis of Second Organopolysiloxane In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 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 (F) was obtained.

The number average molecular weight (Mn) of the obtained polymer (F) was 1100. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (F) had the following average composition formula (F1).

(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 (F1)

  In the above formula (F1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group. The number ratio of the phenyl groups in the obtained polymer (F) was 51.0%.

(Synthesis Example 7) Synthesis of silane compound having azole structure and preparation of solution Imidazole 3.4 g (0.05 mol) was melted at 95 ° C. and stirred under an argon atmosphere while 3-glycidoxypropyltriethylsilane 14 .9 g (0.05 mol) was added dropwise over 30 minutes. After completion of dropping, the reaction was further carried out at 95 ° C. for 1 hour to obtain a silane compound having a liquid azole structure.

  The obtained silane compound having an azole structure was dissolved in methanol to a concentration of 50% by weight to prepare a solution (a) of the silane compound having an azole structure.

(Synthesis Example 8) Synthesis of silane compound having azole structure and preparation of solution While melting 5.5 g (0.05 mol) of 2-ethyl-4-methylimidazole at 60 ° C. and stirring under an argon atmosphere, 3- 13.9 g (0.05 mol) of glycidoxypropyltriethylsilane was added dropwise over 30 minutes. After completion of dropping, the temperature was raised to 95 ° C. and reacted for 1 hour to obtain a silane compound having a liquid azole structure.

  The obtained silane compound having an azole structure was dissolved in methanol to a concentration of 50% by weight to prepare a solution (b) of the silane compound having an azole structure.

(Synthesis Example 9) Synthesis of silane compound having azole structure and preparation of solution While melting 11.1 g (0.05 mol) of 2-undecylimidazole at 80 ° C. and stirring in an argon atmosphere, 3-glycidoxy 13.9 g (0.05 mol) of propyltriethylsilane was added dropwise over 30 minutes. After completion of dropping, the temperature was raised to 95 ° C. and reacted for 1 hour to obtain a silane compound having a liquid azole structure.

  The obtained silane compound having an azole structure was dissolved in methanol to a concentration of 50% by weight to prepare a solution (c) of the silane compound having an azole structure.

Example 1
Polymer A (10 g), Polymer D (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 a solution (a) (0.15 g) of a silane compound having an azole structure were mixed and defoamed to obtain a curable composition for an optical semiconductor device.

(Examples 2 to 19 and Comparative Examples 1 to 6)
The curable composition for optical semiconductors was prepared like Example 1 except having changed the kind and compounding quantity of the compounding component as shown in the following Tables 1-3.

(Evaluation of Examples 1-19 and Comparative Examples 1-6)
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 items were evaluated.

(Gas corrosion test)
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 1 hour, 2 hours, 4 hours, 8 hours, 12 hours and 24 hours. The gas corrosion test was judged according to the following criteria.

[Criteria for gas corrosion test]
○○: 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

(Thermal shock test)
The obtained optical semiconductor device was held at −50 ° C. for 5 minutes using a liquid tank thermal shock tester (“TSB-51” manufactured by ESPEC), then heated to 135 ° C., and 5 at 135 ° C. A cold cycle test was conducted in which the temperature was lowered to -50 ° C after being held for 1 minute, and the cycle was one 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.

(Reflow test)
The obtained optical semiconductor device was conditioned for 168 hours in an atmosphere of a temperature of 30 ° C. and a humidity of 70%. Thereafter, the optical semiconductor device was passed through a reflow apparatus ("UNI-5016F" manufactured by Nippon Antom Co., Ltd.) three times under conditions of preheating 150 ° C x 120 seconds + reflow 260 ° C (max.) X 30 seconds.

  Then, it is immersed in red ink at 23 ° C. for 4 hours, and whether or not ink penetration due to peeling is observed at the interface between the sealant (cured product) and the housing agent and the interface between the sealant and the lead electrode. It observed with the stereomicroscope ("SMZ-10" by Nikon Corporation). Ten samples were tested, and the number of samples (NG number) in which red ink penetration was observed was counted.

(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 at 85 ° C. and a relative humidity of 85 RH% in a state where a current of 20 mA was passed 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 was measured. Calculated. The high temperature and high humidity energization test was judged according to the following criteria.

[Criteria for high-temperature and high-humidity current test]
○: Decrease rate of luminosity is less than 5% △: Decrease rate of luminosity is 5% or more and less than 10% ×: Decrease rate of luminosity is 10% or more

  The results are shown in Tables 1 to 3 below. In Examples 1 to 19, since the cured product was firmly adhered to the housing material and the substrate, discoloration of the electrodes was prevented.

(Example 20)
Polymer B (12 g), Polymer E (8 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 benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) (0.02 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.

(Examples 21 to 35 and Comparative Example 7)
A curable composition for optical semiconductors was prepared in the same manner as in Example 20 except that the types and blending amounts of the blending components were changed as shown in Tables 4 and 5 below. The compounds having an azole structure shown in Tables 4 and 5 below are as follows.

Benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)
1-methylbenzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)
1-aminobenzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)
1- [2- (Trimethylsilyl) ethoxycarbonyloxy] benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)
5-Methylbenzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)
Mixture of 4-carboxybenztriazole and 5-carboxybenztriazole (“C-BTA” manufactured by Daiwa Kasei Co., Ltd.)
Mixture of 4-nitrobenztriazole and 5-nitrobenztriazole (“N-BTA” manufactured by Daiwa Kasei Co., Ltd.)
A mixture of 1- [N, N-bis (2-ethylhexyl) aminomethyl] -4-methylbenzotriazole and 1- [N, N-bis (2-ethylhexyl) aminomethyl] -5-methylbenzotriazole (Yamato "VERZONE OA-386" manufactured by Kasei Co., Ltd.)
5-Chlorobenzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)
Benzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)
1-methylbenzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)
Imidazole (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)
1-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)

(Examples 36 to 39)
The curable composition for optical semiconductors was prepared like Example 20 except having changed the kind and compounding quantity of the compounding component as shown in Table 6 below. The compounds having an azole structure shown in Table 6 below are as follows.

N-cyclopentanyl-1H-1,2,4-triazole-3-carboxamide (manufactured by Sigma-Aldrich, reagent)
3-methyl-N- (4H-1,2,4-triazol-3-yl) benzamide (manufactured by Sigma-Aldrich, reagent)
Methyl-benzotriazole-5-carboxylate (manufactured by Sigma-Aldrich, reagent)
Phenyl-benzotriazole-5-carboxylate (manufactured by Sigma-Aldrich, reagent)

(Examples 40 to 44)
A curable composition for optical semiconductors was prepared in the same manner as in Example 20 except that the types and blending amounts of the blending components were changed as shown in Table 7 below. The compounds having an azole structure shown in Table 7 below are as follows.

5-Carboxybenzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)
5-Nitrobenzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)
5,6-dichloro-2-methylbenzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)
5,5'-bistetrazole (in-house synthesized product)
1,4-di (1H-tetrazol-5-yl) benzene (in-house synthesized product)

(Evaluation of Examples 20 to 44 and Comparative Example 7)
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 items were evaluated.

(Gas corrosion test)
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. 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 6 hours, 7 hours and 8 hours after placing in the oven Observed at. The determination was made according to the criteria of the gas corrosion test in Examples 1 to 19 and Comparative Examples 1 to 6.

(Thermal shock test)
The thermal shock test was evaluated in the same manner as the thermal shock test in Examples 1 to 19 and Comparative Examples 1 to 6.

(Reflow test)
The reflow test was evaluated in the same manner as the evaluation of the reflow test in Examples 1 to 19 and Comparative Examples 1 to 6.

(High temperature and high humidity energization test)
The high temperature and high humidity current test was evaluated in the same manner as the evaluation of the high temperature and high humidity current test in Examples 1 to 19 and Comparative Examples 1 to 6.

  The results are shown in Tables 4-7 below.

  Specific implementation using the first organopolysiloxane represented by the formula (1A) or the formula (1B) and the second organopolysiloxane represented by the formula (51A) or the formula (51B) Examples and comparative examples are shown. A first organopolysiloxane not corresponding to the first organopolysiloxane represented by formula (1A) or formula (1B) and a second organopolysiloxane represented by formula (51A) or formula (51B) Even when a second organopolysiloxane that does not correspond is used, the azole structure is obtained by using the compounds having the azole structure used in Examples 1 to 44 together with the first and second organopolysiloxanes and the catalyst for hydrosilylation reaction. Compared with the case where the compound which has this is not used, it confirmed that the discoloration of an electrode was suppressed by the tendency similar to Examples 1-44 and Comparative Examples 1-7.

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 13 ... Lens 21 ... Optical semiconductor device 22 ... Substrate 22a ... Terminal 23 ... Optical semiconductor element 23a ... Electrode 24 ... Bonding wire 25 ... Lens

Claims (19)

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 an optical semiconductor device, comprising a compound having an azole structure.   The curable composition for optical semiconductor devices according to claim 1, wherein the compound having an azole structure is a silane compound, a compound having an imidazole structure, a compound having a triazole structure, or a compound having a tetrazole structure.   The curable composition for optical semiconductor devices according to claim 2, wherein the compound having an azole structure is a silane compound or a compound having a triazole structure.   The compound having an azole structure is a silane compound, or 3- (N-salicyloyl) amino-1,2,4-triazole, 3-methyl-N- (4H-1,2,4-triazole-3- I) benzamide, N-cyclopentanyl-1H-1,2,4-triazole-3-carboxamide, or a compound having a benzotriazole structure; Composition.   The curable composition for optical semiconductor devices according to claim 4, wherein the compound having an azole structure is the compound having the benzotriazole structure.   The compound having an azole structure is a silane compound, or 3- (N-salicyloyl) amino-1,2,4-triazole, 3-methyl-N- (4H-1,2,4-triazole- The curable composition for optical semiconductor devices according to claim 4, which is 3-yl) benzamide or N-cyclopentanyl-1H-1,2,4-triazole-3-carboxamide.   The curable composition for optical semiconductor devices according to claim 6, wherein the compound having an azole structure is a silane compound. The curable composition for optical semiconductor devices according to claim 2, 3, 4, 6, or 7, wherein the silane compound which is a compound having the azole structure is a silane compound represented by the following formula (S).

In said Formula (S), R4 represents an alkoxy group, R5 and R6 represent a C1-C8 alkyl group or an alkoxy group, respectively. The curable composition for optical semiconductor devices according to claim 8, wherein the silane compound that is a compound having the azole structure is a silane compound represented by any one of the following formulas (S1) to (S6).

In the formulas (S1) to (S6), R1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R2 and R3 are each a hydrogen atom, a vinyl group, an amino group, or an alkyl having 1 to 5 carbon atoms R4 represents an alkoxy group, and R5 and R6 each represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group.   The compound having the azole structure is 3- (N-salicyloyl) amino-1,2,4-triazole, 3-methyl-N- (4H-1,2,4-triazol-3-yl) benzamide or N- The curable composition for optical semiconductor devices according to claim 6 which is cyclopentanyl-1H-1,2,4-triazole-3-carboxamide. Further comprising an adhesion promoter,
The curable composition for optical semiconductor devices according to claim 1, wherein the adhesion-imparting agent is a silane compound having an epoxy group, a vinyl group, or a (meth) acryloyl group.   The adhesion promoter is 3-glycidoxypropyltrialkoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane or 3- (meth) acryloxypropyltrialkoxysilane. The curable composition for optical semiconductor devices according to claim 11. Among all functional groups bonded to silicon atoms in the first organopolysiloxane, the number ratio of methyl groups is 80% or more,
The hardening for optical semiconductor devices according to any one of claims 1 to 12, wherein a number ratio of methyl groups among all functional groups bonded to silicon atoms in the second organopolysiloxane is 80% or more. Sex composition. Of all functional groups bonded to silicon atoms in the first organopolysiloxane, the number ratio of the aryl group is 30% or more and 70% or less,
The light according to any one of claims 1 to 12, wherein the number ratio of the aryl group among all functional groups bonded to silicon atoms in the second organopolysiloxane is 30% or more and 70% or less. Curable composition for 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 claim 1, 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: 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, or the first organopolysiloxane is represented by the following formula (1B And a hydrogen atom bonded to an aryl group and a silicon atom, the first organopolysiloxane having an aryl group and an alkenyl group, wherein 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 13, which is a second organopolysiloxane containing

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. 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 represent 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, R51 to R56 each represents at least one 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 C2-C8 hydrocarbon group,
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. -R56 represents a C1-C8 hydrocarbon group, The curable composition for optical semiconductor devices of Claim 16.   The curable composition for optical semiconductor devices according to any one of claims 1 to 17, which is a sealant for optical semiconductor devices or a lens material for optical semiconductor devices. An optical semiconductor element;
A sealant disposed to seal the optical semiconductor element, or a lens disposed on the optical semiconductor element,
The optical semiconductor device in which the said sealing agent or the said lens is formed by hardening | curing the curable composition for optical semiconductor devices of any one of Claims 1-18.

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