JP7360910B2 - A curable composition and a semiconductor device using the composition as a sealant. - Google Patents

Description

The present invention relates to a curable composition cured by hydrosilylation and a semiconductor device using the composition as a sealant.

In recent years, the output power and heat resistance required for semiconductor devices have been increasing more and more, and the reliability required for sealants for sealing semiconductor devices has also become stricter year by year.

For example, the use of silicon carbide (SiC) power semiconductors is being actively considered. Compared to conventional silicon power semiconductors, SiC power semiconductors have less energy loss when energized and have higher heat resistance, so they can handle larger amounts of power. Due to these characteristics, the heat resistance limit temperature of silicon power semiconductors is 150°C, but use of SiC power semiconductors at temperatures of 200°C or higher is being considered, and the heat resistance required of encapsulants is also increasing. It's coming.

In addition, light-emitting devices that use light-emitting diodes (LEDs) as semiconductors have features such as long life, low power consumption, shock resistance, high-speed response, and can be made lighter, thinner, and smaller. , backlights for information terminals, in-vehicle lighting, indoor/outdoor advertising, indoor/outdoor lighting, etc., and their use in many fields is progressing rapidly. In addition to the diversity of applications, there is also a demand for further improvements in reliability.

Sealing resins used in optical semiconductor devices are required to be colorless and transparent due to their properties, and for example, epoxy resin compositions are used (Patent Document 1). However, a problem with cured epoxy resins is that they become discolored when exposed to high temperatures for a long period of time.

As a resin that does not easily cause such coloring, an addition-curing silicone resin composition has been proposed as a sealing resin (Patent Document 2). However, addition-curable silicone resin compositions generally have a problem of low gas barrier properties. Therefore, when a polysiloxane composition with low gas barrier properties is used as a sealant, a problem arises in that the silver member used in the optical semiconductor device turns black and the luminous efficiency decreases.

Therefore, as a method to improve gas barrier properties, hybrid materials of silicone and organic materials are being tried. As such a hybrid material, for example, a compound having a heterocyclic skeleton in an organic substance has been proposed (Patent Document 3, Patent Document 4).

On the other hand, the output per optical semiconductor device is increasing year by year, and it is becoming increasingly important to ensure long-term reliability when using high output.

In Patent Document 3, compounds having at least two SiH groups in one molecule include silicon compounds having at least two SiH groups in one molecule, and carbon-carbons that are reactive with SiH groups in the examples. It describes a compound obtained by reacting with an organic compound having at least two carbon double bonds in one molecule, and the specification exemplifies chain siloxane and cyclic siloxane, but high output Long-term reliability during use was not sufficient.

Patent Document 4 proposes the use of a compound having both an isocyanuric ring skeleton and a siloxane skeleton and an SiH group in one molecule, but the purpose is to aggregate small particle size phosphors, and The amount added was specified to be 7.5 wt% or less based on the other resin components. Furthermore, although a polysiloxane structure containing a T unit is exemplified in the specification as one of the constituent components of other resin components, there are no particular details regarding the details of the structure or special effects derived from the structure. No description can be found.

Patent No. 3241338 International Publication No. 2015/178475 JP2009-046616A Japanese Patent Application Publication No. 2015-079829

The problem to be solved by the present invention is to provide a curable composition that improves current conduction reliability and a semiconductor device using the curable composition as a sealant.

As a result of intensive research, the present inventors have found that (A) (α1) a compound having at least two hydrosilyl groups in one molecule, and (α2) a compound having at least one hydrosilyl group in one molecule at least two in one molecule, which is a hydrosilylation reaction product of an organic compound having a carbon-carbon double bond (alkenyl group) having (B) A compound having two or more alkenyl groups in one molecule, which does not contain a siloxane structure of T units, (C) A compound having three or more hydrosilyl groups and/or alkenyl groups in one molecule. contains a compound represented by the general formula (1) and containing a siloxane structure of T units, (D) a hydrosilylation catalyst, and the content of component (C) is equal to that of component (A) and (B). By using a curable composition as a sealant whose content is 10% by weight or more and 80% by weight or less when the sum of the components and (C) is 100% by weight, long-term reliability of the resulting semiconductor device during high-power use can be achieved. The inventors have discovered that the properties are improved, and have developed the present invention.

General formula (1): RX _a RY _b SiO _(4-ab)/2
(In the formula, RX is an alkenyl group having 2 to 12 carbon atoms or a hydrogen atom, and each RY is individually a methyl group or a phenyl group or a carbon number of 1 to 10 and an oxygen number of 0 to 2.) It is an organic group, and at least 30 mol% of RY is a phenyl group, and a and b are positive numbers such that a+b=1 or more and 2 or less and a/(a+b)=0.03 or more and 0.25 or less. An alkenyl-functional and/or hydrosilyl-functional phenyl-containing polyorganosiloxane having the average compositional formula represented by

1). (A) (α1) a compound having at least two hydrosilyl groups in one molecule, (α2) a carbon-carbon double bond reactive with at least one hydrosilyl group in one molecule, and at least one A compound having at least two hydrosilyl groups in one molecule, which is a hydrosilylation reaction product with an organic compound having a heterocyclic skeleton having a polar group in the ring skeleton, (B) containing a siloxane structure of T units. (C) a compound having two or more alkenyl groups in one molecule, which has three or more hydrosilyl groups and/or alkenyl groups in one molecule, and is represented by general formula (1), and has a T unit structure (D) a hydrosilylation catalyst, and the content of component (C) is 10% by weight or more when the sum of components (A), (B), and (C) is 100% by weight. A curable composition that is 80% by weight or less.

General formula (1): RX _a RY _b SiO _(4-ab)/2
(In the formula, RX is an alkenyl group having 2 to 12 carbon atoms or a hydrogen atom, and each RY is individually a methyl group or a phenyl group or a carbon number of 1 to 10 and an oxygen number of 0 to 2.) It is an organic group, and at least 30 mol% of RY is a phenyl group, and a and b are positive numbers such that a+b=1 or more and 2 or less and a/(a+b)=0.03 or more and 0.25 or less. 2). Component (A) is an organic compound having, in addition to (α1) and (α2), one epoxy group or oxetanyl group and one carbon-carbon double bond that is reactive with a hydrosilyl group in one molecule. The curable composition according to item 1), which is a compound having at least two hydrosilyl groups in one molecule, which is a hydrosilylation reaction product with compound (α3).

3). 1), wherein the component (C) (C1) has three or more alkenyl groups in one molecule, and the proportion of T units contained in the structure is 50% or more and less than 99%; or The curable composition described in 2).

4). 1), wherein the component (C) (C2) has three or more hydrosilyl groups in one molecule, and the proportion of T units contained in the structure is 50% or more and less than 99%. The curable composition according to any one of 3).

5). The curable composition according to any one of 1) to 4), wherein component (B) is a polysiloxane having two or more alkenyl groups in one molecule.

6). The curable composition according to any one of 1) to 5), wherein component (B) is a chain siloxane having two or more alkenyl groups in one molecule.

7). The curable composition according to any one of 1) to 6), wherein the component (B) is a compound containing an organic skeleton.

8). The curable composition according to any one of 1) to 7), wherein component (B) is a modified product of an organic component and siloxane.

9). A semiconductor device using the curable composition according to any one of 1) to 8) as a sealant.

By using the curable composition of the present invention as a sealant, it is possible to provide a semiconductor device with improved long-term reliability during high-power use.

1 is a schematic cross-sectional view of a surface-mounted light emitting diode (LED), which is an example of a semiconductor device of the present invention.

The present invention will be explained in detail below.

<Semiconductor device>
The semiconductor device of the present invention is not particularly limited, but includes, for example, the structure shown in FIG. FIG. 1 is a schematic cross-sectional view of an optical semiconductor device.

The optical semiconductor device 1 in FIG. 1 of the present invention is not particularly limited, and devices commonly used as LEDs of semiconductor light emitting devices can be used. For example, the emitted light excites a phosphor to emit visible light, and examples thereof include visible light emitting type LEDs and ultraviolet emitting type LEDs. Alternatively, the emitted light is directly emitted from the optical semiconductor, and examples thereof include ultraviolet light emitting type, visible light emitting type, and infrared light emitting type LED. In the optical semiconductor element 1 of the present invention, a plurality of LEDs of the same or different types may be mounted per one semiconductor light emitting device.

The reflector 2 in FIG. 1 of the present invention may be used as needed, and its purpose is to efficiently reflect light from the optical semiconductor element 1. The material may be thermoplastic resin, thermosetting resin, glass epoxy, ceramics, or the like, but is not particularly limited.

The cured product 3 of the polysiloxane composition shown in FIG. 1 of the present invention is a corrosive material that efficiently emits light from the optical semiconductor element 1 to the outside, protects the optical semiconductor element and wires from external forces, dust, etc. It has the effect of preventing gas from entering the device.

The leads 4 in FIG. 1 of the present invention are for ensuring conductivity when mounting the LED and increasing the reflection efficiency of the LED. In particular, since the reflectance in the visible light region is high, a metal surface plated with silver is often used, but it is not limited to silver plating.

The wire 5 in FIG. 1 of the present invention is for electrically connecting the optical semiconductor element 1 and the lead 4, and its material is not particularly limited as long as it is conductive, but may be made of gold, gold alloy, silver, etc. Examples include silver alloys and copper. Moreover, instead of using the wire 5, electrical connection may be made using a conductive adhesive or eutectic solder.

The phosphor 6 of the present invention shown in FIG. 1 may be used as necessary, and absorbs light emitted from the optical semiconductor element 1 and emits light of a different wavelength. There are no particular restrictions on the composition of the phosphor used, but phosphors that emit visible light in the range of 400 nm to 800 nm are generally used. Furthermore, there is no restriction on whether the phosphor is sedimented or floating in the cured product 3.

<Compound (A) having at least two hydrosilyl groups in one molecule>
Component (A) of the present invention comprises (α1) a compound having at least two hydrosilyl groups in one molecule and (α2) a compound having at least one hydrosilyl group in one molecule in the presence of a hydrosilylation catalyst (D) described below. Obtained by hydrosilylation reaction of an organic compound having a carbon-carbon double bond (alkenyl group) reactive with a hydrosilyl group and a heterocyclic skeleton having at least one polar group in the ring skeleton. and/or
(α1) a compound having at least two hydrosilyl groups in one molecule, (α2) a carbon-carbon double bond (alkenyl group) having reactivity with at least one hydrosilyl group in one molecule, and at least one An organic compound having a heterocyclic skeleton having polar groups in the ring skeleton, and (α3) one epoxy group or oxetanyl group in one molecule and a carbon-carbon double bond having reactivity with a hydrosilyl group. It is a compound obtained by reacting an organic compound having one. The method for obtaining a compound having at least two hydrosilyl groups in one molecule is not particularly limited, but as an example, the (α1) component and the (α2) component are reacted, and the (α3) component is further added. After the reaction, volatile unreacted components can be distilled off under, for example, reduced pressure and heating conditions.

In the thus obtained component (A), a portion of the alkenyl group of the component (α2) used in the reaction may remain.

The amount of component (α1) added is such that the number of hydrosilyl groups in component (a1) is preferably 1.1 to 20, more preferably 1.3 to 15, per one alkenyl group in component (α2). , 1.5 to 10 are even more preferred. When the amount added is small, gelation progresses due to the crosslinking reaction, so the handleability of the modified organopolysiloxane may be poor, and when the amount added is large, the physical properties of the cured product may be adversely affected. The amount of component (α3) added is preferably 0 to 20, more preferably 0 to 15, even more preferably 0 to 10, per alkenyl group of component (α2). If the amount added is too large, the heat resistance of the cured product may be adversely affected.

The amount of component (A) added is preferably 10% to 300% by weight, more preferably 10 to 200% by weight, and more preferably 10 to 200% by weight, when the total amount of (B) and (C) is 100% by weight. 100% by weight is more preferred. If the amount of component (A) added is less than 10% by weight based on the total amount of (B) and (C), the gas barrier properties of the resulting curable composition will decrease, and it will be contained in semiconductor devices due to corrosive gases. Metal corrosion may progress. On the other hand, if the amount of compound (A) added is too large relative to the total amount of (B) and (C), the hardness of the obtained cured product will become too high, resulting in poor long-term reliability at high output. There is a risk of decreased sexual performance.

There is no particular restriction on the amount of the hydrosilylation catalyst used during the synthesis of the modified organopolysiloxane, but it is used in the range of 10 ^-1 to 10 ^-10 mol per mol of alkenyl group of the component (α2) used in the reaction. It is better. It is preferably used in a range of 10 ⁻⁴ to 10 ⁻⁸ mol. If there is a large amount of hydrosilylation catalyst, depending on the type of hydrosilylation catalyst, it may absorb short wavelength light, so there is a risk of coloring and a decrease in the light resistance of the cured product. There is also a risk of foaming. Furthermore, if the amount of the hydrosilylation catalyst is small, the reaction may not proceed and the desired product may not be obtained.

The reaction temperature for the hydrosilylation reaction is preferably 30 to 400°C, more preferably 40 to 250°C, and even more preferably 45 to 140°C. If the temperature is too low, the reaction will not proceed sufficiently, and if the temperature is too high, gelation may occur and handling properties may deteriorate.

<Compound having at least two hydrosilyl groups in one molecule (α1)>
The compound (α1) of the present invention having at least two hydrosilyl groups in one molecule is not particularly limited as long as it has two or more hydrosilyl groups in the molecule. Examples include linear siloxanes, cyclic siloxanes, branched siloxanes, and silphenylene compounds having hydrosilyl groups.

Linear siloxanes having a hydrosilyl group include copolymers of dimethylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units, and copolymers of diphenylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units. , a copolymer of methylphenylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units, polydimethylsiloxane whose terminals are capped with dimethylhydrogensilyl groups, polydiphenyl whose terminals are capped with dimethylhydrogensilyl groups Examples include siloxane and polymethylphenylsiloxane end-capped with dimethylhydrogensilyl groups.

In particular, as linear siloxanes having hydrosilyl groups, from the viewpoint of reactivity during modification and heat resistance and light resistance of the obtained cured products, polysiloxanes whose molecular ends are blocked with dimethylhydrogensilyl groups are used. Can be suitably used, specifically, for example, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,5, Preferred examples include 5-tetramethyl-3,3-diphenyltrisiloxane.

As the cyclic siloxane having a hydrosilyl group, cyclotrisiloxane, cyclotetrasiloxane, cyclopentasiloxane, etc. can be used. From the viewpoint of heat resistance, light resistance, etc. of the resulting cured product, cyclotetrasiloxane is preferred. As the cyclotetrasiloxane, from the viewpoint of availability, tetraorganotetrahydrogensiloxane, pentaorganotrihydrogensiloxane, and hexaorganodihydrogensiloxane are preferable. More specifically, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetrahydrogen-1,3,5, 7-tetraphenylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl- 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-1,3,5-trimethylcyclotrisiloxane, 1,3,5,7,9-pentahydrogen-1 , 3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclohexasiloxane, 1 , 1,3,5,7-pentamethyl-3,5,7-trihydrogencyclotetrasiloxane, 1,1,3,3,5,7-hexamethyl-5,7-dihydrogencyclotetrasiloxane, 1 , 1,3,5,5,7-hexamethyl-3,7-dihydrogencyclotetrasiloxane, and the like. The cyclic siloxane used in the present invention is specifically, for example, 1,3,5,7-tetrahydrosiloxane, from the viewpoint of industrial availability and reactivity, or the heat resistance, light resistance, strength, etc. of the cured product obtained. Gen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,1,3,5,7-pentamethyl-3,5,7-trihydrogencyclotetrasiloxane, 1,1,3,3,5 , 7-hexamethyl-5,7-dihydrogencyclotetrasiloxane and 1,1,3,5,5,7-hexamethyl-3,7-dihydrogencyclotetrasiloxane can be suitably used.

Examples of branched siloxanes include 3-[(dimethylsilyl)oxy]-1,1,3,5,5-pentamethyltrisiloxane, 3-[(dimethylsilyl)oxy]-1,1,5,5- Tetramethyl-3-phenyltrisiloxane, 3,3-bis[(dimethylsilyl)oxy]-1,1,5,5-tetramethyltrisiloxane, 3-[(trimethylsilyl)oxy]-1,1,3, 5,5-pentamethyltrisiloxane, 3-[(trimethylsilyl)oxy]-1,1,5,5-tetramethyl-3-phenyltrisiloxane, 3,3-bis[(trimethylsilyl)oxy])-1, Examples include 1,5,5-tetramethyltrisiloxane.

Examples of the silphenylene compound include 1,4-bis(dimethylsilyl)benzene, 1,4-bis(diphenylsilyl)benzene, and 1,4-bis(methylphenylsilyl)benzene.

These (α1) components, compounds having at least two hydrosilyl groups in one molecule, may be used alone or in combination of two or more.

<An organic compound (α2 )＞
An organic compound of the present invention having a carbon-carbon double bond (alkenyl group) reactive with at least one hydrosilyl group in one molecule and a heterocyclic skeleton having at least one polar group in the ring skeleton (α2) is not particularly limited as long as it is an organic compound having an alkenyl group and a heterocyclic skeleton, but from the viewpoint of heat resistance and light resistance of the obtained cured product, the following general formula (2) or (3) The organic compounds represented are preferred.

(In the formula, R ₁ to R ₃ represent a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and R ₁ to R ₃ may be different or the same. Also, R ₁ to R ₃ At least one of them contains an alkenyl group.)

(In the formula, R ₄ to R ₇ represent a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and R ₄ to R ₇ may be different or the same. Also, R ₄ to R ₇ At least one of them contains an alkenyl group.)
The skeleton of the component (α2) may contain a functional group other than the alkenyl group and the heterocyclic skeleton.

Component (α2) is, for example, triallyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monoglycidyl isocyanurate, from the viewpoint of adhesiveness between the curable composition and the base material when the curable composition is cured. Monoallyl isocyanurate, monoallyl dimethyl isocyanurate, monoallyl diglycidyl isocyanurate, tetraallyl glycoluril, diallyl diglycidyl glycoluril, triallyl monoglycidyl glycoluril, monoallyl triglycidyl glycoluril, diallyl dimethyl glycoluril, triallyl It is preferable to use dimethyl glycoluril and monoallyl trimethyl glycoluril. Furthermore, from the viewpoint of heat resistance and light resistance, among the above compounds, compounds having two or more alkenyl groups in one molecule are more preferable. These may be used alone or in combination of two or more.

<Organic compound (α3) having one epoxy group or oxetanyl group and one carbon-carbon double bond reactive with a hydrosilyl group in one molecule>
The compound (α3) is not particularly limited as long as it is an organic compound having one epoxy group or oxetanyl group and one carbon-carbon double bond reactive with a hydrosilyl group in one molecule.

Examples of the epoxy group include the following general formula (4) or (5).

(However, R ₈ is a divalent organic group with 1 to 10 carbon atoms and 0 to 2 oxygen atoms, and R ₉ to R ₁₁ are monovalent organic groups with 1 to 50 carbon atoms or hydrogen atoms. , R ₉ to R ₁₁ may be different or the same)

(However, R ₁₂ is a divalent organic group with 1 to 10 carbon atoms and 0 to 2 oxygen atoms, and R ₁₃ to R ₁₄ are monovalent organic groups with 1 to 50 carbon atoms or hydrogen atoms. , R ₁₃ to R ₁₄ may be different or the same).

Examples of the oxetanyl group include the following general formula (6).

(However, R ₁₅ is a divalent organic group having 1 to 10 carbon atoms and 0 to 2 oxygen atoms, and R ₁₆ is a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom).

As the compound (α3), from the viewpoint of availability, allyl glycidyl ether, vinylcyclohexene oxide, and 3-ethyl-3-allyloxymethyl oxetane are preferable. The various compounds (α3) described above may be used alone or in combination of two or more.

<Hydrosilylation catalyst (D)>
As the hydrosilylation catalyst that can be used in the present invention, those commonly known as hydrosilylation catalysts can be selected, and there are no particular limitations.

Specific examples include platinum-olefin complexes, chloroplatinic acid, simple platinum, solid platinum supported on carriers (alumina, silica, carbon black, polymers, etc.); platinum-vinylsiloxane complexes, for example, Pt _n (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt[(MeViSiO) ₄ ] _m ; platinum-phosphine complex, e.g., Pt(PPh ₃ ) ₄ , Pt(PBu ₃ ) ₄ ; platinum-phosphite complex, e.g., Pt [P(OPh) ₃ ] ₄ , Pt[P(OBu) ₃ ] ₄ (wherein, Me is a methyl group, Bu is a butyl group, Vi is a vinyl group, Ph is a phenyl group, and n and m are integers. ), Pt(acac) ₂ , and the platinum-hydrocarbon complexes described in Ashby et al., U.S. Pat. Also mentioned are platinum alcoholate catalysts.

Further, examples of catalysts other than platinum compounds include RhCl(PPh ₃ ) ₃ , RhCl ₃ , Rh/Al ₂ O ₃ , RuCl ₃ , IrCl 3 , FeCl ₃ , AlCl _{3 ,} PdCl _{2.2H 2} O, NiCl ₂ , TiCl ₄ , and the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes, Pt(acac) ₂ , etc. are preferred.

<Compound (B) that does not contain a T-unit siloxane structure and has two or more alkenyl groups in one molecule>
The compound (B) used in the present invention is a compound that does not contain a siloxane structure of T units and has two or more alkenyl groups in one molecule.

The amount of compound (B) added can be set in various ways, but the number of hydrosilyl groups contained in the entire curable composition is 0.3 to 5, preferably 0.3 to 5, per one alkenyl group contained in the entire curable composition. It is desirable that they be added at a ratio of 5 to 3, more preferably 0.7 to 1.5. If the proportion of alkenyl groups is small, poor appearance due to foaming etc. is likely to occur, and if the proportion of alkenyl groups is large, it may have an adverse effect on the physical properties after curing.

Here, as the compound (B), for example, polysiloxane (B1) having two or more alkenyl groups in one molecule, the above-mentioned organic compound (B2) having two or more alkenyl groups in one molecule, Examples include modified products (B3) having two or more alkenyl groups in one molecule. These compounds having two or more alkenyl groups in one molecule may be used alone or in combination of two or more.

<Polysiloxane (B1) having two or more alkenyl groups in one molecule>
The number of siloxane units of the polysiloxane (B1) having two or more alkenyl groups in one molecule, which may be contained in the curable composition of the present invention, is not particularly limited, but is preferably 2 or more and 1000 or less, and 2 or more. More preferably, the number is from 1 to 100. If the number of siloxane units in one molecule is small, it will easily volatilize from the composition, and desired physical properties may not be obtained after curing. Furthermore, if the number of siloxane units is large, the tackiness of the obtained cured product may deteriorate, making it difficult to handle as an optical semiconductor device.

The polysiloxane having two or more alkenyl groups in one molecule preferably has an aryl group from the viewpoint of gas barrier properties. Further, in the polysiloxane having two or more alkenyl groups in one molecule having an aryl group, it is preferable that the aryl group is bonded directly to the Si atom from the viewpoint of heat resistance and light resistance. Further, the aryl group may be present in either the side chain or the terminal of the molecule, and examples of the molecular structure of such aryl group-containing polysiloxane include a linear structure, a cyclic structure, and a combination of a linear and cyclic structure. It will be done.

Such aryl groups include, for example, phenyl group, naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group. group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 3-isobutylphenyl group, 4-isobutylphenyl group, 3-t-butylphenyl group, 4-t-butylphenyl group, 3-pentylphenyl group, 4-pentylphenyl group, 3-hexylphenyl group, 4-hexylphenyl group, 3-cyclohexylphenyl group, 4-cyclohexylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group group, 3,5-dimethylphenyl group, 2,3-diethylphenyl group, 2,4-diethylphenyl group, 2,5-diethylphenyl group, 2,6-diethylphenyl group, 3,4-diethylphenyl group, 3,5-diethylphenyl group, biphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,4,5-trimethylphenyl group, 3-epoxyphenyl group, 4-epoxy Examples include phenyl group, 3-glycidylphenyl group, and 4-glycidylphenyl group. Among them, a phenyl group is a preferable example from the viewpoint of heat resistance and light resistance. These may be used alone or in combination of two or more.

In the present invention, polysiloxanes having two or more alkenyl groups in one molecule include linear polysiloxanes having two or more alkenyl groups and two or more alkenyl groups at the end of the molecule, from the viewpoint of heat resistance and light resistance. Preferable examples include polysiloxanes having 2 or more alkenyl groups, and cyclic siloxanes having 2 or more alkenyl groups.

Specific examples of linear polysiloxanes having two or more alkenyl groups include copolymers of dimethylsiloxane units, methylvinylsiloxane units, and terminal trimethylsiloxy units, diphenylsiloxane units, methylvinylsiloxane units, and terminal trimethylsiloxy units. copolymer with methylphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, polydimethylsiloxane end-capped with dimethylvinylsilyl group, end-capped with dimethylvinylsilyl group Examples include polydiphenylsiloxane and polymethylphenylsiloxane end-capped with dimethylvinylsilyl groups.

Specific examples of polysiloxanes having two or more alkenyl groups at the molecular ends include polysiloxanes whose ends are capped with dimethylvinylsilyl groups as exemplified above, two or more dimethylvinylsiloxane units, SiO ₂ units, and SiO units. Examples include polysiloxanes consisting of at least one siloxane unit selected from the group consisting of:

Examples of cyclic siloxane compounds having two or more alkenyl groups include 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-vinyl-1-phenyl -3,5,7-trimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3-diphenyl-5,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,5 -diphenyl-3,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3,5-triphenyl-7-methylcyclotetrasiloxane, 1-phenyl-3,5,7-trivinyl- 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-diphenyl-5,7-divinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-1, 3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl-1 , 3,5,7,9,11-hexamethylcyclosiloxane and the like.

These polysiloxanes having two or more alkenyl groups in one molecule may be used alone or in combination of two or more.

<Organic compound (B2) having two or more alkenyl groups in one molecule>
(B2) is not particularly limited as long as it is an organic compound having two or more alkenyl groups in one molecule, but for example, it is an organic compound represented by the following general formula (7) or (8). and an organic compound having two or more alkenyl groups in one molecule.

(In the formula, R ₁₇ to R ₁₉ represent a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and R ₁₇ to R ₁₉ may be different or the same. Also, R ₁₇ to R ₁₉ At least two of them are alkenyl groups.)

(In the formula, R ₂₀ to R ₂₃ represent a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and R ₂₀ to R ₂₃ may be different or the same. Also, R ₂₀ to R ₂₃ At least two of them are alkenyl groups.)
The component (B2) preferably has a number average molecular weight of less than 900 from the viewpoint of compatibility of the resulting curable composition. Furthermore, the skeleton of component (B2) may contain a functional group other than an alkenyl group.

Component (B2) is represented by the above general formula (8) or (9), and has an alkenyl group in one molecule, from the viewpoint of adhesion to the base material when the composition is cured. Preferably, the compound contains two or more of the following, and from the viewpoint of the balance between heat resistance and light resistance, triallyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monoglycidyl isocyanurate, tetraallyl glycoluril, It is preferable to use diallyl diglycidyl glycoluril, triallyl monoglycidyl glycoluril, monoallyl triglycidyl glycoluril, diallyl dimethyl glycoluril, triallyl dimethyl glycoluril, and monoallyl trimethyl glycoluril. These may be used alone or in combination of two or more.

<Modified product (B3) having two or more alkenyl groups in one molecule>
(B3) is not particularly limited as long as it is a modified product having two or more alkenyl groups in one molecule. It may be a modified product formed by a combination of an organic component and an organic component, a modified product formed by a combination of an organic component and an inorganic component, or a modified product formed by a combination of an inorganic component and an inorganic component. From the viewpoint of heat resistance of the resulting cured product, a combination of an organic component and an inorganic component or a combination of an inorganic component and an inorganic component is preferred.

Examples of the combination of an organic component and an inorganic component include a modified product obtained by reacting the component (α1) with the component (B2) in the presence of a hydrosilylation catalyst (D). Examples of the combination of inorganic components include a modified product obtained by reacting the component (α1) with the component (B1) in the presence of the hydrosilylation catalyst (D).

These may be used alone or in combination of two or more.

<Compound (C) having three or more hydrosilyl groups and/or alkenyl groups in one molecule, represented by general formula (1), and containing a T unit structure>
Component (C) is not particularly limited as long as it is a compound having three or more hydrosilyl groups and/or alkenyl groups in one molecule, represented by general formula (1), and containing a T unit structure.

General formula (1): RX _a RY _b SiO _(4-ab)/2
(wherein RX is an alkenyl group or a hydrogen atom having from 2 to 12 carbon atoms, each RY is individually a methyl group or a phenyl group, at least 30 mol% of RY is a phenyl group, and a and b is a positive number such that a+b=1 or more and 2 or less and a/(a+b)=0.03 or more and 0.25 or less) having an alkenyl functionality and/or an average composition formula shown in hydrosilyl-functional phenyl-containing polyorganosiloxane)
The content of the T unit structure is the value of T unit content = T unit / (Q unit + T unit + D unit + M unit) when the siloxane units contained in the structure are classified into Q, T, D, and M units. is preferably 0.5 or more and less than 0.99, more preferably 0.60 or more and less than 0.95, and even more preferably 0.70 or more and less than 0.90. If the T unit content is too high or too low, the effect of improving long-term reliability during high-output use cannot be obtained.

Examples of such compounds include compounds (C1) that have three or more alkenyl groups in one molecule and the proportion of T units contained in the structure is 50% or more and less than 99%; Examples include compounds (C2) having at least 100 hydrosilyl groups and the proportion of T units contained in the structure is 50% or more and less than 99%. (C1) and (C2) may be used alone or in combination of two or more.

Regarding the content of phenyl groups contained in component (C), at least 30 mol% of RY in general formula (1) is a phenyl group, preferably 45 mol% or more, and more preferably 55 mol% or more. If the content of phenyl groups is low, the gas barrier properties of the resulting curable composition will be reduced, and there is a possibility that corrosion of metals contained in the semiconductor device by corrosive gases will progress.

The number average molecular weight of component (C) as a whole may be at least 500, more preferably at least 1,000 and at most 10,000, and even more preferably at least 1,500 and at most 6,000. If the number average molecular weight is too small, the effect of improving long-term reliability during high-output use cannot be obtained, and if the number average molecular weight is too large, handling properties deteriorate.

The values of a and b in general formula (1) contained in component (C) are such that the value of a+b satisfies 1 or more and 2 or less, more preferably 1.05 or more and 1.7 or less, and more preferably 1.05 or more and 1.7 or less. satisfies 1.2 or more and 1.6 or less, and the value of a/(a+b) satisfies 0.03 or more and 0.25 or less, more preferably 0.05 or more and 0.20 or less. If the values of a and b do not satisfy these combinations, the effect of improving long-term reliability during high-power use cannot be obtained.

The amount of component (C) added is preferably 5% by weight or more and 90% by weight or less, and 10% by weight when the total of components (A), (B), and (C) is 100% by weight. % or more and 80% by weight or less, and even more preferably 20% or more and 70% by weight or less. If the amount of component (C) added is too small, the effect of improving long-term reliability during high-power use cannot be obtained, and if the amount of component (C) added is too large, the gas barrier properties will deteriorate and semiconductor devices will be affected by corrosive gases. Corrosion of the metal contained within may progress.

<Compound (C1) having 3 or more alkenyl groups in one molecule and having a proportion of T units in the structure of 50% or more and less than 99%>
Examples of (C1) include combinations of Q units, T units, D units, and M units, combinations of Q units, T units, and M units, combinations of T units, D units, and M units, and combinations of T units and M units. Examples include combinations of units.

Examples of T units include phenylsilsesquioxane units, methylsilsesquioxane units, ethylsilsesquioxane units, glycidylsilsesquioxane units, 3-glycidyloxypropylsilsesquioxane units, and ethylcyclohexene oxide silsesquioxane units. Examples include oxane units, vinyl silsesquioxane units, allyl silsesquioxane units, cyclopentyl silsesquioxane units, and cyclohexyl silsesquioxane units.

Examples of D units include dimethylsiloxane units, methylvinylsiloxane units, methylallylsiloxane units, methylphenylsiloxane units, diphenylsiloxane units, glycidylmethylsiloxane units, 3-glycidyloxypropylmethylsiloxane units, glycidylvinylsiloxane units, and glycidylallyl units. Examples include siloxane units, 3-glycidyloxypropylvinylsiloxane units, and 3-glycidyloxypropylallylsiloxane units.

Examples of the M unit include trimethylsiloxy units, dimethylvinylsiloxy units, dimethylallylsiloxane units, diphenylvinylsiloxy units, diphenylallylsiloxane units, dimethylglycidylsiloxy units, dimethyl-3-glycidyloxypropylsiloxy units, and the like.

Each of these units may be used alone or in combination. From the viewpoint of long-term reliability at high output, it is preferable that at least a phenylsilsesquioxane unit is included as a T unit, and a dimethylvinylsiloxy unit is included as at least an M unit.

<Compound (C2) having three or more hydrosilyl groups in one molecule and having a proportion of T units contained in the structure of 50% or more and less than 99%>
Examples of (C2) include combinations of Q units, T units, D units, and M units, combinations of Q units, T units, and M units, combinations of T units, D units, and M units, and combinations of T units and M units. Examples include combinations of units.

Examples of T units include phenylsilsesquioxane units, methylsilsesquioxane units, ethylsilsesquioxane units, glycidylsilsesquioxane units, 3-glycidyloxypropylsilsesquioxane units, and ethylcyclohexene oxide silsesquioxane units. Examples include oxane units, hydrogen silsesquioxane units, cyclopentanesylsesquioxane units, cyclohexane silsesquioxane units, and the like.

Examples of D units include dimethylsiloxane units, methylhydrogensiloxane units, methylphenylsiloxane units, diphenylsiloxane units, glycidylmethylsiloxane units, 3-glycidyloxypropylmethylsiloxane units, glycidylhydrogensiloxane units, and 3-glycidyloxypropyl units. Examples include hydrogen siloxane units.

Examples of the M unit include trimethylsiloxy units, dimethylhydrogensiloxy units, diphenylhydrogensiloxy units, dimethylglycidylsiloxy units, dimethyl-3-glycidyloxypropylsiloxy units, and the like.

Each of these units may be used alone or in combination. From the viewpoint of long-term reliability at high output, it is preferable that at least a phenylsilsesquioxane unit is included as a T unit, and a dimethylhydrogensiloxy unit is included as at least an M unit.

<Optimum example for component (C)>
Here, to specifically illustrate an example of selectively using component (C1) and component (C2), the alkenyl group contained in component (B) is based on the total number of moles of hydrosilyl group contained in component (A). When the total number of moles of is small, it is desirable to add component (C1), which is a component containing an alkenyl group, because it balances the number of moles of hydrosilyl groups and alkenyl groups. On the other hand, if the total number of moles of alkenyl groups contained in component (B) is greater than the total number of moles of hydrosilyl groups contained in component (A), it is a component containing a hydrosilyl group (C2 ) component is desirable because it balances the number of moles of hydrosilyl groups and alkenyl groups. Moreover, the component (C1) and the component (C2) may be added at the same time.

<Hydrosilylation catalyst (D)>
Any hydrosilylation catalyst described in the above-mentioned hydrosilylation catalyst (D) may be used. One type may be used alone, or two or more types may be used in combination.

<Curable composition>
The polysiloxane-based curable composition used in the semiconductor device of the present invention can be obtained by mixing a curing retardant, an inorganic filler, etc., if necessary.

The viscosity of the curable composition used in the present invention is not particularly limited, but is preferably 0.1 Pa·s to 300 Pa·s, more preferably 0.3 Pa·s to 200 Pa·s at a temperature of 23°C. It is. If the viscosity of the curable composition is low, there is a risk that the phosphor will settle and the chromaticity difference between the individual components will become large, and if the viscosity is high, the handleability of the curable composition may deteriorate.

When applying temperature when curing the curable composition, the temperature is preferably 30 to 400°C, more preferably 50 to 250°C. If the curing temperature is high, the obtained cured product tends to have poor appearance, and if the curing temperature is low, curing will be insufficient. Furthermore, curing may be performed by combining two or more temperature conditions. Specifically, for example, it is preferable to raise the curing temperature stepwise to 70°C, 120°C, and 150°C, since a good cured product can be obtained.

The curing time can be appropriately selected depending on the curing temperature, the amount of the hydrosilylation catalyst used, the amount of the reactive group, and other combinations of the formulation of the curable composition, but examples include 1 minute to 12 hours, A good cured product can be obtained by carrying out the treatment preferably for 10 minutes to 8 hours.

A curing retarder may be used to improve the storage stability of the curable composition used in the present invention or to adjust the hydrosilylation reactivity during the curing process. As the curing retarder, known ones used in addition-curable compositions using hydrosilylation catalysts can be used, and specifically, compounds containing aliphatic unsaturated bonds, organic phosphorus compounds, organic sulfur compounds, Examples include nitrogen-containing compounds, tin-based compounds, and organic peroxides. These may be used alone or in combination of two or more.

Examples of the above-mentioned compounds containing an aliphatic unsaturated bond include 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne, and 3,5-dimethyl-1-butyne. Examples include propargyl alcohols such as hexyn-3-ol and 1-ethynyl-1-cyclohexanol, en-yne compounds, maleic anhydride, and maleic esters such as dimethyl maleate.

Examples of nitrogen-containing compounds include N,N,N',N'-tetramethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, and N,N-dibutyl. -1,3-propanediamine, N,N-dimethyl-1,3-propanediamine, N,N,N',N'-tetraethylethylenediamine, N,N-dibutyl-1,4-butanediamine, 2,2 '-Bipyridine and the like can be exemplified.

The curable composition used in the semiconductor device of the present invention may contain a phosphor. The phosphor absorbs the light emitted by the light emitting element and generates light of a different wavelength, and the phosphor used in the semiconductor device of the present invention is not particularly limited, and may include generally known inorganic phosphors and Organic phosphors and quantum dots can be used, and any one can be selected to obtain the emission color required by the semiconductor device of the present invention. Specifically, for example, YAG-based phosphors, TAG-based phosphors, orthosilicate alkaline earth-based phosphors, α-sialon-based phosphors, β-sialon-based phosphors, Cousin-based phosphors, nitride and oxynitride-based phosphors. , CdSe-based quantum dots, CdSSe-based quantum dots, CdS-based quantum dots, InP-based quantum dots, PbS-based quantum dots, perovskite-type phosphors, etc., but are not limited to these. These phosphors can be used alone or in combination of two or more in any ratio.

There is no particular limit to the amount of phosphor used in the present invention, and any amount can be used to obtain the luminescent color required by the semiconductor device. Preferably 0.1% by weight or more, more preferably 1% by weight or more, even more preferably 2% by weight or more, preferably 200% by weight or less, more preferably 150% by weight or less, even more preferably 100% by weight or less. be. If the amount of phosphor used is small, the wavelength conversion by the phosphor will be insufficient, and the desired emission color may not be obtained. If the amount of phosphor used is too large, the handling properties of the composition may deteriorate. , the utilization efficiency of the phosphor may be lowered due to optical interference.

There are no particular restrictions on the particle size or particle size distribution of the phosphor, and any amount can be used to obtain the emission color required by the semiconductor device.

An adhesion imparting agent can be added to the curable composition used in the semiconductor device of the present invention, if necessary.

The adhesion promoter is, for example, used for the purpose of improving the adhesion between the polysiloxane composition and the base material in the present invention, and is not particularly limited as long as it has such an effect. Silane, etc. A preferred example is a coupling agent.

The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and at least one hydrolyzable silicon group in the molecule. The group reactive with an organic group is preferably at least one functional group selected from an epoxy group, a methacrylic group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling properties. From the viewpoint of properties and adhesive properties, epoxy groups, methacrylic groups, and acrylic groups are particularly preferred. As the hydrolyzable silicon group, an alkoxysilyl group is preferred from the viewpoint of handling properties, and a methoxysilyl group and an ethoxysilyl group are particularly preferred from the viewpoint of reactivity.

Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane. Ethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2- Alkoxysilanes having an epoxy functional group such as (3,4-epoxycyclohexyl)ethylmethyldiethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane , 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, and other alkoxysilanes having a methacrylic group or an acrylic group. Can be mentioned. These may be used alone or in combination of two or more.

An inorganic filler can be added to the curable composition used in the semiconductor device of the present invention, if necessary. By using an inorganic filler, the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical properties, light reflectance, flame retardance, fire resistance, gas barrier properties, etc. of the obtained molded product can be improved. It is possible to improve various physical properties of.

The inorganic filler is not particularly limited as long as it is an inorganic substance or a compound containing an inorganic substance, but specific examples include quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine amorphous silica, etc. Silica-based inorganic filler, alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass fiber, glass flake, alumina fiber, carbon fiber, mica, graphite, carbon black, Examples include ferrite, graphite, diatomaceous earth, clay, clay, talc, aluminum hydroxide, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, potassium titanate, calcium silicate, inorganic balloons, and silver powder. These may be used alone or in combination of two or more.

The inorganic filler may be subjected to appropriate surface treatment. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a silane coupling agent, etc., but are not particularly limited.

Various shapes of the inorganic filler can be used, such as crushed, flaky, spherical, and rod-like. The average particle size and particle size distribution of the inorganic filler are not particularly limited, but from the viewpoint of gas barrier properties, the average particle size is preferably 0.001 to 100 μm, more preferably 0.005 to 70 μm. It is more preferable that there be. Similarly, the BET specific surface area is not particularly limited, but from the viewpoint of gas barrier properties, it is preferably 70 m ² /g or more, more preferably 100 m ² /g or more, and even more preferably 200 m ² /g. It is particularly preferable that it is at least g.

The amount of the inorganic filler added is not particularly limited, but is 0.1 to 1000 parts by weight, more preferably 0.5 to 500 parts by weight, and even more preferably 1 to 300 parts by weight, based on 100 parts by weight of the curable composition. Parts by weight. If the amount of inorganic filler added is large, fluidity may deteriorate, and if the amount of inorganic filler added is small, desired physical properties may not be obtained.

The means for mixing the inorganic filler is not particularly limited, but specific examples include a two-roll or three-roll stirrer, a planetary stirring defoaming device, a homogenizer, a dissolver, a planetary mixer, etc. Examples include melt kneading machines such as plastomills. The inorganic filler may be mixed at room temperature or heated, and may be mixed at normal pressure or under reduced pressure. If the temperature during mixing is high, the composition may harden before molding.

In addition, the curable composition used in the semiconductor device of the present invention may optionally contain various additives such as a colorant and a heat resistance improver, a reaction control agent, a mold release agent, a dispersant for fillers, etc., as necessary. It can be added with. Examples of the dispersant for fillers include diphenylsilanediol, various alkoxysilanes, carbon functional silanes, and low molecular weight siloxanes containing silanol groups. Note that it is preferable that these optional components be added in a minimum amount so as not to impair the effects of the present invention.

The curable composition used in the semiconductor device of the present invention is prepared by uniformly mixing the above-mentioned components using a kneading machine such as a roll, a Banbury mixer, or a kneader, or using a planetary stirring deaerator, and heating as necessary. It may also be processed.

The semiconductor device of the present invention can be used in various conventionally known applications. Specifically, for example, backlights for light receiving and emitting devices such as liquid crystal display devices, lighting, sensor light sources, vehicle instrument light sources, signal lights, indicator lights, display devices, light sources for planar light emitters, displays, decorations, various lights, etc. can be mentioned.

The present invention will be explained in more detail below based on Examples, but the present invention is not limited thereto in any way.

(hydrosilyl value)
A mixed solution containing 0.200 g of the modified product, 0.200 g of dibromoethane, and 1.000 g of deuterated chloroform was prepared. The hydrosilyl value of the modified product was calculated by measuring the obtained solution using a 400 MHz NMR manufactured by Varian Technologies Japan Limited and using the following calculation formula (1).

Hydrosilyl value (mol/kg) = (integral value of the peak attributed to the hydrosilyl group of the modified product) / (integral value of the peak attributed to the methyl group of dibromoethane) x 4 x (weight of dibromoethane in the mixture) /(molecular weight of dibromoethane)/(denatured weight in the mixture) Calculation formula (1)

(alkenyl value)
A mixed solution containing 0.200 g of the modified product, 0.200 g of dibromoethane, and 1.000 g of deuterated chloroform was prepared. The alkenyl value of the modified product was calculated by measuring the obtained solution using a 400MHz NMR manufactured by Varian Technologies Japan Limited and using the following calculation formula (2).

Alkenyl value (mol/kg) = (integral value of the peak attributed to the alkenyl group of the modified product) / (number of H atoms attached to the alkenyl group of the modified product) / (attributed to the methyl group of dibromoethane) (integral value of peak) x 4 x (weight of dibromoethane in the mixture) / (molecular weight of dibromoethane) / (weight of modified weight in the mixture) Calculation formula (2)

(Manufacturing example 1)
500 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (corresponding to (α1)) and 1800 g of toluene were mixed uniformly and stirred at 105°C under a nitrogen atmosphere. did. 180 g of triallyl isocyanurate (corresponding to (α2)), 300 g of allyl glycidyl ether (corresponding to (α3)), 350 g of toluene, and a xylene solution of platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, UmiCo Precious) A mixed solution of 0.1 g of Pt-VTSC-3X (manufactured by Metals Japan) was added dropwise over 40 minutes and reacted at 105° C. for 4 hours. By distilling off unreacted components and toluene under reduced pressure, a reaction product of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, allyl glycidyl ether, and triallyl isocyanurate was obtained. 700 g (hydrosilyl number 3.5 mol/kg: component (A)) was obtained.

(Manufacturing example 2)
626 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 602 g of toluene (equivalent to (α1)) were mixed uniformly and stirred at 105°C under a nitrogen atmosphere. did. 90 g of triallylisocyanurate (corresponding to (α2)), 90 g of toluene, and a xylene solution of platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% of platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) 0. 1 g of the mixed solution was added dropwise over 40 minutes, and the mixture was reacted at 105° C. for 4 hours. By distilling off unreacted components and toluene under reduced pressure, 310 g of a reaction product of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and triallylisocyanurate (hydrosilyl value 8.8 mol/kg of (A) component) was obtained.

(Manufacturing example 3)
90 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (corresponding to (α1)) and 40 g of toluene were mixed uniformly and stirred at 105°C under a nitrogen atmosphere. did. 100 g of diallyl monomethyl isocyanurate (corresponding to (α2)), 200 g of toluene, and a xylene solution of platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% of platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) 0. 15 g of the mixed solution was added dropwise over 40 minutes and reacted at 105° C. for 4 hours. By distilling off unreacted components and toluene under reduced pressure, 120 g of the reaction product of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and diallyl monomethyl isocyanurate (hydrosilyl value Several 6.1 mol/kg of component (A) was obtained.

(Example 1)
To 4.64 g of the reaction product obtained in Production Example 1 (component (A)), 2.6 g of diallyl monomethyl isocyanurate (component (B)), compound 2 consisting of phenylsilsesquioxane units and dimethylhydrogensiloxy units. .75 g (component (C)), xylene solution of platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) 4.0 μL, ethynylcyclohexanol 7. After adding 2 μL and 0.4 μL of dimethyl maleate and stirring and mixing uniformly, further perform stirring for 3 minutes, defoaming for 3 minutes, and stirring for 3 minutes using Awatori Rentaro AR-250 manufactured by Thinky. A curable composition was prepared.

Separately, a 3030 reflector manufactured by SDI (product number: SDI4G62) was prepared, in which two 20 mil x 40 mil square blue LED chips (product number: B2040CCI4 V31 P45C-31) manufactured by Generites were mounted. Ar plasma irradiation was performed on the prepared unsealed LED using a plasma cleaner manufactured by SAMCO (irradiation for 10 seconds at 20 Pa, 130 W, and 5 SCCM). The obtained curable composition is injected into an unsealed LED within 1 hour of plasma irradiation within 30 minutes after the completion of the above stirring and defoaming using a Musashi Engineering dispenser ML5000-XII, Within 30 minutes after injection, the temperature was raised in the order of 80° C. for 120 minutes, 100° C. for 60 minutes, and 150° C. for 300 minutes in a convection oven to obtain an optical semiconductor device.

(Long-term reliability test at high output)
Twenty optical semiconductor devices produced in the above example were mounted on an aluminum base substrate using lead-free solder paste manufactured by Matsuo Handa (product number: FLF01-BZ(L)) by reflow at 260°C. The mounted optical semiconductor device was connected to an LED aging device manufactured by Technologue (product number: LX6136A) and placed in a constant temperature and humidity chamber (LH43-13M manufactured by Nagano Science) at 85°C and relative humidity of 85%. A continuous LED energization test was conducted by applying a current of 200 mA. The junction temperature at this time was within 135°C±5°C. A product is judged to be NG if at least one of the following occurs: LED not lighting up, peeling at the interface between the sealant and reflector, and cracks in the sealant, and the number of NG products exceeds 10% of the number tested. The number of cycles was defined as the reliability test life (hours) of the sample.

(Gas barrier test)
Five optical semiconductor devices manufactured in the above example were placed in a flow type gas corrosion tester (KG130S manufactured by Fact-Ki) and exposed to hydrogen sulfide for 96 hours under the conditions of 40°C, 80% RH, and 3 ppm of hydrogen sulfide. The test was conducted. If the average value of the total luminous flux maintenance rate after the test compared to before the test was 60% or more, it was rated ○, and if it was 60% or less, it was rated ×.

(Examples 2 to 15, Comparative Examples 1 to 10)
A test was conducted in the same manner as in Example 1, except that a curable composition was prepared according to the blending ratio shown in Table 1.

The formulation composition and reliability test life of Examples and Comparative Examples are listed in Table 1.

Comparative Examples 1 to 4 lack reliability because they do not contain component (C). Comparative Examples 5 and 6 contain a component (Other-1) having a siloxane skeleton containing a T unit structure, but the values of a and b are outside the range specified as component (C) and have poor reliability. . Regarding Comparative Example 7, since the amount of component (A) added was small, gas barrier properties were poor. Regarding Comparative Example 8, the gas barrier properties were poor due to the large amount of component (C) added. Regarding Comparative Examples 9 and 10, a siloxane component (other components-2 or 3) that does not contain a T unit structure was added, resulting in poor reliability.

As shown in Table 1, in the semiconductor device using the curable composition of the present invention, the reliability test life was extended compared to the comparative example, and the long-term reliability at high output was improved.
The abbreviations used in the table are as follows.

(B) Component (B-1): Diallyl monomethyl isocyanurate (B-2): 1,5-divinyl-1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane

Component (C) Consists of the structural units shown below, and has a number average molecular weight determined by GPC, T unit ratio, ratio of Ph group in R2 in general formula (1), and values of a and b as shown in Table 2. a certain compound.

(C-1): Compound consisting of phenylsilsesquioxane units and dimethylhydrogensiloxy units (C-2): Compound consisting of phenylsilsesquioxane units and dimethylhydrogensiloxy units (C-3): Phenylsil Compound (C-4) consisting of sesquioxane units and dimethylhydrogensiloxy units: Compound (C-5) consisting of phenylsilsesquioxane units and dimethylvinylsiloxy units: Phenylsilsesquioxane units and dimethylvinylsiloxy units Compound (C-6) consisting of: Compound consisting of phenylsilsesquioxane units and dimethylvinylsiloxy units

(D) Component (D-1): Xylene solution of platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% of platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X)

(Other ingredients)
(Others-1): HDP-111 (manufactured by Gelest, a compound consisting of phenyl (dimethyl hydrogen siloxy) siloxane units and dimethyl hydrogen siloxy units, number average molecular weight by GPC, T unit ratio, general formula (1) Compounds in which the ratio of Ph groups in R2 and the values of a and b are the values shown in Table 2)
(Others-2): Chain siloxane having two hydrosilyl groups in one molecule consisting of diphenylsiloxane units and dimethylhydrogensiloxy units (hydrosilyl value: 1.64 mmol/g, viscosity 7800 mPa・s)
(Other-3): 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane

1 LED chip 2 Reflector 3 Cured product of polysiloxane composition 4 Lead 5 Bonding wire 6 Phosphor

Claims (5)

(A) (α1) a compound having at least two hydrosilyl groups in one molecule;
(α2) Hydrosilylation with an organic compound having a carbon-carbon double bond reactive with at least one hydrosilyl group in one molecule and a heterocyclic skeleton having at least one polar group in the ring skeleton A compound having at least two hydrosilyl groups in one molecule, which is a reactant;
(B) A compound that does not contain a siloxane structure of T units and has two or more alkenyl groups in one molecule;
(C) a compound having three or more hydrosilyl groups and/or alkenyl groups in one molecule, represented by general formula (1), and containing a T unit structure;
(D) hydrosilylation catalyst;
The content of component (C) is 10% by weight or more and 80% by weight or less when the sum of components (A), (B) and (C) is 100% by weight,
A curable composition , wherein the compound (B) is an organic compound represented by the following general formula (7) or (8).
General formula (1): RX _a RY _b SiO _(4-ab)/2
((General formula (1), where RX is an alkenyl group having 2 to 12 carbon atoms or a hydrogen atom, and each RY is individually a methyl group or a phenyl group or a carbon number of 1 to 10 , is an organic group having 0 to 2 oxygen atoms, at least 30 mol% of RY is a phenyl group, a and b satisfy a+b=1 or more and 2 or less, and a/(a+b)=0.03 or more and 0.25 It is an alkenyl _- functional and / or hydrosilyl-functional phenyl _- containing polyorganosiloxane having the average composition formula shown in It represents 1 to 50 monovalent organic groups or hydrogen atoms, and R ₁₇ to R ₁₉ may be different or the same. Also, at least two of R ₁₇ to R ₁₉ are alkenyl groups. In the general formula (8), R ₂₀ to R ₂₃ represent _a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and R ₂₀ to R ₂₃ may be different or the same. ~ At least two of R ₂₃ are alkenyl groups.)
An organic compound in which component (A) has, in addition to (α1) and (α2), one epoxy group or oxetanyl group and one carbon-carbon double bond that is reactive with a hydrosilyl group in one molecule. The curable composition according to claim 1, which is a compound having at least two hydrosilyl groups in one molecule, which is a hydrosilylation reaction product with (α3). Claim 1, wherein the component (C) (C1) has three or more alkenyl groups in one molecule, and the proportion of T units contained in the structure is 50% or more and less than 99%. Or the curable composition according to 2. Claim 1, wherein the component (C) (C2) has three or more hydrosilyl groups in one molecule, and the proportion of T units contained in the structure is 50% or more and less than 99%. The curable composition according to any one of items 1 to 3. A semiconductor device using the curable composition according to any one of claims 1 to 4 as a sealant.