JP7360911B2 - 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). Furthermore, attempts have been made to improve gas barrier properties using polyhedral structure polysiloxane (Patent Documents 4 and 5).

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, as a compound having at least two SiH groups in one molecule, examples include a silicon compound having at least two SiH groups in one molecule, and a carbon-carbon having reactivity with the SiH group. A compound obtained by reacting with an organic compound having at least two double bonds in one molecule is described, and the specification also exemplifies chain siloxane and cyclic siloxane, but high output Long-term reliability during use was not sufficient.

Patent Documents 4 and 5 describe in the specifications that a branched polysiloxane structure may be used as an example of an organopolysiloxane having two or more alkenyl groups in one molecule. However, the examples did not include any examples having a branched structure, and there were no descriptions of special effects caused by the structure, and the long-term reliability during high-power use was not sufficient. .

Patent No. 3241338 International Publication No. 2015/178475 JP 2017-55139 Publication JP2013-216827A International Publication No. 2012/039322

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 extensive research, the present inventors have discovered that (A) a compound consisting of the following components (A1) and/or (A2), (where (A1): a polyhedral structure polysiloxane compound having an alkenyl group ( (A2): Polyhedral structure polysiloxane modified product obtained by hydrosilylation reaction of α1) and a compound (α2) having a hydrosilyl group, (A2): a polyhedral structure polysiloxane compound (α1) having an alkenyl group and a hydrosilyl group-containing compound (α2). A polyhedral structure polysiloxane modified product obtained by hydrosilylation reaction of a compound (α2) having an organosilicon compound (α3) having one alkenyl group in one molecule. Polyhedral structure polysiloxane modified product characterized by having a structure derived from),
(B) A compound that does not contain a T unit siloxane structure and has two or more alkenyl groups in one molecule, and (C) a compound that has three or more hydrosilyl groups and/or alkenyl groups in one molecule and has the following formula ( A compound represented by 1) and containing a T unit structure, and (D) a hydrosilylation catalyst, and the content of component (C) is the sum of component (A), component (B), and component (C). By using a curable resin composition having a content of 10% by weight or more and 70% by weight or less when 100% by weight as an encapsulant, the long-term reliability of the resulting semiconductor device during high-power use is improved. This heading led to 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 composition shown in
That is, the present invention has the following configuration.

1). (A) Hydrosilylation reaction of a compound consisting of the following components (A1) and/or (A2), (A1) a polyhedral structure polysiloxane compound (α1) having an alkenyl group, and a compound (α2) having a hydrosilyl group. (A2) Polyhedral polysiloxane modified product obtained by hydrosilylation reaction of a polyhedral polysiloxane compound (α1) having an alkenyl group and a compound (α2) having a hydrosilyl group. A polyhedral structure polysiloxane modified product (B ) A compound having two or more alkenyl groups in one molecule that does not contain a siloxane structure of T units, and (C) a compound having three or more hydrosilyl groups and/or alkenyl groups in one molecule, and having the following formula (1) and contains a compound having a T unit structure, and (D) a hydrosilylation catalyst, and the content of component (C) is the sum of components (A), (B), and (C) to 100%. A curable resin composition which is 10% by weight or more and 70% by weight or less when expressed as weight%.

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 composition shown in

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

3). 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%; or The curable composition described in 2).

4). The curable composition according to items 1) to 3), wherein component (B) is a polysiloxane having two or more alkenyl groups in one molecule.

5). The curable composition according to any one of 1) to 4), wherein component (B) is a chain siloxane 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 compound containing an organic skeleton.

7). The curable composition according to any one of 1) to 6), wherein component (B) is a modified product of an organic component and siloxane.

8). A compound (β1) having at least two hydrosilyl groups in one molecule, a carbon-carbon double bond reactive with at least one hydrosilyl group in one molecule, and at least one polar group in a ring skeleton. A compound (E1) having at least three hydrosilyl groups in one molecule, which is a hydrosilylation reaction product with an organic compound (ε2) having a heterocyclic skeleton, is added to the components (A) to (D). In addition, the curable resin composition according to any one of 1) to 7), further comprising:

9). A compound (β1) having at least two hydrosilyl groups in one molecule, a carbon-carbon double bond reactive with at least one hydrosilyl group in one molecule, and at least one polar group in the ring skeleton. In addition to an organic compound (ε2) having a heterocyclic skeleton, one epoxy group and/or oxetanyl group and one carbon-carbon double bond having reactivity with a hydrosilyl group in one molecule. In addition to the components (A) to (D), it further contains a compound (E2) having at least three hydrosilyl groups in one molecule, which is a hydrosilylation reaction product with an organic compound (ε3) having The curable composition according to any one of 1) to 8).

10). A cured product of the curable composition according to any one of 1) to 9).

11). A sealant containing the curable composition according to any one of 1) to 10).

12). A semiconductor device using the curable composition according to any one of 1) to 11) 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 an optical 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.

<Polyhedral structure polysiloxane compound having alkenyl group (α1)>
The polyhedral structure polysiloxane compound (α1) having an alkenyl group in the present invention is not particularly limited as long as it is a polysiloxane having a polyhedral skeleton and having an alkenyl group in the molecule. Specifically, for example, the following formula [R ¹ SiO _3/2 ] _x [R ² SiO _3/2 ] _y
(x+y is an integer of 6 to 24; x is an integer of 1 or more; y is an integer of 0 or 1 or more; R ¹ is an alkenyl group or a group having an alkenyl group; R ² is any organic group, or An alkenyl group-containing polyhedral structure polysiloxane compound composed of siloxane units _represented by the following ⁽ groups linked to other polyhedral structure polysiloxanes) can be suitably used; SiO _3/2 ] _a1 [R ⁴ ₃ SiO-SiO _3/2 ] _a2 (2)
(a1+a2 is an integer of 6 to 24, a1 is an integer of 1 or more, a2 is an integer of 0 or 1 or more; A1 is an alkenyl group; R ³ is an alkyl group or an aryl group; R ⁴ is a hydrogen atom, an alkyl group , aryl group, or group linked to other polyhedral skeleton polysiloxane)
Preferred examples include alkenyl group-containing polyhedral structure polysiloxane compounds composed of siloxane units represented by the following.

Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a hexenyl group, and the like, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.

R ³ is an alkyl group or an aryl group. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, cyclohexyl group, cyclopentyl group, etc., and examples of the aryl group include aryl groups such as phenyl group and tolyl group. be done. In the present invention, R ³ is preferably a methyl group from the viewpoint of heat resistance and light resistance.

R ⁴ is a hydrogen atom, an alkyl group, an aryl group, or a group connected to another polyhedral skeleton polysiloxane. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, cyclohexyl group, cyclopentyl group, etc., and examples of the aryl group include aryl groups such as phenyl group and tolyl group. be done. In the present invention, R ⁴ is preferably a methyl group from the viewpoint of heat resistance and light resistance.

a1 is not particularly limited as long as it is an integer of 1 or more, but from the viewpoint of the handling properties of the compound and the physical properties of the obtained cured product, a1 is preferably 2 or more, and more preferably 3 or more. Further, a2 is not particularly limited as long as it is an integer of 0 or 1 or more.

The sum of a1 and a2 (=a1+a2) is an integer of 6 to 24, but from the viewpoint of the stability of the compound and the stability of the obtained cured product, it is preferably 6 to 12, and more preferably 6 to 10. preferable.

The method for synthesizing the component (α1) is not particularly limited, and can be synthesized using a known method. As a synthesis method, for example, a silane of R ⁵ SiX ^a3 ₃ (in the formula, R ⁵ represents the above-mentioned R ¹ and R ² , and X ^a3 represents a hydrolyzable functional group such as a halogen atom or an alkoxy group) Obtained by hydrolytic condensation reaction of compounds. Alternatively, a trisilanol compound having three silanol groups in the molecule is synthesized by a hydrolytic condensation reaction of R ⁵ SiX ^a3 ₃ , and then the ring is closed by reacting with the same or different trifunctional silane compound to form a polyhedron. Methods of synthesizing structural polysiloxanes are also known.

Other examples include a method in which tetraalkoxysilane such as tetraethoxysilane is hydrolyzed and condensed in the presence of a base such as quaternary ammonium hydroxide. In this synthesis method, a silicate having a polyhedral structure is obtained by a hydrolytic condensation reaction of a tetraalkoxysilane, and by further reacting the obtained silicate with a silylating agent such as an alkenyl group-containing silyl chloride. , it becomes possible to obtain a polyhedral structure polysiloxane in which Si atoms and alkenyl groups forming a polyhedral structure are bonded via siloxane bonds. In the present invention, it is also possible to obtain a similar polyhedral polysiloxane from a substance containing silica, such as silica or rice husk, instead of tetraalkoxylan.

<Compound having a hydrosilyl group (α2)>
The compound (α2) having a hydrosilyl group used in the present invention is not particularly limited as long as it has one or more hydrosilyl groups in the molecule, but the heat resistance and light resistance of the polyhedral structure polysiloxane modified product obtained From this point of view, a compound having two or more hydrosilyl groups in the molecule is preferable, and a compound having three or more hydrosilyl groups in the molecule is more preferable. Furthermore, from the viewpoint of transparency, heat resistance, and light resistance of the obtained modified polyhedral polysiloxane, a siloxane compound having a hydrosilyl group is preferable, and furthermore, a cyclic siloxane or a linear polysiloxane having a hydrosilyl group is preferable. It is preferable that In particular, from the viewpoint of heat resistance, light resistance, blue laser resistance, and gas barrier properties, cyclic siloxanes are preferred.

Linear polysiloxanes 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. Copolymer of methylphenylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units, polydimethylsiloxane whose terminals are blocked with dimethylhydrogensilyl groups, poly whose terminals are blocked with dimethylhydrogensilyl groups Examples include diphenylsiloxane and polymethylphenylsiloxane end-capped with dimethylhydrogensilyl groups.

In particular, as a linear polysiloxane having a hydrosilyl group, from the viewpoint of reactivity during modification and heat resistance and light resistance of the resulting cured product, polysiloxane whose molecular terminals are blocked with dimethylhydrogensilyl groups is recommended. , and furthermore, polydimethylsiloxane whose molecular terminals are capped with dimethylhydrogensilyl groups, polymethylphenylsiloxane whose molecular terminals are capped with dimethylhydrogensilyl groups, and polydiphenyl whose molecular terminals are capped with dimethylhydrogensilyl groups. Siloxane can be suitably used.

Examples of the cyclic siloxane having a hydrosilyl group include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 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, Examples include 9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclohexasiloxane. 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 can be preferably used.

These compounds having a hydrosilyl group, which are component (α2), may be used alone or in combination of two or more.

<Organosilicon compound (α3) having one alkenyl group in one molecule>
In the present invention, the organosilicon compound (α3) having one alkenyl group in one molecule reacts with the hydrosilyl group of the compound (α2) having a hydrosilyl group. By using the (α3) component, the elastic modulus of the obtained cured product can be lowered, and the cold shock resistance can be improved. In addition, it is possible to control the viscosity of the resulting composition, for example, suppressing aggregation of phosphor when used as an LED encapsulant, and improving handling properties when used as an LED encapsulant. becomes possible.

Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a hexenyl group, and the like, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.

The component (α3) in the present invention is not particularly limited as long as it is an organosilicon compound having one alkenyl group in one molecule, but it is preferable that the component (α3) contains at least one aryl group in one molecule. It is preferable from the viewpoint of properties and refractive index, and furthermore, it is more preferable from the viewpoint of heat resistance and light resistance that the aryl group is directly bonded to the silicon atom.

The component (α3) in the present invention is preferably silane or polysiloxane from the viewpoint of heat resistance and light resistance. When such a component (α3) is a silane having one alkenyl group in one molecule, specific examples include trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, triphenylvinylsilane, triethylvinylsilane, diethylphenylvinylsilane. , ethyldiphenylvinylsilane, allyltrimethylsilane, allyldimethylphenylsilane, allylmethyldiphenylsilane, allyltriphenylsilane, allyltriethylsilane, allyldiethylphenylsilane, allylethyldiphenylsilane and the like. Among them, preferred examples include trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, and triphenylvinylsilane from the viewpoint of heat resistance and light resistance, and dimethylphenylvinylsilane and methyldiphenylvinylsilane from the viewpoint of gas barrier properties and refractive index. , triphenylvinylsilane are mentioned as preferred examples.

When the component (α3) is a polysiloxane, examples thereof include a linear polysiloxane having one alkenyl group, a polysiloxane having one alkenyl group at the end of the molecule, and a cyclic siloxane having one alkenyl group. .

When the component (α3) is a polysiloxane with a linear structure having one alkenyl group, specific examples include polydimethylsiloxane whose ends are each capped with one dimethylvinylsilyl group and one trimethylsilyl group, and dimethylvinylsiloxane. Polymethylphenylsiloxane with one end capped with one silyl group and one trimethylsilyl group, polydiphenylsiloxane with one end capped with one dimethylvinylsilyl group and one trimethylsilyl group, and one end capped with dimethylvinylsilyl group and trimethylsilyl group. A copolymer of a dimethylsiloxane unit and a methylphenylsiloxane unit each of which is blocked with one terminal, and a copolymer of a dimethylsiloxane unit and a diphenylsiloxane unit whose terminals are each blocked with one dimethylvinylsilyl group and one trimethylsilyl group. Examples include a copolymer of a methylphenylsiloxane unit and a diphenylsiloxane unit each having one end capped with a dimethylvinylsilyl group and a trimethylsilyl group.

In the case of a polysiloxane having one alkenyl group at the end of the molecule, for example, polysiloxane whose end is capped with one dimethylvinylsilyl group and one trimethylsilyl group, SiO ₂ units, SiO _{3 /} Examples include polysiloxanes consisting of at least one siloxane unit selected from the group consisting of 2 units, SiO units _, and SiO _1/2 units, and one dimethylvinylsiloxane unit.

When the component (α3) is a cyclic siloxane having one alkenyl group, specific examples include 1-vinyl-1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 1-vinyl -3-phenyl-1,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1-vinyl-3,5-diphenyl-1,3,5,7,7-pentamethylcyclotetrasiloxane, 1 -vinyl-3,5,7-triphenyl-1,3,5,7-tetramethylcyclotetrasiloxane and the like.

These (α3) components, organosilicon compounds having one alkenyl group in one molecule, may be used alone or in combination of two or more.

<Modified polyhedral structure polysiloxane (A)>
As the modified polyhedral polysiloxane which is component (A) of the present invention, a polyhedral polysiloxane compound having an alkenyl group (α1) and a compound having a hydrosilyl group (α2) are combined in the presence of a hydrosilylation catalyst described below. It is a compound obtained by a hydrosilylation reaction, and includes a modified polyhedral polysiloxane (A1) having structures derived from (α1) and (α2).

In addition, in the presence of a hydrosilylation catalyst described below, a polyhedral structure polysiloxane compound (α1) having an alkenyl group and an organosilicon compound (α3) having one alkenyl group in one molecule are mixed into a compound having a hydrosilyl group (α2). Compound (A2) obtained by a hydrosilylation reaction with

The method for obtaining the modified polyhedral polysiloxane of the present invention is not particularly limited, and various methods can be used. Regarding the modified product consisting of three components α1 to α3, the (α1) component and the (α2) component may be reacted in advance, and then the (α3) component may be reacted, or the (α2) component and (α3) may be reacted in advance. After reacting the components, the (α1) component may be reacted, or the (α1) component and the (α3) component may be allowed to coexist and react with the (α2) component. After each reaction is completed, volatile unreacted components may be distilled off, for example, under reduced pressure and heating conditions, and may be used as a target product or an intermediate for the next step. In order to suppress the formation of a compound in which only the (α2) component and the (α3) component react and do not contain the (α1) component, the (α1) component and the (α2) component should be reacted, and the unreacted (α2) component should be reacted with the (α2) component. A preferred method is to react the component (α3) after distilling off the component. From the viewpoint of heat resistance, it is preferable to suppress the formation of a compound in which only the (α2) component and the (α3) component react, and which does not contain the (α1) component. From the viewpoint of industrial simplicity, it is preferable that the (α1) component and the (α3) component coexist and react with the (α2) component.

In the modified polyhedral polysiloxane thus obtained, a portion of the alkenyl group of the component (α1) used in the reaction may remain.

The amount of component (α2) added is preferably such that the number of hydrosilyl groups is 2.5 to 20 per one alkenyl group possessed by component (α1). When the amount added is small, gelation progresses due to the crosslinking reaction, so the handling properties of the modified polyhedral structure polysiloxane 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 such that the number of alkenyl groups is 0 to 0.6 per one hydrosilyl group possessed by component (α2). If the amount added is large, the heat resistance of the resulting cured product may decrease.

There is no particular limit to the amount of the hydrosilylation catalyst used in the synthesis of the modified polyhedral polysiloxane, but it is 10 ^-1 to 10 ^- per mole of the alkenyl group of the (α1) component and (α3) component used in the reaction. It is preferable to use it in a range of ¹⁰ moles. 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, which may cause coloring or reduce 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.

Another preferable example of the modified polyhedral polysiloxane which is the component (A) of the present invention has the formula [XR ⁶ ₂ SiO-SiO _3/2 ] _a3 [R ⁷ ₃ SiO-SiO _3/2 ] _a4
[a3+a4 is an integer of 6 to 24, a3 is an integer of 1 or more, a4 is an integer of 0 or 1 or more; R ⁶ is an alkyl group or an aryl group; R ⁷ is an alkenyl group, a hydrogen atom, an alkyl group, an aryl group , or a group connected to another polyhedral skeleton polysiloxane, X has a structure of either the following general formula (2) or general formula (3), and when there is a plurality of X, the group X has the structure of the general formula (2) ) or the structures of general formula (3) may be different, or the structures of general formula (2) or general formula (3) may be mixed.

{l is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or is bonded to the polyhedral polysiloxane via an alkylene chain. These are the parts that are connected to each other and may be the same or different. ;Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a moiety bonded to the polyhedral polysiloxane via an alkylene chain, and may be the same or different. However, at least one of Y or Z is a hydrogen atom, and at least one has the structure of the following general formula (4).

(o is an integer of 2 or more; ^R8 is a group containing an organosilicon compound); R is an alkyl group or an aryl group}]
It is characterized by being composed of siloxane units represented by

Here, from the viewpoint of heat resistance, light resistance, blue laser resistance, gas barrier property, etc., it is preferable to contain a structure represented by general formula (4).

Further, R ⁸ is not particularly limited as long as it is a group containing a silicon compound, but it is preferable from the viewpoint of gas barrier properties and refractive index that it contains at least one aryl group in one molecule. From the viewpoint of heat resistance and light resistance, it is preferable that the aryl group is directly bonded to the silicon atom.

The modified polyhedral structure polysiloxane, which is the component (A) in the present invention, can ensure compatibility with a siloxane compound or an organic compound, specifically, the component (B) and the component (C) described below. Furthermore, for example, since it contains a hydrosilyl group in the molecule, it becomes possible to react with various alkenyl-containing compounds. Specifically, by reacting with the below-mentioned compounds (B), (C) and/or (E), it is possible to obtain a cured product with excellent heat resistance, light resistance, blue laser resistance, gas barrier properties, etc. can.

The modified polyhedral polysiloxane which is component (A) in the present invention can also be made into a liquid state at a temperature of 20°C. It is preferable to make the polyhedral structure polysiloxane modified product into a liquid form because it provides excellent handling properties.

In addition, from the viewpoint of the strength, heat resistance, light resistance, and gas barrier properties of the cured product obtained, the modified polyhedral structure polysiloxane which is the component (A) in the present invention has an average of three or more hydrosilyl groups in the molecule. It is preferable to contain.

<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(PΑ3u ₃ ) ₄ ; platinum-phosphite complex, e.g., Pt [P(OPh) ₃ ] ₄ , Pt[P(OΑ3u) ₃ ] ₄ (wherein, Me is a methyl group, A3u is a butyl group, Vi is a vinyl group, Ph is a phenyl group, and n and m are integers. ), Pt(α1cα1c) ₂ , also the platinum-hydrocarbon complexes described in U.S. Pat. Also mentioned are platinum alcoholate catalysts.

Examples of _catalysts other than platinum compounds include RhCl( _PPh3 ) ₃ , _RhCl3 , Rh/ _A1l2O3 , _RuCl3 , _IrCl3 , _FeCl3 , _{A11Cl3 , PdCl2.2H2O} , _NiCl2 , 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(α1cα1c) 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 not particularly limited as long as it has two or more alkenyl groups in one molecule (excluding siloxane structures containing T units).

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 (5) or (6). and an organic compound having two or more alkenyl groups in one molecule.

(In the formula, R ₉ to R ₁₁ represent a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and R ₉ to R ₁₁ may be different or the same. Also, R ₉ to R ₁₁ At least two of them are alkenyl groups.)

(In the formula, R ₁₂ to R ₁₅ represent a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and R ₁₂ to R ₁₅ may be different or the same. Also, R ₁₂ to R ₁₅ 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 (5) or (6), 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.

As a combination of an organic component and an inorganic component, for example, a compound having at least two hydrosilyl groups in one molecule (β1) and the component (B2) may be reacted in the presence of a hydrosilylation catalyst (α4). Examples include modified forms. Examples of the combination of inorganic components include a modified product obtained by reacting component (β1) with component (B1) in the presence of a hydrosilylation catalyst (α4).

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

<Compound having at least two hydrosilyl groups in one molecule (β1)>
The compound (β1) 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 and does not have a siloxane structure containing a T unit. . Examples include linear siloxanes, cyclic 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 the silphenylene compound include 1,4-bis(dimethylsilyl)benzene, 1,4-bis(diphenylsilyl)benzene, and 1,4-bis(methylphenylsilyl)benzene.

These (β1) components, compounds having at least two hydrosilyl groups in one molecule, 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 that satisfies 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 an average composition shown in .

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 the component (C) as a whole may be 500 or more, but is more preferably 1,000 or more and 20,000 or less, and even more preferably 1,500 or more and 10,000 or less. 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 10% by weight or more and 80% by weight or less, and 20% by weight when the total of components (A), (B), and (C) is 100% by weight. % or more and 75% by weight or less, and even more preferably 30% 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.

<Compound (E) having at least three hydrosilyl groups in one molecule>
Component (E) of the present invention comprises the aforementioned compound (β1) having at least two hydrosilyl groups in one molecule, and a carbon-carbon double bond having reactivity with at least one hydrosilyl group in one molecule. (alkenyl group) and an organic compound (ε2) having a heterocyclic skeleton having at least one polar group in the ring skeleton in the presence of a hydrosilylation catalyst (D). (E1) or
A compound (β1) having at least two hydrosilyl groups in one molecule, a carbon-carbon double bond (alkenyl group) reactive with at least one hydrosilyl group in one molecule, and at least one polar An organic compound having a heterocyclic skeleton having a group in the ring skeleton (ε2), one epoxy group and/or oxetanyl group in one molecule, and a carbon-carbon double bond having reactivity with a hydrosilyl group. This is a compound (E2) obtained by subjecting one organic compound (ε3) to a hydrosilylation reaction in the presence of a hydrosilylation catalyst (D).

The method for obtaining a compound having at least three hydrosilyl groups in one molecule is not particularly limited, but as an example, when adding the (β1) component and the (ε2) component, the (β1) component and the (ε2) component are added. ) components and then distilling off volatile unreacted components under reduced pressure and heating conditions. In the thus obtained component (E), a portion of the alkenyl group of the component (ε2) used in the reaction may remain.

The amount of component (β1) added is such that the number of hydrosilyl groups in component (β1) is preferably 1.1 to 20, more preferably 1.3 to 15, per one alkenyl group in component (ε2). , 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 (ε3) added is preferably 0 to 20, more preferably 0 to 15, and even more preferably 0 to 10 per alkenyl group of component (ε2). If the amount added is too large, the heat resistance of the cured product may be adversely affected.

By adding component (E), the adhesive strength of the resin to the member is improved, and as a result, the effect of improving the luminous flux maintenance rate (sulfidation resistance) in an environment where a sulfur-based corrosive gas is present can be obtained.

The amount of component (E) added is preferably from 5% by weight to 100% by weight, more preferably from 10 to 60% by weight, when the amount of component (A) added is 100% by weight. If the amount of component (E) added is less than 5% by weight relative to the amount of component (A) added, there is a risk that the effect of improving sulfidation resistance will not be sufficiently achieved. On the other hand, if the amount of component (E) added is more than 100% by weight relative to the amount of component (A) added, the hardness of the obtained cured product becomes too high, resulting in poor long-term reliability during high-power use. There is a risk that sexual performance may decrease.

There is no particular restriction on the amount of the hydrosilylation catalyst used in the synthesis of the modified organopolysiloxane, but it is used in the range of 10 ^-1 to 10 ^-10 mol per mol of the alkenyl group of the (ε2) component 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 light with a short wavelength, which may cause coloring, and the light resistance of the resulting cured product may decrease. There is also a risk that things may foam. 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.

<An organic compound 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 (ε2 )＞
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 (ε2) 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 (7) or (8) The organic compounds represented are preferred.

(In the formula, R ₁₆ to R ₁₈ represent a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and R ₁₆ to R ₁₈ may be different or the same. Also, R ₁₆ to R ₁₈ At least one of them is an alkenyl group.)

(In the formula, R ₁₉ to R ₂₂ represent a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and R ₁₉ to R ₂₂ may be different or the same. Also, R ₁₉ to R ₂₂ At least one of them is an alkenyl group.)
(ε2) The component may have a functional group other than the alkenyl group and the heterocyclic skeleton in its skeleton.

The (ε2) component is represented by the above general formula (7) or (8), and is expressed in one molecule from the viewpoint of adhesion between the curable composition and the base material when the curable composition is cured. Preferably, the compound contains one or more alkenyl groups, and from the viewpoint of the balance between heat resistance and light resistance, triallyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monoglycidyl isocyanurate, monoallyl isocyanurate, etc. Nurate, monoallyl dimethyl isocyanurate, monoallyl diglycidyl isocyanurate, tetraallyl glycoluril, diallyl diglycidyl glycoluril, triallyl monoglycidyl glycoluril, monoallyl triglycidyl glycoluril, diallyl dimethyl glycoluril, triallyl dimethyl glycoluril , monoallyltrimethylglycoluril is preferably used. These may be used alone or in combination of two or more.

<Organic compound (ε3) having one epoxy group or oxetanyl group and one carbon-carbon double bond reactive with a hydrosilyl group in one molecule>
The compound (ε3) 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.

As the epoxy group, the following general formula (9) or (10) is used.

(However, R ₂₃ is a divalent organic group with 1 to 10 carbon atoms and 0 to 2 oxygen atoms, and R ₂₄ to R ₂₆ are monovalent organic groups with 1 to 50 carbon atoms or hydrogen atoms. , R ₂₄ to R ₂₆ may be different or the same)

(However, R ₂₇ is a divalent organic group with 1 to 10 carbon atoms and 0 to 2 oxygen atoms, and R ₂₈ to R ₂₉ are monovalent organic groups with 1 to 50 carbon atoms or hydrogen atoms. , R ₂₈ to R ₂₉ may be different or the same).

As the oxetanyl group, the following general formula (11) is used.

(However, R ₃₀ is a divalent organic group having 1 to 10 carbon atoms and 0 to 2 oxygen atoms, and R ₃₁ is a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom.) It will be done.

As the compound (ε3), from the viewpoint of availability, allyl glycidyl ether, vinylcyclohexene oxide, and 3-ethyl-3-allyloxymethyl oxetane are preferable. The various compounds (ε3) described above may be used alone or in combination of two or more.

<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.

The amount of the silane coupling agent added is preferably 0.05 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the curable composition. If the amount added is small, the effect of improving adhesion will not be exhibited, and if the amount added is too large, it may have an adverse effect on the physical properties of the cured product.

Moreover, in order to enhance the effect of the adhesion promoter, a known adhesion promoter can also be used. Adhesion promoters include, but are not limited to, epoxy-containing compounds, epoxy resins, boronate ester compounds, organoaluminum compounds, and organotitanium compounds.

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 400 MHz 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)
1459 g of tetraethoxysilane was added to 1803 g of a 48% choline aqueous solution (trimethyl-2hydroxyethylammonium hydroxide aqueous solution), and the mixture was vigorously stirred at room temperature for 2 hours. When the reaction system generated heat and became a homogeneous solution, stirring was slowed down and the reaction was allowed to proceed for an additional 12 hours. Next, 1400 mL of methanol was added to the solid matter produced in the reaction system to form a homogeneous solution.

While vigorously stirring a solution of 1149 g of dimethylvinylchlorosilane, 830 g of trimethylsilyl chloride, and 1400 mL of hexane, the methanol solution was slowly added dropwise. After the dropwise addition was completed, the reaction was allowed to proceed for 1 hour, and then the organic layer was extracted and concentrated to obtain a solid substance. Next, the generated solid is washed by vigorous stirring in methanol and filtered to obtain tetrakis, which is an alkenyl group-containing polysiloxane compound having 16 Si atoms and 4 vinyl groups. 760 g of (vinyldimethylsiloxy)tetrakis(trimethylsiloxy)octasilsesquioxane (Fw=1175.8) was obtained as a white solid.

(Manufacturing example 2)
30.0 g of the polysiloxane compound having an alkenyl group obtained in Production Example 1 (corresponding to (α1)) was dissolved in 123.0 g of toluene, and 31.5 g of methyldiphenylvinylsilane (corresponding to (α3)) and platinum vinyl were dissolved. 1.46 μL of a xylene solution of a siloxane complex (platinum vinyl siloxane complex containing 3 wt% platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) was added. The solution thus obtained was mixed with 24.6 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (corresponding to (α2)) and 24.6 g of toluene. was slowly added dropwise to the solution and reacted at 105°C for 2 hours. After the reaction, 2.8 μl of ethynylcyclohexanol and 0.65 μl of dimethyl maleate were added, and toluene and unreacted components were distilled off to obtain 80.8 g of a liquid modified polysiloxane (hydrosilyl number 1.8 mol/ kg: (A2) component) obtained.

(Manufacturing example 3)
Uniformly mix 500 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (corresponding to (β1)) and 1800 g of toluene, and stir at 105°C under a nitrogen atmosphere. did. 180 g of triallyl isocyanurate (equivalent to (ε2)), 300 g of allyl glycidyl ether (equivalent to (ε3)), 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 (E2)) was obtained.

(Manufacturing example 4)
90 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (corresponding to (β1)) and 40 g of toluene were mixed uniformly and stirred at 105°C under a nitrogen atmosphere. did. 100 g of diallyl monomethyl isocyanurate (equivalent to (ε2)), 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 6.00 mol/kg (component (E1)) was obtained.

(Manufacturing example 5)
20 g of the polyhedral polysiloxane compound obtained in Production Example 1 and 4.72 μL of a xylene solution of a platinum vinyl siloxane complex (manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) were dissolved in 80 g of toluene. The solution thus obtained was slowly added dropwise to a solution of 37.88 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane dissolved in 39 g of toluene. The mixture was reacted at 95° C. for 3 hours, and then cooled to room temperature. After the reaction, toluene and excess 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane were distilled off to obtain 33 g of a liquid modified polysiloxane. (Hydrosilyl valence 4.5 mol/kg: component (A1)) was obtained.

(Example 1)
To 2.45 g of the reaction product obtained in Production Example 2, 1.48 g of diallyl monomethyl isocyanurate, 2.03 g of dimethylvinylsilyl end-blocked polymethylphenylsiloxane (number average molecular weight in terms of polystyrene measured by GPC = 2800), 4.04 g of a compound consisting of phenylsilsesquioxane units and dimethyl hydrogen siloxy units (component (C)), xylene solution of platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan) , Pt-VTSC-3 A curable composition was prepared by sequentially performing 3 minutes of degassing, 3 minutes of defoaming, and 3 minutes of stirring.

Separately, a 3030 reflector manufactured by SDI (product number: SDI4G62) was prepared, in which one 30 mil x 43 mil square blue LED chip (product number: ES-EMDBF30C) manufactured by EPISTAR was 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 a current of 600 mA was applied for 30 minutes in an environment of 25°C and 50% RH, and then the current was not applied for 30 minutes. An ON-OFF energization test was conducted using the process of "no" as one cycle. The junction temperature during energization was within 170°C±10°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 (number of cycles) 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 12, 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.

Table 1 shows the compounding composition, gas barrier test results, and life cycle numbers of Examples and Comparative Examples.

Comparative Examples 1 to 5 lack reliability because they do not contain component (C). Regarding Comparative Example 6, since the component (A) was not included, the gas barrier properties were poor. Comparative Example 7 contains a component (Other-1) having a siloxane skeleton containing a T unit structure, but the values of a and b are outside the range defined as component (C), and is poor in reliability. Regarding Comparative Examples 8 and 9, a siloxane component (Other-2 or 3) not containing a T unit structure was added, and the reliability was poor. Regarding Comparative Example 10, since the component (A) was not included, the gas barrier property was poor.

As shown in Table 1, the optical semiconductor device using the curable composition of the present invention had both good gas barrier properties and long-term reliability at high output compared to the comparative example.

The abbreviations used in the table are as follows.
(B) Component (B-1): Diallyl monomethyl isocyanurate (B-2): Dimethylvinylsilyl end-blocked polymethylphenylsiloxane (number average molecular weight in terms of polystyrene by GPC measurement = 2800)
Component (C) Consists of the structural units shown below, and has a number average molecular weight determined by GPC, a T unit ratio, a ratio of Ph groups in RY 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 (D) consisting of phenylsilsesquioxane units and dimethylvinylsiloxy units Component (D-1): Xylene solution of platinum vinyl siloxane complex (platinum vinyl siloxane containing 3 wt% as platinum) Complex, 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 RY 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 (8)

(A) a compound consisting of the following components (A1) and/or (A2);
(A1) A polyhedral polysiloxane modified product obtained by hydrosilylation reaction of a polyhedral polysiloxane compound (α1) having an alkenyl group and a compound (α2) having a hydrosilyl group,
(A2) A polyhedral polysiloxane modified product obtained by hydrosilylation reaction of a polyhedral polysiloxane compound (α1) having an alkenyl group and a compound (α2) having a hydrosilyl group, the polyhedral polysiloxane The modified product includes a polyhedral structure polysiloxane modified product characterized by having a structure derived from an organosilicon compound (α3) having one alkenyl group in one molecule,
(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 the following formula (1), and containing a T unit structure;
(D) a hydrosilylation catalyst;
The content of component (C) is 10% by weight or more and 70% by weight or less when the sum of components (A), (B), and (C) is 100% by weight, and the content of component (C) is 10% by weight or more and 70% by weight or less, and B) is a curable resin composition characterized in that it is an organic compound represented by general formula (5) or (6) .
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 ~50 monovalent organic groups or hydrogen atoms, R ₉ to R ₁₁ may be different or the same, and at least two of R ₉ to R ₁₁ are alkenyl groups. General formula ( 6 ₎ R ₁₂ to R ₁₅ represent a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and R ₁₂ to R ₁₅ may _be different or the same ; At least two are alkenyl groups.)
The curable composition according to 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%. Composition. 3. The component (C) according to claim 1 or 2, wherein the component (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%. Curable composition. A compound (β1) having at least two hydrosilyl groups in one molecule, a carbon-carbon double bond reactive with at least one hydrosilyl group in one molecule, and at least one polar group in a ring skeleton. A compound (E1) having at least three hydrosilyl groups in one molecule, which is a hydrosilylation reaction product with an organic compound (ε2) having a heterocyclic skeleton, is added to the components (A) to (D). In addition, the curable resin composition according to any one of claims 1 to 3 , further comprising: A compound (β1) having at least two hydrosilyl groups in one molecule, a carbon-carbon double bond reactive with at least one hydrosilyl group in one molecule, and at least one polar group in the ring skeleton. In addition to an organic compound (ε2) having a heterocyclic skeleton, one epoxy group and/or oxetanyl group and one carbon-carbon double bond having reactivity with a hydrosilyl group in one molecule. Claim 1 further comprising, in addition to the components (A) to (D), a compound (E2) having at least three hydrosilyl groups in one molecule, which is a hydrosilylation reaction product with an organic compound (ε3) having - 4. The curable composition according to item 1. A cured product of the curable composition according to any one of claims 1 to 5 . A sealant containing the curable composition according to any one of claims 1 to 5 . A semiconductor device using the curable composition according to any one of claims 1 to 5 as a sealant.