JP5695334B2 - Curable resin composition for semiconductor package - Google Patents

Description

  The present invention relates to a resin composition for a semiconductor package, and more specifically, a resin composition for a semiconductor package, which has good moldability and high light resistance and heat resistance, and is produced using the same. It relates to semiconductors.

Conventionally, semiconductors having various types of packages have been proposed. In particular, among these, the light resistance required for the package is that in which the semiconductor is a light emitting diode.
Conventionally, as a light emitting diode, a surface-mount type using a package has been manufactured, but as a material for the package, ceramic, polyamide resin, polyester resin or the like is mainly used (for example, Patent Document 1). .

  However, when ceramic is used as a packaging material, ceramic molding processability is not excellent, and industrial applicability is generally narrow. In addition, for the manufacture of light emitting diodes, it is common to fill a package with a sealing agent (mold material) such as an epoxy resin. In that case, the linear expansion coefficient between the ceramic and the sealing agent such as an epoxy resin Therefore, there is also a problem that the reliability of the light emitting diode is lowered due to the occurrence of cracks in the sealant due to thermal stress or the like.

  When a polyamide resin is used as a packaging material, there is a problem that the polyamide resin is colored due to light resistance deterioration, and therefore, when used for a long time, there is a problem that the reflectance on the package surface is lowered and the luminance of the light emitting diode is lowered. . In addition, there is also a problem that the reliability of the light emitting diode is lowered due to a decrease in adhesiveness with the sealing agent due to light resistance deterioration of the polyamide resin. When a polyester resin is used as a packaging material, the heat resistance is not sufficient, so that there is a problem that the solder reflow resistance is poor and the industrial applicability is limited.

JP2007-227925A

  Accordingly, an object of the present invention is to provide a curable resin composition for a light emitting diode package having good moldability and high light resistance and heat resistance.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have made the present invention. The present invention has the following configuration.

  1). For the polyhedral polysiloxane compound (a) containing an alkenyl group and / or a hydrosilyl group, the compound (b) having a hydrosilyl group and / or alkenyl group capable of hydrosilylation reaction with the component (a) is modified. A curable resin composition for a semiconductor package, comprising the polyhedral polysiloxane modified product (A) obtained as a required component.

  2). (A) The curable resin composition for semiconductor packages according to 1), wherein the component is liquid at a temperature of 20 ° C.

  3). The curable resin composition for a semiconductor package according to 1) or 2), wherein the compound (b) is a cyclic siloxane containing a hydrosilyl group and / or an alkenyl group.

  4). The curable resin composition for a semiconductor package according to 1) or 2), wherein the compound (b) is a linear siloxane containing a hydrosilyl group and / or an alkenyl group at the molecular end.

  5). The curable resin composition for a semiconductor package according to any one of 1) to 4), wherein the compound (b) has at least three hydrosilyl groups or alkenyl groups in the molecule.

  6). The number of hydrogen atoms and / or alkenyl groups directly bonded to the Si atom of the compound (b) having a hydrosilyl group and / or alkenyl group is such that the polyhedral polysiloxane compound (a) has an alkenyl group and / or hydrosilyl group. It is modified by adding 2.5 to 20 hydrogen atoms per alkenyl group and / or Si atom directly connected to the Si atom, and is obtained by distilling off the unreacted compound (b). The curable resin composition for semiconductor packages according to any one of 1) to 5).

7). (A) component is
[XR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ¹ is an alkyl group or an aryl group; R ² is an alkyl group, an aryl group, an alkenyl group, a hydrogen atom Or a group linked to another polyhedral polysiloxane; X has a structure represented by the following general formula (1) or general formula (2), and when there are a plurality of X, the general formula (1 ) Or the structure of the general formula (2) may be different, or the structure of the general formula (1) or the general formula (2) 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 bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain Yes, and may be the same or different, provided that at least one of Y or Z is a hydrogen atom or an alkenyl group; R is an alkyl group or an aryl group; 1) or the structure of formula (2) may be different, or the structure of formula (1) or formula (2) may be mixed. Semiconductor package curable resin composition according to any one of).

8). Formula [AR ¹ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group and / or a hydrogen atom provided that at least one is an alkenyl group;. R ¹ is An alkyl group or an aryl group; R ⁴ is a substituent other than an alkenyl group and a hydrogen atom, for example, an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane or siloxane compound) In the polyhedral polysiloxane compound (a) composed of siloxane units, the compound (b) having a hydrosilyl group is within a range of 2.5 to 20 hydrogen atoms directly bonded to Si atoms per alkenyl group. 1) to 7 obtained by adding an excess amount to modify by hydrosilylation reaction and distilling off compound (b) having an unreacted hydrosilyl group. ) The curable resin composition for semiconductor packages according to any one of the above.

9). Formula [BR ¹ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is zero or an integer of 1 or more; B is alkenyl and / or hydrogen atom, provided that at least one is hydrogen atom;. R ¹ is An alkyl group or an aryl group; R ⁴ is a substituent other than an alkenyl group and a hydrogen atom, for example, an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane or siloxane compound) The range in which the polyhedral polysiloxane compound (a) composed of siloxane units has 2.5 to 20 alkenyl groups per hydrogen atom directly bonded to the Si atom of the compound (b) having an alkenyl group. 1) to 7), wherein the compound (b) is obtained by distilling off the unreacted alkenyl group-containing compound (b) by adding an excessive amount of The curable resin composition for semiconductor packages according to any one of the above.

  10). The curable resin composition for a semiconductor package according to any one of 1) to 9), further comprising a curing agent (B).

  11). The curable resin composition for a semiconductor package according to any one of 1) to 10), which further comprises a hydrosilylation catalyst (C).

  12). The curable resin composition for a semiconductor package according to any one of 1) to 11), wherein the semiconductor is a light emitting diode.

  13). The curable resin composition for a semiconductor package according to any one of 1) to 12), which contains an inorganic filler (D).

  14). The curable resin composition for a semiconductor package according to 13), wherein the inorganic filler (D) is titanium oxide and / or silica.

  15). The curable resin composition for a semiconductor package according to 13) or 14), wherein the content of the inorganic filler (D) is 70 to 90% by weight of the whole composition.

  16). A curable resin composition for a semiconductor package, wherein the curable resin composition for a semiconductor package according to any one of 1) to 15) is B-staged.

  17). A semiconductor package, wherein the curable resin composition for a semiconductor package according to any one of 1) to 16) is molded.

  18). The curable resin composition for a semiconductor package according to any one of 1) to 16), which has fluidity at a temperature of 150 ° C. or less and has a gelation time at 150 ° C. of 60 seconds or less. A semiconductor package, wherein a resin composition is molded by transfer molding.

  19). A semiconductor package characterized by molding the curable resin composition for a semiconductor package according to any one of 1) to 16), wherein the semiconductor is a light-emitting diode, and the package emits light from the light-emitting diode. A semiconductor package designed to receive light.

  20). The semiconductor manufactured using the curable resin composition for semiconductor packages in any one of 1) -16).

  Since the resin composition of the present invention has good moldability and high light resistance and heat resistance, when used as a semiconductor package, an industrially highly practical and reliable semiconductor is produced. be able to.

It is an example of the package of a light emitting diode.

  The present invention is described in detail below.

<Modified polyhedral polysiloxane>
The polyhedral polysiloxane-modified product in the present invention is a polyhedral polysiloxane compound (a) containing an alkenyl group and / or a hydrosilyl group, a hydrosilyl group capable of hydrosilylation reaction with the component (a) and / or It can be obtained by modifying the compound (b) having an alkenyl group. In the present invention, the modified polyhedral polysiloxane is not gelled at the time of synthesizing the modified product, and the resulting polyhedral polysiloxane modified product can be made liquid at a temperature of 20 ° C. from the viewpoint of handling properties and molding processability.

  As the modified polyhedral polysiloxane in the present invention, a modified product obtained by modifying the polyhedral polysiloxane compound (a) containing an alkenyl group with the compound (b) having a hydrosilyl group is produced. From the viewpoints of ease and productivity.

The preferred polyhedral polysiloxane-modified product in the present invention will be specifically described below. A preferred polyhedral polysiloxane modified product in the present invention is characterized in that [XR ¹ ₂ SiO—SiO _3/2 ] is an essential unit as a siloxane unit having a reactive functional group, and if necessary, An arbitrary siloxane unit [R ² ₃ SiO—SiO _3/2 ] as a physical property adjusting unit is contained as a structural unit, and the following formula:
[XR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; X is a group represented by the general formula (1) or (2); R ¹ is an alkyl group or aryl R ² is an alkyl group, an aryl group, an alkenyl group, a hydrogen atom, or a group connected to another polyhedral polysiloxane, and a modified polyhedral polysiloxane composed of a siloxane unit represented by Is exemplified. Here, a is an average of 1 or more, preferably 2 or more, and b is 0 or an integer of 1 or more. a + b is an integer of 6 to 24, preferably an integer of 6 to 12.

(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 bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain Yes, it may be the same or different, provided that at least one of Y or Z is an alkenyl group or a hydrogen atom; R is an alkyl group or an aryl group; 1) or the structure of formula (2) may be different, and the structure of formula (1) or formula (2) may be mixed))
Hereinafter, the siloxane unit [XR ¹ ₂ SiO—SiO _3/2 ] having a reactive functional group will be described.

The siloxane unit having a functional group capable of reacting, for example, causes a crosslinking reaction with a curing agent by a hydrosilylation reaction in the presence of a hydrosilylation catalyst described later, or in the presence of a thermal curing initiator or a photocuring initiator. It is a unit that plays a role of crosslinking and curing.
Here, the group X having a preferable reactive functional group is not particularly limited as long as it is a group represented by any one of the general formula (1) and the general formula (2), but m is 1 to 7. And n is preferably an integer of 2 to 4.

(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 bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain Yes, it may be the same or different, provided that at least one of Y or Z is an alkenyl group or a hydrogen atom; R is an alkyl group or an aryl group; The structure of 1) or formula (2) may be different, or the structure of formula (1) or formula (2) may be mixed).

As R ¹ in the siloxane unit having a reactive functional group, a substituent having substantially no reactivity, specifically, for example, an alkyl group or an aryl group can be used.
The siloxane unit having a functional group capable of reacting in the present invention preferably contains, on average, two or more siloxane units constituting the polyhedral skeleton. That is, a in the general formula (1) is preferably 2 or more. When there are few siloxane units containing the reactive functional group to contain, sclerosis | hardenability will become inadequate and there exists a possibility that the intensity | strength of the hardened | cured material obtained may fall.

Next, an arbitrary siloxane unit [R ² ₃ SiO—SiO _3/2 ] will be described.
This siloxane unit is a unit for adjusting the physical properties of the modified polyhedral polysiloxane and the resulting cured product in the present invention. Since the present siloxane unit does not substantially contain a reactive substituent, it is possible to adjust the crosslinking density, improve the film property, leveling property, improve brittleness, and the like.

As R ² in the present siloxane unit, an alkyl group, an aryl group, an alkenyl group, a hydrogen atom, or a group linked to another polyhedral polysiloxane can be preferably used. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like. May be replaced. Specific examples of the alkyl group partially substituted with a substituent having substantially no reactivity include, for example, a polysiloxanylalkyl group. Leveling properties and film properties, and a curing agent described later and Compatibility with a curing initiator can be imparted, and the properties of the compound can be made liquid.

  Examples of the group linked to the other polyhedral polysiloxane include groups linked via polymer components such as polysiloxane, poly (meth) acrylate, and polyisobutylene.

<Method for producing modified polyhedral polysiloxane>
The manufacturing method of the polyhedral polysiloxane modified body in the present invention will be described.
First, the polyhedral siloxane compound (a) will be described.

Examples of the synthesis method of the polyhedral siloxane compound (a) containing the alkenyl group and / or hydrosilyl group include R ³ SiX ^a ₃ (wherein R ³ represents an alkenyl group or a hydrogen atom, and Xa represents (Representing a hydrolyzable functional group such as a halogen atom or an alkoxy group)).

Alternatively, after synthesizing a trisilanol compound having three silanol groups in the molecule by hydrolysis condensation reaction of R ³ SiX ^a _3, the ring is closed by reacting the same or different trifunctional silane compounds. The method of doing is also known. Furthermore, a partial cleavage polyhedral polysiloxane can be synthesized by reacting the trisilanol compound with a monofunctional silane and / or a bifunctional silane.

  As another method for synthesizing the polyhedral siloxane compound (a), for example, a tetraalkoxysilane such as tetraethoxysilane is replaced with a quaternary ammonium hydroxy such as trimethyl (2-hydroxyethyl) ammonium hydroxide or tetramethylammonium hydroxide. A silicate having a polyhedral structure is obtained by a hydrolysis condensation reaction in the presence of a base such as a hydrogen atom, and the obtained silicate is further reacted with a silylating agent such as a silyl chloride having an alkenyl group and / or a hydrosilyl group. Can be synthesized. In the present invention, the same polyhedral polysiloxane can be obtained from a substance containing silica such as silica or rice husk instead of tetraalkoxylane.

As a preferable example of the polyhedral polysiloxane compound (a) in the present invention, specifically, for example, a polyhedral polysiloxane compound having an alkenyl group represented by the following formula:
[AR ¹ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group and / or a hydrogen atom, provided that at least one is an alkenyl group; Group or aryl group; R ⁴ is a substituent other than an alkenyl group and a hydrogen atom, for example, an alkyl group, an aryl group, or a group linked to other polyhedral polysiloxane or siloxane compound).

  When such a component (a) is used, by using a compound having a hydrosilyl group as the component (b), for example, to obtain a modified polyhedral polysiloxane by a hydrosilylation reaction in the presence of a hydrosilylation catalyst described later. Can do. At this time, all the alkenyl groups of the polyhedral siloxane compound (a) do not need to react and may partially remain. A plurality of polyhedral polysiloxane compounds (a) and a compound (b) having a plurality of hydrosilyl groups may react.

As other preferable examples of the polyhedral polysiloxane compound (a) in the present invention, specifically, for example,
[BR ¹ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; B is alkenyl and / or hydrogen atom, provided that at least one is hydrogen atom;. R ¹ is An alkyl group or an aryl group; R ⁴ is a substituent other than an alkenyl group and a hydrogen atom, for example, an alkyl group, an aryl group, or a group linked to another polyhedral polysiloxane or siloxane compound) .

  When such a component (a) is used, by using a compound having an alkenyl group as the component (b), for example, a modified polyhedral polysiloxane is obtained by a hydrosilylation reaction in the presence of a hydrosilylation catalyst described later. Can do. At this time, all the hydrogen atoms of the polyhedral siloxane compound (a) do not need to react and may partially remain. A plurality of polyhedral polysiloxane compounds (a) and a compound (b) having a plurality of alkenyl groups may react.

  Next, the compound (b) having a hydrosilyl group and / or an alkenyl group will be described.

  The compound having a hydrosilyl group has a hydrosilyl group (a hydrogen atom directly bonded to an Si atom) and reacts with the alkenyl group of the polyhedral siloxane compound (a) to form a new polyhedral polysiloxane molecule. It is a component for introducing a group having a reactive functional group.

  As a compound having a preferred hydrosilyl group in the present invention, specifically, for example, a compound having a hydrosilyl group (a hydrogen atom directly bonded to a Si atom) reacts with an alkenyl group of the polyhedral siloxane compound (a). And those that form a reactive functional group X represented by any one of the following general formula (1) and general formula (2).

(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 bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain Each of which may be the same or different, provided that at least one of Y or Z is a hydrogen atom; R is an alkyl group or an aryl group; The structure of the formula (2) may be different, and the structure of the formula (1) or the formula (2) may be mixed).

  Preferred examples of the compound having a hydrosilyl group include a hydrosilyl group-containing siloxane compound, specifically, for example, a linear polysiloxane having a hydrosilyl group at both ends, a cyclic siloxane having a hydrosilyl group, and the like. Furthermore, a cyclic siloxane containing a hydrosilyl group is preferable from the viewpoints of industrial availability and good reactivity when reacted, and excellent cured blue laser resistance of the obtained cured product. These compounds having a hydrosilyl group may be used alone or in combination of two or more.

  Specific examples of the linear polysiloxane having hydrosilyl groups at both ends include poly or oligosiloxanes whose ends are blocked with dimethylhydrogensilyl groups, tetramethyldisiloxane, hexamethyltrisiloxane and the like. The

  As cyclic siloxanes containing hydrosilyl groups, 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-trihydro Gen-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexahydrogen Examples include -1,3,5,7,9,11-hexamethylcyclosiloxane.

  The amount of the hydrosilyl group-containing compound (b), in particular, the hydrosilyl group-containing siloxane compound is such that the number of hydrogen atoms directly bonded to Si atoms is one per alkenyl group in the polyhedral polysiloxane compound (a). Although it is preferable to use so that it may become 2.5-20, it is dependent on a compound. When the addition amount is small, gelation occurs due to a crosslinking reaction, resulting in a modified polysiloxane having poor handling properties. When it is too large, the physical properties of the cured product may be adversely affected. Furthermore, in order to allow an excessive amount of the hydrosilyl group-containing siloxane compound to exist, it is preferable to remove the unreacted hydrosilyl group-containing siloxane compound, for example, under reduced pressure and heating conditions.

The compound (b) having an alkenyl group has an alkenyl group, and reacts with the hydrosilyl group of the polyhedral siloxane compound (a) to introduce a new functional group into the polyhedral polysiloxane molecule. It is an ingredient.
Preferred examples of the compound (b) having an alkenyl group include an alkenyl group-containing siloxane compound, specifically, for example, a linear polysiloxane having an alkenyl group at both ends, and a cyclic siloxane having an alkenyl group. . These compounds having an alkenyl group may be used alone or in combination of two or more.

  Specific examples of linear polysiloxanes having alkenyl groups at both ends include poly or oligosiloxanes whose ends are blocked with dimethylvinylsilyl groups, tetramethyldivinyldisiloxane, hexamethyldivinyltrisiloxane, and the like. .

  Examples of the cyclic siloxane containing an alkenyl group include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1,3. , 5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-trimethylcyclosiloxane, , 3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl-1,3,5,7,9, Examples thereof include 11-hexamethylcyclosiloxane.

  The addition amount of the alkenyl group-containing compound (b), particularly the alkenyl group-containing siloxane compound, is 2.5 to 20 alkenyl groups per hydrogen atom directly bonded to the Si atom of the polyhedral siloxane intermediate. However, it depends on the compound. If the addition amount is small, gelation occurs due to a crosslinking reaction, resulting in a modified polysiloxane having poor handling properties. If the addition amount is too large, the physical properties of the resulting package may be adversely affected.

In the present invention, from the viewpoint of heat resistance and light resistance, the Si atom is preferably composed of a hydrogen atom, a vinyl group and a methyl group.
The modified polyhedral polysiloxane of the present invention is preferably a liquid in terms of handling properties and the like, and is preferably transparent in terms of the reflectance of the package from which the molded body is obtained.

<Curing agent (B)>
Next, the curing agent (B) used in the present invention will be described.
The curing agent (B) can be properly used depending on the type of main reactive group of the modified polyhedral polysiloxane. When the modified polyhedral polysiloxane has a hydrosilyl group as a main reactive group, a compound having an alkenyl group can be used as a curing agent, and when it has an alkenyl group as a main reactive group, a compound having a hydrosilyl group can be used as a curing agent. . Details will be described below.

  The curing agent having an alkenyl group is not particularly limited as long as it is a compound having an alkenyl group, but preferably contains at least two alkenyl groups in one molecule, a linear polysiloxane having an alkenyl group, A siloxane compound such as a polysiloxane having an alkenyl group at the molecular end or a cyclic siloxane containing an alkenyl group is more preferred, and a polysiloxane having a linear structure is particularly preferred from the viewpoint of crack resistance during high-temperature heating. . These compounds having an alkenyl group may be used alone or in combination of two or more.

  Specific examples of the alkenyl group-containing polysiloxane having a linear structure include copolymers of dimethylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units. Copolymer, Copolymer of methylphenylsiloxane unit, methylvinylsiloxane unit and terminal trimethylsiloxy unit, Polydimethylsiloxane blocked with dimethylvinylsilyl group, Polydiphenyl blocked with dimethylvinylsilyl group Examples thereof include siloxane and polymethylphenylsiloxane whose end is blocked with a dimethylvinylsilyl group.

  The alkenyl group-containing polysiloxane having a linear structure in the present invention preferably has an alkenyl group at the molecular end from the viewpoint of the strength of the resulting package.

Specific examples of the polysiloxane having an alkenyl group at the molecular end include polysiloxanes whose ends are blocked with the dimethylalkenyl groups exemplified above, dimethylalkenylsiloxane units and SiO ₂ units, SiO _3/2 units, SiO _2/2 Examples thereof include polysiloxane composed of at least one siloxane unit selected from the group consisting of units.

  Examples of the cyclic siloxane compound containing an alkenyl group include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1, 3,5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-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.

  The curing agent having a hydrosilyl group is not particularly limited as long as it is a compound having a hydrosilyl group, but preferably contains at least two hydrosilyl groups in one molecule, a linear polysiloxane having a hydrosilyl group, Siloxane compounds such as polysiloxane having a hydrosilyl group at the molecular terminal and cyclic siloxane having a hydrosilyl group are particularly preferred. These compounds having a hydrosilyl group may be used alone or in combination of two or more.

  Specific examples of hydrosilyl group-containing polysiloxanes having a linear structure include copolymers of dimethylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units. A copolymer of methylphenylsiloxane units with methylhydrogensiloxane units and terminal trimethylsiloxy units, polydimethylsiloxane blocked with dimethylhydrogensilyl groups, and terminal with dimethylhydrogensilyl groups. Examples thereof include polydiphenylsiloxane blocked, polymethylphenylsiloxane blocked at the end with a dimethylhydrogensilyl group, and the like.

Specific examples of the polysiloxane having a hydrosilyl group at the molecular end include polysiloxanes whose ends are blocked with dimethylhydrogensilyl groups exemplified above, dimethylhydrogensiloxane units (H (CH ₃ ) ₂ SiO _1/2 units And a polysiloxane composed of at least one siloxane unit selected from the group consisting of SiO ₂ units, SiO _3/2 units, and SiO _2/2 units.

  Examples of the cyclic siloxane compound containing 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-tri Hydrogen-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexahydro Examples include Gen-1,3,5,7,9,11-hexamethylcyclosiloxane.

  In the present invention, from the viewpoint of heat resistance and light resistance, the Si atom is preferably composed of a hydrogen atom, a vinyl group and a methyl group.

  Although the addition amount of the curing agent can be variously set, it is desirable that the amount of hydrogen atoms directly bonded to Si atoms is 0.3 to 5, preferably 0.5 to 3, per alkenyl group. If the ratio of the alkenyl group is too small, appearance defects due to foaming and the like are likely to occur, and if too large, the physical properties of the cured product may be adversely affected.

<Hydrosilylation catalyst (C)>
Next, the hydrosilylation catalyst (C) used in the present invention will be described.
In the present invention, a hydrosilylation catalyst can be used in synthesizing a polyhedral polysiloxane modified product and curing the composition using the modified product.
As a hydrosilylation catalyst used by this invention, what is normally used as a hydrosilylation catalyst can be used, there is no restriction | limiting in particular, Arbitrary things can be used.

Specifically, for example, a platinum-olefin complex, chloroplatinic acid, a simple substance of platinum, a carrier (alumina, silica, carbon black, etc.) supported by solid platinum; a platinum-vinylsiloxane complex, for example, Pt _n (ViMe ₂ SiOSiMe ₂ Vi) _m , Pt [(MeViSiO) ₄ ] _m ; platinum-phosphine complex, such as Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ; platinum-phosphite complex, such as Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent an integer) , Pt (acac) _2, also platinum described in U.S. Patent 3,159,601 and in Pat 3159662 of Ashby et al - hydrocarbon complex, and Lamoreaux et al U.S. Patent Platinum is described in the 3220972 Pat Arcola - DOO catalysts may be mentioned.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl ₄ , and the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac) _{2 and the} like are preferable.

The addition amount of the hydrosilylation catalyst used at the time of synthesis and curing of the modified polyhedral polysiloxane is not particularly limited, but is, for example, 10 ⁻¹ to 1 mol per mol of the alkenyl group of the polyhedral polysiloxane compound (a). It is preferable to use in the range of 10 ⁻¹⁰ mol. Preferably, it is used in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. If there are too many hydrosilylation catalysts, depending on the type of hydrosilylation catalyst, it absorbs light at short wavelengths, so the light resistance of the resulting cured product may be reduced, and the cured product may also foam. . Moreover, when there are too few hydrosilylation catalysts, reaction may not progress and there exists a possibility that a target object may not be obtained.

  Moreover, as reaction temperature of hydrosilylation reaction of polyhedral polysiloxane modified body, it is 30-400 degreeC, More preferably, it is preferable that it is 40-250 degreeC, More preferably, it is 45-140 degreeC. If the temperature is too low, the reaction does not proceed sufficiently, and if the temperature is too high, gelation may occur and handling properties may deteriorate.

<Inorganic filler (D)>
Various inorganic fillers are used. For example, silica-based inorganic fillers such as quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, and ultrafine powder amorphous silica, alumina, zircon , Titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass fiber, alumina fiber, carbon fiber, mica, graphite, carbon black, graphite, diatomaceous earth, white clay, clay, talc, aluminum hydroxide, calcium carbonate, Inorganic fillers generally used and / or proposed as fillers for conventional sealing materials such as epoxy-based materials, including inorganic fillers such as magnesium carbonate, barium sulfate, potassium titanate, calcium silicate, inorganic balloons, silver powder, etc. Etc. The inorganic filler is preferably low radiation from the viewpoint of hardly damaging the semiconductor element.

  The inorganic filler may be appropriately surface treated. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a coupling agent, and the like.

  Examples of the coupling agent in this case include a silane 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 one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling. From the viewpoints of adhesion and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacrylic or acrylic groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Alkoxysilanes which can be exemplified.

  In addition, the method of adding an inorganic filler is mentioned. For example, a hydrolyzable silane monomer or oligomer such as alkoxysilane, acyloxysilane, or halogenated silane, or an alkoxide, acyloxide, or halide of a metal such as titanium or aluminum is added to the composition of the present invention. A method of reacting in a partial reaction product in the composition or in the composition to form an inorganic filler in the composition can also be mentioned.

  Of the inorganic fillers as described above, silica-based inorganic fillers are preferable from the viewpoints that the curing reaction is hardly inhibited, the effect of reducing the linear expansion coefficient is large, and the adhesiveness to the lead frame is likely to be high. Furthermore, fused silica is preferable in terms of a good balance of physical properties such as moldability and electrical characteristics, and crystalline silica is preferable in terms of easy package thermal conductivity and high heat dissipation. Alumina is preferable in that heat dissipation tends to be higher. Titanium oxide is preferred in that the light reflectance of the package resin is high and the light extraction efficiency of the resulting light emitting diode tends to be high. In addition, glass fiber, potassium titanate, and calcium silicate are preferable in that the reinforcing effect is high and the strength of the package tends to be high.

  As the average particle size and particle size distribution of the inorganic filler, various types are used without particular limitation, including those used or / and proposed as fillers for conventional sealing materials such as epoxy-based materials. The lower limit of the average particle size used is 0.1 μm, preferably 0.5 μm from the viewpoint that the fluidity tends to be good, and the upper limit of the average particle size usually used is 120 μm, the fluidity tends to be good. To preferably 60 μm, more preferably 15 μm.

  The specific surface area of the inorganic filler can also be variously set, including those used and / or proposed as fillers for conventional sealing materials such as epoxy-based fillers.

  As the shape of the inorganic filler, various types such as a crushed shape, a piece shape, a spherical shape, and a rod shape are used. Various aspect ratios are used. The aspect ratio of 10 or more is preferable in that the strength of the obtained cured product tends to increase. From the viewpoint of isotropic shrinkage of the resin, a powder form is preferable to a fiber form. Or the spherical thing is preferable at the point that the fluidity | liquidity at the time of shaping | molding becomes easy also at the time of high filling. These inorganic fillers may be used alone or in combination of two or more.

  The addition amount of the inorganic filler is not particularly limited, but from the viewpoint that the effect of reducing the linear expansion coefficient is high and the fluidity of the composition at the time of molding is good, the preferred lower limit of the addition amount is in the total composition It is 30% by weight, more preferably 50% by weight, still more preferably 70% by weight, and the upper limit of the preferable addition amount is 95% by weight in the total composition, more preferably 90% by weight.

  As the mixing order of the inorganic filler, various methods can be used, but the inorganic filler (D) is mixed with the component (B) in that the storage stability of the intermediate raw material of the composition tends to be good. A method of mixing the component and the component (A) is preferable. In addition, (A) component, (B) component, (C) in that (A) component, (B) component, and (C) component which are reaction components are well mixed and a stable molded product is easily obtained. It is preferable to mix the inorganic filler (D) with a mixture of components.

  As means for mixing these inorganic fillers, various means conventionally used for epoxy resins or / and proposed can be used. Examples thereof include a two-roll or three-roll, a planetary stirring and deaerator, a stirrer such as a homogenizer, a dissolver, and a planetary mixer, and a melt kneader such as a plast mill. Of these, a three-roller and a melt kneader are preferred in that sufficient dispersibility of the inorganic filler is easily obtained even with high filling.

  The mixing of the inorganic filler may be performed at normal temperature or may be performed by heating. Moreover, you may carry out under a normal pressure and may carry out in a pressure-reduced state. In view that sufficient dispersibility of the inorganic filler is easily obtained even at high filling, it is preferable to mix in a heated state, and it is easy to obtain sufficient dispersibility by improving the wettability of the inorganic filler surface. Is preferably mixed under reduced pressure.

<Composition>
Next, the composition obtained by the present invention will be described. In the present invention, the polyhedral polysiloxane modified product (A) is obtained by adding a curing agent (B), a hydrosilylation catalyst (C), an inorganic filler (D), a curing retarder, an adhesion promoter, and the like. Can do.

  When a temperature is applied when the composition containing the modified polyhedral polysiloxane (A) is cured by a hydrosilylation reaction, the temperature is preferably 30 to 400 ° C, more preferably 50 to 250 ° C. If the curing temperature is too high, the resulting cured product tends to have poor appearance, and if it is too low, curing is insufficient. Moreover, you may make it harden | cure combining the temperature conditions of two or more steps.

  Specifically, for example, by raising the curing temperature stepwise such as 70 ° C., 120 ° C., and 150 ° C., a preferable cured product can be obtained, which is preferable. The curing time can be appropriately selected depending on the curing temperature, the amount of hydrosilylation catalyst to be used and the amount of hydrosilyl group, and other combinations of the composition of the present application. Furthermore, a good cured product can be obtained by performing the treatment for 5 minutes to 10 hours.

<Curing retarder>
Next, the curing retarder used in the present invention will be described.
The curing retarder is a component for improving the storage stability of the modified polyhedral polysiloxane of the present invention and the composition or adjusting the reactivity of the hydrosilylation reaction during the curing process. In the present invention, as the retarder, known compounds used in addition-type curable compositions with hydrosilylation catalysts can be used. Specifically, compounds containing aliphatic unsaturated bonds, organophosphorus compounds , Organic sulfur compounds, nitrogen-containing compounds, tin compounds, organic peroxides, and the like. These may be used alone or in combination of two or more.

  Specific examples of the compound containing an aliphatic unsaturated bond include 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne, and 3,5-dimethyl-1- Examples thereof include propargyl alcohols such as hexyn-3-ol and 1-ethynyl-1-cyclohexanol, ene-yne compounds, maleic acid esters such as maleic anhydride and dimethyl maleate, and the like.

  Specific examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite.

  Specific examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide, and the like.

  Specific 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 Examples include '-bipyridine.

  Specific examples of tin compounds include stannous halide dihydrate, stannous carboxylate, and the like.

  Specific examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate. Of these, dimethyl maleate, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol can be exemplified as particularly preferred curing retarders.

  The addition amount of the curing retardant is not particularly limited, but it is preferably used in the range of 10-1 to 103 mol, more preferably in the range of 1 to 500 mol, with respect to 1 mol of the hydrosilylation catalyst. . Moreover, these hardening retarders may be used independently and may be used in combination of 2 or more types.

<Adhesive agent>
The adhesion-imparting agent is used for the purpose of improving the adhesion between the composition of the present invention and a substrate (for example, a lead described later), and such an effect is sometimes not limited. A coupling agent and an epoxy compound can be illustrated as preferable examples.

  Specifically, for example, a polyhedral polysiloxane modified product containing a hydrosilyl group as a modified polyhedral polysiloxane has a composition in which a curing agent, a hydrosilylation catalyst, and an adhesion imparting agent are also blended, so that the cured product adheres to the substrate. It can be made into a composition with good properties.

  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 one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling. From the viewpoints of adhesion and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Preferable silane coupling agents are specifically 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- ( 3,4-epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3 -Methacrylic groups such as acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, Alkoxysilanes having a drill group can be exemplified.

  The addition amount of the silane coupling agent is preferably 0.05 to 30% by weight of the total weight of the modified polyhedral polysiloxane (A) and the curing agent (C), more preferably 0.1 to 0.1%. 15% by weight. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the physical properties of the cured product may be adversely affected.

  Examples of the epoxy compound include novolak phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and 2,2′-bis (4-glycidyloxycyclohexyl). Propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3 -Dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate and the like.

  The addition amount of the epoxy compound is preferably 0.1 to 50% by weight, more preferably 0.2 to 15% by weight, based on the total weight of the polyhedral polysiloxane modified body and the curing agent. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the physical properties of the cured product may be adversely affected. A silane coupling agent, an epoxy compound, etc. may be used independently and may be used together 2 types.

  In the present invention, a known adhesion promoter can be used to enhance the effect of the adhesion promoter. Examples of the adhesion promoter include, but are not limited to, boronic acid ester compounds, organoaluminum compounds, and organotitanium compounds.

<Anti-aging agent>
An antioxidant may be added to the composition of the present invention. Examples of the anti-aging agent include citric acid, phosphoric acid, sulfur-based anti-aging agent and the like in addition to the anti-aging agents generally used such as hindered phenol type.

  As the hindered phenol-based anti-aging agent, various types such as Irganox 1010 available from Ciba Specialty Chemicals are used.

Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylic acid esters, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.
Moreover, these anti-aging agents may be used independently and may be used together 2 or more types.

<Radical inhibitor>
A radical inhibitor may be added to the composition of the present invention. Examples of the radical inhibitor include 2,6-di-t-butyl-3-methylphenol (BHT), 2,2′-methylene-bis (4-methyl-6-t-butylphenol), tetrakis (methylene- Phenol radical inhibitors such as 3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane, phenyl-β-naphthylamine, α-naphthylamine, N, N′-secondary butyl-p- Examples include amine radical inhibitors such as phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine, and the like.
Moreover, these radical inhibitors may be used alone or in combination of two or more.

<Ultraviolet absorber>
An ultraviolet absorber may be added to the composition of the present invention. Examples of the ultraviolet absorber include 2 (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate and the like. Can be mentioned. These ultraviolet absorbers may be used alone or in combination of two or more.

<Other additives>
The composition of the present invention includes other colorants, mold release agents, flame retardants, flame retardant aids, surfactants, antifoaming agents, emulsifiers, leveling agents, anti-fogging agents, and ion trapping agents such as antimony-bismuth. , Thixotropic agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, heat stabilizer, conductivity enhancer , Antistatic agents, radiation blocking agents, nucleating agents, phosphorus peroxide decomposing agents, lubricants, pigments, metal deactivators, thermal conductivity imparting agents, physical property modifiers, etc., without detracting from the purpose and effect of the present invention Can be added in a range.

<Additives for light-emitting diodes>
Furthermore, you may add the additive for various light emitting diode characteristic improvement to the composition of this invention as needed. Examples of additives include phosphors such as yttrium, aluminum, and garnet phosphors activated with cerium that absorb light from the light emitting element to emit longer wavelength fluorescence, and blue that absorbs a specific wavelength. Coloring agents such as ing agents, diffusion materials such as titanium oxide, aluminum oxide, melamine resin, CTU guanamine resin, benzoguanamine resin for diffusing light, metal oxides such as aluminosilicate, aluminum nitride, boron nitride, etc. Examples thereof include thermally conductive fillers such as metal nitrides.

  The additive for improving the characteristics of the light emitting diode may be contained uniformly, or the content may be added with a gradient.

<Release agent>
Various release agents may be added to the composition of the present invention in order to improve the releasability at the time of molding.
Various conventionally used release agents are used. For example, metal soap, waxes and the like can be mentioned. The metal soap here is generally a combination of long-chain fatty acids and metal ions. The nonpolar or low polarity part based on the fatty acid and the polar part based on the metal binding part are combined in one molecule. Can be used.

  Examples of the long chain fatty acid include saturated fatty acids having 1 to 18 carbon atoms, unsaturated fatty acids having 3 to 18 carbon atoms, and aliphatic dicarboxylic acids. Among these, saturated fatty acids having 1 to 18 carbon atoms are preferable from the viewpoint of easy availability and high industrial feasibility, and 6 to 18 carbon atoms from the viewpoint of high effect of releasability. The saturated fatty acid is more preferable.

  Examples of metal ions include zinc, cobalt, aluminum, strontium, and the like in addition to alkali metals and alkaline earth metals. Specific examples of metal soaps include lithium stearate, lithium 12-hydroxystearate, lithium laurate, lithium oleate, lithium 2-ethylhexanoate, sodium stearate, sodium 12-hydroxystearate, lauric acid Sodium, sodium oleate, sodium 2-ethylhexanoate, potassium stearate, potassium 12-hydroxystearate, potassium laurate, potassium oleate, potassium 2-ethylhexanoate, magnesium stearate, magnesium 12-hydroxystearate, Magnesium laurate, magnesium oleate, magnesium 2-ethylhexanoate, calcium stearate, calcium 12-hydroxystearate, calcium laurate , Calcium oleate, calcium 2-ethylhexanoate, barium stearate, barium 12-hydroxystearate, barium laurate, zinc stearate, zinc 12-hydroxystearate, zinc laurate, zinc oleate, 2-ethylhexane Examples include zinc acid, lead stearate, lead 12-hydroxystearate, cobalt stearate, aluminum stearate, manganese oleate, barium ricinoleate, and the like.

  Among these metal soaps, metal stearates are preferred from the viewpoint of easy availability, safety and industrial feasibility, and calcium stearate, magnesium stearate, stearin are particularly preferred from the viewpoint of economy. Most preferred is one or more selected from the group consisting of zinc acid.

  Although there is no restriction | limiting in particular as addition amount of this metal soap, The minimum of a preferable amount is 0.025 with respect to 100 weight part of the whole composition, More preferably, it is 0.05 weight part, The upper limit of a preferable amount is a composition. The amount is 5 parts by weight, more preferably 4 parts by weight with respect to 100 parts by weight as a whole. When the addition amount is too large, the physical properties of the cured product are deteriorated. When the addition amount is too small, mold releasability may not be obtained.

Examples of waxes include natural wax, synthetic wax, oxidized or non-oxidized polyolefin, and polyethylene wax.
In addition, it is better not to use a release agent when sufficient release properties can be obtained without adding a release agent.

<B stage>
The composition of the present invention may be used as it is as a mixture of each component and additive, or may be used after partially reacting (B-stage) by heating or the like. Viscosity can be adjusted by using B-stage, and transfer moldability can also be adjusted.

<Composition properties>
As described above, various combinations can be used as the composition of the present invention. However, in terms of good moldability by transfer molding, the composition has fluidity at a temperature of 150 ° C. or lower. preferable. The curability of the composition can be arbitrarily set, but the gelation time at 120 ° C. is preferably within 120 seconds, and more preferably within 60 seconds in that the molding cycle can be shortened.

  Further, the gelation time at 150 ° C. is preferably within 60 seconds, and more preferably within 30 seconds. Further, the gelation time at 100 ° C. is preferably within 180 seconds, and more preferably within 120 seconds. The gelation time in this case is examined as follows. An aluminum foil having a thickness of 50 μm is placed on a hot plate adjusted to a preset temperature, and 100 mg of the composition is placed thereon to measure the time until gelation is taken as the gelation time.

<Curing>
The composition of the present invention can be used after being cured by reacting in advance with a carbon-carbon double bond having reactivity and a part or all of hydrosilyl (SiH) groups in the composition.

  In the case of curing by reacting the composition, the required amount of each component (A), (B), (C) (and (D)) may be mixed and reacted at one time, but partly mixed After reacting, only a part of the functional group in the composition is reacted (B by controlling the reaction conditions after mixing and utilizing the difference in the reactivity of the substituents). It is also possible to take a method of further curing by performing a process such as molding after being staged). According to these methods, viscosity adjustment at the time of molding becomes easy.

  As a curing method, the reaction can be performed by simply mixing, or the reaction can be performed by heating. A method of heating and reacting is preferable from the viewpoint that the reaction is fast and generally a material having high heat resistance is easily obtained.

  Although the curing temperature can be variously set, the lower limit of the preferable temperature is 30 ° C, more preferably 100 ° C, and the upper limit of the preferable temperature is 300 ° C, more preferably 250 ° C. If the reaction temperature is low, the reaction time for sufficient reaction will be long, and if the reaction temperature is high, molding will tend to be difficult.

  Curing may be performed at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. It is preferable to carry out the reaction while raising the temperature in a multistage manner or continuously, as compared with the case where the temperature is constant, in that a uniform cured product without distortion can be easily obtained. Moreover, it is preferable to perform at a constant temperature in that the molding cycle can be shortened.

  Although various curing times can be set, it is preferable to react at a relatively low temperature for a long time rather than reacting at a high temperature for a short time because a uniform cured product without distortion can be easily obtained. Conversely, the reaction at a high temperature in a short time is preferable in that the molding cycle can be shortened.

  The pressure during the reaction can be variously set as required, and the reaction can be carried out under normal pressure, high pressure, or reduced pressure. In view of easy removal of volatile matter generated in some cases, it is preferable to cure under reduced pressure. In terms of preventing cracks in the molded body, it is preferable to cure under pressure.

  In the manufacturing process in which the composition is used, the weight loss during curing is 5% by weight or less from the viewpoint that generation of voids in the composition and process problems due to outgas from the composition hardly occur. Is preferably 3% by weight or less, more preferably 1% or less.

  The weight loss during curing is examined as follows. Using a thermogravimetric analyzer, 10 mg of the sealant is heated from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, and can be determined as a ratio of the initial weight of the reduced weight.

<Curing property>
From the viewpoint of good heat resistance, a cured product obtained by curing the composition preferably has a Tg of 100 ° C or higher, more preferably 150 ° C or higher.
In this case, Tg is examined as follows. Dynamic viscoelasticity measurement using a 3 mm x 5 mm x 30 mm prismatic test piece under the conditions of tensile mode, measurement frequency 10 Hz, strain 0.1%, static / power ratio 1.5, temperature rising side 5 ° C / min ( Let Tg be the peak temperature of tan δ of DVA-200 manufactured by IT Measurement & Control Co.).

  In addition, in terms of high reliability and less likely to cause problems such as ion migration in the lead frame and the like, the content of ions extracted from the cured product is preferably less than 10 ppm, more preferably less than 5 ppm, More preferably, it is less than 1 ppm.

  In this case, the extracted ion content is examined as follows. 1 g of the cut cured product is put in a Teflon (registered trademark) container together with 50 ml of ultrapure water and sealed, and treated under conditions of 121 ° C., 2 atm and 20 hours. The obtained extract was analyzed by ICP mass spectrometry (using HP-4500 manufactured by Yokogawa Analytical Systems), and the obtained Na and K content values were converted to the concentration in the cured product used. Ask. On the other hand, the same extract was analyzed by ion chromatography (using Dionex DX-500, column: AS12-SC), and the resulting Cl and Br content values were converted to the concentration in the cured product used. Ask. The contents of Na, K, Cl, and Br obtained as described above in the cured product are totaled to obtain the extracted ion content.

  Various colors are used for the cured product, but white is preferable in that the light extraction efficiency of the light emitting diode tends to be high, and the contrast tends to be high when the light emitting diode is used in a display device. In black, black is preferable.

  The linear expansion coefficient of the cured product is not particularly limited, but the linear expansion coefficient may be 50 ppm or less at 100 ° C. in terms of easy adhesion to metals such as lead frames and ceramics. Preferably, it is 30 ppm or less. Further, in terms of easy adhesion to an organic material such as a sealing resin, the linear expansion coefficient is preferably 70 ppm or more at 100 ° C., and more preferably 100 ppm or more. In addition, the temperature of the linear expansion coefficient and the linear expansion coefficient close to that of the sealant is that they are less likely to generate stress between the package and the sealant during the thermal test after curing, and in that the reliability tends to be high. It is preferable to have dependency.

<Semiconductor package>
The semiconductor package referred to in the present invention is a member provided for supporting and / or protecting a semiconductor element or / and an external extraction electrode. In this case, various types of semiconductor elements can be mentioned. For example, an integrated circuit such as an IC or LSI, an element such as a transistor, a diode, or a light emitting diode, or a light receiving element such as a CCD can be used. Among these, the effect of the present invention can be more remarkable when the semiconductor is a light emitting diode.

  In the case where the semiconductor is a light emitting diode element, it is preferably designed so that light emitted from the light emitting diode element is irradiated, and more preferably, the light emitted from the light emitting diode element is reflected and taken out to the outside. It is designed. There are no particular restrictions on the shape and the like. For example, as shown in FIG. 1, it may have a shape having a recess for mounting a light emitting diode element, or may simply have a flat plate shape. The surface of the light emitting diode package of the present invention may be smooth or may have a non-smooth surface such as embossing.

<Molding method>
Various methods are used as a method for forming a semiconductor package in the present invention. For example, various molding methods generally used for thermosetting resins such as thermoplastic resins and epoxy resins, such as injection molding, transfer molding, RIM molding, casting molding, and press molding, are used. Of these, transfer molding is preferred in that the molding cycle is short and the moldability is good.

  The molding conditions can be arbitrarily set, for example, the molding temperature is also arbitrary. However, in terms of fast curing and a short molding cycle, the moldability tends to be good, more preferably 100 ° C. or higher, more preferably 120 ° C. or higher. A temperature of 150 ° C. or higher is preferable. After molding by the various methods as described above, post-curing (after-curing) is optional as required. Post-curing tends to increase heat resistance.

<Light emitting diode element>
The various light emitting diode elements of the light emitting diode referred to in the present invention are not particularly limited, and the light emitting diode elements used in conventionally known light emitting diodes can be used.
The size and number of the light emitting diode elements can be used without any particular limitation.
Any light emitting output of the light emitting diode element can be used without any particular limitation. However, when a light emitting element of 1 mW or more is used at 20 mA, the effect of the present invention is remarkable, and a light emitting element of 4 mW or more at 20 mA is used. When used, the effect of the present invention is remarkable. When a light emitting element of 5 mW or more is used at 20 mA, the effect of the present invention is further remarkable.

Various light emission wavelengths of the light emitting diode element can be used from the ultraviolet region to the infrared region, but the effect of the present invention is particularly remarkable when the main light emission peak wavelength is 550 nm or less.
One type of light emitting diode element may be used to emit monochromatic light, or a plurality of light emitting diode elements may be used to emit monochromatic or multicolor light.

<Lead>
The lead terminal used in the semiconductor of the present invention preferably has good adhesion with an electrical connecting member such as a bonding wire, electrical conductivity, etc., and the electrical resistance of the lead terminal is preferably 300 μΩ-cm or less, More preferably, it is 3 μΩ-cm or less. Examples of these lead terminal materials include iron, copper, iron-containing copper, tin-containing copper, and those plated with gold, silver, nickel, palladium, and the like. The glossiness of these lead terminals may be adjusted as appropriate in order to obtain a good light spread.

<Sealant>
Various semiconductor sealing agents of the present invention can be used. For example, conventionally used sealing resins such as epoxy resins, silicone resins, acrylic resins, urea resins, and imide resins can be used.

  Further, a curable composition containing an organic compound having at least two carbon-carbon double bonds reactive with SiH groups in one molecule, a compound having at least two SiH groups in one molecule, and a hydrosilylation catalyst. Sealants made of the composition may be used. These are proposed in Japanese Patent Application Laid-Open Nos. 2002-80733 and 2002-88244. Furthermore, a sealing agent characterized by containing a polyhedral polysiloxane modified as an essential component can also be used. As the modified polyhedral polysiloxane, a modified product as proposed in WO2008 / 133138 can be used.

  The use of these sealants is preferable in that the adhesiveness to the package resin is high and the effect that the transparency and the light resistance of the package of the present invention are high is remarkable. On the other hand, it is possible to cover with glass or the like and seal with hermetic sealing without using resin sealing.

<Applications of light emitting diodes>
The semiconductor light emitting diode of the present invention can be used for various known applications. Specifically, for example, backlights such as liquid crystal display devices, illumination, sensor light sources, vehicle instrument light sources, signal lights, display lights, display devices, planar light source, display, decoration, various lights, etc. it can.

  Next, although the composition of this invention is demonstrated in detail based on an Example, this invention is not limited only to these Examples.

(Production Example 1)
A mixed solution of 34.5 g of 48% choline aqueous solution and 27.9 g of tetraethoxysilane was stirred at room temperature for 4 hours, and then 30 mL of methanol was added to obtain a uniform solution. Next, the previously prepared solution was slowly added dropwise to a stirring solution of 16.15 g of dimethylchlorovinylsilane, 14.53 g of trimethylchlorosilane, and hexane (50 mL). After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours, hexane was added to extract the organic layer, and the mixture was concentrated under reduced pressure. The crude product is washed with methanol, subjected to suction filtration, and octasilsesquioxane containing vinyldimethylsiloxy group and trimethylsiloxy group whose average composition is represented by the following formula:
[CH ₂ = CH (CH ₃ ) ₂ SiO—SiO _3/2 ] _3.7 10 g of [(CH ₃ ) ₃ SiO—SiO _3/2 ] _4.3 was obtained.

(Production Example 2)
10 g of polyhedral polysiloxane compound obtained in Production Example 1, platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) 1.2 μL, toluene 40 g The mixed solution was added dropwise to a mixed solution of 18.94 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 18.9 g of toluene, and 6.5 at 100 ° C. After warming for hours, it was cooled to room temperature.

After completion of the reaction, 1,31,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane added in excess with toluene was distilled off to obtain 15.31 g of a polysiloxane modified product. Obtained. The obtained modified product is a colorless transparent liquid, and SiH groups derived from 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane are introduced by ¹ H-NMR. Confirmed that it has been.

Example 1
49 g of the product obtained in Production Example 2 as component (A) of the present invention, 100 g of MVD8MV (manufactured by Clariant) as component (B) of the present invention, xylene solution of platinum vinylsiloxane complex (platinum) as component (C) of the present invention As a curable composition by mixing 10 μL and 13 μL of 1-ethynyl-1-cyclohexanol.

  To this, 75 g of titanium oxide (Ishihara Sangyo Co., Ltd., Tyco R820) and 750 g of fused silica (manufactured by Tatsumori Co., Ltd., Furex RD-8) are added as components (D) of the present invention. This roll was kneaded three times to obtain a curable resin composition for a semiconductor package of the present invention. This was a hard paste at room temperature, but when a small amount was placed on a hot plate heated to 150 ° C., the viscosity once decreased to a fluid state and gelled after 40 seconds.

This semiconductor package curable resin composition was subjected to transfer molding using an MF-0 type transfer molding machine manufactured by Maruhichi Iron Works. Using a mold of 6 test pieces of 10 × 10 × 3 mm, molding was performed under the conditions of raw material pot temperature: room temperature, mold temperature: 150 ° C., molding pressure: 70 kgf / cm ² , molding time: 60 seconds. A good molded body free from cracks and voids was obtained. In addition, molding was performed under the conditions of a raw material pot temperature: room temperature, a mold temperature: 140 ° C., a molding pressure: 70 kgf / cm ² , and a molding time: 120 seconds, using a mold having four test pieces of 44 × 10 × 5 mm. A good molded body free from burrs, cracks, voids and the like was obtained. The obtained molded body was post-cured by heating in a hot air circulating oven at 150 ° C. for 1 hour under air to obtain a white cured product.

(Measurement Example 1) and (Comparative Example 1)
The durability of the cured product obtained in Example 1 was examined. Moreover, the same evaluation was performed also about Amodel A-4122 (glass fiber filling polyamide resin) by Solvay Advanced Polymers Co., Ltd. conventionally used for the package of a semiconductor as the comparative example 1. FIG. As a heat resistance test, the discoloration was examined by heating for 15 minutes in a hot air circulating oven at 260 ° C. in air. As a light resistance test, the light irradiation surface was examined for discoloration by a light irradiation treatment under the condition of an integrated irradiation intensity of 100 MJ (black panel temperature = 120 ° C.) with a metalling weather meter. The light resistance test was performed using a metering weather meter M6T manufactured by Suga Test Instruments Co., Ltd.

  As a result of the evaluation, the cured product obtained in Example 1 did not show discoloration or the like in any of the heat resistance test and the light resistance test, and was a good result. On the other hand, Amodel A-4122 which is Comparative Example 1 showed brown discoloration in both the heat resistance test and the light resistance test. That is, it can be seen that the cured product obtained by curing the composition of the present invention has excellent heat and light resistance.

DESCRIPTION OF SYMBOLS 1 Light emitting diode package 2 Light emitting diode element 3 Bonding wire 4 Lead

Claims (17)

For the polyhedral polysiloxane compound (a) containing an alkenyl group and / or a hydrosilyl group, the compound (b) having a hydrosilyl group and / or alkenyl group capable of hydrosilylation reaction with the component (a) is modified. A polyhedral polysiloxane modified product (A) obtained in the above, and a curable resin composition for a package of a light-emitting diode containing an inorganic filler (D) as an essential component,
The content of the inorganic filler (D) is 50 to 95% by weight in the curable resin composition,
A curable resin composition for a white or black light-emitting diode package designed to reflect light emitted from a light-emitting diode element and extract the light to the outside. The curable resin composition for a white or black light-emitting diode package according to claim 1, wherein the component (A) is liquid at a temperature of 20 ° C. The curable resin composition for a white or black light-emitting diode package according to claim 1 or 2, wherein the compound (b) is a cyclic siloxane containing a hydrosilyl group and / or an alkenyl group. The curability for packaging of a white or black light-emitting diode according to claim 1 or 2, wherein the compound (b) is a linear siloxane containing a hydrosilyl group and / or an alkenyl group at the molecular end. Resin composition. The curable composition for white or black light-emitting diode packages according to any one of claims 1 to 4, wherein the compound (b) has at least three hydrosilyl groups or alkenyl groups in the molecule. Resin composition. The number of hydrogen atoms and / or alkenyl groups directly bonded to the Si atom of the compound (b) having a hydrosilyl group and / or alkenyl group is such that the polyhedral polysiloxane compound (a) has an alkenyl group and / or hydrosilyl group. It is modified by adding 2.5 to 20 hydrogen atoms per alkenyl group and / or Si atom directly connected to the Si atom, and is obtained by distilling off the unreacted compound (b). The curable resin composition for a package of a white or black light emitting diode according to any one of claims 1 to 5. (A) component is
[XR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ¹ is an alkyl group or an aryl group; R ² is an alkyl group, an aryl group, an alkenyl group, a hydrogen atom Or a group linked to another polyhedral polysiloxane; X has a structure represented by the following general formula (1) or general formula (2), and when there are a plurality of X, the general formula (1 ) Or the structure of the general formula (2) may be different, or the structure of the general formula (1) or the general formula (2) 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 bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain Yes, and may be the same or different, provided that at least one of Y or Z is a hydrogen atom or an alkenyl group; R is an alkyl group or an aryl group; (1) or the structure of formula (2) may be different, or the structure of formula (1) or formula (2) may be mixed). White or package curable resin composition for light-emitting diodes black according to any one of 6. Formula [AR ¹ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group and / or a hydrogen atom provided that at least one is an alkenyl group;. ^{R 1} is An alkyl group or an aryl group; R ⁴ is a substituent other than an alkenyl group and a hydrogen atom, for example, an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane or siloxane compound) In the polyhedral polysiloxane compound (a) composed of siloxane units, the compound (b) having a hydrosilyl group is within a range of 2.5 to 20 hydrogen atoms directly bonded to Si atoms per alkenyl group. It is obtained by dehydrating a compound (b) having an unreacted hydrosilyl group by adding an excessive amount to modify the hydrosilylation reaction, White or package curable resin composition for light-emitting diodes black according to any one of 1 to 7. Formula [BR ¹ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; B is alkenyl and / or hydrogen atom, provided that at least one is hydrogen atom;. ^{R 1} is An alkyl group or an aryl group; R ⁴ is a substituent other than an alkenyl group and a hydrogen atom, for example, an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane or siloxane compound) The range in which the polyhedral polysiloxane compound (a) composed of siloxane units has 2.5 to 20 alkenyl groups per hydrogen atom directly bonded to the Si atom of the compound (b) having an alkenyl group. It is obtained by diluting the compound (b) having an unreacted alkenyl group by adding an excessive amount thereof to modify by hydrosilylation reaction. White or package curable resin composition for light-emitting diodes black according to any one of. The curable resin composition for a white or black light-emitting diode package according to claim 1, comprising a curing agent (B). The curable resin composition for a white or black light emitting diode package according to any one of claims 1 to 10, comprising a hydrosilylation catalyst (C). The curable resin composition for a white or black light-emitting diode package according to any one of claims 1 to 11, wherein the inorganic filler (D) is titanium oxide and / or silica. The curable resin for a white or black light-emitting diode package according to any one of claims 1 to 12, wherein the content of the inorganic filler (D) is 70 to 90% by weight of the entire composition. Composition. White or package curable resin composition of the black light-emitting diode white or black light-emitting diodes, characterized in that the package curable resin composition was B-staged as claimed in any one of claims 1 to 13 object. The light emitting diode package of white or black, characterized in that the molded package curable resin composition for a white or black light-emitting diode according to any one of claims 1 to 14. The curable resin composition for a white or black light-emitting diode package according to any one of claims 1 to 14, which has fluidity at a temperature of 150 ° C or lower and has a gelation time at 150 ° C. A white or black light-emitting diode package, wherein a curable resin composition having a length of 60 seconds or less is formed by transfer molding. Any one white or black light-emitting diode package curable resin composition of white or black light-emitting diode fabricated using the described of claims 1-14.