JP2010043136A - Silicone resin composition, silicone resin using the same and optical semiconductor sealed-body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicone resin composition excellent in productivity and capable of being converted into a silicon resin excellent in surface tackiness. <P>SOLUTION: This silicone resin composition includes: (A) a polysiloxane having at least two alkenyl groups bonded to a silicon atom; (B) a polysiloxane crosslinker having at least two hydrogen groups bonded to a silicon atom; (C) at least one organic metal compound selected from the group consisting of an organic zirconyl compound having an organic group of 3 or more carbon atoms, an organic zinc compound, an organic magnesium compound and an organic potassium compound, and there are provided also a silicone resin obtained by curing the silicone resin composition and an optical semiconductor element sealed-body in which an LED chip is sealed with the silicone resin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a silicone resin composition, a silicone resin using the same, and an optical semiconductor element sealing body.

Conventionally, when an optical semiconductor element such as an LED or the like is sealed with silicone rubber, there is a problem that dust and dust are likely to adhere to the surface of the optical semiconductor element sealing material, and the quality of the optical semiconductor element is likely to be deteriorated. The adhesion of dust and dust to the surface of the optical semiconductor element sealing material was considered to be due to the tack of the silicone rubber.
For this reason, as a method of reducing the surface tack of the optical semiconductor element sealing material, it has been proposed that the optical semiconductor element sealing material has a two-layer structure having a soft lower layer and a hard upper layer (for example, Patent Document 1). ).
The manufacture of a two-layer optical semiconductor element encapsulant is usually performed after a lower layer forming step in which a soft resin is cured in the lower layer to form the lower layer, and then an upper layer is formed by curing a resin-like hard resin as the upper layer on the lower layer. And an upper layer forming step.

JP 2007-103494 A

However, the optical semiconductor element sealing material having a two-layer structure has a problem in that the production requires two steps of an upper layer forming step and a lower layer forming step, and the productivity is low.
Therefore, an object of the present invention is to provide a silicone resin composition that can be a silicone resin excellent in surface tackiness and excellent in productivity.

  As a result of diligent research to solve the above problems, the present inventor has found that the present inventor is from the group consisting of organic zirconyl compounds, organic zinc compounds, organic magnesium compounds and organic potassium compounds having an organic group having 3 or more carbon atoms. It has been found that at least one selected organometallic compound bleeds out on the surface of the silicone resin and acts as a tack mitigating component to reduce the surface tack of the silicone resin. Further, a polysiloxane having an alkenyl group bonded to a silicon atom. From siloxane, (B) a polysiloxane crosslinking agent having a hydrogen group bonded to a silicon atom, and (C) an organic zirconyl compound, an organic zinc compound, an organic magnesium compound and an organic potassium compound having an organic group having 3 or more carbon atoms. And at least one organometallic compound selected from the group consisting of Recone resin composition can be a silicone resin excellent in surface tackiness, it found that high productivity thereby possible to simplify the manufacturing process, it was completed the present invention.

That is, the present invention provides the following (1) to (8).
(1) (A) a polysiloxane having at least two alkenyl groups bonded to a silicon atom;
(B) a polysiloxane crosslinking agent having at least two hydrogen groups bonded to silicon atoms;
(C) A silicone resin composition comprising at least one organic metal compound selected from the group consisting of an organic zirconyl compound having an organic group having 3 or more carbon atoms, an organic zinc compound, an organic magnesium compound, and an organic potassium compound.
(2) The silicone resin composition according to (1), wherein the alkenyl group is a vinyl group or a (meth) acryloyl group.
(3) The silicone resin according to any one of (1) and (2), wherein the organometallic compound is a chelate or salt of at least one metal selected from the group consisting of zirconium, zinc, magnesium and potassium. Composition.
(4) Any of the above (1) to (3), wherein the organometallic compound is used in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the polysiloxane and the polysiloxane crosslinking agent. The silicone resin composition as described in 2.
(5) A silicone resin obtained by curing the silicone resin composition according to any one of (1) to (4).
(6) The silicone resin according to (5), wherein the JIS A hardness after the curing is 70 or less.
(7) A sealed optical semiconductor element in which the LED chip is sealed with the silicone resin described in (5) or (6) above.
(8) An application step of applying the silicone resin composition according to any one of (1) to (4) to the LED chip, and heating the LED chip to which the silicone resin composition is applied to heat the silicone resin. The manufacturing method of the optical semiconductor element sealing body which has a hardening process which hardens a composition and makes it hardened | cured and bleeds out the said organometallic compound on the surface of the said hardened | cured material.

The silicone resin composition of the present invention can be a silicone resin excellent in surface tackiness and excellent in productivity.
The silicone resin of the present invention is excellent in surface tackiness and excellent in productivity.
The sealed optical semiconductor element of the present invention is excellent in surface tackiness and excellent in productivity.

The present invention will be described in detail below.
The silicone resin composition of the present invention is
(A) a polysiloxane having at least two alkenyl groups bonded to a silicon atom;
(B) a polysiloxane crosslinking agent having at least two hydrogen groups bonded to silicon atoms;
(C) A silicone resin composition comprising an organic zirconyl compound having an organic group having 3 or more carbon atoms, an organic zinc compound, an organic magnesium compound, and at least one organic metal compound selected from the group consisting of an organic potassium compound. .

The polysiloxane will be described below.
The polysiloxane contained in the silicone resin composition of the present invention is not particularly limited as long as it is an organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule and having a polysiloxane structure as a main chain.

Polysiloxane is the main ingredient (base polymer) of the silicone resin composition of the present invention.
From the viewpoint of excellent toughness and elongation, the polysiloxane preferably has two or more alkenyl groups bonded to a silicon atom in one molecule, more preferably 2 to 20, more preferably about 2 to 10. .

  The alkenyl group can be bonded to the silicon atom via an organic group. The organic group is not particularly limited, and can have, for example, a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.

Examples of the alkenyl group include an unsaturated hydrocarbon group having 2 to 8 carbon atoms such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group; and a (meth) acryloyl group.
Of these, the alkenyl group is preferably a vinyl group or a (meth) acryloyl group, more preferably a vinyl group, from the viewpoint that the surface tackiness of the silicone resin can be further reduced and the curability is excellent.
In the present invention, the (meth) acryloyl group means one or both of an acryloyl group and a methacryloyl group.

  Examples of the bonding position of the alkenyl group include one or both of the molecular chain terminal and the molecular chain side chain of polysiloxane. The alkenyl group can be bonded to one end or both ends of the polysiloxane molecular chain.

Examples of organic groups bonded to silicon atoms other than alkenyl groups in polysiloxane include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl groups; phenyl and tolyl groups Aryl groups such as xylyl group and naphthyl group; aralkyl groups such as benzyl group and phenethyl group; halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group It is done.
Of these, a methyl group and a phenyl group are preferable from the viewpoint of excellent heat resistance.

Examples of the main chain of polysiloxane include organopolysiloxane. Specific examples include polydimethylsiloxane, methylphenyl polysiloxane, and diphenyl polysiloxane.
Of these, polydimethylsiloxane is preferred from the viewpoint of excellent heat resistance and light resistance.
In the present invention, light resistance refers to durability against light emission from an LED (for example, discoloration and burning are less likely to occur).

The polysiloxane is not particularly limited with respect to the molecular structure. Examples thereof include a straight chain, a partially branched straight chain, a ring, a branched chain, and a three-dimensional network. One preferred embodiment is linear.
Polysiloxane has a molecular structure in which the main chain is preferably composed of repeating diorganosiloxane units.
Further, the molecular terminal of the polysiloxane can be terminated with a silanol group (silicon atom-bonded hydroxyl group) or an alkoxysilyl group, or can be blocked with a triorganosiloxy group such as a trimethylsiloxy group.

式中、Ｒ¹、Ｒ²、Ｒ³はそれぞれ独立にアルケニル基であり、Ｒ⁴はそれぞれ独立にアルケニル基以外の一価の炭化水素基、ヒドロキシ基、アルコキシ基であり、Ｒはそれぞれ独立に有機基であり、ａ＋ｂ＋ｎは２以上であり、ａ、ｂは０〜３の整数であり、ｍ、ｎは０以上の整数である。 Examples of the polysiloxane include those represented by the following formula (I).

In the formula, R ¹ , R ² and R ³ are each independently an alkenyl group, R ⁴ is each independently a monovalent hydrocarbon group other than an alkenyl group, a hydroxy group or an alkoxy group, and R is independently It is an organic group, a + b + n is 2 or more, a and b are integers of 0 to 3, and m and n are integers of 0 or more.

When the polysiloxane is a polysiloxane having an unsaturated hydrocarbon group as an alkenyl group, the surface tack of the resulting silicone resin can be further reduced.
Examples of the polysiloxane having an unsaturated hydrocarbon group as an alkenyl group include a siloxane unit represented by the formula: R ¹ ₃ SiO _1/2 and a siloxane represented by the formula: R ¹ ₂ R ² SiO _1/2 units and formula siloxane units of the formula R ¹ ₂ SiO _2/2: organosiloxane copolymers composed of siloxane units represented by SiO _4/2, wherein: the siloxane units represented by R ¹ ₃ SiO _1/2 preparative formula siloxane units represented by the formula R ¹ ₂ R ² SiO _1/2: organosiloxane copolymers composed of siloxane units represented by SiO _4/2, wherein: represented by R ¹ ₂ R ² SiO _1/2 An organosiloxane copolymer comprising a siloxane unit represented by the formula: R ¹ ₂ SiO _2/2 and a siloxane unit represented by the formula: SiO _4/2 , represented by the formula: R ¹ R ² SiO _2/2 Siloxa And an organosiloxane copolymer comprising a siloxane unit represented by the formula: R ¹ SiO _3/2 or a siloxane unit represented by the formula: R ² SiO _3/2 .

Here, R ¹ in the above formula is a monovalent hydrocarbon group other than an alkenyl group.
Examples of the monovalent hydrocarbon group other than the alkenyl group include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Aryl groups such as benzyl group and phenethyl group; and halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group.
R ² in the above formula is an unsaturated hydrocarbon group. Examples of the unsaturated hydrocarbon group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group.

When polysiloxane has a vinyl group as an alkenyl group, the surface tack of the resulting silicone resin can be further reduced.
Hereinafter, a polysiloxane having a vinyl group as an alkenyl group may be referred to as a “vinyl group-containing polysiloxane”.

When the polysiloxane is a polysiloxane having a (meth) acryloyl group as an alkenyl group, the surface tack of the resulting silicone resin can be further reduced.
Hereinafter, a polysiloxane having a (meth) acryloyl group as an alkenyl group may be referred to as “(meth) acryloyl group-containing polysiloxane”.

Examples of the (meth) acryloyl group-containing polysiloxane include those represented by the average composition formula (I).
R ¹ _a R ² _b SiO _{(4-ab) / 2} (I)

Wherein, R ¹ represents a hydrogen atom, a hydroxy group, an alkyl group or an aryl group having 1 to 10 carbon atoms, R ² is ^{_{CH 2 = CR 3 -CO-O-}} (CH 2) c - represented by In the (meth) acryloxyalkyl group (CH ₂ ═CR ³ —CO—O— (CH ₂ ) _c —, R ³ is a hydrogen atom or a methyl group, c is an integer of 2 to 6, 3 is preferably 3 or 4.), a is from 0.8 to 2.4, preferably from 1 to 1.8, b is from 0.1 to 1.2, and It is preferably 2 to 1, more preferably 0.4 to 1, and a + b is 2 to 2.5, preferably 2 to 2.2.

Wherein the alkyl group of R ^1, the aryl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl, heptyl, or similar alkyl groups; phenyl, tolyl, xylyl, An aryl group such as a naphthyl group can be mentioned.
Of these, a methyl group, an ethyl group, a propyl group, and a phenyl group are preferable, and a methyl group is particularly preferable.

The molecular weight (weight average molecular weight) of the polysiloxane is preferably 500 to 100,000 from the viewpoint of being able to further reduce the surface tack of the resulting silicone resin and being excellent in toughness, elongation, and workability. It is preferable that it is 1,000-100,000, and it is further more preferable that it is 5,000-50,000.
In addition, in this-application specification, a weight average molecular weight is a polystyrene conversion value by GCP (gel permeation column chromatography).

The viscosity of polysiloxane at 23 ° C. is preferably 5 to 10,000 mPa · s because the physical properties of the resulting silicone resin are good and the handling workability of the silicone resin composition is good. More preferably, it is 1,000 mPa · s.
In the present invention, the viscosity is measured with an E-type viscometer at 23 ° C.

  Polysiloxanes can be used alone or in combination of two or more. Polysiloxane is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.

(B) The polysiloxane crosslinking agent will be described below.
The polysiloxane crosslinking agent contained in the silicone resin composition of the present invention has an organohydro having at least two hydrogen groups bonded to silicon atoms (that is, SiH groups) in one molecule and having a polysiloxane structure as a main chain. If it is a genpolysiloxane, it will not restrict | limit in particular.

The polysiloxane crosslinking agent preferably has about 2 to 300 hydrogen groups bonded to silicon atoms in one molecule, more preferably 3 or more (for example, about 3 to 150).
Examples of the molecular structure of the polysiloxane crosslinking agent include linear, branched, cyclic, and three-dimensional network structures.

  Examples of the bonding position of the hydrogen group bonded to the silicon atom include one or both of the molecular chain terminal and the molecular chain side chain of polysiloxane. Moreover, the hydrogen group bonded to the silicon atom can be bonded to one end or both ends of the molecular chain of the polysiloxane.

Examples of the polysiloxane crosslinking agent include organohydrogenpolysiloxanes represented by the following average composition formula (1).
H _a R ³ _b SiO _{(4-ab) / 2} (1)
(Wherein R ³ is an unsubstituted or substituted monovalent hydrocarbon group independently containing no aliphatic unsaturated bond, and a and b are 0 <a <2, 0.8 ≦ b ≦ 2, and 0 .8 <a + b ≦ 3, preferably 0.05 ≦ a ≦ 1, 0.9 ≦ b ≦ 2, and 1.0 ≦ a + b ≦ 2.7. The number of silicon atoms is 2 to 300, preferably 3 to 200.)

In the formula, examples of the unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond represented by R ³ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Alkyl groups; aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group; aralkyl groups such as benzyl group and phenethyl group; chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group And halogenated alkyl groups.
Among these, from the viewpoint of excellent heat resistance and light resistance, a lower alkyl group having 1 to 3 carbon atoms such as a methyl group, a phenyl group, and a 3,3,3-trifluoropropyl group are preferable.

Examples of the polysiloxane crosslinking agent include, for example, molecular chain both ends trimethylsiloxy group-blocked methylhydrogen polysiloxane, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends silanol group-blocked methyl. Hydrogen polysiloxane, Silanol group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, Molecular chain both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, Molecular chain both ends dimethylhydrogensiloxy group-blocked methylhydrogen Polysiloxane, dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, etc .; R ³ ₂ (H) From SiO _1/2 unit and SiO _4/2 unit R ³ ₃ SiO _1/2 unit, R ³ ₂ SiO _2/2 unit, R ³ (H) SiO _2/2 unit, (H) SiO _3/2 unit or R ³ SiO _3/2 unit In addition to silicone resins that may be included (wherein R ³ is the same as the above-mentioned unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond), in these exemplified compounds, a methyl group In which a part or all of is substituted with another alkyl group such as an ethyl group or a propyl group or a phenyl group.

（但し、式中Ｒ³は上述のＲ³の脂肪族不飽和結合を含有しない非置換又は置換の１価炭化水素基と同じであり、ｃは０又は１以上の整数であり、ｄは１以上の整数である。）
で表されるものが挙げられる。
ポリシロキサン架橋剤はそれぞれ単独でまたは２種以上を組み合わせて使用することができる。 Also, the following formula:

(In the formula, R ³ is the same as the above-mentioned unsubstituted or substituted monovalent hydrocarbon group not containing the aliphatic unsaturated bond of R ³ , c is 0 or an integer of 1 or more, and d is 1) (It is an integer above.)
The thing represented by is mentioned.
Polysiloxane crosslinking agents can be used alone or in combination of two or more.

The polysiloxane crosslinking agent is not particularly limited for its production. For example, a conventionally well-known thing is mentioned. Specifically, for example, the following general formulas: R ³ SiHCl ₂ and R ³ ₂ SiHCl (wherein R ³ is the same as the unsubstituted or substituted monovalent hydrocarbon group not containing the aliphatic unsaturated bond). Or at least one chlorosilane selected from the group, or the chlorosilane and the following general formula: R ³ ₃ SiCl and R ³ ₂ SiCl ₂ (wherein R ³ represents the above aliphatic unsaturated bond). It is the same as an unsubstituted or substituted monovalent hydrocarbon group that does not contain.) It can be obtained by combining and co-hydrolyzing at least one chlorosilane selected from. Moreover, what equilibrated polysiloxane obtained by cohydrolysis can be used as a polysiloxane crosslinking agent.

From the viewpoint that the polysiloxane crosslinking agent is excellent in rubber physical properties (toughness, elongation) after curing, the hydrogen atom bonded to the silicon atom of the polysiloxane crosslinking agent per mole of alkenyl group in the polysiloxane is 0.00. It is preferably used in an amount of 1 to 5 mol, more preferably 0.5 to 2.5 mol, and still more preferably 1.0 to 2.0 mol.
When the amount of SiH group is 0.1 mol or more, a cured rubber product (silicone resin) having sufficient curing and strength can be obtained.
When the amount of SiH groups is 5 mol or less, a hardened rubber cured product is obtained such that the cured product does not become brittle.
In the present invention, the polysiloxane (A) and the polysiloxane crosslinking agent (B) can be used as a mixture of the polysiloxane (A) and the polysiloxane crosslinking agent (B).

The organometallic compound will be described below.
The organometallic compound contained in the silicone resin composition of the present invention is at least one selected from the group consisting of organic zirconyl compounds, organic zinc compounds, organic magnesium compounds and organic potassium compounds having an organic group having 3 or more carbon atoms. is there.
The organometallic compound contained in the silicone resin composition of the present invention has a function of bleeding out on the surface of the silicone resin and reducing the surface tack of the silicone resin.

  The organometallic compound is not particularly limited as long as it is a compound formed by an organic group and a metal. In the present invention, the metal contained in the organometallic compound is at least one selected from the group consisting of zirconium, zinc, magnesium and potassium. In the present invention, zirconium as a metal included in the organometallic compound is zirconyl.

  Among these, zinc and zirconium are preferable as the metal contained in the organic metal compound from the viewpoint that the surface tackiness of the silicone resin is superior.

Examples of the organic group used for forming the organometallic compound include hydrocarbon groups having a hetero atom such as an oxygen atom, a nitrogen atom, and a sulfur atom.
The organic zirconyl compound has 3 or more carbon atoms in the organic group.
The number of carbon atoms in the organic group of the organic metal compound other than the organic zirconyl compound is preferably 3-20.
Examples of the hydrocarbon group include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, 2-ethylhexyl groups, nonyl groups, and decyl groups. An aryl group such as a phenyl group or a p-methylphenyl group;

Examples of the organic group include an alkoxy group such as a methoxy group, an ethoxy group, and an isopropoxy group; an aryloxy group such as a phenoxy group and a p-methylphenoxy group; an acetoxy group, a propionyloxy group, an isopropionyloxy group, and a butyronyloxy group. Group, octylonyloxy group, 2-ethylhexylonyloxy group, acyloxy group such as stearoyloxy group; acetyl group, propionyl group, isopropionyl group, butyronyl group, octylonyl group, 2-ethylhexylonyl group, Examples include acyl groups such as stearoyl groups.
The organic groups can be used alone or in combination of two or more.
The organic group which the organometallic compound has is preferably an octylonyloxy group, a 2-ethylhexylonyloxy group or an acetylacetonate from the viewpoint that the surface tackiness is superior.

Examples of the organometallic compound include salts and chelates.
The organometallic compound is preferably a chelate or salt of at least one metal selected from the group consisting of zirconium, zinc, magnesium and potassium, from the viewpoint of being superior in the surface tackiness of the silicone resin.

When the organometallic compound is a chelate, examples of the organic group include organic ligands such as β-diketone type compounds and o-hydroxyketone type compounds.
Examples of the β-diketone type compound include the following formulas (1) to (3).
R ³ —CO—CH ₂ —CO—R ³ (1)
R ³ —CO—CH ₂ —CO—OR ³ (2)
_{^{R 3 O-CO-CH 2}} -CO-OR 3 (3)
In the formula, R ³ represents an alkyl group such as a methyl group or a halogen-substituted alkyl group.

式中、それぞれのＲ⁴は独立に、アルキル基、ハロゲン化置換アルキル基、アルコキシ基を表す。
キレートが有する配位子としては、アセチルアセトナート、エチルアセチルアセトナートが好ましい態様として挙げられる。 Examples of the o-hydroxyketone type compound include the following formula (4).

Wherein each of R ⁴ independently represent an alkyl group, a halogen-substituted alkyl group, an alkoxy group.
As a ligand which a chelate has, acetylacetonate and ethylacetylacetonate are mentioned as a preferable aspect.

In the case where the organometallic compound is a salt, the salt of the organometallic compound is a preferred embodiment in which it is a carboxylate.
Carboxylic acid is not particularly limited. Examples include aliphatic carboxylic acids, alicyclic carboxylic acids, and aromatic carboxylic acids.

An organic zirconyl compound as an organometallic compound is a compound having an organic group having 3 or more carbon atoms and zirconyl [(ZrO) ²⁺ ].
The organic group contained in the organic zirconyl compound has 3 or more carbon atoms and more preferably 5 to 15 from the viewpoint that the surface tackiness is excellent and the compatibility is excellent.
Examples of the organic group possessed by the organic zirconyl compound include an acyloxy group having 3 or more carbon atoms and a β-diketone type compound. Specifically, for example, an acyloxy group such as a propionyloxy group, an isopropionyloxy group, a butyronyloxy group, an octylonyloxy group, a 2-ethylhexylonyloxy group, an acyloxy group derived from naphthenic acid; Such β-diketone type compounds can be mentioned.

Examples of the organic zirconyl compound include carboxylates such as bis (2-ethylhexanoic acid) zirconyl, zirconyl octylate, and zirconyl naphthenate.
Bis (2-ethylhexanoic acid) zirconyl is a compound represented by ZrO [CH ₃ CH ₂ CH ₂ CH ₂ CH (CH ₂ CH ₃ ) CO ₂ ] ₂ .

The organozinc compound as the organometallic compound is not particularly limited as long as it is a compound having zinc and an organic group. Specifically, for example, zinc octylate, zinc neodecanoate, zinc laurate, zinc stearate, zinc alicyclic carboxylate such as zinc naphthenate, zinc benzoate, zinc benzoate, p-tert - carboxylates and aromatic carboxylic acids, zinc, such as butyl benzoate zinc; Zn (II) acetylacetonate _{[Zn (acac) 2],} 2,2,6,6- tetramethyl-3,5-heptane Zinc chelates such as dinate Zn.

  The organomagnesium compound as the organometallic compound is not particularly limited as long as it is a compound having magnesium and an organic group. Specific examples include carboxylates such as magnesium octylate, magnesium laurate, and magnesium naphthenate; and chelates such as magnesium acetylacetonate.

  The organic potassium compound as the organic metal compound is not particularly limited as long as it is a compound having potassium and an organic group. Specific examples include carboxylates such as potassium octylate; chelates such as potassium acetylacetonate.

Among these, bis (2-ethylhexanoic acid) zirconyl, octylic acid zirconyl, zinc octylate, Zn (II) acetylacetonate [Zn (acac) ₂ ], octylic acid from the viewpoint of being superior in the surface tackiness of the silicone resin Potassium and magnesium octylate are preferable, and bis (2-ethylhexanoic acid) zirconyl and Zn (II) acetylacetonate [Zn (acac) ₂ ] are more preferable.
The organometallic compounds can be used alone or in combination of two or more.

  The organometallic compound is preferably used in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the polysiloxane and the polysiloxane crosslinking agent from the viewpoint that the surface tackiness of the silicone resin is superior. 0.1 to 10 parts by mass is more preferable, 0.5 to 5 parts by mass is further preferable, and 1 to 3 parts by mass is particularly preferable.

The silicone resin composition of the present invention can contain an organometallic compound having a metal other than zirconium, zinc, magnesium or potassium as the organometallic compound.
Examples of metals other than zirconium, zinc, magnesium, or potassium include alkali metals such as sodium; alkaline earth metals such as calcium; aluminum, iron, tin, titanium, gallium, indium, germanium, scandium, and yttrium. It is done. The organic group that the organometallic compound having a metal other than zirconium, zinc, magnesium, or potassium has is not particularly limited. For example, a conventionally well-known thing is mentioned.
Moreover, the silicone resin composition of this invention can contain organic zirconium compounds other than the organic zirconyl compound which has a C3 or more organic group.

  Examples of the organic zirconium compound other than the organic zirconyl compound having an organic group having 3 or more carbon atoms include, for example, an organic zirconyl compound having an organic group having 2 or less carbon atoms such as zirconyl diacetate; zirconium normal propylate, zirconium normal Zirconium carboxylates such as butyrate, zirconium acetate, zirconium monostearate, zirconium tristearate; zirconium bisacetylacetonate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium monoethylacetoacetate, zirconium acetylacetate Zirconium chelates such as nate bisester acetoacetate.

In the present invention, the organometallic compound is used as a tack reducing component that bleeds out on the surface of the silicone resin and reduces the surface tack of the silicone resin.
In the present invention, it is considered that the organometallic compound does not contribute to the hydrosilylation reaction between the polysiloxane and the polysiloxane crosslinking agent.

The silicone resin composition of the present invention preferably further contains a hydrosilylation reaction catalyst (polysiloxane catalyst) from the viewpoint of excellent curability.
The hydrosilylation reaction catalyst (polysiloxane catalyst) that can be used in the silicone resin composition of the present invention includes an alkenyl group possessed by the polysiloxane and a hydrogen atom bonded to a silicon atom possessed by the polysiloxane crosslinking agent (that is, SiH). It is a catalyst for promoting the addition reaction with the group.

The hydrosilylation reaction catalyst (polysiloxane catalyst) is not particularly limited. For example, a conventionally well-known thing is mentioned.
Specific examples include, for example, platinum group metals such as platinum (including platinum black), rhodium, palladium, etc .; H ₂ PtCl ₄ · nH ₂ O, H ₂ PtCl ₆ · nH ₂ O, NaHPtCl ₆ · nH ₂ O, _{KHPtCl 6 · nH 2 O, Na} 2 PtCl 6 · nH 2 O, K 2 PtCl 4 · nH 2 O, PtCl 4 · nH 2 O, PtCl 2, Na 2 HPtCl 4 · nH 2 O ( where, in wherein, n Is an integer from 0 to 6, preferably 0 or 6), such as platinum chloride, chloroplatinic acid and chloroplatinate; alcohol-modified chloroplatinic acid (see US Pat. No. 3,220,972) A complex of chloroplatinic acid and an olefin (see US Pat. Nos. 3,159,601, 3,159,662, and 3,775,452); platinum black, palladium Platinum group metals such as Al Supported on a carrier such as Mina, silica, carbon, etc .; rhodium-olefin complex; chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst); platinum chloride, chloroplatinic acid or chloroplatinate and vinyl group-containing siloxane, especially Examples thereof include platinum group metal catalysts such as a complex with a vinyl group-containing cyclic siloxane.

The hydrosilylation reaction catalyst (polysiloxane catalyst) can be used in a catalytic amount range. Usually, it can be 0.1-500 ppm in conversion of the mass of the platinum group metal with respect to the total amount of polysiloxane and polysiloxane crosslinking agent.
The hydrosilylation reaction catalyst (polysiloxane catalyst) can be used as a mixture with the polysiloxane (A).

The silicone resin composition of the present invention contains additives other than polysiloxane, polysiloxane crosslinking agent, organometallic compound, and hydrosilylation reaction catalyst (polysiloxane catalyst) as necessary, as long as the object and effect of the present invention are not impaired. Can be contained.
Examples of additives include inorganic fillers, antioxidants, lubricants, ultraviolet absorbers, thermal light stabilizers, dispersants, antistatic agents, polymerization inhibitors, antifoaming agents, curing accelerators, solvents, inorganic phosphors, Anti-aging agent, radical inhibitor, adhesion improver, flame retardant, surfactant, storage stability improver, ozone anti-aging agent, thickener, plasticizer, radiation blocker, nucleating agent, coupling agent, conductive Examples include property-imparting agents, phosphorus peroxide decomposers, pigments, metal deactivators, and physical property modifiers. Various additives are not particularly limited. For example, a conventionally well-known thing is mentioned.

  The inorganic filler is not particularly limited, and examples thereof include fine particles that do not deteriorate optical properties. Specific examples include alumina, aluminum hydroxide, fused silica, crystalline silica, ultrafine powder amorphous silica, hydrophobic ultrafine silica, talc, calcium carbonate, and barium sulfate.

Examples of inorganic phosphors include yttrium, aluminum, garnet-based YAG phosphors, ZnS phosphors, Y ₂ O ₂ S phosphors, red-emitting phosphors, and blue-emitting phosphors that are widely used in LEDs. Body, green light emitting phosphor.

The production of the silicone resin composition of the present invention is not particularly limited. For example, it can be produced by mixing a polysiloxane, a polysiloxane crosslinking agent, an organometallic compound, and a hydrosilylation reaction catalyst and additives that can be used as necessary.
The silicone resin composition of the present invention can be a one-component type or a two-component type.

  When the silicone resin composition of the present invention is made into a two-pack type, it is manufactured separately into a first liquid containing a polysiloxane crosslinking agent and a hydrosilylation reaction catalyst and a second liquid containing a polysiloxane and an organometallic compound. be able to. The additive can be added to one or both of the first liquid and the second liquid.

The silicone resin composition of the present invention has a condition of 23 ° C. after mixing the liquid containing the component other than the polysiloxane crosslinking agent and the polysiloxane crosslinking agent from the viewpoint that the length of the pot life is appropriate. The viscosity after 24 hours below is preferably 5 to 10,000 mPa · s, more preferably 5 to 5,000 mPa · s.
In the present invention, the silicone resin composition of the present invention is mixed and placed at 23 ° C., and the viscosity of the composition after 24 hours from the mixing is measured using an E-type viscometer at 23 ° C. Suppose that the humidity is 55%.

Examples of the method of using the silicone resin composition of the present invention include applying the composition of the present invention to a substrate (for example, an optical semiconductor element) and curing the composition.
The method for applying and curing the silicone resin composition of the present invention is not particularly limited. Examples thereof include a method using a dispenser, a potting method, screen printing, transfer molding, and injection molding.

The silicone resin composition of the present invention can be cured by heating.
The heating temperature when the silicone resin composition of the present invention is heated and cured is usually 100 ° C. or higher, and preferably 120 ° C. or higher, from the viewpoint of being superior in the surface tackiness of the silicone resin. More preferably, it is 120 degreeC, and it is still more preferable that it is 120-180 degreeC.

When the heating temperature is within such a range, the organometallic compound tends to bleed out on the surface of the silicone resin. For this reason, it is considered that the organometallic compound can more easily form a coating of the organometallic compound on the surface of the silicone resin, and as a result, the surface tack of the silicone resin can be further reduced.
The above mechanism is the inventor's inference, and even if the mechanism is different, it is within the scope of the present invention.

  Further, the silicone resin obtained by curing the silicone resin composition of the present invention is a silicone resin having no tack on the surface, that is, a surface tack-free.

The silicone resin composition of the present invention is not particularly limited for its use. For example, the sealing material composition for electronic materials, the sealing material composition for buildings, the sealing material composition for motor vehicles, and the adhesive composition are mentioned.
Electronic materials include, for example, lead frames, wired tape carriers, wiring boards, glass, silicon wafers and other supporting members; optical semiconductor elements; active elements such as semiconductor chips, transistors, diodes, thyristors; capacitors, resistors, Examples include passive elements such as coils.

  The silicone resin composition of the present invention is used in applications such as display materials, optical recording medium materials, optical equipment materials, optical component materials, optical fiber materials, optical / electronic functional organic materials, and semiconductor integrated circuit peripheral materials. be able to.

In the silicone resin composition of the present invention, the addition of an organometallic compound to the polysiloxane and the polysiloxane crosslinking agent can reduce the surface tack of the silicone resin and impart sufficient rubber elasticity to the silicone resin. can do.
That is, the silicone resin obtained from the silicone resin composition of the present invention is excellent in the balance between surface tackiness and rubber elasticity.

  In the present invention, the polysiloxane and the polysiloxane cross-linking agent can be substantially free of alkoxysilyl groups and silanol groups from the viewpoint of being excellent in the surface tackiness of the silicone resin.

Next, the silicone resin of the present invention will be described below.
The silicone resin of the present invention is obtained by curing the silicone resin composition of the present invention.

The composition used for the silicone resin of the present invention is not particularly limited as long as it is the silicone resin composition of the present invention.
By using the silicone resin composition of the present invention, a silicone resin excellent in surface tackiness can be obtained.
Moreover, when using the silicone resin of this invention as a sealing body, it is excellent in the surface tack property of a sealing body, formation of a sealing body can be performed by 1 process, it is excellent in productivity, and a sealing body is 1 layer. It can be a structure.

The curing will be described below.
In the present invention, the silicone resin composition can be cured by heating.

  When the silicone resin composition is cured by heating, it is easy to bleed out the organometallic compound, the surface tackiness of the silicone resin is excellent, the curability is excellent, and the curing time and pot life can be set to an appropriate length. From the viewpoint that the alcohol as a by-product due to the condensation reaction can be prevented from foaming, cracks in the silicone resin can be suppressed, and the smoothness, moldability, and physical properties of the silicone resin are excellent. A method of curing at 20 ° C. (preferably 150 ° C.) within 20 hours (preferably 12 hours) is preferable.

  The silicone resin of the present invention is excellent in surface tackiness and rubber elasticity. Evaluation of the surface tack which the silicone resin of this invention has is as having described in the Example of this-application specification.

The silicone resin of the present invention preferably has a JIS A hardness of 70 or less. In such a range, the silicone resin has a reduced tack on its surface, and has rubber elasticity and excellent mechanical strength.
The silicone resin preferably has a JIS A hardness of 10 to 50 and more preferably 10 to 20 from the viewpoint that the surface tack is further reduced, the rubber elasticity is excellent, and the flexibility is excellent. .

  In the present invention, the JIS A hardness is obtained by curing a silicone resin composition at 150 ° C. for 12 hours to prepare a sample having a size of 5 cm long × 5 cm wide × 2 mm thick. The JIS A hardness is measured in accordance with JIS K6253: 2006.

The silicone resin of the present invention can be used as a sealing material for LED chips.
The LED chip is not particularly limited with respect to its emission color. For example, blue, red, yellow, green, and white are mentioned.
The LED chips can be used alone or in combination of two or more.

Next, the sealed optical semiconductor element of the present invention will be described below.
In the sealed optical semiconductor element of the present invention, the LED chip is sealed with the silicone resin of the present invention.

If the silicone resin used for the optical semiconductor element sealing body of this invention is a silicone resin of this invention, it will not restrict | limit in particular.
In the encapsulated optical semiconductor element of the present invention, by using the silicone resin composition of the present invention as the silicone resin composition, the obtained optical semiconductor element encapsulated body has reduced surface tack and excellent surface tackiness. It is excellent in rubber elasticity and flexibility, can form the sealing body in one step, is excellent in productivity, and can have a single layer structure.

Moreover, the LED chip used for the optical semiconductor element sealing body of this invention is not restrict | limited in particular about the luminescent color.
For example, a blue LED chip can be coated with a silicone resin composition containing a fluorescent material such as yttrium, aluminum, and garnet to obtain a white LED.
When the red, green, and blue LED chips are used to make the emission color white, for example, each LED chip is sealed with the silicone resin composition of the present invention, and a sealed body of these three color LED chips. Can be used, or three-color LED chips can be combined and sealed with the silicone resin composition of the present invention to form one light source.
The size and shape of the LED chip are not particularly limited.
The type of the LED chip is not particularly limited, and examples thereof include a high power LED, a high luminance LED, a general luminance LED, a white LED, and a blue LED.

In addition to LEDs, examples of the optical semiconductor element used in the sealed optical semiconductor element of the present invention include an organic electroluminescent element (organic EL), a laser diode, and an LED array.
As an optical semiconductor element used for the optical semiconductor element sealing body of the present invention, for example, an optical semiconductor element is bonded to a substrate such as a lead frame by die bonding, and the substrate or the like is bonded by chip bonding, wire bonding, wireless bonding, or the like. The connected one can be used.
The hardened | cured material used for the optical semiconductor element sealing body of this invention should just seal the optical semiconductor element. As the optical semiconductor element sealing body of the present invention, for example, when the cured product directly seals the optical semiconductor element, when it is a shell type, when it is a surface mounting type, a plurality of optical semiconductor element sealing bodies The case where it fills between is mentioned.

As a manufacturing method of the optical semiconductor element sealing body of the present invention,
An application step of applying the silicone resin composition of the present invention to an LED chip, and heating the LED chip coated with the silicone resin composition to cure the silicone resin composition to obtain a cured product, And a curing step of bleeding out the metal compound on the surface of the cured product.

In the coating step, the silicone resin composition of the present invention is applied to the LED chip to obtain an LED chip coated with the silicone resin composition.
The LED chip used in the coating process has the same meaning as described above. The silicone resin composition used is not particularly limited as long as it is the silicone resin composition of the present invention.
The method of application is not particularly limited. For example, a potting method, transfer molding, injection molding, and a screen printing method are mentioned.

Next, in the curing step, the LED chip coated with the silicone resin composition is heated to cure the silicone resin composition to obtain a cured product, and the organometallic compound is bleed on the surface of the cured product. By making it out, the sealed optical semiconductor element of the present invention can be obtained.
Regarding the bleed-out of the organometallic compound, the organometallic compound is easily cured from the viewpoint of obtaining a cured product having a coating of the organometallic compound in the upper layer and a silicone resin portion as the lower layer. One preferred embodiment is at least a bleed-out on the upper surface of the object.
The temperature which heats a silicone resin composition is synonymous with the thing in the silicone resin of this invention.

The optical semiconductor element sealing body of the present invention will be described below with reference to the accompanying drawings. The sealed optical semiconductor element of the present invention is not limited to the attached drawings.
6 is a top view schematically showing an example of the sealed optical semiconductor element of the present invention, and FIG. 7 is a cross-sectional view schematically showing an AA cross section of the sealed optical semiconductor element shown in FIG. is there.
In FIG. 6, reference numeral 600 denotes a sealed optical semiconductor element according to the present invention, and the sealed optical semiconductor element 600 includes an LED chip 601 and a silicone resin 603 that seals the LED chip 601. The composition of the present invention can be used for the silicone resin 603. In FIG. 6, the leads, wires, and substrate 609 are omitted.
In FIG. 7, an LED chip 601 is bonded to a substrate 609 with, for example, an adhesive or solder (not shown). Examples of the substrate include ceramics, multilayer ceramics, multilayer prints, and lead frames. In FIG. 7, wires are omitted.
Further, T in FIG. 7 indicates the thickness of the silicone resin 603. That is, T is a value when the thickness of the silicone resin 603 is measured from an arbitrary point 605 on the surface of the LED chip 601 in a direction perpendicular to the surface 607 to which the point 605 belongs.
From the viewpoint of ensuring transparency and excellent sealing properties, the sealed optical semiconductor element of the present invention preferably has a thickness (T in FIG. 7) of 0.1 mm or more, 0.5 to 1 mm. It is more preferable that

The case where a white LED is used as an example of the sealed optical semiconductor element of the present invention will be described below with reference to the accompanying drawings.
FIG. 1 is a cross-sectional view schematically showing an example of a sealed optical semiconductor element of the present invention.
FIG. 3 is a cross-sectional view schematically showing an example of the sealed optical semiconductor element of the present invention.
The sealed optical semiconductor element of the present invention is not limited to the attached drawings.

In FIG. 1, the white LED 200 has a ceramic package 204 on a substrate 210.
The package 204 is provided with a cavity (not shown) that is lowered by one step inside. A blue LED chip 203 and a silicone resin 202 are arranged in the cavity. The silicone resin 202 is obtained by curing the silicone resin composition of the present invention, and can contain yttrium, aluminum, and garnet activated with cerium as a fluorescent material.
The blue LED chip 203 is fixed on the substrate 210 with a mount member 201.
Each electrode (not shown) of the blue LED chip 203 and the external electrode 209 provided on the package 204 are wire-bonded by a conductive wire 207.
In the cavity (not shown) of the package 204, the hatched portion 206 may be filled with the silicone resin composition of the present invention. When the silicone resin composition of the present invention is filled up to the shaded portion 206, the silicone resin 202 is a combination of the shaded portion 206.
As shown in FIG. 1, the silicone resin 202 can seal the LED chip with a single layer.

In FIG. 3, the white LED 300 includes a substrate 310, a blue LED chip 303, and inner leads 305 inside a silicone resin 306 having a lamp function.
The substrate 310 is provided with a cavity (not shown) that is lowered by one step on the head. A blue LED chip 303 and a silicone resin 302 are arranged in the cavity. The silicone resin 302 is obtained by curing the silicone resin composition of the present invention, and can contain yttrium, aluminum, and garnet activated with cerium as a fluorescent material. Further, the silicone resin 306 can be formed using the silicone resin composition of the present invention.
The blue LED chip 303 is fixed on the substrate 310 with a mount member 301.
Each electrode (not shown) of the blue LED chip 303 is bonded to the substrate 310 and the inner lead 305 by a conductive wire 307.

  Although the LED chip is described as a blue LED chip in FIGS. 1 and 3, LED chips of three colors of red, green, and blue can be arranged in the cavity. The portions of the silicone resins 202 and 302 can be sealed with the silicone resin composition of the present invention by, for example, a potting method to form a sealed optical semiconductor element.

The encapsulated optical semiconductor element of the present invention is particularly limited in its production except that the silicone resin of the present invention (the raw material of the silicone resin of the present invention is the silicone resin composition of the present invention) is used as the silicone resin. Not. For example, a conventionally well-known thing is mentioned.
Further, the heating temperature at the time of producing the sealed optical semiconductor element of the present invention is the same as the heating temperature at the time of curing the silicone resin composition of the present invention. It is preferable from the viewpoint that it is more excellent in performance.

A case where the sealed optical semiconductor element of the present invention is used for an LED display will be described with reference to the accompanying drawings.
FIG. 4 is a diagram schematically showing an example of an LED display using the sealed optical semiconductor element of the present invention.
FIG. 5 is a block diagram of an LED display device using the LED display shown in FIG.
The LED display and the LED display device in which the sealed optical semiconductor element of the present invention is used are not limited to the attached drawings.

  In FIG. 4, the LED display 400 is configured by arranging white LEDs 401 in a matrix form inside a housing 404, fixing the white LEDs 401 with a filler 406, and arranging a light shielding member 405 in a part of the housing 404. Has been. The silicone resin composition of the present invention can be used as the filler 406.

  In FIG. 5, the LED display device 500 includes an LED display 501 using a white LED sealing body. The LED display 501 is electrically connected to a lighting circuit that is a drive circuit. A display or the like that can display various images by output pulses from the driving circuit can be provided. The driving circuit includes a RAM (Random, Access, Memory) 504 that temporarily stores input display data, and a gradation for lighting individual white LEDs to a predetermined brightness from the data stored in the RAM 504. A gradation control circuit (CPU) 503 that calculates a signal and a driver 502 that is switched by an output signal of the gradation control circuit (CPU) 503 and turns on a white LED are provided. A gradation control circuit (CPU) 503 calculates the lighting time of the white LED from the data stored in the RAM 504 and outputs a pulse signal. In addition, the optical semiconductor element sealing body of this invention can be used for the LED display and LED display apparatus which can perform color display.

  Applications of the sealed optical semiconductor element of the present invention include, for example, automotive lamps (head lamps, tail lamps, directional lamps, etc.), household lighting fixtures, industrial lighting fixtures, stage lighting fixtures, displays, signals, and projectors. Is mentioned.

The sealed optical semiconductor element of the present invention and the silicone resin of the present invention are excellent in surface tackiness, hardly adhere to dust and dust, can suppress deterioration in the quality of the optical semiconductor element, are elastic, flexible, and flexible. Excellent in balance and excellent balance between surface tack and rubber elasticity. In addition, the transmittance of the silicone resin is less likely to decrease due to heat and light during the manufacture of the sealed optical semiconductor element or when used as an LED (especially a white LED). Excellent in adhesion and adhesion to the optical semiconductor element. Moreover, the optical semiconductor element sealing body of this invention can make a silicone resin into 1 layer, and can make the sealing body formation process conventionally required 2 processes into 1 process, and is excellent in productivity.
In addition, the silicone resin composition of the present invention is excellent in surface tackiness, can realize a silicone resin excellent in balance between surface tackiness and rubber elasticity, and can seal an electronic material in a single step, thereby improving productivity. Excellent curing time and pot life, low curing temperature, excellent curability, excellent thermosetting, excellent transparency, heat-resistant coloring stability, moldability, cracks and bubbles are unlikely to occur It becomes a silicone resin excellent in mechanical strength.
Conventionally, a composition containing a polysiloxane having at least two alkenyl groups bonded to a silicon atom, a polysiloxane crosslinking agent having at least two hydrogen groups bonded to a silicon atom, a platinum catalyst, and a zirconium-based compound is provided. In the case where the system has an epoxy group or an alkoxy group as an adhesive component, the zirconium-based compound has been used as an adhesion promoter. That is, when the composition has an epoxy group, the zirconium compound acts as an epoxy group ring-opening accelerator, and when the composition has an alkoxy group, the zirconium compound reacts with the alkoxy group and the substrate as the adherend. Acts as an accelerator.
Conventionally, organometallic compounds have been used as condensation catalysts for organopolysiloxanes having alkoxysilyl groups or silanol groups.
On the other hand, the organometallic compound in the present invention is used as a tack mitigating component that reduces the surface tack of the silicone resin by bleeding out on the surface of the silicone resin to form a film.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
1. Evaluation As shown below, surface tackiness (finger touch, shirasu spraying) and JIS A hardness were evaluated. The results are shown in Table 1.

(1) Surface tackiness (finger touch)
The surface of the sample for evaluation was touched with a finger to confirm surface tackiness.
The evaluation criteria are “○” when the sample surface has no tack and the finger slides on the sample surface, and “△” when there is a slight grip (the finger does not slide on the sample surface). The case was set as “x”.

(2) Surface tackiness (shirasu spraying)
The sample was 5 cm in length and 5 cm in width, and 0.47 g of shirasu 677 (particle size 100 μm) was sprinkled over the entire surface of the sample, and then N _{2 with} a pressure of 0.15 MPa was applied from above the shirasu using a hose with an inner diameter of 5 mm. Gas (nitrogen gas) was injected for 10 seconds. At this time, the air injection angle with respect to the sample was set to 45 degrees.

The weight of the sample before applying the shirasu and the weight of the sample after injecting N ₂ gas (nitrogen gas) were measured, and the removal rate of the shirasu adhering to the sample was calculated.
Exclusion rate(%)
= 100-[(weight of sample after injecting N ₂ gas) − (weight of sample before applying shirasu)] / 0.47 × 100

  The removal rate of shirasu is preferably 98 to 100%, and more preferably 99 to 100%.

(3) JIS A hardness The sample was 5 cm long x 5 cm wide x 2 mm thick, and the JIS A hardness of the sample was measured in accordance with JIS K6253: 2006.

2. Sample Preparation (1) Sample Preparation Sample preparation will be described below with reference to the accompanying drawings.
FIG. 2 is a cross-sectional view schematically showing a mold used for curing the silicone resin composition of the present invention in Examples.
In FIG. 2, a mold 8 includes a PET film 5 disposed on a glass 3 (the size of the glass 3 is 10 cm long, 10 cm wide, 4 mm thick), and a silicon mold spacer 1 ( 5 cm in length, 5 cm in width, and 2 mm in height) are arranged.
Silicone resin composition 6 is poured into spacer 1 using mold 8, the sample is cured as follows, silicone resin composition 6 is cured, silicone resin is removed from mold 8, and silicone resin 6 (thickness) 2 mm) is obtained.

(2) Curing of sample The mold 8 filled with the silicone resin composition was put in an electric oven, and the composition was heated and cured at the treatment temperature shown in Table 1 for 12 hours to obtain a silicone resin having a thickness of 2 mm. It was.
The obtained silicone resin was used as a sample for evaluation.

3. Preparation of silicone resin composition The components shown in Table 1 below were uniformly mixed in the amounts shown in the same table (unit: parts by mass) using a vacuum stirrer to prepare a composition.

Each component shown in Table 1 is as follows.
-Mixture of polysiloxane and polysiloxane crosslinking agent: Mixture of vinyl polysiloxane as the main polysiloxane and hydrogen polysiloxane as the polysiloxane crosslinking agent (trade name KE106, manufactured by Shin-Etsu Chemical Co., Ltd.)
Polysiloxane catalyst: Trade name CAT-RG (mixture of Pt catalyst and vinylpolysiloxane at both ends), manufactured by Shin-Etsu Chemical Co., Ltd. Organometallic compound 1: Zn (acac) ₂ , manufactured by Kanto Chemical Co., Ltd. Organometallic compound 2 : Zinc octylate (Octope Zn, manufactured by Hope Pharmaceutical Co., Ltd.)
Organic metal compound 3: Nikka octix zirconium (bis (2-ethylhexanoic acid) zirconyl, Zr 12%, manufactured by Nippon Chemical Industry Co., Ltd.)
Organic metal compound 4: Magnesium octylate (manufactured by Nippon Chemical Industry Co., Ltd.)
・ Organic metal compound 5: Potassium octylate (manufactured by Nippon Chemical Industry Co., Ltd.)
In Table 1, organometallic compound 2 is shown as the net amount of zinc octylate.
Moreover, the organometallic compound 3 was described as the net amount of bis (2-ethylhexanoic acid) zirconyl.

As is apparent from the results shown in Table 1, Comparative Example 1 containing no organometallic compound was inferior in surface tackiness.
On the other hand, Examples 1-7 became a silicone resin excellent in surface tackiness.
Moreover, the silicone resin obtained from Examples 1-7 was excellent in the balance of surface tack property and hardness (rubber elasticity).
In Examples 1-4, 6, and 7, a silicone resin having particularly excellent surface tackiness could be obtained by setting the treatment temperature of the silicone resin composition to 150 ° C.
The silicone resin of the present invention will be described below with reference to FIGS. 2 and 8 which are attached drawings. The silicone resin of the present invention is not limited to the attached drawings.
FIG. 8 is a cross-sectional view schematically showing an example of a cross section of a cured product obtained by removing the silicone resin obtained using the mold shown in FIG. 2 from the mold.
In FIG. 8, the cured product 6 is a silicone resin obtained using the silicone resin composition of the present invention (the silicone resin compositions of Examples 1 to 7).
The cured product 6 has a silicone resin portion 18 and a coating 14 of an organometallic compound on the surface of the silicone resin portion 18.
The cured product 6 is not in a state where powder is blown on the surface 10 of the cured product 6 and is entirely transparent. In FIG. 8, the boundary 16 between the silicone resin portion 18 and the coating 14 is indicated by a dotted line. However, since the cured product 6 is transparent, the boundary 16 cannot be visually confirmed.
However, on the surface 10 of the cured product 6, the organometallic compound bleeds out to form the coating 14, so that the surface 10 is tack-free. In the embodiment, the finger slips on the surface 10, while the cured product 6 However, tack remained on the back surface 12 in contact with the mold 8.
Further, when the cured product 6 was bent 180 ° with the surface 10 on the inner side, it was possible to visually confirm that the surface 10 had numerous fine white wrinkles. On the other hand, even if the back surface 12 of the cured product 6 was bent in the same manner, the back surface 12 was not wrinkled and remained transparent as a whole.
Moreover, the hardened | cured material 6 had the softness | flexibility on the whole rather than the state whose surface 10 was especially hard compared with the back surface 12. FIG.
On the other hand, in Comparative Example 1, the entire surface (not shown) of the cured product had tack, and the tack on the front surface and the back surface was similar.
For these reasons, the cured product 6 obtained from the silicone resin composition of the present invention is considered to have a coating 14 on the surface 10. Further, from the components contained in the silicone resin composition of the present invention, the organometallic compound (C) bleeds out from the silicone resin portion 18 cured by the reaction of the polysiloxane (A) and the polysiloxane crosslinking agent (B). The inventor of the present application estimates that the coating film 14 is formed.

FIG. 1 is a cross-sectional view schematically showing an example of a sealed optical semiconductor element of the present invention. FIG. 2 is a cross-sectional view schematically showing a mold used for curing the composition of the present invention in Examples. FIG. 3 is a cross-sectional view schematically showing an example of the sealed optical semiconductor element of the present invention. FIG. 4 is a diagram schematically showing an example of an LED display using the sealed optical semiconductor element of the present invention. FIG. 5 is a block diagram of an LED display device using the LED display shown in FIG. FIG. 6 is a top view schematically showing an example of the sealed optical semiconductor element of the present invention. 7 is a cross-sectional view schematically showing an AA cross section of the sealed optical semiconductor element shown in FIG. FIG. 8 is a cross-sectional view schematically showing an example of a cross section of a cured product obtained by removing the silicone resin obtained using the mold shown in FIG. 2 from the mold.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Spacer 3 Glass 5 PET film 6 Silicone resin composition (after hardening, it becomes silicone resin 6 and hardened material 6)
Type 8
DESCRIPTION OF SYMBOLS 10 Front surface 12 Back surface 14 Coating 16 Boundary 18 Silicone resin part 200, 300 White LED 201, 301 Mount member 202, 302 Silicone resin 203, 303 Blue LED chip 204 Package 206 Diagonal part 306 Silicone resin 207, 307 Conductive wire 209 External electrode 210, 310 Substrate 305 Inner lead 400, 501 LED display 401 White LED 404 Case 405 Light shielding member 406 Filler 500 LED display device 502 Driver 501 LED display 503 Gradation control means (CPU)
504 Image data storage means (RAM) 600 Optical semiconductor element sealing body of the present invention 601 LED chip 603 Silicone resin 605 point 607 Surface to which point 605 belongs 609 Substrate 611 Shaded part T Silicone resin 603 thickness

Claims (8)

(A) a polysiloxane having at least two alkenyl groups bonded to a silicon atom;
(B) a polysiloxane crosslinking agent having at least two hydrogen groups bonded to silicon atoms;
(C) A silicone resin composition comprising at least one organic metal compound selected from the group consisting of an organic zirconyl compound having an organic group having 3 or more carbon atoms, an organic zinc compound, an organic magnesium compound, and an organic potassium compound.   The silicone resin composition according to claim 1, wherein the alkenyl group is a vinyl group or a (meth) acryloyl group.   The silicone resin composition according to claim 1 or 2, wherein the organometallic compound is a chelate or salt of at least one metal selected from the group consisting of zirconium, zinc, magnesium and potassium.   The silicone resin composition according to any one of claims 1 to 3, wherein the organometallic compound is used in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the polysiloxane and the polysiloxane crosslinking agent. object.   The silicone resin obtained by hardening the silicone resin composition in any one of Claims 1-4.   6. The silicone resin according to claim 5, wherein the JIS A hardness after the curing is 70 or less.   The optical semiconductor element sealing body by which the LED chip is sealed with the silicone resin of Claim 5 or 6.   An application step of applying the silicone resin composition according to any one of claims 1 to 4 to the LED chip, and heating the LED chip to which the silicone resin composition has been applied to cure the silicone resin composition. The manufacturing method of the optical semiconductor element sealing body which has a hardening process which makes it a hardened | cured material and bleeds out the said organometallic compound on the surface of the said hardened | cured material.

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