JP4788837B2 - Silicone resin composition and method for using the same, silicone resin, silicone resin-containing structure, and optical semiconductor element sealing body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicone resin composition which can maintain transparency and is excellent in sulfur resistance, a method for using the same, a silicone resin, a silicone resin-containing structure, and an optical semiconductor device sealed body. <P>SOLUTION: The silicone resin composition includes a component (A): a polysiloxane having at least two alkenyl groups each combined with a silicon atom, a component (B): a polysiloxane crosslinking agent having at least two hydrogen groups each combined with a silicon atom, a component (C): a hydrosilylation reaction catalyst, and a component (D): a zinc compound. The component (D) is contained in an amount of 0.1-5 pts.mass based on 100 pts.mass of the sum of the component (A) and the component (B). <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a silicone resin composition and a method for using the same, a silicone resin, a silicone resin-containing structure, and a sealed optical semiconductor element.

Conventionally, it has been proposed to use an epoxy resin as a resin for a composition for sealing an optical semiconductor (for example, Patent Document 1). However, the encapsulant obtained from the composition containing the epoxy resin has a problem that the color of the encapsulant is yellowed by heat generated from the white LED element.
A room temperature-curable organopolysiloxane containing an organopolysiloxane having two silanol groups, a silane compound having two or more hydrolyzable groups bonded to a silicon atom in one molecule, and an organic zirconium compound. Siloxane compositions have been proposed (for example, Patent Documents 2 and 3).
It has also been proposed to mix and heat a condensation catalyst to diorganopolysiloxane having two silanol groups and silane having three or more alkoxy groups (for example, Patent Documents 4 and 5).

Japanese Patent Laid-Open No. 10-228249 Japanese Patent Laid-Open No. 2001-200161 Japanese Patent Laid-Open No. 2-196860 JP 2007-224089 A JP 2006-206700 A

However, in the case of silicone resin, gas permeability is higher than epoxy resin and air easily passes through, so the silver plating of the optical semiconductor package is easily discolored over time due to hydrogen sulfide in the air. Tends to decrease.
In addition, in the case of a silicone resin, it is generally performed to harden the resin in order to improve the sulfidation resistance. In that case, however, there is a risk of curing shrinkage, peeling from the LED package, and wire breakage. .

The present inventors have found that by adding a zinc compound to a silicone resin composition, the anti-sulfurity is exhibited and the discoloration of silver is suppressed, and the present invention has been completed. That is, the present invention provides a silicone resin composition that can maintain transparency and has excellent sulfidation resistance, a method for using the same, a silicone resin, a silicone resin-containing structure, and a sealed optical semiconductor element. .
In addition, the present inventors have clarified that when a zinc compound is added to the silicone resin composition, a decrease in long-term reliability at high temperatures may be observed, and further, by adding predetermined components, It was found that the long-term reliability is excellent.

That is, this invention provides the following 1-14.
1. (A) component: polysiloxane having at least two alkenyl groups bonded to silicon atoms;
(B) component: a polysiloxane crosslinking agent having at least two hydrogen groups bonded to silicon atoms;
(C) component: a hydrosilylation reaction catalyst;
(D) component: zinc bisacetylacetonate and / or carboxylic acid zinc salt ,
The silicone resin composition which contains 0.1-5 mass parts of said (D) component with respect to a total of 100 mass parts of said (A) component and said (B) component.

2. 2. The silicone resin composition according to 1 above, wherein the content of the silicon compound having a silanol group is less than 0.1% by mass .
3. 3. The silicone resin composition according to 1 or 2 above , wherein the zinc carboxylate is zinc bis 2-ethylhexanoate .
4). 4. The silicone resin composition according to any one of 1 to 3, wherein the alkenyl group is a vinyl group or a (meth) acryloyl group.
5. 5. The silicone resin composition according to any one of 1 to 4 above, which is used for sealing an optical semiconductor element.
6). 6. The silicone resin composition according to any one of 1 to 5 above, which is used in the presence of silver.
7). Furthermore, the silicone resin composition in any one of said 1-6 containing (E) component: A boron compound and / or (F) component: Phosphate ester.
8). Furthermore, the silicone resin composition in any one of said 1-7 containing a bis (alkoxy) alkane and / or an isocyanurate derivative.
9. It is a silicone resin composition in any one of said 1-8,
On the metal layer obtained using a Group 11 metal, the silicone resin composition is applied to a thickness of 1 mm and cured to form a laminate having the metal layer and the silicone resin layer,
A sulfidation test is performed in which the laminate is placed in 560 ppm hydrogen sulfide gas at 23 ° C., and the spectral reflectance of the laminate is measured before the sulfidation test and 24 hours after the start of the sulfidation test. Measured using a spectral reflectometer and calculated by fitting the spectral reflectance to the formula [spectral reflectance maintenance ratio = (spectral reflectance after sulfidation test / spectral reflectance before sulfidation test) × 100]. A silicone resin composition having a spectral reflectance maintenance factor of 80% or more.
10. The silicone resin obtained by hardening the silicone resin composition in any one of said 1-9.
11. 11. A silicone resin-containing structure comprising the silicone resin according to 10 and a member containing silver.
12 11. A sealed optical semiconductor element in which an LED chip is sealed with the silicone resin described in 10 above.
13. 13. The sealed optical semiconductor element according to 12, further comprising a member containing silver.
14 The usage method of a silicone resin composition including the process of hardening the silicone resin composition in any one of said 1-8 in presence of silver.

The silicone resin composition of the present invention contains the zinc compound as component (D) in an amount of 0.1 to 5 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B). By using the product, it is possible to produce an encapsulated optical semiconductor that can impart sulfidation resistance even to a cured silicone resin, maintain transparency, and excellent in sulfidation resistance.
Since the silicone resin and the optical semiconductor encapsulant of the present invention are formed using the above composition, cracks are hardly generated and the sulfide resistance and transparency are excellent.

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

Hereinafter, the silicone resin composition of the present invention and the method for using the same, the silicone resin, the silicone resin-containing structure, and the sealed optical semiconductor element will be described in detail.
1. Silicone resin composition The silicone resin composition of the present invention comprises:
(A) component: polysiloxane having at least two alkenyl groups bonded to silicon atoms;
(B) component: a polysiloxane crosslinking agent having at least two hydrogen groups bonded to silicon atoms;
(C) component: a hydrosilylation reaction catalyst;
(D) component: a zinc compound,
(D) 0.1-5 mass parts is contained with respect to 100 mass parts of total of (A) component and (B) component.

1.1. Component (A) The component (A) 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.

(A) A component is the main ingredient (base polymer) of the silicone resin composition of this invention. The component (A) preferably has two or more alkenyl groups bonded to a silicon atom in one molecule from the viewpoint of excellent toughness and elongation, more preferably 2 to 20, more preferably 2 to 10 Have a degree.
In addition, the component (A) may be a polysiloxane having one vinyl group and / or hydrosilyl group in one molecule from the viewpoint that the viscosity of the composition is low.

  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. Among these, from the viewpoint of excellent curability, the alkenyl group is preferably a vinyl group or a (meth) acryloyl group, and more preferably a vinyl group.
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.

In the component (A), examples of the organic group bonded to the silicon atom 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, Aryl groups such as tolyl group, xylyl group and naphthyl group; aralkyl groups such as benzyl group and phenethyl group; alkyl halide groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group; Examples thereof include cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. Moreover, the polysiloxane as the component (A) may have a hydrosilyl group.
Of these, a methyl group and a phenyl group are preferable from the viewpoint of excellent heat resistance.

  As the main chain of the component (A), for example, organopolysiloxane can be mentioned. 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 component (A) 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.
(A) As a molecular structure, component (A) is mentioned as one of preferred embodiments in which the main chain is composed of repeating diorganosiloxane units.
When the vinyl group-containing polysiloxane and / or the hydrosilyl group-containing polysiloxane is used as the component (A), the structure of the component (A) may have an alkylene group and / or a phenylene skeleton.
In addition, the molecular terminal of the component (A) 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 or a vinyl group.

  Examples of component (A) include those represented by the following formula (I).

(Wherein 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 And 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 curability is superior.
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 formula: (R ¹ ) ₂ R ² SiO _1/2. An organosiloxane copolymer comprising a siloxane unit represented by formula: (R ¹ ) ₂ SiO _2/2 and a siloxane unit represented by formula: SiO _4/2 , formula: (R ¹ ) ₃ SiO _An organosiloxane copolymer comprising a siloxane unit represented by _1/2 and a siloxane unit represented by the formula: (R ¹ ) ₂ R ² SiO _1/2 and a siloxane unit represented by the formula: SiO _4/2 ; siloxane units of the formula _{^{R 1) 2 R 2 SiO 1/2}} : ( siloxane units of the formula _R 1) _{2 SiO 2/2:} with _{SiO 4/2} Organosiloxane copolymers consisting of siloxane units of the ^formula: siloxane units of the formula _{^{(R 1) 2 R 2 SiO}} 1/2: siloxane units or of the formula represented by R _{1 SiO ^3/2:} R 2 _{SiO An} organosiloxane copolymer composed of siloxane units represented by _3/2 is exemplified.
When the polysiloxane is a polysiloxane having an unsaturated hydrocarbon group as an alkenyl group, the polysiloxane structure may have an alkylene group and / or a phenylene skeleton.

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 the component (A) has a vinyl group as an alkenyl group, it is more excellent in curability. The polysiloxane having a vinyl group as an alkenyl group may be hereinafter referred to as “vinyl group-containing polysiloxane”.

  When the component (A) is a polysiloxane having a (meth) acryloyl group as an alkenyl group, it is more excellent in curability. In addition, polysiloxane having a (meth) acryloyl group as an alkenyl group may be hereinafter referred to as “(meth) acryloyl group-containing polysiloxane”.

Examples of the (meth) acryloyl group-containing polysiloxane include those represented by the following average composition formula (II).
R ¹ _a R ² _b SiO _{(4-ab) / 2} (II)
(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 - are 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 0.8 to 2.4, preferably 1 to 1.8, b is 0.1 to 1.2, 0 .2 to 1 is preferable, 0.4 to 1 is more preferable, and a + b is 2 to 2.5, and preferably 2 to 2.2.)

In the formula, examples of the alkyl group and aryl group of R ¹ include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group; phenyl group, tolyl group, xylyl group, 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 component (A) is preferably 500 to 100,000, more preferably 1,000 to 100,000, from the viewpoint of being excellent in curability and excellent in toughness, elongation, and workability. It is 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 at 23 ° C. of the component (A) 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.

  (A) A component can be used individually or in combination of 2 or more types, respectively. The component (A) is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.

1.2. (B) Component The polysiloxane crosslinking agent as component (B) is an organohydro having at least two hydrogen groups (ie, SiH groups) bonded to silicon atoms in one molecule and having a polysiloxane structure as the main chain. If it is a genpolysiloxane, it will not restrict | limit in particular.

  The component (B) 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 component (B) include linear, branched, cyclic, and three-dimensional network structures.

  In the component (B), 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 component (B) include organohydrogenpolysiloxanes represented by the following average composition formula (III).
H _a R ³ _b SiO _{(4-ab) / 2} (III)
(Wherein R ³ independently represents an unsubstituted or substituted monovalent hydrocarbon group that does not contain an 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 of 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.

As the component (B), for example, molecular chain both ends trimethylsiloxy group-capped methylhydrogen polysiloxane, molecular chain both ends trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends silanol group-capped 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 with both molecular chain terminals blocked with dimethylhydrogensiloxy groups dimethylsiloxane-methylhydrogensiloxane ^copolymers; _(R 3) or 2 _{HSiO 1/2} units and _{SiO 4/2} units It optionally ^(R _{3) 3 SiO 1/2} ^units, _(R 3) _{2 SiO 2/2} ^units, R 3 _{HSiO 2/2} units, _{(H) SiO 3/2} unit or ^R 3 _{SiO 3/2} units In which R ³ is the same as the above-mentioned unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond. Examples thereof include those in which part or all of the groups are substituted with other alkyl groups such as an ethyl group and a propyl group, a phenyl group, and a hydrosilyl group.

  Also, the following formula:

(In the formula, R ³ is the same as the above-described 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 (It is an integer of 1 or more.)
The thing represented by is mentioned.
(B) component can be used individually or in combination of 2 types or more, respectively.

The component (B) 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 an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond) Or the like, or the following general formula: (R ³ ) ₃ SiCl and (R ³ ) ₂ SiCl ₂ (wherein R ³ is the same as defined above). It is the same as an unsubstituted or substituted monovalent hydrocarbon group which does not contain an aliphatic unsaturated bond.) And can be obtained by cohydrolyzing at least one chlorosilane selected from the group. Moreover, what equilibrated polysiloxane obtained by cohydrolysis can be used as (B) component.

From the viewpoint that the component (B) is excellent in rubber physical properties (toughness and elongation) after curing, the hydrogen atom bonded to the silicon atom (SiH) of the component (B) per mole of the alkenyl group in the component (A) Group) is preferably used in an amount of 0.1 to 5 mol, more preferably 0.5 to 2.5 mol, and still more preferably 1.0 to 2.0 mol. The
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 component (A) and the component (B) can be used as a mixture of the component (A) and the component (B).

1.3. Component (C) The hydrosilylation reaction catalyst (polysiloxane catalyst) that is component (C) is composed of an alkenyl group that component (A) has and a hydrogen atom (that is, SiH group) that is bonded to a silicon atom that component (B) has. ) To promote the addition reaction. The silicone resin composition of this invention is excellent in sclerosis | hardenability by including (C) component.

The component (C) 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, and palladium; 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 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 , Platinum group metals such as palladium supported on alumina, silica, carbon or the like; rhodium-olefin complex; chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst); platinum chloride, chloroplatinic acid or chloroplatinic acid Examples thereof include platinum group metal catalysts such as a complex of a salt and a vinyl group-containing siloxane, particularly a vinyl group-containing cyclic siloxane.

  (C) component can be used in the range of the catalyst amount. From the viewpoint of exhibiting excellent curability, it can be 0.1 to 500 ppm (preferably 10 to 100 ppm) in terms of mass of the platinum group metal with respect to the total amount of component (A) and component (B).

1.4. (D) Component The zinc compound which is (D) component is a compound containing zinc, for example, a complex and / or metal salt containing zinc. When the composition of the present invention contains 0.1 to 5 parts by mass of the zinc compound as the component (D) with respect to 100 parts by mass in total of the component (A) and the component (B), the zinc compound is sulfur and By bonding, sulfide resistance can be imparted to the cured product. Thereby, discoloration (corrosion) of silver can be prevented and transparency can be maintained. Moreover, the hardened | cured material obtained using the composition of this invention has sufficient sulfidation resistance, without hardening resin. For this reason, the said hardened | cured material can be a silicone resin which a crack does not produce easily. For this reason, when hardened | cured material is used as an optical semiconductor sealing body, the disconnection of the wire contained in this sealing body can be prevented.
Examples of the complex and metal salt containing zinc as component (D) include carboxylic acid salts such as zinc bisacetylacetonate, zinc bis-2-ethylhexanoate, zinc (meth) acrylate, and zinc neodecanate. Inorganic zinc compounds typified by zinc oxides such as organic zinc compounds, zinc white and zinc stannate.
For example, when the cured product formed using the composition of the present invention requires transparency, the component (D) has a resin transmittance when the component (D) is added to the resin. For example, a zinc compound having a transmittance of light having a wavelength of 400 nm of 70% or more is preferable.

From the viewpoint that the silicone resin composition of the present invention can suppress coloring due to heat and can reliably exhibit transparency and resistance to sulfidation, (D) component is a total of 100 components (A) and (B). It is preferable to contain 0.1-1 mass part with respect to a mass part, It is more preferable that it is 0.1-0.5 mass part, It is further more preferable that it is 0.12-0.5 mass part. Here, when the component (D) exceeds 5 parts by mass with respect to the total of 100 parts by mass of the component (A) and the component (B), coloring due to heat tends to occur, and the transparency may decrease. If the amount is less than 0.1 parts by mass, sulfidation resistance may not be sufficiently exhibited.
(D) component can be used individually or in combination of 2 or more types, respectively.

Examples of the method for producing the component (D) include a method of reacting 1.5 to 3 mol of an inorganic acid and / or an organic acid with respect to 1 mol of zinc oxide and / or zinc carbonate.
At this time, examples of the inorganic acid include phosphoric acid, and examples of the organic acid include stearic acid, palmitic acid, lauric acid, 2-ethylhexanoic acid, (meth) acrylic acid, and neodecanoic acid. .

1.5. (E) component The silicone resin composition of this invention is excellent in long-term reliability under high temperature by containing (E) component: a boron compound.

  The component (E) is not particularly limited as long as it is a boron compound that is a compound containing boron, and examples thereof include boron complexes and boric acid esters.

The boron complex refers to a complex having a boron atom, and examples thereof include a boron trifluoride complex.
The boron trifluoride complex refers to a complex formed from boron trifluoride and a compound such as water, alcohol, carboxylic acid, acid anhydride, ester, ether, ketone, or aldehyde.
Examples of alcohols that form boron trifluoride complexes include primary alcohols having 1 to 10 carbon atoms such as methanol, ethanol, n-propanol, n-butanol, and n-decanol; carbons such as i-propanol and sec-butanol. Secondary alcohols of several 3 to 10; and the like. Examples of the carboxylic acid include aliphatic carboxylic acids having 2 to 10 carbon atoms such as acetic acid, propionic acid, butyric acid, valeric acid, and succinic acid; aromatic carboxylic acids such as benzoic acid and phthalic acid; As an acid anhydride, the anhydride of the said carboxylic acid is mentioned, for example. Examples of the ester include alkyl esters having 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, and n-butyl of the above carboxylic acid. Examples of the ether include dimethyl ether, diethyl ether, dibutyl ether and the like. Examples of ketones include acetone and methyl ethyl ketone. Examples of aldehydes include acetaldehyde and benzaldehyde.
As such a boron trifluoride complex, for example, a boron trifluoride ether complex is preferable, and boron trifluoride diethyl etherate and boron trifluoride dibutyl etherate are more preferable.

The borate ester refers to a compound obtained by a condensation reaction between a boric acid such as orthoboric acid, metaboric acid, and hypoboric acid, and a compound having a hydroxy group (—OH).
Examples of the boric acid ester include compounds represented by any of the following formulas (e1) to (e5).

  In formulas (e1) to (e5), R independently represents a hydrogen atom, an alkyl group, an allyl group, an aryl group, a silyl group, or a phosphine group, and R ′ independently represents a divalent group. A hydrocarbon group is shown.

  The alkyl group represented by R in the formulas (e1) to (e5) is preferably an alkyl group having 1 to 18 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n- Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, An n-decyl group etc. are mentioned.

The allyl group represented by R in the formulas (e1) to (e5) is a 2-propenyl group (—CH ₂ CH═CH ₂ ).

  The aryl group represented by R in the formulas (e1) to (e5) is preferably an aryl group having 1 to 18 carbon atoms, such as a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a mesityl group. Can be mentioned.

  Examples of the silyl group represented by R in the formulas (e1) to (e5) include an unsubstituted silyl group; a monoalkylsilyl group such as a methylsilyl group; a dialkylsilyl group such as a dimethylsilyl group; a trimethylsilyl group, a triethylsilyl group, Trialkylsilyl groups such as dimethylethylsilyl group and tributylsilyl group; alkoxydialkylsilyl groups such as methoxydimethylsilyl group; dialkoxyalkylsilyl groups such as dimethoxymethylsilyl group; trialkoxysilyl groups such as trimethoxysilyl group; etc. Is mentioned.

  Examples of the phosphine group represented by R in the formulas (e1) to (e5) include a dimethylphosphine group, a diphenylphosphine group, a ditolylphosphine group, and a dinaphthylphosphine group.

  The divalent hydrocarbon group represented by R ′ in formulas (e1) to (e5) is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably an alkylene having 1 to 20 carbon atoms. A methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a heptane-1,5-diyl group, a hexane-1,6-diyl group, and the like. It is done.

  Examples of the component (E) represented by the formulas (e1) to (e5) include 2-isopropoxy-4,4,5,5-tetramethyl-1,3 represented by the following formula (e6). 2-dioxaborolane, tris (trimethylsilyl) borate represented by the following formula (e7), 2,4,6-trimethoxyboroxine represented by the following formula (e8), bis (2) represented by the following formula (e9) Pinacolate) diboron and the like.

Among these, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, tris (trimethylsilyl) borate, 2, because long-term reliability at high temperatures is superior. 4,6-trimethoxyboroxine and bis (pinacolato) diboron are preferred.
(E) A component can be used individually or in combination of 2 types or more, respectively.

  The amount of the component (E) is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the component (A) described above, because the long-term reliability at high temperatures is more excellent. It is more preferable that it is 1-3 mass parts.

1.6. (F) component The silicone resin composition of this invention is excellent in long-term reliability under high temperature by containing (F) component: phosphate ester.

As phosphate ester, what is represented by a following formula (f2) is mentioned, for example.
O = P− (OR ⁶ ) ₃ (f2)
In formula (f2), each R ⁶ independently represents an alkyl group having 1 to 18 carbon atoms, an aryl group or a silyl group, and R ⁶ in formula (f1) described above represents an alkyl having 1 to 18 carbon atoms. Synonymous with group, aryl group or silyl group.
R ⁶ in formula (f2) is preferably an alkyl group having 1 to 18 carbon atoms, and preferably an alkyl group having 1 to 6 carbon atoms, because it has excellent compatibility with the component (A). More preferred.

Examples of the phosphate ester include monoesters such as propyl phosphate ester, butyl phosphate ester and hexyl phosphate ester; diesters such as dipropyl phosphate ester, dibutyl phosphate ester and dihexyl phosphate ester; triethyl phosphate and tripropyl phosphate ester , Tributyl phosphate ester, trihexyl phosphate ester, triester (trimethylsilyl) phosphate and the like; polyethylene oxide alkyl ether phosphate ester such as polyethylene oxide dodecyl ether phosphate; and the like.
Of these, a triester is preferable because it has better long-term reliability at high temperatures, and triethyl phosphate and tris (trimethylsilyl) phosphate are more preferable.

The component (F) is preferably a normal phosphate ester that does not have an unshared electron pair directly on the phosphorus atom because it is difficult to inhibit the hydrosilylation reaction.
(F) A component may be used individually by 1 type and may use 2 or more types together.

  The amount of the component (F) (when the above-described component (E) is used in combination, the total amount of the component (E) and the component (F)) is described above because the long-term reliability at high temperatures is more excellent. (A) It is preferable that it is 0.01-5 mass parts with respect to 100 mass parts of component, and it is more preferable that it is 0.1-3 mass parts.

In addition to the (A) component, the (B) component, the (C) component and the (D) component, and the (E) component and / or the (F) component, the silicone resin composition of the present invention is As long as the effect is not impaired, an additive can be contained as necessary.
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, physical property modifiers, adhesion imparting agents, and adhesion assistants. Various additives are not particularly limited. For example, a conventionally well-known thing is mentioned.
Examples of the adhesion-imparting agent or adhesion assistant include known epoxy-based silane coupling agents, bis (alkoxy) alkanes, isocyanurate derivatives, etc. Among them, bis (alkoxy) alkanes and / or isocyanurate derivatives are preferred. Preferably there is.
Examples of the bis (alkoxy) alkane include 1,2-bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,7-bis (trimethoxysilyl) heptane, 1,8- It is preferably at least one selected from the group consisting of bis (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane and 1,10-bis (trimethoxysilyl) decane, Bis (trimethoxysilyl) hexane is more preferred.
It is preferable that the isocyanurate derivative is represented by the following formula.

In the above formulae, each R independently represents a monovalent hydrocarbon group having an organic group or an aliphatic unsaturated bond, and a substituent such as an epoxy group, a glycidoxy group, an alkoxysilyl group, or a (meth) acryloyl group. You may have.
The organic group represented by R in the above formula is not particularly limited, and examples thereof include alkyl groups such as methyl, ethyl, propyl, and butyl groups; aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups. Aralkyl groups such as benzyl group and phenethyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkyl halide groups;
In addition, the monovalent hydrocarbon group having an aliphatic unsaturated bond represented by R in the above formula is not particularly limited, and examples thereof include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group. And an unsaturated hydrocarbon group having 2 to 8 carbon atoms.
Examples of the isocyanurate derivative represented by the above formula include tris- (3-trimethoxysilylpropyl) isocyanurate.
These adhesion promoters or adhesion assistants can be used alone or in combination of two or more.

  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 and green light emitting phosphor.

  The production of the silicone resin composition of the present invention is not particularly limited. For example, (A) component, (B) component, (C) component and (D) component, and optionally (E) component and / or (F) component, and hydrosilylation reaction that can be used as necessary It can be produced by mixing a catalyst and an additive. Moreover, 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 a two-component type, it is divided into a first solution containing the component (B) and the component (C) and a second solution containing the component (A) and the component (D). Can be manufactured. The component (E) and / or the component (F) and 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 23 ° C. condition after mixing the liquid containing the component other than the component (B) and the component (B) 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 that it is more excellent in curability. Is more preferable, and it is still more preferable that it is 120-180 degreeC.

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.

The silicone resin composition of the present invention can be substantially free from a silicon compound having a silanol group from the viewpoint of storage stability.
The silicone resin composition of the present invention can be used in the presence of silver. By producing the silicone resin by curing the silicone resin composition of the present invention in the presence of silver, the discoloration (corrosion) of silver can be prevented, and the transparency of the resulting silicone resin can be maintained.

In the present invention, the spectral reflectance maintenance factor can be calculated as follows.
First, the silicone resin composition of the present invention is applied to a thickness of 1 mm on a metal layer obtained using a Group 11 metal (for example, silver) and cured to have the metal layer and the silicone resin layer. A laminate is used.
Next, a sulfidation resistance test is performed in which the laminate is placed in 560 ppm hydrogen sulfide gas at 23 ° C., and the spectrum of the laminate is measured before the sulfidation test and 24 hours after the start of the sulfidation test. The reflectance is measured using a spectral reflectometer.
Then, the spectral reflectance is calculated by fitting into the formula [spectral reflectance maintenance ratio = (spectral reflectance after sulfidation test / spectral reflectance before sulfidation test) × 100].
In the present invention, from the viewpoint of sulfidation resistance, the spectral reflectance maintenance factor is preferably 80% or more.

2. Silicone Resin The silicone resin of the present invention is obtained by curing the silicone resin composition of the present invention. By using the silicone resin composition of the present invention, for example, a silicone resin excellent in sulfidation resistance can be obtained.

  The curing will be described below. The silicone resin of the present invention can be obtained by curing the silicone resin composition of the present invention by heating.

  When the silicone resin composition is cured by heating, it has excellent curability, the curing time and pot life can be set to appropriate lengths, foaming can be suppressed, and cracks in the silicone resin can be suppressed. From the viewpoint of excellent smoothness, moldability, and physical properties, a method of curing the silicone resin composition at 120 to 180 ° C. (preferably 150 ° C.) within 20 hours (preferably 12 hours) is preferable.

  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.

3. Encapsulated optical semiconductor element The encapsulated 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.
By using the silicone resin composition of the present invention as the silicone resin composition in the sealed optical semiconductor element of the present invention, the resulting sealed optical semiconductor element has excellent sulfidation resistance, rubber elasticity, and Excellent flexibility.

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 of the present invention containing a fluorescent material such as yttrium, aluminum, and garnet to form 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, the optical semiconductor element is bonded to a substrate such as a lead frame by die bonding, and the substrate or the like 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 method for producing a sealed optical semiconductor element 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 heat the silicone resin A composition having a curing step of curing the composition to obtain a cured product and bleeding out the zinc 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 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. Here, the temperature which heats the said silicone resin composition is synonymous with what was shown at the process of manufacturing 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.
FIG. 1 is a top view schematically showing an example of an optical semiconductor element sealing body of the present invention, and FIG. 2 is a cross-sectional view schematically showing an AA cross section of the optical semiconductor element sealing body shown in FIG. is there.
In FIG. 1, 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. 1 , the leads, wires, and substrate 609 are omitted.
In FIG. 2, 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 addition, the wire is abbreviate | omitted in FIG. A silver film 602 is provided over the substrate 609 as a member containing silver. Silver film 602 is deposited on the substrate 60 9, for example, by plating. In the optical semiconductor element encapsulation material shown in FIG. 2, an example in which silver film 602 is in contact with the silicone resin 60 3, it may not be in contact with the silicone resin 60 3. For example, a silicone resin may be disposed on another layer (not shown) provided on the silver film 602.
2 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. 2) 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. 3 is a cross-sectional view schematically showing the sealed optical semiconductor element of the present invention. FIG. 4 is a cross-sectional view schematically showing 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. 3, 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 filling the hatched portion 206 with the silicone resin composition of the present invention, the silicone resin 202 is a combination of the shaded portion 206. As shown in FIG. 3, the silicone resin 202 can seal the LED chip with a single layer.

In FIG. 4, a 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.

  3 and 4, the LED chip is described as a blue LED chip, but 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. Moreover, the viewpoint that the heating temperature at the time of manufacturing the optical semiconductor element sealing body of the present invention is the same as the heating temperature at the time of curing the silicone resin composition of the present invention can exhibit excellent curability. To preferred.

  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. 5 is a diagram schematically showing an example of an LED display using the sealed optical semiconductor element of the present invention. FIG. 6 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. 5, 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. 6, 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.

4). EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

4.1. Evaluation As shown below, the transmittance, heat-resistant coloring stability, sulfidation resistance, cured state, adhesion, and long-term reliability under high temperature were evaluated. The results are shown in Table 1.

4.1.1. Transmittance Evaluation Test In the transmittance evaluation test, an initial cured product obtained by curing the silicone resin composition obtained as described below at 150 ° C. for 12 hours, and a heat resistance test (an initial cured product A test of heating for 10 days under the condition of 150 ° C.) For each cured product (both having a thickness of 2 mm), an ultraviolet / visible absorption spectrum measuring device (manufactured by Shimadzu Corporation) was used in accordance with JIS K0115: 2004. The transmittance at a wavelength of 400 nm was measured. Moreover, the retention with respect to the initial transmittance of the transmittance after the heat test was obtained by the following calculation formula.
Transmittance retention rate (%) = (Transmittance after heat resistance test) / (Initial transmittance) × 100

4.1.2. Heat-resistant coloring stability evaluation test An initial cured product obtained by curing the silicone resin composition obtained as described below at 150 ° C. for 4 hours, and a heat resistance test (initial cured product under the condition of 150 ° C. Test for heating for 10 days.) Regarding the cured product after the heat treatment (both having a thickness of 2 mm), it was visually observed whether the cured product after the heat resistance test was yellow compared with the initial cured product.

4.1.3. Sulfide resistance Cured sample preparation: The silicone resin compositions of the examples and comparative examples were applied on silver plating to a thickness of about 1 mm and cured by heating at 150 ° C. for 3 hours to obtain a laminate (“cured” Also referred to as “sample”.
Sulfur resistance test: Place 10 g of powdered iron sulfide (a large excess with respect to 0.5 mmol of hydrochloric acid) on the bottom of a 10-liter desiccator and place it above the iron sulfide so that it does not come into contact with the iron sulfide. (Having through-holes) was mounted in a desiccator, and the cured sample was placed on the eye plate. Next, 0.25 mmol of hydrogen sulfide (theoretical value of concentration: 560 ppm) was generated by dropping 0.5 mmol of hydrochloric acid into a large excess of iron sulfide (reaction formula: FeS + 2HCl → FeCl ₂ + H ₂ S). .
Next, the spectral reflectance was measured as described below, and the spectral reflectance maintenance factor was calculated.
Spectral reflectivity measurement: Spectral reflectivity (UREO manufactured by Ushio Electric Co., Ltd.) was measured before the sulfidation test and 24 hours after the start of the sulfidation test (hydrogen sulfide generation). -30) was used under the condition of 475 nm.
Evaluation method: The obtained spectral reflectance after the anti-sulfurization test and the spectral reflectance before the anti-sulfurization test are expressed by the formula [spectral reflectance maintenance ratio = (spectral reflectance after the anti-sulfurization test / spectral reflection before the anti-sulfurization test]. Ratio) × 100], and the spectral reflectance maintenance factor was calculated.
In Table 1, when the calculated spectral reflectance maintenance factor is 80% or more, it is evaluated as “◯” as being excellent in sulfur resistance, and when it is less than 80%, it is inferior in sulfur resistance. As “×”.
Furthermore, the discoloration of silver was confirmed visually every hour. In Table 1, the case where no discoloration was confirmed by visual observation was “◯”, and the case where discoloration was confirmed by visual observation was “x”.

4.1.4. Adhesiveness The silicone resin composition obtained as described below was poured into an LED package (manufactured by Enomoto) and cured under conditions of 150 ° C. for 3 hours to obtain an evaluation sample.
Next, about the obtained sample for evaluation, the presence or absence of peeling of hardened | cured material was confirmed visually, and when peeling was not confirmed, the adhesiveness of hardened | cured material was evaluated using the spatula.
If peeling of the cured product was not confirmed with the naked eye, it was evaluated as “△” as being somewhat excellent in adhesion, and if the cured product was not easily peeled off even using a spatula, When it was peeled off with a spatula, and the cured product was accompanied by cohesive failure, it was evaluated as “◎” as being excellent in adhesion.
On the other hand, when peeling of hardened | cured material was confirmed visually or when hardened | cured material peeled easily by using a spatula, it evaluated as "x" as inferior to adhesiveness.

4.1.5. Long-term reliability under high temperature The silicone resin composition obtained as described below was poured into an LED package (manufactured by Enomoto) and cured under conditions of 150 ° C. for 3 hours to obtain an evaluation sample. . Next, the obtained sample for evaluation was exposed for 500 hours under the condition of 150 ° C., and then the presence or absence of cracks or peeling of the cured product was confirmed by visual observation. Was used to evaluate the adhesion of the cured product.
If no cracks or peeling were confirmed by visual inspection, the product was rated as “△” as being somewhat excellent in long-term reliability at high temperatures, and the cured product did not peel easily even when a spatula was used. Is evaluated as “○” as having excellent long-term reliability under high temperature, and when the cured product is accompanied by cohesive failure when peeled off with a spatula, it is superior in long-term reliability under high temperature. The product was evaluated as “◎”.
On the other hand, when a crack and peeling were confirmed visually, it evaluated as "x" as being inferior to long-term reliability under high temperature.

4.2. Sample preparation (for evaluation of transmittance, heat-resistant coloring stability and curing state)
The production of the sample will be described below with reference to the accompanying drawings.
FIG. 7 is a cross-sectional view schematically showing a mold used for curing the silicone resin composition of the present invention in Examples.
In FIG. 7, a mold 8 has 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.
The composition 6 was poured into the interior 6 of the spacer 1 using the mold 8, and the sample was cured as follows.

  The mold 8 filled with the composition 6 was placed in an electric oven and heated under the above-described evaluation conditions to cure the composition 6 to produce a cured product 6 (initial cured product) having a thickness of 2 mm. The obtained cured product 6 was used as a sample for evaluating transmittance, heat-resistant coloring stability, and a cured state.

4.3. Production of Silicone Resin Composition The components shown in Table 1 below were uniformly mixed in the amounts (unit: parts by mass) shown in the same table using a vacuum stirrer to produce a silicone resin composition.
The compositions of Examples 1 to 8 in Table 1 contain the component (D). The compositions of Examples 9 to 21 contain the component (E) and / or the component (F). On the other hand, the compositions of Comparative Examples 1 to 6 and 9 in Table 1 do not contain the component (D). Further, in the compositions of Comparative Examples 7 and 8 in Table 1, the content of the component (D) is in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). Outside. Comparative Example 1 contains the same components as in Example 1 except that it does not contain the component (D), and Comparative Examples 2 to 6 are an aluminum compound, a magnesium compound, an iron compound, and cobalt, respectively, instead of the component (D). Contains compounds or manganese compounds. Comparative Example 9 is an example using an epoxy resin.

Each component shown in Table 1 is as follows.
(A) (B) (C) mixture: a mixed liquid (liquid A) of vinylpolysiloxane (component (A)) as the main agent and hydrogen polysiloxane (component (B)) as the crosslinking agent, Mixture (trade name KE106, manufactured by CATRAG Shin-Etsu Chemical Co., Ltd.) of a mixture of vinyl polysiloxane (component (B)) and hydrosilylation catalyst (component (C)) (liquid B: CAT-RG)
(A) Polysiloxane 2: both ends vinyl-blocked dimethylpolysiloxane (trade name: DMS-V31, manufactured by Gelest)
(B) Polysiloxane crosslinking agent 2: Hydrogen polysiloxane (trade name: KF-9901, manufactured by Shin-Etsu Chemical Co., Ltd.)
(C) hydrosilylation reaction catalyst 2: platinum-cyclovinylmethylsiloxane complex (trade name: SIP6832.2, manufactured by Gelest)
Epoxy resin: bisphenol A diglycidyl ether epoxy liquid resin (trade name: EP4100, manufactured by Tohto Kasei)
(D) zinc compound 1: zinc bisacetylacetonate, manufactured by Kanto Chemical Co., Ltd. (D) zinc compound 2: zinc bis-2-ethylhexanoate, manufactured by Hope Pharmaceutical Co., Ltd. Aluminum compound: ethyl acetate aluminum diisopropylate (trade name: AL-CH, manufactured by Kawaken Fine Chemicals)
Magnesium compound: Magnesium bis (2-ethylhexanoate) (trade name: Nikka Octix Magnesium, manufactured by Nippon Chemical Industry Co., Ltd.)
Iron compound: iron (III) acetylacetonate (Gelest)
・ Cobalt compound: Cobalt (III) acetylacetonate (Matsumoto Trading Co., Ltd.)
Manganese compound: Manganese (III) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.)
Cationic polymerization catalyst: BF ₃ · Et ₂ O (BF ₃ ethyl etherate complex, manufactured by Tokyo Chemical Industry Co., Ltd.)
-Adhesive agent 1: Epoxysilane oligomer (trade name: X-41-1053, manufactured by Shin-Etsu Chemical Co., Ltd.)
Adhesion imparting agent 2: 1,6-bis (trimethoxysilyl) hexane (trade name: Z-6830, manufactured by Toray Dow Corning)
Adhesion imparting agent 3: Tris- (3-trimethoxysilylpropyl) isocyanurate (trade name: X-12-965, manufactured by Shin-Etsu Chemical Co., Ltd.)

(E) Boron compound 1: 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (manufactured by Tokyo Chemical Industry Co., Ltd.)
(E) Boron compound 2: Tris (trimethylsilyl) borate (manufactured by Tokyo Chemical Industry Co., Ltd.)
(E) Boron compound 3: 2,4,6-trimethoxyboroxine (manufactured by Tokyo Chemical Industry Co., Ltd.)
(E) Boron compound 4: bis (pinacolate) diboron (manufactured by Tokyo Chemical Industry Co., Ltd.)
(E) Boron compound 5: Boron trifluoride diethyl etherate (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ (F) Phosphate ester 1: Triethyl phosphate (Tokyo Chemical Industry)
(F) Phosphate ester 2: Tris (trimethylsilyl) phosphate (manufactured by Gelest)

4.4. Results As is apparent from the results shown in Table 1, the component (D) is not contained, or the content of the component (D) is 0 with respect to 100 parts by mass in total of the components (A) and (B). The cured products obtained using the compositions of Comparative Examples 1 and 8 that were less than 1 part by mass were inferior in sulfur resistance. Moreover, the hardened | cured material obtained using the composition of the comparative example 7 in which content of (D) component exceeds 5 mass parts with respect to a total of 100 mass parts of (A) component and (B) component became cloudy. Furthermore, the cured products obtained using the compositions of Comparative Examples 2 and 3 using an aluminum compound or a magnesium compound in place of the component (D) are inferior in sulfidation resistance, and instead of the component (D). The cured products obtained using the compositions of Comparative Examples 4 to 6 each using an iron compound, a cobalt compound, or a manganese compound are colored and are unsuitable as sealing materials (each compound itself is colored). ) Moreover, the hardened | cured material obtained using the composition of the comparative example 9 containing an epoxy resin colored and was inferior to the transmittance | permeability.
On the other hand, the cured products obtained using the compositions of Examples 1 to 7 are excellent in sulfidation resistance, and can maintain transparency because of high transmittance and transmittance retention, It can be understood that the thickening after mixing is low and the storage stability is excellent.

  Moreover, from the result shown in Table 1, Examples 9-21 containing (E) component and / or (F) component are Examples 1-8 which do not contain (E) component and / or (F) component. It was found that the long-term reliability at high temperatures is superior to

DESCRIPTION OF SYMBOLS 1 Spacer 3 Glass 5 PET film 6 Silicone resin composition (It becomes silicone resin 6 and hardened | cured material 6 after hardening)
8 type 10 surface 12 back surface 14 coating 16 boundary 18 silicone resin portion 200, 300 white LED 201, 301 mount member 202, 302 silicone resin 203, 303 blue LED chip 204 package 206 hatched portion 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 501 LED display 502 Driver 503 Gradation control means (CPU)
504 Image data storage means (RAM)
600 Optical semiconductor element sealing body 601 of the present invention LED chip 602 Silver film 603 Silicone resin 605 Point 607 Surface 609 to which point 605 belongs Substrate 611 Shaded portion T Silicone resin 603 thickness

Claims (14)

(A) component: polysiloxane having at least two alkenyl groups bonded to silicon atoms;
(B) component: a polysiloxane crosslinking agent having at least two hydrogen groups bonded to silicon atoms;
(C) component: a hydrosilylation reaction catalyst;
Component (D): zinc bisacetylacetonate and / or carboxylic acid zinc salt ;
Including
The silicone resin composition which contains 0.1-5 mass parts of said (D) component with respect to a total of 100 mass parts of said (A) component and said (B) component. The silicone resin composition according to claim 1, wherein the content of the silicon compound having a silanol group is less than 0.1% by mass . The silicone resin composition according to claim 1 or 2, wherein the zinc carboxylate is zinc bis 2-ethylhexanoate .   The silicone resin composition according to any one of claims 1 to 3, wherein the alkenyl group is a vinyl group or a (meth) acryloyl group.   The silicone resin composition of any one of Claims 1-4 used for optical semiconductor element sealing.   The silicone resin composition according to any one of claims 1 to 5, which is used in the presence of silver.   Furthermore, the silicone resin composition of any one of Claims 1-6 containing (E) component: Boron compound and / or (F) component: Phosphate ester.   Furthermore, the silicone resin composition of any one of Claims 1-7 containing a bis (alkoxy) alkane and / or an isocyanurate derivative. The silicone resin composition according to any one of claims 1 to 8,
On the metal layer obtained using a Group 11 metal, the silicone resin composition is applied to a thickness of 1 mm and cured to form a laminate having the metal layer and the silicone resin layer,
A sulfidation test is performed in which the laminate is placed in 560 ppm hydrogen sulfide gas at 23 ° C., and the spectral reflectance of the laminate is measured before the sulfidation test and 24 hours after the start of the sulfidation test. Measured using a spectral reflectometer and calculated by fitting the spectral reflectance to the formula [spectral reflectance maintenance ratio = (spectral reflectance after sulfidation test / spectral reflectance before sulfidation test) × 100]. A silicone resin composition having a spectral reflectance maintenance factor of 80% or more.   The silicone resin obtained by hardening the silicone resin composition of any one of Claims 1-9.   A silicone resin-containing structure comprising the silicone resin according to claim 10 and a member containing silver.   A sealed optical semiconductor element in which an LED chip is sealed with the silicone resin according to claim 10.   The sealed optical semiconductor element according to claim 12, further comprising a member containing silver.   The usage method of a silicone resin composition including the process of hardening the silicone resin composition of any one of Claims 1-8 in presence of silver.