JP2012107127A - Silicone resin composition, silicone-resin-containing structure obtained by using the same and optical semiconductor element sealed body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silicone resin composition having excellent sulfidation resistance and excellent long-term reliability at a high temperature.SOLUTION: The silicone resin composition comprises an organopolysiloxane (A) containing one or more of at least one reactive functional group selected from the group consisting of an epoxy group, (meth) acryloyl group, amino group, carbinol group, mercapto group, carboxy group and phenol group in one molecule, a zinc compound (B) a boron compound (C) and/or a phosphoric ester (D). The content of the zinc compound (B) is 0.01-5 pts.mass based on 100 pts.mass of the organopolysiloxane (A) and the content of the boron compound (C) and/or the phosphoric ester (D) is 0.01-5 pts.mass based on 100 pts.mass of the organopolysiloxane (A).

Description

  The present invention relates to a silicone resin composition, and a silicone resin-containing structure and an optical semiconductor element encapsulant obtained using the same.

  Organopolysiloxane has high gas permeability due to its structural characteristics, and silicone resin compositions containing organopolysiloxane are used for light-emitting element sealing materials and the like (see, for example, Patent Documents 1 to 3).

JP 2007-302825 A JP 2004-203923 A Japanese Patent Laid-Open No. 7-97433

  When an encapsulated body in which a metal is encapsulated with an encapsulant formed using a silicone resin composition containing an organopolysiloxane is placed in a corrosive gas (such as hydrogen sulfide) atmosphere, the air of the organopolysiloxane Since the permeability is high, there is a problem that the corrosive gas permeates the sealing material and the sealed metal is corroded (for example, silver discoloration).

  With respect to such problems, the present inventors have found that corrosive gas can be captured and corrosion of metal can be prevented by containing a specific amount of zinc compound in the silicone resin composition.

  However, the present inventors have clarified that the silicone resin composition containing a zinc compound may be inferior in long-term reliability at high temperatures.

  Then, an object of this invention is to provide the silicone resin composition which is excellent in sulfidation resistance, and is excellent also in the long-term reliability under high temperature.

As a result of intensive studies to solve the above problems, the present inventor further added a specific amount of a boron compound and / or a phosphate ester to a silicone resin composition containing a zinc compound at a high temperature. As a result, the present invention has been completed.
That is, the present invention provides the following (1) to (7).

  (1) having at least one reactive functional group selected from the group consisting of an epoxy group, a (meth) acryloyl group, an amino group, a carbinol group, a mercapto group, a carboxy group and a phenol group in one molecule An organopolysiloxane (A), a zinc compound (B), a boron compound (C) and / or a phosphoric ester (D) are contained, and the content of the zinc compound (B) is the organopolysiloxane. (A) It is 0.01-5 mass parts with respect to 100 mass parts, and content of the said boron compound (C) and / or the said phosphate ester (D) is 100 mass parts of said organopolysiloxane (A). The silicone resin composition which is 0.01-5 mass parts with respect to.

  (2) The silicone resin composition according to (1), wherein the boron compound (C) is a boric acid ester.

  (3) The silicone resin composition according to (2), wherein the boron compound (C) is a compound represented by any of the following formulas (c1) to (c5).

(In formulas (c1) to (c5), 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. Represents a hydrocarbon group.)

  (4) The silicone resin composition according to any one of (1) to (3), wherein the phosphate ester (D) is an organic phosphite ester (D1) and / or an organic phosphate ester (D2). object.

(5) The silicone resin according to (4), wherein the organic phosphite ester (D1) is represented by the following formula (d1), and the organic phosphate ester (D2) is represented by the following formula (d2). Composition.
P- (OR ^d1 ) ₃ (d1)
O = P- (OR ^d2 ) ₃ (d2)
(In formulas (d1) and (d2), R ^d1 and R ^d2 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group, or a silyl group.)

  (6) A silicone resin-containing structure comprising: a member containing silver; and a silicone resin layer obtained by curing the silicone resin composition according to any one of (1) to (5) that covers the member. .

  (7) A frame having a recess, an optical semiconductor element disposed at the bottom of the recess, a member including silver disposed on an inner surface of the recess, the optical semiconductor element and the member filled in the recess And a sealing material obtained by curing the silicone resin composition according to any one of (1) to (5), which seals a member.

  According to the present invention, it is possible to provide a silicone resin composition having excellent sulfidation resistance and excellent long-term reliability at high temperatures.

It is sectional drawing which shows typically an example of the laminated body as a silicone resin containing structure of this invention. It is sectional drawing which shows typically another example of the laminated body as a silicone resin containing structure of this invention. It is sectional drawing which shows typically an example of the optical semiconductor element sealing body of this invention. It is sectional drawing which shows typically another example of the optical semiconductor element sealing body of this invention. It is sectional drawing which shows typically another example of the optical semiconductor element sealing body of this invention. It is a schematic diagram which shows an example of the LED display using the composition of this invention and / or the optical semiconductor element sealing body of this invention.

<Silicone resin composition>
The silicone resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) is a group consisting of an epoxy group, a (meth) acryloyl group, an amino group, a carbinol group, a mercapto group, a carboxy group, and a phenol group. An organopolysiloxane (A) having at least one reactive functional group selected from one molecule per molecule, a zinc compound (B), a boron compound (C) and / or a phosphate ester (D); The zinc compound (B) content is 0.01 to 5 parts by mass with respect to 100 parts by mass of the organopolysiloxane (A), and the boron compound (C) and / or the phosphorus It is a silicone resin composition whose content of acid ester (D) is 0.01-5 mass parts with respect to 100 mass parts of said organopolysiloxane (A).
Hereinafter, each component contained in the composition of the present invention will be described in detail.

<Organopolysiloxane (A)>
The organopolysiloxane (A) contained in the composition of the present invention is at least one selected from the group consisting of epoxy groups, (meth) acryloyl groups, amino groups, carbinol groups, mercapto groups, carboxy groups, and phenol groups. This is a silicone having an organopolysiloxane skeleton having at least one reactive functional group per molecule.

  The organopolysiloxane (A) has a hydrocarbon group, and the hydrocarbon group is not particularly limited, and examples thereof include an aromatic group such as a phenyl group; an alkyl group; an alkenyl group;

Examples of the organopolysiloxane (A) include silicone oil, silicone rubber, and silicone resin, and any of these may be used.
The organopolysiloxane (A) is preferably a diorganopolysiloxane.
The main chain of the organopolysiloxane (A) may be linear, branched or three-dimensional.

Examples of the organopolysiloxane (A) include at least one reactive functional group selected from the group consisting of an epoxy group, a (meth) acryloyl group, an amino group, a carbinol group, a mercapto group, a carboxy group, and a phenol group. An organopolydialkylsiloxane having one or more in one molecule is exemplified.
The organopolysiloxane (A) is preferably an organopolydialkylsiloxane having two or more reactive functional groups in one molecule because it is excellent in curability.

The reactive functional group can be bonded to the end or both ends of the organopolysiloxane (A), and can be bonded as a side chain.
The reactive functional group can be bonded to the organopolysiloxane (A) via an organic group. Here, the organic group is not particularly limited, and for example, a divalent aliphatic hydrocarbon group (including a chain and a branch), an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a combination thereof, and the like. Is mentioned.
The carboxy group as the reactive functional group includes, for example, an acid anhydride group such as a succinic anhydride group and a maleic anhydride group.

  Examples of the organopolysiloxane (A) include those represented by the following formula (a1).

In formula (a1), R ¹ is the same or different and represents an alkyl group or aryl group having 1 to 18 carbon atoms, and X ¹ , X ² and X ³ are each independently an epoxy group, (meth) acryloyl At least one reactive functional group selected from the group consisting of a group, an amino group, a carbinol group, a mercapto group, a carboxy group and a phenol group, and the reactive functional group is bonded to a silicon atom via an organic group. In this case, X ¹ , X ² and X ³ may each contain an organic group, n is an integer of 1 or more, m is an integer of 0 or more, and m + n is an integer of 1 or more. , A, b and c are each an integer of 0 or more, and a + b + c is an integer of 1 or more.

Examples of the alkyl group having 1 to 18 carbon atoms represented by R ¹ in the formula (a1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, 1- An ethylpentyl group etc. are mentioned.
Examples of the aryl group represented by R ¹ in the formula (a1) include a phenyl group and a naphthyl group. The aryl group can have 18 or less carbon atoms.
The group represented by R ¹ in formula (a1) is preferably a methyl group or a phenyl group, and more preferably a methyl group. R ¹ may be the same or different.

  Moreover, n in Formula (a1) can be made into the numerical value corresponding to the weight average molecular weight of organopolysiloxane (A), and it is preferable that m + n is an integer of 10-15,000.

The method for producing the organopolysiloxane (A) is not particularly limited, and for example, a conventionally known production method can be used.
The molecular weight of the organopolysiloxane (A) is preferably 500 to 1,000,000, and more preferably 6,000 to 100,000.
In the present invention, the molecular weight of the organopolysiloxane (A) is a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) using chloroform as a solvent.

Organopolysiloxane (A) may be used individually by 1 type, and may use 2 or more types together.
When two or more organopolysiloxanes (A) are used in combination, two or more organopolysiloxanes (A) may have the same reactive functional group or different reactive functional groups. Good.

When two or more organopolysiloxanes (A) are used in combination, the organopolysiloxane (A) having one kind of reactive functional group reacts with the reactive functional group and serves as a curing agent. An organopolysiloxane (A) having a reactive functional group that works can also be combined.
For example, an organopolysiloxane having an epoxy group (A) and an organopolysiloxane having at least one selected from the group consisting of (meth) acryloyl group, amino group, carbinol group, mercapto group, carboxy group and phenol group ( Combinations with A); Combinations of organopolysiloxanes (A) having (meth) acryloyl groups and organopolysiloxanes (A) having mercapto groups; and the like.

  When combining an organopolysiloxane (A) having a reactive functional group that reacts with the reactive functional group and acting as a curing agent with respect to the organopolysiloxane (A) having one kind of reactive functional group, The amount of the latter organopolysiloxane (A) is such that the reactive functional group is 0.1 to 2 equivalents relative to the reactive functional group of the former organopolysiloxane (A). it can.

<Zinc compound (B)>
The composition of the present invention contains 0.01 to 5 parts by mass of the zinc compound (B) with respect to 100 parts by mass of the organopolysiloxane (A). Thereby, the composition of this invention is excellent in sulfidation resistance.
This is because, in the encapsulant obtained by curing the composition of the present invention, the zinc compound (B) is a corrosive gas in the air (for example, a gas having an unshared electron pair such as hydrogen sulfide and amines). In order to capture, it is thought that corrosion (for example, discoloration) of the metal by corrosive gas can be prevented. However, such a mechanism is speculation, and even another mechanism is within the scope of the present invention.

The zinc compound (B) is not particularly limited as long as it is a compound containing zinc. For example, zinc salt; zinc complex; zinc alcoholate; zinc oxide such as zinc white and zinc stannate; binary metal salt containing zinc Or a complex; a multi-metal salt containing zinc and a complex;
Among these, a zinc salt and / or a zinc complex is preferable from the viewpoint of superior sulfidation resistance and transparency.
Here, the zinc salt is not particularly limited as long as it is a salt formed from zinc and an acid (including an inorganic acid and an organic acid). Further, the zinc complex is not particularly limited as long as it is a chelate compound formed from zinc and a ligand.

  Specific examples of the zinc compound (B) include those represented by the following formula (B1) or (B2); a zinc complex of a salicylic acid compound; a zinc complex of a diamine compound;

First, the formula (B1) is as follows.
Zn (O—CO—R ² ) ₂ (B1)
In Formula (B1), R ² represents an alkyl group or aryl group having 1 to 18 carbon atoms, and has the same meaning as the above-described alkyl group or aryl group having 1 to 18 carbon atoms represented by R ¹ in Formula (a1). It is. Further, CO in the formula (B1) is a carbonyl group (C═O).
When the zinc compound (B) represented by the formula (B1) is a salt, examples of the zinc salt include those represented by the following formula (B1 ′).

Wherein (B1 '), R ² is the same as R ² in the formula (B1).
Examples of the zinc compound (B) represented by the formula (B1) include zinc acetate, zinc 2-ethylhexanoate, zinc octoate, zinc neodecanate, zinc acetyl acetate, zinc (meth) acrylate, and zinc salicylate. It is done.

Next, Formula (B2) is as follows.
Zn (R ³ COCHCOR ⁴ ) ₂ (B2)
In formula (B2), R ³ and R ⁴ are the same or different and each represents a monovalent hydrocarbon group or alkoxy group having 1 to 18 carbon atoms. (R ³ COCHCOR ⁴ ) in the formula (B2) is any one of the following formulas, and is bonded to zinc by “C—O—”.

  When the zinc compound (B) represented by the formula (B2) is a complex, examples of the zinc complex include those represented by the following formula (B2 ′).

Wherein (B2 '), R ^3, R ⁴ has the same meaning as R ^3, R ⁴ in the formula (B2), R ^3, R ⁴ that are located in the same (R ³ COCHCOR ⁴⁾ are interchanged May be.

Examples of the monovalent hydrocarbon group having 1 to 18 carbon atoms represented by R ³ and R ^{4 in} formula (B2) include an alkyl group having 1 to 18 carbon atoms or an aryl group (R ^{1 in} formula (a1)). Are the same as those of an alkyl group having 1 to 18 carbon atoms or an aryl group.
Examples of the alkoxy group represented by R ³ and R ⁴ in the formula (B2) include a methoxy group, an ethoxy group, and a propoxy group.
Examples of the zinc compound (B) represented by the formula (B2) include bis (acetylacetonato) zinc complex, 2,2,6,6,6 tetramethyl-3,5-heptanedionate zinc complex, and the like. Can be mentioned.

The zinc compound (B) is preferably a compound represented by the formula (B1) or the formula (B2), or a combination thereof, because it can make the sulfidation resistance more excellent. Zinc acetate, zinc 2-ethylhexanoate, zinc octoate, zinc neodecanate, zinc acetyl acetate, zinc (meth) acrylate, zinc salicylate, bis (acetylacetonato) zinc complex, 2,2,6,6,6 tetramethyl It is more preferably a −3,5-heptanedionate zinc complex.
A zinc compound (B) may be used individually by 1 main, and may use 2 or more types together.

As a method for producing the zinc compound (B), for example, an acid is used in an amount of 1. per mol of at least one selected from the group consisting of zinc oxide, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate and zinc nitrate. What is obtained by making it react 5 mol or more and less than 3 mol can be used.
The acid used in this case is not particularly limited. For example, inorganic acids such as phosphoric acid; organic acids such as stearic acid, palmitic acid, lauric acid, 2-ethylhexanoic acid and (meth) acrylic acid; and esters thereof And the like.

  The amount of the zinc compound (B) is preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the organopolysiloxane (A) because it is superior in sulfur resistance and excellent in transparency.

<Boron compound (C) and / or phosphate ester (D)>
The composition of the present invention contains 0.01 to 5 parts by mass of the boron compound (C) and / or the phosphate ester (D) with respect to 100 parts by mass of the organopolysiloxane (A). Thereby, the composition of this invention is excellent in the long-term reliability under high temperature.
In the case of the boron compound (C), the boron atom in the boron compound (C) coordinates to the oxygen atom in the organopolysiloxane (A), and the bond between the organosiloxane (A) and the metal is broken. This is thought to be due to the inhibition. Further, in the case of the phosphate ester (D), the adhesion inhibition by the zinc compound (B) is improved by the coordination of the phosphate ester (D) to the zinc atom in the zinc compound (B). it is conceivable that. However, such a mechanism is speculation, and even another mechanism is within the scope of the present invention.

  Moreover, the composition of this invention contains 0.01-5 mass parts of boron compounds (C) and / or phosphate ester (D) with respect to 100 mass parts of organopolysiloxane (A), Excellent adhesion to adherends.

[Boron Compound (C)]
First, the boron compound (C) will be described. Here, the “boron compound” refers to a compound containing boron.
Although it will not specifically limit as a boron compound (C) if it is a "boron compound", For example, it is preferable that they are a boron complex and boric acid ester.

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 (c1) to (c5).

  In formulas (c1) to (c5), 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 (c1) to (c5) is preferably an alkyl group having 1 to 18 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an 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 (c1) to (c5) is a 2-propenyl group (—CH ₂ CH═CH ₂ ).

  The aryl group represented by R in formulas (c1) to (c5) 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 (c1) to (c5) 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 (c1) to (c5) include a dimethylphosphine group, a diphenylphosphine group, a ditolylphosphine group, a dinaphthylphosphine group, and the like.

  The divalent hydrocarbon group represented by R ′ in formulas (c1) to (c5) 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 boron compound (C) represented by the formulas (c1) to (c5) include 2-isopropoxy-4,4,5,5-tetramethyl-1,3 represented by the following formula (c6). , 2-dioxaborolane, tris (trimethylsilyl) borate represented by the following formula (c7), 2,4,6-trimethoxyboroxine represented by the following formula (c8), bis represented by the following formula (c9) (Pinacolate) diboron, 2-cyclopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2- (3,5-dimethylphenyl) -4,4,5,5-tetramethyl -1,3,2-oxaborolane and the like.
A boron compound (C) may be used individually by 1 type, and may use 2 or more types together.

  Among these, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, Tris (for the reason that the composition of the present invention is more excellent in long-term reliability at high temperatures. Trimethylsilyl) borate, 2,4,6-trimethoxyboroxine and bis (pinacolato) diboron are preferred.

[Phosphate ester (D)]
Next, phosphate ester (D) is demonstrated.
The phosphate ester (D) contained in the composition of the present invention is preferably an organic phosphite ester (D1) and / or an organic phosphate ester (D2).

  In the present invention, the organic phosphite (D1) refers to an ester (including monoesters, diesters, and triesters) of phosphorous acid and an alcohol or an aromatic compound having a hydroxy group.

Examples of the organic phosphite (D1) include those represented by the following formula (d1).
P- (OR ^d1 ) ₃ (d1)
In formula (d1), R ^d1 independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group, or a silyl group.
Examples of the alkyl group having 1 to 18 carbon atoms represented by R ^d1 in the formula (d1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, Examples include various pentyl groups, hexyl groups, 2-ethylhexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, and the like.
Examples of the aryl group represented by R ^d1 in formula (d1) include a phenyl group, a tolyl group, and a naphthyl group.
Examples of the silyl group represented by R ^d1 in the formula (d1) include trialkylsilyl groups such as trimethylsilyl group, triethylsilyl group, and dimethylethylsilyl group; alkoxydialkylsilyl groups such as methoxydimethylsilyl group; dimethoxymethylsilyl group Dialkoxyalkylsilyl groups such as; trialkoxysilyl groups such as trimethoxysilyl group; and the like.
R ^d1 in formula (d1) is preferably an alkyl group having 1 to 18 carbon atoms, and preferably an alkyl group having 1 to 6 carbon atoms, because it is excellent in compatibility with the organopolysiloxane (A). Is more preferable.

  Examples of the organic phosphite (D1) include tri-2-ethyl hexane phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, triethyl phosphite, tributyl phosphite, and tris (2-ethylhexyl) phosphite. , Tridecyl phosphite, tris (tridecyl) phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl decyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra (tridecyl) ) Pentaerythritol tetraphosphite, trilauryl trithiophosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol Phosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, tris phosphite (trimethylsilyl) And the like. Triester bodies such as: diester bodies or monoester bodies obtained by partially hydrolyzing these triester bodies;

  In the present invention, the organic phosphate ester (D2) refers to an ester (including monoesters, diesters, and triesters) of phosphoric acid and an alcohol or an aromatic compound having a hydroxy group.

Examples of the organic phosphate ester (D2) include those represented by the following formula (d2).
O = P- (OR ^d2 ) ₃ (d2)
In formula (d2), R ^d2 independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group, or a silyl group, and R ^d2 in formula (d1) has 1 to 18 carbon atoms. It is synonymous with an alkyl group, an aryl group, or a silyl group.
R ^d2 in the formula (d2) is preferably an alkyl group having 1 to 18 carbon atoms, and preferably an alkyl group having 1 to 6 carbon atoms, because of excellent compatibility with the organopolysiloxane (A). Is more preferable.

  Examples of the organic phosphate ester (D2) 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; Triesters such as propyl phosphate ester, tributyl phosphate ester, trihexyl phosphate ester and tris (trimethylsilyl) phosphate; polyethylene oxide alkyl ether phosphate ester such as polyethylene oxide dodecyl ether phosphate; and the like.

As the phosphoric ester (D), phosphoric acid ester is preferable because it is more excellent in the long-term reliability of the transparency of the present invention at high temperature, and ethyl phosphate, triphenyl phosphate, tris phosphate (methylsilyl) are preferable. Is more preferable.
As the phosphate ester (D), the organic phosphate ester (D2) represented by the formula (d2) is preferable because the long-term reliability of the transparency of the present invention at a high temperature is more excellent, and triethyl phosphate is preferable. Tris (trimethylsilyl) phosphate is more preferable.
Phosphate ester (D) may be used individually by 1 type, and may use 2 or more types together.

The amount of the boron compound (C) and / or the phosphate ester (D) is superior to the long-term reliability of the composition of the present invention at a high temperature, with respect to 100 parts by mass of the organopolysiloxane (A). It is preferable that it is 0.01-10 mass parts, and it is more preferable that it is 0.1-1 mass part.
In addition, when phosphate ester (D) is organic phosphite ester (D1) and organic phosphate ester (D2), the quantity of phosphate ester (D) is these total.

<Other ingredients>
The composition of the present invention can further contain a curing agent. The curing agent that can be contained in the composition of the present invention is not particularly limited, and can be appropriately selected according to the type of the reactive functional group that the organopolysiloxane (A) has, such as a polyamine compound, a polyamide compound, Examples include dicyandiamide, acid anhydrides, carboxylic acid compounds, and phenol resins.

  Specific examples of the curing agent include aliphatic amines such as ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid-modified ethylenediamine, N-ethylaminopiperazine, and isophoronediamine; metaphenylenediamine, paraphenylenediamine. , 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenol sulfone, 4,4′-diaminodiphenol methane, 4,4′-diaminodiphenol ether, etc .; mercaptopropion Mercaptans such as acid esters and terminal mercapto compounds of epoxy resins; bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, biphenol, dihydroxynaphthalene, 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- ( 4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) phenol resins such as bisphenol, phenol novolac, cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak; Polyols with hydrogenated aromatic rings of phenolic resins; polyazeline anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydro Hydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid anhydride, norbornane-2,3-dicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, methyl-norbornane-2,3 -Alicyclic acid anhydrides such as dicarboxylic acid anhydride; Aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride; 2-methylimidazole, 2-ethyl-4-methylimidazole , Imidazoles such as 2-phenylimidazole and salts thereof, amine adducts obtained by reaction of the above aliphatic amines, aromatic amines and / or imidazoles with epoxy resins; hydrazines such as adipic acid dihydrazide; dimethyl Benzylamine, 1,8-diazabicyclo [5,4,0] undec-7-ene, etc. Tertiary amines; organic phosphines such as triphenylphosphine; dicyandiamide; and the like.

  The amount of the curing agent (the total amount when the organopolysiloxane (A) is used as the curing agent) is such that the functional group of the curing agent is 0.1 with respect to the reactive functional group of the organopolysiloxane (A). It is preferable that the amount is ˜2 equivalents.

The composition of the present invention may further contain an additive as necessary within the range not impairing the object and effects of the present invention.
Examples of the additive include a radical initiator (including a thermal radical initiator and a photo radical initiator), an inorganic filler, an antioxidant, a lubricant, an ultraviolet absorber, a thermal light stabilizer, a dispersant, an antistatic agent, Polymerization inhibitor, antifoaming agent, curing accelerator, solvent, fluorescent substance (including inorganic and organic substances), 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, conductivity imparting agent, phosphorus peroxide decomposing agent, pigment, metal deactivator, physical property modifier, screw Examples thereof include adhesion imparting agents such as alkoxysilylalkanes and coupling agents, isocyanurate compounds (adhesion imparting agents), and the like.

  Bis (alkoxysilyl) alkane as an additive is an adhesion-imparting agent and is a compound having a divalent alkane (alkylene group) and two alkoxysilyls. When the composition of the present invention further contains a bis (alkoxysilyl) alkane, the adhesiveness and adhesion are excellent. The alkoxysilyl group can have, for example, an alkyl group such as a methyl group or an ethyl group in addition to the alkoxy group. The divalent alkane can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Specifically, the divalent alkane can have an imino group (—NH—), for example. The divalent alkane may be one in which two alkylene groups are bonded via a hetero atom [eg, imino group (—NH—)]. Examples of the bis (alkoxysilyl) alkane include those represented by the following formula (I).

In the formula, R ^{7 to} R ⁸ are each an alkyl group, R ⁹ is a divalent alkane (alkylene group) which may have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, and a is Each is an integer of 1 to 3. Examples of the alkyl group include a methyl group and an ethyl group. Examples of the divalent alkane as R ⁹ include an alkylene group having 1 to 10 carbon atoms. A divalent alkane has the same meaning as described above.

  Examples of the bis (alkoxysilyl) alkane include 1,2-bis (triethoxysilyl) ethane, 1,4-bis (trimethoxysilyl) butane, 1-methyldimethoxysilyl-4-trimethoxysilylbutane, 4-bis (methyldimethoxysilyl) butane, 1,5-bis (trimethoxysilyl) pentane, 1,4-bis (trimethoxysilyl) pentane, 1-methyldimethoxysilyl-5-trimethoxysilylpentane, 1,5 -Bis (methyldimethoxysilyl) pentane, 1,6-bis (trimethoxysilyl) hexane, 1,4-bis (trimethoxysilyl) hexane, 1,5-bis (trimethoxysilyl) hexane, 2,5-bis (Trimethoxysilyl) hexane, 1,6-bis (methyldimethoxysilyl) hexane, 1,7- Sus (trimethoxysilyl) heptane, 2,5-bis (trimethoxysilyl) heptane, 2,6-bis (trimethoxysilyl) heptane, 1,8-bis (trimethoxysilyl) octane, 2,5-bis ( Trimethoxysilyl) octane, 2,7-bis (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane, 2,7-bis (trimethoxysilyl) nonane, 1,10-bis (trimethoxy) Silyl) decane, 3,8-bis (trimethoxysilyl) decane; divalent alkanes such as bis- (3-trimethoxysilylpropyl) amine having a nitrogen atom.

The bis (alkoxysilyl) alkane is preferably represented by the formula (I), more preferably bis (trialkoxysilyl) alkane, bis- (3-trimethoxysilylpropyl) amine, 1,2-bis (tri Ethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,7-bis (trimethoxysilyl) heptane, 1,8-bis (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) ) At least one selected from the group consisting of nonane and 1,10-bis (trimethoxysilyl) decane, more preferably 1,6-bis (trimethoxysilyl) hexane, bis- (3-trimethoxysilylpropyl) amine Is more preferable.
Bis (alkoxysilyl) alkanes can be used alone or in combination of two or more.

  The amount of bis (alkoxysilyl) alkane is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass in total of the organopolysiloxane (A) and the silane compound (B) described above.

  The isocyanurate compound as an additive is not particularly limited as long as it is a compound that forms an isocyanurate skeleton by a polyisocyanate trimer. When the composition of the present invention further contains an isocyanurate compound, the adhesiveness and adhesion are excellent. As an isocyanurate compound, the compound represented by following formula (II) is mentioned, for example.

In the formula, each R is an organic group or a monovalent hydrocarbon group having an aliphatic unsaturated bond. Furthermore, R can include an epoxy group, a glycidoxy group, an alkoxysilyl group, a (meth) acryloyl group, and the like. R represents at least one selected from the group consisting of an epoxy group, a glycidoxy group, an alkoxysilyl group, and a (meth) acryloyl group, and a hydrocarbon group [for example, an aliphatic hydrocarbon group (either chained, branched, or cyclic). And an unsaturated bond may be included.), An aromatic hydrocarbon group, and a combination thereof. ] Can be combined. Examples of the organic group are the same as described above. The alkoxysilyl group can have 1 to 3 alkoxy groups, and the alkoxy group can have 1 or more carbon atoms. The alkoxysilyl group can have a hydrocarbon group in addition to the alkoxy group. The hydrocarbon group is not particularly limited.
Examples of the isocyanurate derivative represented by the above formula include tris- (3-trimethoxysilylpropyl) isocyanurate.
The isocyanurate compounds can be used alone or in combination of two or more.
The amount of the isocyanurate compound is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the organopolysiloxane (A) and the silane compound (B) described above, and 0.1 to 5 parts by mass. More preferably.

Examples of the fluorescent substance (inorganic substance) include a YAG phosphor, a ZnS phosphor, a Y ₂ O ₂ S phosphor, a red light emitting phosphor, a blue light emitting phosphor, and a green light emitting phosphor.

The composition of the present invention is mentioned as one of the preferred embodiments that is substantially free of water because of its excellent storage stability. In the present invention, “substantially free of water” means that the amount of water in the composition of the present invention is 0.1% by mass or less.
In addition, the composition of the present invention can be mentioned as one of preferred embodiments that substantially does not contain a solvent because it is excellent in work environment. In the present invention, “substantially free of solvent” means that the amount of the solvent in the composition of the present invention is 1% by mass or less.

  The production method of the composition of the present invention is not particularly limited. For example, organopolysiloxane (A), zinc compound (B), boron compound (C) and / or phosphate ester (D), and as necessary The method of manufacturing by mixing the additive etc. which can be used is used. The composition of the present invention can be produced as a one-pack type or a two-pack type.

The composition of this invention can be used as a sealing material (for example, for optical semiconductor elements), for example. As an optical semiconductor element which can use the composition of this invention as a sealing material, a light emitting diode (LED), an organic electroluminescent element (organic EL), a laser diode, an LED array etc. are mentioned, for example. Examples of the LED include a high power LED, a high luminance LED, and a general luminance LED.
The composition of the present invention can be used for 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. .

Examples of the adherend of the composition of the present invention include metals (eg, Group 11 metals), glass, rubber, semiconductors (eg, optical semiconductor elements), resins such as polyphthalamide, and the like. The Group 11 metal is preferably at least one selected from the group consisting of copper, silver and gold.
The composition of the present invention is preferably used in the presence of a silver-containing member because it is more excellent in transparency and sulfidation resistance. The silicone resin layer obtained from the composition of the present invention can be adhered to an adherend.

<How to use>
As a usage method of the composition of this invention, the usage method provided with the hardening process which hardens the composition of this invention in presence of the member containing silver, for example is mentioned. Hereinafter, the said usage method is demonstrated as a usage method (henceforth "the usage method of this invention") of the composition of this invention.

  As a member containing silver used for the usage method of this invention, silver, silver plating, etc. are mentioned, for example, A reflector etc. are mentioned as a specific example.

  The curing step may be a step of curing the composition of the present invention by heating and / or light irradiation. As temperature which heats the composition of this invention, 80 to 150 degreeC vicinity is preferable and 150 degreeC vicinity is more preferable. Moreover, as light used when light irradiating the composition of this invention, an ultraviolet-ray, an electron beam etc. are mentioned, for example.

<Silicone resin-containing structure>
The silicone resin-containing structure of the present invention includes a member containing silver and a silicone resin layer obtained by curing the composition of the present invention that covers the member. The said silicone resin layer may cover the said member directly, and may cover it through another layer (for example, a resin layer, a glass layer, an air layer).

The silicone resin-containing structure of the present invention preferably has an optical semiconductor element. It does not specifically limit as an optical semiconductor element, For example, what was illustrated as an optical semiconductor element which can use the composition of this invention as a sealing material is mentioned.
As an aspect in which the silicone resin-containing structure of the present invention has an optical semiconductor element, for example, an aspect in which the silicone resin layer covers the member via the optical semiconductor element (that is, the optical semiconductor element is the silicone resin layer). And the above-mentioned member); an embodiment in which the above-mentioned silicone resin layer directly covers the optical semiconductor element and the above-mentioned member arranged in parallel; Moreover, in the latter aspect, the optical semiconductor element may be arrange | positioned between the two said members arrange | positioned in parallel at intervals.

Next, the laminated body (laminated body 100, laminated body 200) as the silicone resin-containing structure of the present invention will be described based on FIG. 1 and FIG.
FIG. 1 is a cross-sectional view schematically showing an example of a laminate as the silicone resin-containing structure of the present invention. As shown in FIG. 1, the laminated body 100 is provided with the member 120 containing silver. A silicone resin layer 102 is directly disposed on the member 120.
FIG. 2 is a cross-sectional view schematically showing another example of a laminate as the silicone resin-containing structure of the present invention. As shown in FIG. 2, the stacked body 200 includes a member 220 containing silver. The optical semiconductor element 203 is directly disposed on the member 220, and the silicone resin layer 202 is directly disposed on the optical semiconductor element 203. Note that a transparent layer (for example, a resin layer, a glass layer, an air layer, etc.) (not shown) may be disposed between the silicone resin layer 202 and the optical semiconductor element 203.

<Optical semiconductor element sealing body>
The sealed optical semiconductor element of the present invention includes a frame having a recess, an optical semiconductor element disposed at the bottom of the recess, a member including silver disposed on the inner surface of the recess, and filling the recess. And a sealing material obtained by curing the composition of the present invention, which seals the optical semiconductor element and the member.
It does not specifically limit as a member containing silver, For example, what was illustrated as a member containing silver used for the usage method of this invention is mentioned. Moreover, it does not specifically limit as an optical semiconductor element, For example, what was illustrated as an optical semiconductor element which can use the composition of this invention as a sealing material is mentioned. The sealed optical semiconductor element of the present invention can have one or two or more of the above optical semiconductor elements per one.

Next, the sealed optical semiconductor element of the present invention will be described with reference to FIGS.
FIG. 3 is a cross-sectional view schematically showing an example of the sealed optical semiconductor element of the present invention. As shown in FIG. 3, the optical semiconductor element sealing body 300 includes a frame 304 having a recess 302. The bottom surface of the recess 302 is open. Therefore, the frame body 304 is formed with end portions (end portion 312 and end portion 314) so as to surround the opening. A substrate 310 having an external electrode 309 is disposed below the frame body 304. The substrate 310 forms the bottom of the recess 302. An optical semiconductor element 303 is disposed at the bottom of the recess 302. The optical semiconductor element 303 is disposed in the concave portion 302 so that the upper surface is a light emitting layer (not shown). The lower surface of the optical semiconductor element 303 is fixed by the mount member 301. The mount member 301 is, for example, silver paste, resin, or the like. Each electrode (not shown) of the optical semiconductor element 303 and the external electrode 309 are wire bonded by a conductive wire 307.

On the inner side surface of the recess 302, a reflector 320 is disposed as a member containing silver. The concave portion 302 is filled with a sealing material 308, and the sealing material 308 seals the optical semiconductor element 303 and the reflector 320. Here, the sealing material 308 is obtained by curing the composition of the present invention.
The sealing material 308 may be filled up to the hatched portion 306 in the recess 302. Further, the portion indicated by 308 in the recess 302 may be another transparent layer, and the sealing material 308 may be disposed only in the hatched portion 306. Such a sealing material 308 can contain a fluorescent material or the like.

  Note that the optical semiconductor element sealing body 300 may have a mode in which the end portions (the end portion 312 and the end portion 314) of the frame body 304 are integrally coupled to form the bottom portion of the recess 302. In this embodiment, the reflector 320 is disposed not only on the inner surface of the recess 302 but also on the bottom of the recess 302. The optical semiconductor element 303 is disposed on the reflector 320 disposed at the bottom of the recess 302.

Since the encapsulating material 308 obtained by curing the composition of the present invention is used in such an optical semiconductor element encapsulant 300, corrosion (for example, discoloration) of the reflector 320, which is a member containing silver, is used. ) Can be suppressed.
Further, since the sealing material 308 filled in the recess 302 has low hardness and small curing shrinkage, it can be prevented from being peeled off from the recess 302 due to the curing shrinkage or the conductive wire 307 being disconnected.

  FIG. 4 is a cross-sectional view schematically showing another example of the sealed optical semiconductor element of the present invention. A sealed optical semiconductor element 400 shown in FIG. 4 is obtained by arranging a lens 401 on the sealed optical semiconductor element 300 shown in FIG. As the lens 401, a lens formed using the composition of the present invention can be used.

FIG. 5 is a cross-sectional view schematically showing still another example of the sealed optical semiconductor element of the present invention. In the sealed optical semiconductor element 500 shown in FIG. 5, a substrate 510 and inner leads 505 are arranged inside a resin 506 having a lamp function. The substrate 510 has a frame having a recess, an optical semiconductor element 503 is disposed at the bottom of the recess, and a reflector 520 is disposed on the inner surface of the recess, and the composition of the present invention is cured in the recess. A sealing material 502 obtained in this manner is disposed.
The reflector 520 may be disposed at the bottom of this recess. The optical semiconductor element 503 is fixed on the substrate 510 with a mount member 501. Each electrode (not shown) of the optical semiconductor element 503 is wire-bonded by a conductive wire 507. The resin 506 may be formed using the composition of the present invention.

Next, the case where the composition of the present invention and / or the sealed optical semiconductor element of the present invention is used for an LED display will be described with reference to FIG.
FIG. 6 is a schematic view showing an example of an LED display using the composition of the present invention and / or the sealed optical semiconductor element of the present invention.
An LED display 600 shown in FIG. 6 includes a housing 604 in which a light shielding member 605 is disposed. A plurality of optical semiconductor element sealing bodies 601 are arranged in a matrix in the housing 604. The optical semiconductor element sealing body 601 is sealed with a sealing material 606.
Here, as the sealing material 606, a sealing material obtained by curing the composition of the present invention can be used. Moreover, as the optical semiconductor element sealing body 601, the optical semiconductor element sealing body of this invention can be used.

  Examples of uses of the silicone resin-containing structure of the present invention and the sealed optical semiconductor element of the present invention include automobile lamps (for example, headlamps, tail lamps, directional lamps, etc.), household lighting equipment, and industrial use. Illuminating fixtures, stage lighting fixtures, displays, signals, projectors, and the like.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

<Manufacture of silicone resin composition>
The components shown in Table 1 below are used in the amounts shown in the table (unit: parts by mass), and these are uniformly mixed with a vacuum stirrer to form a silicone resin composition (hereinafter simply referred to as “silicone resin composition”). Manufactured.

<Evaluation>
The following methods were used to evaluate adhesion, long-term reliability at high temperatures, sulfidation resistance, and transparency. The results are shown in Table 1 below.

<Adhesiveness>
Pour the produced silicone resin composition into the LED package (manufactured by Enomoto Co., Ltd.), cure it under the curing conditions described below, and determine whether the silicone resin composition is peeled off from polyphthalamide (PPA) or silver plating at the time of curing. It was confirmed visually.
When peeling was not confirmed, it evaluated as "(circle)" as what is excellent in adhesiveness, and when peeling was confirmed, it evaluated as "x" as inferior to adhesiveness.

<Long-term reliability at high temperatures>
The manufactured silicone resin composition was poured into an LED package (manufactured by Enomoto) and cured under the curing conditions described below. Thereafter, the adhesion between the cured silicone resin composition and polyphthalamide (PPA) or silver plating was visually confirmed in the LED package after 500 hours had passed at 150 ° C.
If no abnormality such as peeling or cracking is confirmed, it is evaluated as “○” as being excellent in long-term reliability at high temperature, and if abnormality such as peeling or cracking is confirmed, it is long-term at high temperature. It evaluated as "x" as inferior to reliability.

<Sulfurization resistance>
[Curing cured sample]
The manufactured silicone resin composition was applied on silver plating so as to have a thickness of about 1 mm, and cured under the curing conditions described later to obtain a cured sample for evaluation of sulfidation resistance.

[Sulfuration resistance test]
About 10 g of iron sulfide pulverized into a powder form (large excess with respect to 0.5 mmol of hydrochloric acid) was placed on the bottom of a 10 L desiccator. Next, an eye plate (having a through hole) was attached to the upper position of the iron sulfide in the desiccator so as not to contact the iron sulfide, and the cured sample was placed on the eye plate. Next, by dropping 0.5 mmol of hydrochloric acid into iron sulfide, 0.25 mmol of hydrogen sulfide (concentration: 560 ppm as a theoretical value) was generated (reaction formula: FeS + 2HCl → FeCl ₂ + H ₂ S).

[Evaluation criteria for sulfidation resistance]
After 24 hours from the start of the above-described sulfidation resistance test (generation of hydrogen sulfide), the discoloration of silver in the cured sample was confirmed visually. When no discoloration was confirmed, “◯” was evaluated as being excellent in sulfidation resistance, and “X” was evaluated as being poor in sulfidation resistance when discoloration was confirmed.

<Transparency>
The initial cured product (thickness: 2 mm) obtained by curing the obtained silicone resin composition under the curing conditions described later, in accordance with JIS K0115: 2004, an ultraviolet / visible absorption spectrum measuring apparatus (Shimadzu Corporation) The transmittance at a wavelength of 400 nm was measured. If the transmittance (%) is 80% or more, it can be evaluated as having excellent transparency.

<Curing conditions>
-When the silicone resin composition contains an amine compound described later: heated at 150 ° C for 3 hours-When the silicone resin composition contains a thermal radical polymerization initiator described later: heated at 150 ° C for 3 hours-Silicone resin composition Contains a radical photopolymerization initiator which will be described later: Integrated light quantity 8000 mJ / cm ² irradiation under high-pressure mercury lamp irradiation conditions

The following components were used as the components in Table 1.
Organopolysiloxane 1: Epoxy-modified silicone (x-22-163B, manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight: 3,500, reactive functional group: epoxy group, average number of functional groups: 2)
Organopolysiloxane 2: Succinic anhydride-modified silicone represented by the following structural formula (DMS-Z21, manufactured by Gelest, weight average molecular weight: 700, average number of functional groups: 2)

-Organopolysiloxane 3: Epoxy-modified silicone (KF105, manufactured by Shin-Etsu Chemical Co., Ltd.)
Organopolysiloxane 4: amino-modified silicone (x-22-161A, manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight: 1,600, average number of functional groups: 2)
Organopolysiloxane 5: Methacrylated silicone produced as follows (weight average molecular weight: 35,000, average number of functional groups: 2)
100 parts by mass of polydimethylsiloxane having silanol groups at both ends (ss70, weight average molecular weight: 28,000, manufactured by Shin-Etsu Chemical Co., Ltd.), 4 parts by mass of methacryloxypropyltrimethoxysilane (KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.), and 0.01 parts by mass of tin 2-ethylhexanoate (manufactured by Kanto Chemical Co., Inc.) as a catalyst was placed in a reaction vessel and reacted for 6 hours while maintaining the pressure at 10 mmHg and the temperature at 80 ° C.
The obtained reaction product was subjected to ¹ H-NMR analysis to confirm that both ends of the polydimethylsiloxane were methacryloxypropyldimethoxysilyl groups. The obtained reaction product was designated as organopolysiloxane 5.

Organopolysiloxane 6: Mercapto-modified silicone (KF-2001, manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight: 6,000, average number of functional groups: 3)
Organopolysiloxane 7: carboxy-modified silicone (x-22-3701E, manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight: 30,000, average number of functional groups: 7)

・ Amine compound: Special amine (manufactured by San Apro)
Thermal radical polymerization initiator: 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate (Perocta O, manufactured by NOF Corporation)
Photoradical polymerization initiator: 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Japan)

-Zinc compound 1 (1.6-2EHA-Zn): 1.6 mol of 2-ethylhexanoic acid (manufactured by Kanto Chemical Co.) is added to 1 mol of zinc oxide (manufactured by Kanto Chemical Co., Ltd.) and stirred at room temperature. A clear, uniform liquid was obtained. The obtained liquid was set to 1.6-2EHA-Zn.
Zinc compound 2 (1.8-2EHA-Zn): produced in the same manner as 1.6-2EHA-Zn except that the amount of 2-ethylhexanoic acid was changed to 1.8 mol, and was transparent and uniform Liquid was obtained. The obtained liquid was defined as 1.8-2EHA-Zn.
Zinc compound 3 (2.0-2EHA-Zn): produced in the same manner as 1.6-2EHA-Zn except that the amount of 2-ethylhexanoic acid was changed to 2.0 mol, and was transparent and uniform Liquid was obtained. The obtained liquid was set to 2.0-2EHA-Zn.

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

・ Organic phosphite ester 1: Tri-2-ethyl hexane phosphite
・ Organic phosphate ester 1: Triethyl phosphate (Tokyo Chemical Industry)
・ Organic phosphate ester 2: Tris (trimethylsilyl) phosphate (manufactured by Gelest)

From the results shown in Table 1, it was found that all of Examples 1 to 13 were excellent in sulfidation resistance and long-term reliability under high temperature, and were excellent in transparency and adhesiveness.
On the other hand, Comparative Example 1, which does not contain any zinc compound (B) and boron compound (C) and / or phosphate ester (D), is inferior in both sulfidation resistance and long-term reliability at high temperatures. I understood that.
Moreover, it turned out that Comparative Examples 2-6 which contains only a boron compound (C) and / or phosphate ester (D) are inferior to sulfidation resistance. In addition, Reference Examples 1 to 4 containing only the zinc compound (B) were inferior in long-term reliability at high temperatures.
Further, in Comparative Example 7 in which the content of the zinc compound (B) exceeds the upper limit of the range of the present invention, curing did not proceed sufficiently, and long-term reliability at a high temperature could not be evaluated. Further, since white turbidity was observed, evaluation of sulfidation resistance was not carried out (those not evaluated were indicated by “−” in Table 1).

100,200 Laminate (silicone resin-containing structure)
102, 202 Silicone resin layer 120, 220 Member 203, 303, 503 Optical semiconductor element 300, 400, 500, 601 Optical semiconductor element sealing body 301, 501 Mount member 302 Recess 304 Frame body 306 Shaded portion 307, 507 Conductive wire 308, 502, 606 Sealing material (other transparent layer)
309 External electrodes 312 and 314 End portions 310 and 510 Substrate 320 and 520 Reflector 401 Lens 506 Resin 600 LED display 604 Case 605 Light shielding member

Claims (7)

Organopolysiloxane having at least one reactive functional group in one molecule selected from the group consisting of epoxy group, (meth) acryloyl group, amino group, carbinol group, mercapto group, carboxy group and phenol group (A) and
A zinc compound (B);
A boron compound (C) and / or a phosphate ester (D),
Content of the said zinc compound (B) is 0.01-5 mass parts with respect to 100 mass parts of said organopolysiloxane (A),
The silicone resin composition whose content of the said boron compound (C) and / or the said phosphate ester (D) is 0.01-5 mass parts with respect to 100 mass parts of said organopolysiloxane (A).   The silicone resin composition according to claim 1, wherein the boron compound (C) is a boric acid ester. The silicone resin composition according to claim 2, wherein the boron compound (C) is a compound represented by any of the following formulas (c1) to (c5).

(In formulas (c1) to (c5), 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. Represents a hydrocarbon group.)   The silicone resin composition according to any one of claims 1 to 3, wherein the phosphate ester (D) is an organic phosphite ester (D1) and / or an organic phosphate ester (D2). The silicone resin composition according to claim 4, wherein the organic phosphite ester (D1) is represented by the following formula (d1), and the organic phosphate ester (D2) is represented by the following formula (d2).
P- (OR ^d1 ) ₃ (d1)
O = P- (OR ^d2 ) ₃ (d2)
(In formulas (d1) and (d2), R ^d1 and R ^d2 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group, or a silyl group.) A member containing silver;
A silicone resin layer obtained by curing the silicone resin composition according to any one of claims 1 to 5, which covers the member;
A silicone resin-containing structure comprising: A frame having a recess;
An optical semiconductor element disposed at the bottom of the recess;
A member containing silver disposed on the inner surface of the recess;
A sealing material obtained by curing the silicone resin composition according to any one of claims 1 to 5, which is filled in the concave portion and seals the optical semiconductor element and the member;
An optical semiconductor element sealing body comprising: