JP2012111850A - Silicone resin composition, and structure containing silicone resin obtained using the same and sealed optical semiconductor element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silicone resin composition which is superior in adhesiveness to an adherend without deteriorating the excellent sulfuration resistance.SOLUTION: The silicone resin composition contains 0.01-5 pts.mass of a zinc compound (B) and 0.01-5 pts.mass of a compound (C) having a polyalkylene oxide chain relative to 100 pts.mass of a curable silicone resin composition (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.

Silicone resin is excellent in heat resistance, but has higher gas permeability than epoxy resin or the like. Therefore, the silver plating sealed with the silicone resin may be corroded by hydrogen sulfide in the air and discolored over time.
As countermeasures against such discoloration over time, a method of increasing the crosslink density of the silicone resin to harden the resin, a method of copolymerizing a silicone resin and a resin having a high gas barrier property, etc. have been proposed (for example, patent documents). 1).

JP 2003-188503 A

The present inventors have clarified that sufficient sulfur resistance cannot be obtained by the above-described method conventionally employed as a countermeasure against discoloration of silver over time, and a predetermined amount of zinc compound is added to the silicone resin. It was found that excellent sulfidation resistance can be obtained by blending.
However, it has been found that a silicone resin containing a predetermined amount of a zinc compound may have poor adhesion to an adherend after curing.

  Then, an object of this invention is to provide the silicone resin composition which was excellent in the adhesiveness with respect to a to-be-adhered body, without impairing the outstanding sulfidation resistance.

As a result of diligent studies to solve the above problems, the present inventor further blended a predetermined amount of a compound (C) having a polyalkylene oxide chain with a curable silicone resin containing a predetermined amount of a zinc compound. The inventors have found that the adhesion can be improved without impairing the sulfidation resistance, and have completed the present invention.
That is, the present invention provides the following (1) to (7).

  (1) 0.01 to 5 parts by mass of the zinc compound (B) and 0.01 to 5 parts by mass of the compound (C) having a polyalkylene oxide chain with respect to 100 parts by mass of the curable silicone resin composition (A) And a silicone resin composition.

  (2) Organopolysiloxane (a) in which the curable silicone resin composition (A) has at least two hydrolyzable groups bonded to silanol groups or silicon atoms, hydrolyzable silane, and hydrolyzate thereof And at least one silane compound (b) selected from the group consisting of the hydrolysis condensate thereof, and a condensation catalyst (c), and the silicone according to (1) above Resin composition.

  (3) The curable silicone resin composition (A) comprises an organopolysiloxane (d) having at least two alkenyl groups bonded to silicon atoms and a polyorganohydro having at least two hydrogen atoms bonded to silicon atoms. Genpolysiloxane (e) and a hydrosilylation catalyst (f), wherein the amount of the hydrogen atom is 0.1 to 5.0 mol per mol of the alkenyl group (1) or ( The silicone resin composition as described in 2).

  (4) The curable silicone resin composition (A) comprises an organopolysiloxane (g) having two or more (meth) acryloyl groups in one molecule, a thermal polymerization initiator and / or a photopolymerization initiator ( h), and the silicone resin composition according to any one of the above (1) to (3).

  (5) The silicone resin composition according to any one of (1) to (4), wherein the curable silicone resin composition (A) contains an organopolysiloxane (i) having an epoxy 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 that does not impair excellent sulfidation resistance and has excellent adhesion to an adherend.

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 0.01 to 5 mass of the zinc compound (B) with respect to 100 mass parts of the curable silicone resin composition (A). Part and the compound (C) which has a polyalkylene oxide chain 0.01-5 mass parts.
Hereinafter, each component contained in the composition of the present invention will be described in detail.

<Curable silicone resin composition (A)>
The curable silicone resin composition (A) contained in the composition of the present invention is not particularly limited as long as it is a composition containing a curable silicone resin (A1).

Examples of the curable silicone resin (A1) include silanol groups (hydroxy groups bonded to silicon atoms), hydrolyzable groups bonded to silicon atoms, alkenyl groups bonded to silicon atoms, hydrogensilyl groups, (meth) Reactive functional groups such as acryloyl group, epoxy group, amino group, carbinol group, mercapto group, carboxy group, and phenol group; aromatic groups such as phenyl group; hydrocarbon groups such as alkyl group and alkenyl group; etc. be able to.
The curable silicone resin (A1) may have two or more reactive functional groups in one molecule, and may have a reactive functional group at the terminal or both terminals and / or side chains.

  Examples of the skeleton of the curable silicone resin (A1) include silane, silicone oligomer, silicone resin, organosiloxane, diorganosiloxane, organopolysiloxane, diorganopolysiloxane, and the like. Or any of a branch may be sufficient.

Examples of the organosiloxane as the skeleton of the curable silicone resin (A1) (hereinafter also referred to as “organosiloxane (A11)”) include those represented by the following formula (1).
_{^{X 1 -SiR 1 2 -O- [SiR}} 1 2 -O] n -SiR 1 2 -X 2 (1)
The formula (1), R ¹ represents an alkyl group or an aryl group having from 1 to 18 carbon atoms, each of the plurality of R ¹ may be different even in the same, X ¹ and X ² are each independently A reactive functional group is shown, and n is an integer of 1 or more.
In the above formula (1), examples of the alkyl group having 1 to 18 carbon atoms represented by R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. Can be mentioned. Examples of the aryl group represented by R ¹ include a phenyl group and a naphthyl group. Of these, the group represented by R ¹ is preferably a methyl group or a phenyl group, and more preferably a methyl group.
In said formula (1), n can be made into the numerical value corresponding to the weight average molecular weight of the said organosiloxane (A11), and it is preferable that it is an integer of 10-15000.

Moreover, the said organosiloxane (A11) may be single 1 type, or 2 or more types may be used together. When two or more organosiloxanes (A11) are used in combination, two or more organosiloxanes (A11) may have the same reactive functional group or different reactive functional groups. May be.
At this time, the organosiloxane (A11) having a reactive functional group is combined with the organosiloxane (A11) having a reactive functional group that reacts with the reactive functional group and acts as a curing agent. be able to. In this case, the amount of the latter organosiloxane (A11) is 0.1 to 10 equivalents relative to the reactive functional group of the former organosiloxane (A11). It can be an amount.

  Specific examples of the curable silicone resin composition (A) include the following silicone resin compositions [1] to [4].

Curable silicone resin composition [1]: organopolysiloxane (a) having at least two hydrolyzable groups bonded to silanol groups or silicon atoms, hydrolyzable silane, hydrolyzate thereof, and A curable silicone resin composition comprising one or both of at least one silane compound (b) selected from the group consisting of hydrolysis condensates and a condensation catalyst (c).
In the curable silicone resin composition [1], the organopolysiloxane (a) and / or the silane compound (b) can be a silicone resin.

Curable silicone resin composition [2]: polyorganohydrogenpolysiloxane (d) having at least two alkenyl groups bonded to silicon atoms and polyorganohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms ( A curable silicone resin composition containing e) and a hydrosilylation catalyst (f).
The amount of the hydrogen atom is preferably 0.1 to 5.0 mol per mol of the alkenyl group.

  Curable silicone resin composition [3]: organopolysiloxane (g) having two or more (meth) acryloyl groups in one molecule, a thermal polymerization initiator and / or a photopolymerization initiator (h), A curable silicone resin composition containing

Curable silicone resin composition [4]: A curable silicone resin composition containing an organopolysiloxane (i) having an epoxy group.
The curable silicone resin composition [4] further contains, as an optional component, for example, at least one (j) selected from the group consisting of an acid anhydride, a carboxylic acid, an amine compound, a Lewis acid catalyst, and a Lewis base catalyst. can do.

  As each component contained in the said curable silicone resin composition [1]-[4], it does not specifically limit, For example, a conventionally well-known thing is mentioned.

It does not specifically limit as a manufacturing method of the said organosiloxane (a), (d), (g), and (i), For example, a conventionally well-known thing is mentioned.
The molecular weight of these organosiloxanes is preferably 1,000 to 1,000,000, and more preferably 6,000 to 100,000.
In the present invention, the molecular weight is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) using chloroform as a solvent.

It does not specifically limit as a manufacturing method of the said curable silicone resin composition [1]-[4].
The said curable silicone resin composition [1]-[4] may be used individually by 1 type, and may use 2 or more types together.
Of the curable silicone resin compositions [1] to [4], the curable silicone resin composition [1] is preferable.

<Curable silicone resin composition [1]>
Next, each component contained in the curable silicone resin composition [1] will be described in detail.

[Organopolysiloxane (a)]
The organopolysiloxane (a) is an organopolysiloxane having at least two hydrolyzable groups bonded to silanol groups or silicon atoms, and having at least two hydrolyzable groups bonded to silanol groups or silicon atoms. An organopolysiloxane is preferred, and an organopolydimethylsiloxane having at least two hydrolyzable groups bonded to silanol groups or silicon atoms is more preferred.
As said organopolysiloxane (a), what is represented by following formula (2) is mentioned, for example.

  In said formula (2), m can be made into the numerical value corresponding to the weight average molecular weight of the said organopolysiloxane (a), and it is preferable that it is an integer of 10-15000.

Moreover, examples of the organopolysiloxane (a) include silicone resins having a network of main chains. Examples of such a silicone resin include, for example, R ₃ SiO _1/2 units (wherein each R independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms) and SiO _{4 /} Examples include silicone resin a1 having ₂ units as a repeating unit.

In the silicone resin a1, R in R ₃ SiO _1/2 unit is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, tert-butyl group, pentyl. Group, alkyl group such as hexyl group; cycloalkyl group such as cyclopentyl group, cyclohexyl group; alkenyl group such as vinyl group, allyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group; aryl group such as phenyl group; Halogenated alkyl groups such as a chloromethyl group, a 3-chloropropyl group, a 1-chloro-2-methylpropyl group, and a 3,3,3-trifluoropropyl group; among others, a methyl group, a vinyl group, A phenyl group is preferable, and a methyl group is more preferable.

In the silicone resin a1, the ratio of R ₃ SiO _1/2 units to 1 mol of SiO _4/2 units is 0.5 to 1.2 mol, preferably 0.65 to 1.15 mol. When the ratio of R ₃ SiO _1/2 units is within this range, the cured product of the composition of the present invention has appropriate strength and excellent transparency.

Further, the silicone resin a1 has an R ₂ SiO _2/2 unit and an RSiO _3/2 unit (wherein R is independently an unsubstituted or substituted carbon number of 1 to 6 with respect to 1 mol of SiO _4/2 units. At least one of each unit may be 1.0 mol or less and the total of each unit may be 1.0 mol or less, more preferably Are 0.2 to 0.8 mol of each unit of R ₂ SiO _2/2 unit and RSiO _3/2 unit, and the total of each unit is 1.0 mol or less. Thus, if it is a mixture ratio, the composition of this invention is excellent in transparency. Specific examples of such a blending ratio include a combination of 0.2 mol of R ₂ SiO _2/2 units and 0.7 mol of RSiO _3/2 units with respect to 1 mol of SiO _4/2 units.

  Furthermore, the silicone resin a1 has a silanol group of less than 6.0% by mass. The content of silanol groups is preferably 0.1% by weight or more, and more preferably 0.2 to 3.0% by weight. When the content of the silanol group is within this range, the hardness of the cured product of the composition of the present invention is appropriate, the adhesiveness is good, and the strength is also appropriate.

The method for producing the silicone resin a1 is not particularly limited, and can be produced by a conventionally known method. For example, the alkoxy group-containing silane compound corresponding to each unit can be substantially hydrolyzed and condensed in an organic solvent. Can be obtained as containing no volatile components.
Specifically, for example, if R ₃ SiOMe and Si (OMe) ₄ are co-hydrolyzed and condensed in an organic solvent together with R ₂ Si (OMe) ₂ and / or RSi (OMe) ₃ as desired. (In each formula, R independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and Me represents a methyl group).
As the organic solvent, those capable of dissolving organopolysiloxane produced by cohydrolysis / condensation reaction are preferable, and specific examples thereof include toluene, xylene, methylene chloride, naphtha mineral spirit and the like.

  As such silicone resin a1, a commercial item can be used, for example, “SR1000” which is trimethoxysilicate manufactured by Momentive Performance Materials Japan GK.

[Silane Compound (b)]
The silane compound (b) is at least one selected from the group consisting of a hydrolyzable silane, a hydrolyzate thereof, and a hydrolysis condensate thereof.
The hydrolyzable silane is not particularly limited as long as it has one silicon atom in one molecule and a hydrolyzable group such as an alkoxy group or a phenoxy group. Hereinafter, such a hydrolyzable silane may be referred to as “silane compound b1”.
The hydrolyzate of hydrolyzable silane is not particularly limited as long as it is obtained by hydrolyzing the silane compound b1. The hydrolysis may be partial hydrolysis.
The hydrolysis condensate of hydrolyzable silane is not particularly limited as long as it is obtained by hydrolyzing and condensing the silane compound b1. The hydrolysis condensation may be a partial hydrolysis condensation. Hereinafter, such a hydrolysis-condensation product may be referred to as “silane compound b2”.

  The silane compound (b) can have one or more organic groups in one molecule. Examples of the organic group that the silane compound (b) can have include a hydrocarbon group that may contain at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. Examples include an alkyl group (preferably having 1 to 6 carbon atoms), a (meth) acrylate group, an alkenyl group, an aryl group, a combination thereof, and the like. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 2-methyl-1-propenyl group, and a 2-methylallyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Among these, a methyl group, a (meth) acrylate group, and a (meth) acryloxyalkyl group are preferable because of excellent heat-resistant coloring stability.

[Silane compound b1]
As said silane compound b1, what is represented by following formula (3) is mentioned, for example.
Si (OR ² ) _n R ³ _4-n (3)
In the above formula (3), n is 2, 3 or 4, R ² is an alkyl group, R ³ is an organic group, and is described as an organic group that the silane compound (b) can have It is synonymous with.

Examples of the silane compound b1 include dialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane; methyltrimethoxysilane, methyltriethoxysilane Trialkoxysilanes such as ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane; tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropyloxysilane; γ- (meth) acrylic (Meth) acryloxyalkyltrialkoxysilanes such as loxypropyltrimethoxysilane and γ- (meth) acryloxypropyltriethoxysilane And the like.
Note that (meth) acryloxytrialkoxysilane means acryloxytrialkoxysilane or methacryloxytrialkoxysilane. The same applies to (meth) acrylate groups and (meth) acryloxyalkyl groups.

[Silane compound b2]
As said silane compound b2, the compound represented by following formula (4) is mentioned, for example.
R ⁴ _m Si (OR ⁵ ) _n O _{(4-mn) / 2} (4)
In the above formula (4), R ⁴ is an organic group, R ⁵ is an alkyl group, m is 0 <m <2, n is 0 <n <2, and m + n is 0 <m + n ≦ 3. Here, the organic group represented by R ⁴ has the same meaning as that described as the organic group that the silane compound (b) can have, and the alkyl group represented by R ⁵ has the silane compound (b). It is synonymous with what was described as an alkyl group as an organic group which can be.

Examples of the silane compound b2 include silicone alkoxy oligomers such as methyl methoxy oligomer.
The silicone alkoxy oligomer is a silicone resin having a main chain of polyorganosiloxane and a molecular terminal blocked with an alkoxysilyl group.
The methylmethoxy oligomer corresponds to the compound represented by the above formula (4), and specific examples thereof include those represented by the following formula (5).

In said formula (5), R < ⁶ > is a methyl group, a is an integer of 1-100, b is an integer of 0-100.
A commercial item can be used for the methyl methoxy oligomer, for example, x-40-9246 (weight average molecular weight 6000, the Shin-Etsu Chemical Co., Ltd. make) is mentioned.

As the silane compound b2, for example, a compound having an alkoxysilyl group at least at one end and having three or more alkoxy groups (derived from an alkoxysilyl group) in one molecule (hereinafter referred to as “silane compound b3”). Is also referred to as a preferred form.
The silane compound b3 can be obtained, for example, as a reaction product obtained by dealcoholizing 1 mol or more of a silane compound having an alkoxylyl group with respect to 1 mol of a polysiloxane having a both-end silanol group.
Examples of the silane compound having an alkoxy group used for producing the silane compound b3 include a compound represented by the above formula (3) and a compound represented by the above formula (4).
Examples of the polysiloxane having both terminal silanol groups used for producing the silane compound b3 include compounds represented by the above formula (2).
As said silane compound b3, what is represented by following formula (6) is mentioned, for example.

In said formula (6), n can be made into the numerical value corresponding to the molecular weight of the said silane compound b3.
The compound represented by the above formula (6) is produced, for example, by modifying polysiloxane having silanol groups at both ends with tetramethoxysilane (corresponding to the compound represented by the above formula (3)). be able to.

  The silane compound (b) is preferably represented by the above formula (3) or the above formula (4), and includes tetraalkoxysilane such as tetraethoxysilane; γ- (meth) acryloxypropyltrimethoxysilane ( More preferred are (meth) acryloxyalkyltrialkoxysilanes; methylmethoxy oligomers.

The molecular weight of the silane compound (b) is preferably 100 to 1,000,000, and more preferably 1000 to 100,000.
In addition, when the said silane compound (b) is the said silane compound b2, the molecular weight shall be the weight average molecular weight of polystyrene conversion by the gel permeation chromatography (GPC) which uses chloroform as a solvent.

It does not specifically limit as a manufacturing method of the said silane compound (b), For example, a conventionally well-known thing is mentioned.
The said silane compound (b) may be used individually by 1 main, and may use 2 or more types together.

  When the silane compound (b) is used in combination with the organopolysiloxane (a), the amount of the silane compound (b) is 1 to 2000 parts by mass with respect to 100 parts by mass of the organopolysiloxane. It is preferable that it is 10 to 1000 parts by mass.

[Condensation catalyst (c)]
The condensation catalyst (c) is not particularly limited as long as it can hydrolyze and condense a hydrolyzable group-containing silyl group or silanol group. For example, tin, aluminum, titanium, zirconium, hafnium, calcium And metal compounds containing a metal such as barium; boron compounds; and the like. Among these, zirconium compounds (c1) and / or tin compounds (c2) are preferable.

[Zirconium compound (c1)]
As said zirconium compound (c1), the zirconium metal salt represented by following formula (7) is mentioned, for example.

In the above formula (7), n is an integer of 1-3, R ⁷ is a hydrocarbon group of 1 to 16 carbon atoms, R ⁸ is a hydrocarbon group having 1 to 18 carbon atoms.
In the above formula (7), when n is 2 or more, the plurality of R ⁷ may be the same or different. Moreover, when n is 1-2, several R < ⁸ > may be the same or different.
The hydrocarbon group represented by R ^{7 in the} above formula (7) preferably has 3 to 16 carbon atoms, and more preferably 4 to 16 carbon atoms.
The hydrocarbon group represented by R ^{7 in the} formula (7) may be linear or branched and may have an unsaturated bond, for example, a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. You can also.
Examples of the hydrocarbon group represented by R ^{7 in the} above formula (7) include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof.

Examples of the alicyclic hydrocarbon group as the hydrocarbon group represented by R ^{7 in the} above formula (7) include cycloalkyl such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group. Naphthene ring (cycloparaffin ring derived from naphthenic acid); condensed ring hydrocarbon group such as adamantyl group and norbornyl group; and the like. Among them, cyclopropyl group, cyclopentyl group, cyclohexyl group, naphthene ring, adamantyl group Is preferred.
Examples of the aromatic hydrocarbon group as the hydrocarbon group represented by R ^{7 in the} above formula (7) include a phenyl group, a naphthyl group, and azulene. Among them, a phenyl group is preferable.
Examples of the aliphatic hydrocarbon group as the hydrocarbon group represented by R ^{7 in the} above formula (7) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, and 2 -Ethylpentyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, etc. are mentioned.

The number of carbon atoms of the hydrocarbon group represented by R ^{8 in the} above formula (7) is preferably 3 to 8 because it is superior in heat-resistant coloring stability and thin film curability and is excellent in compatibility.
Examples of the hydrocarbon group represented by R ^{8 in} the above formula (7) include those described as the hydrocarbon group represented by R ^{7 in the} above formula (7). Among them, an aliphatic hydrocarbon group is preferable. preferable.

In the above formula (7), examples of the alkoxy group represented by R ⁸ O— include a methoxy group, an ethoxy group, a propoxy group (n-propoxy group, isopropoxy group), a butoxy group, a pentyloxy group, and hexyloxy. A methoxy group, an ethoxy group, a propoxy group (n-propoxy group, isopropoxy group), a butoxy group, and a pentyloxy group.

  The zirconium metal salt represented by the above formula (7) is preferably zirconium tributoxy mononaphthate, zirconium tributoxy monoisobutyrate, or zirconium tributoxy mono 2-ethylhexanoate.

The said zirconium compound (c1) may be used individually by 1 type, and may use 2 or more types together.
As a method for producing the zirconium compound (c1) is, for example, Zr (OR ⁸⁾ ₄ (zirconium tetraalkoxide .R ⁸ is a hydrocarbon group having 1 to 18 carbon atoms, synonymous with R ⁸ in the formula (7) Carboxylic acid represented by R ⁷ —COOH with respect to 1 mol (R ⁷ is a hydrocarbon group having 1 to 16 carbon atoms and has the same meaning as R ^{7 in the} above formula (7).) The method of manufacturing by stirring on 20-80 degreeC conditions in nitrogen atmosphere using 1 mol or more and less than 4 mol is mentioned.

Examples of Zr (OR ⁸ ) ₄ used for producing the zirconium compound (c1) include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetranormal propoxide, zirconium tetrapropoxide, zirconium tetranormal butoxide and the like. Can be mentioned.

  Examples of the carboxylic acid used to produce the zirconium compound (c1) include aliphatic carboxylic acids such as acetic acid, propionic acid, isobutanoic acid, octylic acid, 2-ethylhexanoic acid, nonanoic acid, and lauric acid; naphthenic acid , Cyclopropane carboxylic acid, cyclopentane carboxylic acid, cyclohexyl carboxylic acid (cyclohexane carboxylic acid), alicyclic carboxylic acid such as adamantane carboxylic acid, norbornane carboxylic acid; aromatic carboxylic acid such as benzoic acid;

[Tin compound (c2)]
The tin compound (c2) is not particularly limited, and examples thereof include a tetravalent tin compound. Examples of the tetravalent tin compound include a tetravalent tin compound having at least one alkyl group and at least one acyl group, and can have an acyl group as an ester bond.

Examples of the tetravalent tin compound as the tin compound (c2) include those represented by the following formula (8); bis type and polymer type represented by the following formula (8).
_{^{R 9 a -Sn- [O-CO}} -R 10] 4-a (8)
In said formula (8), R < ⁹ > is an alkyl group, R < ¹⁰ > is a hydrocarbon group, a is an integer of 1-3.
Examples of the alkyl group represented by R ⁹ include those having 1 or more carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and an octyl group.
The hydrocarbon group represented by R ¹⁰ is not particularly limited, and examples thereof include those described as the hydrocarbon group represented by R ^{7 in the} above formula (7).

Examples of the tin compound (c2) include dialkyltin compounds such as dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dioctyltin diacetate, and dioctyltin maleate (expressed by the above formula (8), where a is 2 Dibutyltin oxyacetate dibutytin oxyoctylate, dibutyltin oxylaurate dibutyltin bismethylmalate, dialkyltin dimer such as dibutyltin oxyoleate; polymers such as dibutyltin maleate polymer, dioctyltin maleate polymer Monobutyltin tris (2-ethylhexanoate) (represented by the above formula (8), a is 1); and the like.
Among them, dibutyltin diacetate, dibutyltin dioleate, dibutyltin dilaurate, dibutyltin oxyacetate dibutyltin oxyoctylate, dibutyltin are superior because of transparency, resistance to sulfidation, heat resistance coloring stability, and excellent thin film curability. Oxylaurate and monobutyltin tris (2-ethylhexanoate) are preferred.

The method for producing the condensation catalyst (c) is not particularly limited.
The amount of the condensation catalyst (c) is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the organopolysiloxane (a) and / or the silane compound (b). More preferably, it is 0.5 parts by mass.

The said condensation catalyst (c) may be used individually by 1 type, and may use 2 or more types together.
When the zirconium compound (c1) and the tin compound (c2) are used in combination, the amount of the tin compound (c2) is 0.1 mol or more and less than 4 mol with respect to 1 mol of the zirconium compound (c1). It is preferable that it is 0.5 to 1.5 mol.

<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 curable silicone resin composition (A). Thereby, the composition of this invention is excellent in sulfidation resistance. This is presumably because hydrogen sulfide is coordinated to zinc contained in the zinc compound (B), and hydrogen sulfide is trapped.

As the zinc compound (B), an acid is contained in an amount of 1.5 mol or more and 2 mols 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 less than mol can be used.
The acid used in this case is not particularly limited, and examples thereof include inorganic acids, organic acids (for example, organic carboxylic acids), and esters thereof.
Examples of the inorganic acid include phosphoric acid and boric acid.
In the organic acid, the hydrocarbon group that the organic carboxylic acid has other than the carboxy group is not particularly limited, and examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof. Can be mentioned. Examples of such an organic acid include saturated carboxylic acids having 1 to 30 carbon atoms such as stearic acid, palmitic acid, lauric acid, and 2-ethylhexanoic acid; unsaturated carboxylic acids such as (meth) acrylic acid; It is done.
In the acid ester, the hydrocarbon group forming the ester is not particularly limited, and examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof.
Of these, phosphoric acid, 2-ethylhexanoic acid, naphthenic acid, and esters thereof are preferred.

Examples of the zinc compound (B) include those represented by the formula Zn _a (O) _x (OH) _y (—O—CO—R ¹¹ ) _z . In the formula, R ¹¹ is a hydrocarbon group, and examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof. R ¹¹ is plural, may be different even multiple R ¹¹ are each identical. In the formula, a is a number of 1 or more, x and y are numbers of 0 or more, z is a number of 1 or more, z / a is less than 2, and [(2x + y + z) / a] = 2.
a is preferably a number from 1 to 2, x is preferably a number from 0 to 1, y is preferably a number from 0 to 1, and z is a number from 1 to 2. Is preferred.
Specific examples of the zinc compound (B) include Zn (OH) (— O—CO—R ¹¹ ), R ¹¹ —CO—O—Zn—O—Zn—O—CO—R ^{11, and the} like.
Moreover, the said zinc compound (B) can have bonds, such as -Zn-O-Zn-, in the structure, when x is one or more. Such a bond can be formed by, for example, dehydration condensation of the product in the process of producing the zinc compound (B).

  The method for producing the zinc compound (B) is not particularly limited. For example, at least one selected from the group consisting of zinc oxide, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate, and zinc nitrate, and an acid are used. And a method of producing by stirring at room temperature or by heating.

  The amount of the zinc compound (B) is 0.01% with respect to 100 parts by mass of the curable silicone resin composition (A) because the composition of the present invention is superior to sulfidation resistance and transparency. It is preferable that it is -10 mass parts, and it is more preferable that it is 0.01-1 mass part.

<Compound (C) having a polyalkylene oxide chain>
In the composition of the present invention, the compound (C) having a polyalkylene oxide chain (hereinafter, referred to as “alkylene oxide compound (C)” may be referred to 100 parts by mass of the curable silicone resin composition (A). .) Is contained in an amount of 0.01 to 5 parts by mass. Thereby, the composition of this invention is excellent also in the adhesiveness with respect to a to-be-adhered body, without impairing the sulfidation resistance obtained by containing the said zinc compound (B).
This is because the polyalkylene oxide chain of the alkylene oxide compound (C) is partially coordinated with zinc of the zinc compound (B) to such an extent that the sulfidation resistance by the zinc compound (B) is not impaired. This is thought to alleviate the close inhibition caused by).

The alkylene oxide compound (C) is not particularly limited as long as it has a polyalkylene oxide chain in one molecule.
As a polyalkylene oxide chain | strand which the said alkylene oxide compound (C) has, the polymer which the repeating unit shown by following formula (9) superposed | polymerized is mentioned, for example.
^{- (R 12 -O) - (} 9)
In the above formula (9), R ¹² represents an alkylene group having 1 to 18 carbon atoms, and the alkylene group may be linear or branched. For example, a methylene group, an ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, iso-propylene group, iso-butylene group, 2-methylpropylene group, iso-pentylene group, 2-methylbutylene group, 1,2 Examples include dimethylpropylene group, 1,3-dimethylpropylene group, 1,1-dimethylpropylene group, 2,2-dimethylpropylene group, iso-hexylene group, 2-methylpentylene group, and 3-methylpentylene group. , Methylene group and ethylene group are preferable.

Even if the polyalkylene oxide chain of the alkylene oxide compound (C) is a polymer in which the repeating unit represented by the formula (9) is a single polymer, a copolymer in which two or more are polymerized ( A block copolymer or a random copolymer).
In the polyalkylene oxide chain of the alkylene oxide compound (C), the degree of polymerization of the repeating unit represented by the formula (9) (number of repeating units) is preferably 1 to 1000. More preferably, the number is -100.

Examples of the alkylene oxide compound (C) include polyethylene glycol (PEG), polypropylene glycol (PPG), polybutylene glycol, polytetramethylene ether glycol (PTMG), polyhexamethylene ether glycol, Examples include coalescence.
Among these, polyethylene glycol (PEG) and polytetramethylene ether glycol (PTMG) are preferable because the adhesiveness of the composition of the present invention is more excellent.

The alkylene oxide compound (C) may be one in which a polyalkylene oxide chain is introduced into another main chain. For example, a modified silicone in which a polyalkylene oxide chain is introduced into silicone (modified silicone oil) ) Can be suitably used.
As such a modified silicone, for example, a part of methyl groups at both ends, one end, side chain, etc. of dimethylpolysiloxane may be represented by —R (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b R ′ substituted (wherein R represents an alkylene group having 1 or more carbon atoms, R ′ represents a hydrogen atom or an alkyl group having 1 or more carbon atoms, a and b represent an integer of 0 or more, and a + b> As commercial products, X-22-4741, KF-1002, X-22-4952, X-22-4272, X-22-6266 (all manufactured by Shin-Etsu Chemical Co., Ltd.) ).

  As a weight average molecular weight of the said alkylene oxide compound (C), it is preferable that it is 200-5000, and it is more preferable that it is 200-2000.

In the composition of the present invention, the alkylene oxide compound (C) may be used alone or in combination of two or more.
Moreover, the amount of the alkylene oxide compound (C) is 0.1 to 10 with respect to 100 parts by mass of the curable silicone resin composition (A) because the adhesiveness of the composition of the present invention is more excellent. It is preferable that it is a mass part, and it is more preferable that it is 0.3-3 mass part.

<Components that can be used in combination with the zinc compound (B)>
Moreover, the composition of this invention can contain a tin compound, a lanthanoid compound, a zirconium compound, a hafnium compound, etc. further together with a zinc compound (B) from a viewpoint of catalyst activity.

The tin compound contained in the composition of the present invention is not particularly limited as long as it is a compound containing tin, and examples thereof include a divalent tin compound and a tetravalent tin compound.
Examples of the divalent tin compound include bis (2-ethylhexanoic acid) tin, di (n-octylic acid) tin, dinaphthenic acid tin, and distearic acid tin.
Examples of the tetravalent tin compound include dioctyltin bis (acetylacetonate), a reaction product of dioctyltin salt and normal ethyl silicate, and the like.

  The lanthanoid compound contained in the composition of the present invention is not particularly limited as long as it is a compound having a lanthanoid atom (Ln) such as lanthanum (La), cerium (Ce), dysprosium (Dy), and ytterbium (Yb). Examples thereof include lanthanum, cerium, dysprosium or ytterbium 2-ethylhexanoate.

  The zirconium compound contained in the composition of the present invention is not particularly limited as long as it is a compound having a zirconium atom and an organic group. For example, zirconyl dioctylate, zirconyl naphthenate; zirconium tributoxy mononaphthate, zirconium Tributoxy monoisobutyrate, zirconium tributoxy mono 2-ethylhexanoate, zirconium tributoxy monocyclopropane carboxylate, zirconium tributoxy monocyclopentane carboxylate, zirconium tributoxy monocyclohexane carboxylate, zirconium tributoxy monoadamantane carboxylate Zirconium tributoxy mononaphthate; Zirconium tributoxy mononaphthate, Zirconium tributoxy monoisobutyrate , Zirconium tributoxy mono 2-ethylhexanoate; and the like.

  The hafnium compound contained in the composition of the present invention is not particularly limited as long as it is a compound having a hafnium atom and an organic group. For example, hafnium tributoxy mononaphthate, hafnium tributoxy monoisobutyrate, hafnium tri Butoxymono 2-ethylhexanoate, hafnium tributoxy monocyclopropane carboxylate, hafnium tributoxy monocyclopentane carboxylate, hafnium tributoxy monocyclohexane carboxylate, hafnium trialkoxy monobenzene carboxylate, hafnium tributoxy monoadamantane carboxylate, Hafnium dibutoxy dinaphthate, hafnium tripropoxy mononaphthate; hafnium di-n-butoxide (bis-2,4-pentadio Over G), hafnium -2,4-penta dionate, hafnium tetramethylpentadecane dionate, hafnium trifluoro penta dionate; and the like.

<Other ingredients>
The composition of this invention can contain an additive further as needed in the range which does not impair the objective and effect of this invention other than said component.
Examples of additives include curing agents, metal compounds other than zinc compounds, catalysts (for example, condensation catalysts, hydrosilylation catalysts, Lewis acid catalysts, Lewis base catalysts, and cationic polymerization catalysts), polymerization initiators (for example, thermal polymerization). Initiators, photopolymerization initiators, etc.), inorganic fillers, antioxidants, lubricants, UV absorbers, thermal light stabilizers, dispersants, antistatic agents, polymerization inhibitors, antifoaming agents, curing accelerators, solvents, fluorescence Substances (including inorganic and organic substances), anti-aging agents, radical inhibitors, adhesion improvers, flame retardants, surfactants, storage stability improvers, ozone anti-aging agents, thickeners, plasticizers, radiation blockers , Nucleating agent, coupling agent, conductivity imparting agent, phosphorus peroxide decomposing agent, pigment, metal deactivator, physical property adjusting agent and the like.

  The curing agent is not particularly limited, and examples thereof include amine compounds (polyamine compounds), polyamide compounds, dicyandiamide, acid anhydrides, carboxylic acid compounds, and phenol resins. Specific examples include ethylenediamine and triethylenepentamine. Aliphatic amines such as hexamethylenediamine, dimer acid-modified ethylenediamine, N-ethylaminopiperazine, isophoronediamine; metaphenylenediamine, paraphenylenediamine, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodipheno Aromatic amines such as sulfone, 4,4′-diaminodiphenormethane, 4,4′-diaminodiphenol ether; mercaptans such as mercaptopropionic acid ester and terminal mercapto compound of epoxy resin; 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) bisphenol, phenol novolac, Phenolic resins such as cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak; the aromatic ring of the above phenolic resin is water Polyols: polyazeline acid anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornane-2 , 3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, alicyclic acid anhydrides such as methyl-norbornane-2,3-dicarboxylic anhydride; phthalic anhydride, anhydrous Aromatic acid anhydrides such as trimellitic acid and pyromellitic anhydride; imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole; and salts thereof; By reaction of aromatic amines and / or imidazoles with epoxy resins Amine adducts obtained; hydrazines such as adipic acid dihydrazide; tertiary amines such as dimethylbenzylamine and 1,8-diazabicyclo [5,4,0] undec-7-ene; organic phosphines such as triphenylphosphine Class; dicyandiamide; and the like.

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 production method of the composition of the present invention is not particularly limited. For example, the curable silicone resin composition (A), the zinc compound (B), and additives that can be used as necessary are mixed. The method of manufacturing by doing is mentioned. 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 an adhesive agent, a primer, a sealing material (for example, for optical semiconductor elements) etc., 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 were used in the amounts shown in the same table (unit: parts by mass), and these were uniformly mixed with a vacuum stirrer to produce a silicone resin composition.

<Evaluation>
Evaluation was performed by the following method. The results are shown in Table 1 below.
<Transmissivity>
The manufactured silicone resin composition was cured under the curing conditions described later to obtain a cured sample for measuring transmittance (thickness: 2 mm). About the obtained sample, based on JISK0115: 2004, the transmittance | permeability in wavelength 400nm was measured using the ultraviolet-visible absorption spectrum measuring device (made by Shimadzu Corporation Corp.).
If the transmittance is 80% or more, it can be evaluated as having excellent transparency. In addition, when the obtained hardening sample was cloudy, it described as "white cloudy" in the following Table 1.

<Adhesion>
The produced silicone resin composition is poured onto an adherend (polyphthalamide plate) using a spacer having a length of 25 mm, a width of 10 mm, and a thickness of 1 mm, and cured under the curing conditions described below to obtain a cured product and a coated product. A laminate with a kimono was obtained.
Next, about the obtained laminated body, the hardened | cured material was hand-separated from the to-be-adhered body using the spatula, and adhesiveness was evaluated by the destruction mode in that case. That is, when the fracture mode is cohesive fracture, it is evaluated as “◯” as having excellent adhesion, and when the fracture mode is interfacial fracture, it is evaluated as “×” as being inferior in adhesion. did. In addition, when adhesiveness evaluation was not performed, it described as "-" in the following Table 1.

<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 below) was placed on the bottom of a 10 L desiccator. Next, an eye plate (having a through hole) was attached above the iron sulfide in the desiccator so as not to contact the iron sulfide, and the cured sample was placed on the attached eye plate. Next, by dropping 0.5 mmol of hydrochloric acid on iron sulfide, 0.25 mmol of hydrogen sulfide is generated (reaction formula: FeS + 2HCl → FeCl ₂ + H ₂ S), and the concentration of hydrogen sulfide in the desiccator is 0.05 mass%. (Theoretical value: about 560 ppm).

[Evaluation criteria for sulfidation resistance]
After 24 hours and 72 hours from the start of the above sulfidation resistance test (generation of hydrogen sulfide), the discoloration of silver in the cured sample was visually confirmed. If no discoloration was confirmed, it was evaluated as “◯” as being excellent in sulfur resistance, and if slight discoloration was confirmed, it was evaluated as “△” as slightly superior in sulfur resistance, and discoloration was confirmed. When it was, it was evaluated as “x” as being inferior in sulfidation resistance. In addition, when evaluation of sulfidation resistance was not performed, “−” was described in Table 1 below.

<Heat resistant coloring stability>
The manufactured silicone resin composition was cured under the curing conditions described later to obtain an initial cured product. Furthermore, the obtained initial cured product was heated at 150 ° C. for 10 days to obtain a heat-resistant cured product. When the transmittance of the heat-resistant cured product was 80% or more with respect to the transmittance of the initial cured product, it was evaluated as “◯” as having excellent heat-resistant coloring stability, and was 70% or more and less than 80%. In this case, “△” was evaluated as being somewhat excellent in heat-resistant coloring stability, and “X” was evaluated as being inferior in heat-resistant coloring stability when it was less than 70%. In addition, when evaluation of heat-resistant coloring stability was not performed, it described as "-" in the following Table 1.

<Curing conditions>
When the silicone resin composition contains condensation catalyst 1 or condensation catalyst 2 described later: heated at 150 ° C. for 24 hours. When the silicone resin composition contains a hydrosilylation catalyst described later: heated at 150 ° C. for 6 hours. When the silicone resin composition contains a thermal polymerization initiator described later: heated at 150 ° C. for 3 hours. When the silicone resin composition contains a photopolymerization initiator: an accumulated light amount of 8000 mJ / cm under irradiation with a high-pressure mercury lamp. ² Irradiation ・ When the silicone resin composition contains an acid anhydride and an amine compound: heated at 150 ° C. for 3 hours • When the silicone resin composition contains a Lewis acid catalyst: heated at 150 ° C. for 3 hours

The following components were used as the components in Table 1.
(A) Polysiloxane 1: Polydimethylsiloxane-α, ω-diol (ss10, Shin-Etsu Chemical Co., Ltd., weight average molecular weight: 49000, reactive functional group: silanol group, average number of functional groups: 2)

(A) Polysiloxane 2: both ends trimethoxysilylsiloxane produced as follows (weight average molecular weight: 55000, reactive functional group: methoxysilyl group, average functional group number: 6)
A 500 mL three-necked flask is equipped with a stirrer and a reflux condenser, and 100 parts by mass of polysiloxane having silanol groups at both ends (ss10, manufactured by Shin-Etsu Chemical Co., Ltd.), 10 parts by mass of tetramethoxysilane, and 0 parts of acetic acid. 0.1 mass part was added, it was made to react at 100 degreeC under nitrogen atmosphere for 6 hours, the loss | disappearance of the silanol group which ss10 has was confirmed by < ¹ > H-NMR analysis, and the obtained reaction material was made into polysiloxane 2. The main structure of the polysiloxane 2 is represented by the following formula.

(A) Polysiloxane 3: terminal polymethoxysilylsiloxane produced as follows (weight average molecular weight: 60000, reactive functional group: methoxysilyl group, average functional group number: 14)
A 500 mL three-necked flask is equipped with a stirrer and a reflux condenser, 100 parts by mass of polysiloxane (ss10) having silanol groups at both ends, and a partial hydrolyzate of methyltrimethoxysilane (KC-89, Shin-Etsu Chemical Co., Ltd.) 10 parts by mass) and 0.1 part by mass of acetic acid were added, reacted at 140 ° C. for 15 hours under a nitrogen atmosphere, and disappearance of silanol groups possessed by ss10 was confirmed by ¹ H-NMR analysis. The reaction product was polysiloxane 3. The main structure of the polysiloxane 3 is represented by the following formula.

(A) Polysiloxane 4: Silanol dimethyl silicone oil at both ends (PRX-413, manufactured by Dow Corning Toray, weight average molecular weight: 4000, reactive functional group: silanol group, average number of functional groups: 2)
(B) Polysiloxane 5: Silicone alkoxy oligomer (x-40-9246, manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight: 6000, reactive functional group: alkoxysilyl group, average functional group number: 0 <n <2)

(C) Condensation catalyst 1: Mixture of tributoxynaphthenic acid Zr (0.03 parts by mass) and dibutyltin acetate (0.02 parts by mass, manufactured by Nitto Kasei Co., Ltd.) It is.
17.5 g (0.026 mol) of zirconium tetrabutoxide having a concentration of 87.5% by mass (manufactured by Kanto Chemical Co., Ltd.) and naphthenic acid (manufactured by Tokyo Chemical Industry Co., Ltd., average number of carbon atoms of the hydrocarbon group bonded to the carboxy group: 15 , 6.6 g (0.026 mol) was charged into a three-necked flask and stirred at room temperature for about 2 hours under a nitrogen atmosphere to obtain the target compound.
The neutralization value of naphthenic acid is the amount of KOH required to neutralize 1 g of naphthenic acid.
The qualitative property of the synthesized product was measured using a Fourier transform infrared spectrophotometer (FT-IR). As a result, absorption near 1700 cm ⁻¹ attributed to COOH derived from carboxylic acid disappeared after the reaction, and a peak derived from COOZr near 1450 to 1560 cm ⁻¹ was confirmed.
The average number of carbon atoms of R in the naphthate group (RCOO—) of the tributoxynaphthenic acid Zr is 15.
(C) Condensation catalyst 2: monobutyltris 2-ethylhexanoate tin (manufactured by Nitto Kasei Co., Ltd.)

(D) Polysiloxane 6: dimethylpolysiloxane having a vinyl group (DMS-V35, manufactured by Gelest, weight average molecular weight: 49500, reactive functional group: vinyl group, average number of functional groups: 2)
(E) Polysiloxane 7: Dimethylposilyloxane copolymer methylhydrogen polysiloxane having hydrogensilyl group (KF-9901, manufactured by Shin-Etsu Chemical Co., Ltd., reactive functional group: hydrogensilyl group)
(F) Hydrosilylation catalyst: Platinum-cyclovinylmethylsiloxane complex (SIP6832.2, manufactured by Gelest)

(G) Polysiloxane 8: produced as follows, polydimethylsiloxane having methacryloxypropyldimethoxysilyl groups at both ends (weight average molecular weight: 35000, reactive functional group: methacryloxy group, average number of functional groups: 2 )
100 parts by mass of polydimethylsiloxane having silanol groups at both ends (ss70, manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight: 28,000), and 4 parts by mass of methacryloxypropyltrimethoxysilane (KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) Then, 0.01 parts by mass of tin 2-ethylhexanoate (manufactured by Kanto Chemical Co., Ltd.) as a catalyst is placed in a reaction vessel, and reacted for 6 hours while maintaining the pressure at 10 mmHg and the temperature at 80 ° C. Obtained.
The obtained reaction product was subjected to ¹ H-NMR analysis, and it was confirmed that both ends of polydimethylsiloxane were methacryloxypropyldimethoxysilyl groups.
The polydimethylsiloxane having methacryloxypropyldimethoxysilyl groups at both ends thus obtained was designated as polysiloxane 8 (M-ss70).

・ (H) Thermal polymerization initiator: Perbutyl O (manufactured by NOF Corporation)
(H) Photopolymerization initiator: Irgacure 184 (manufactured by Ciba Japan)
-(I) Polysiloxane 9: Polysiloxane containing epoxy groups at both ends (x-22-163B, manufactured by Shin-Etsu Chemical Co., Ltd., reactive functional group: epoxy group, average number of functional groups: 2)
(J) Acid anhydride: succinic anhydride-modified silicone represented by the following formula (DMS-Z21, manufactured by Gelest, weight average molecular weight: 500)

・ (J) Amine compound: Special amine (manufactured by San Apro)
(J) Lewis acid catalyst: trifluoroboron ethyl etherate complex (manufactured by Tokyo Chemical Industry Co., Ltd.)

1.6-2EHA-Zn: 1.6 mol of 2-ethylhexanoic acid (Hope Pharmaceutical Co., Ltd.) is added to 1 mol of zinc oxide (Hope Pharmaceutical Co., Ltd.), and the mixture is stirred at room temperature. A liquid was obtained. The obtained liquid was set to 1.6-2EHA-Zn.
1.8-2EHA-Zn: A transparent uniform liquid was obtained in the same manner as 1.6-2EHA-Zn except that the amount of 2-ethylhexanoic acid was changed to 1.8 mol. . The obtained liquid was defined as 1.8-2EHA-Zn.
-2.0-2EHA-Zn: Manufactured in the same manner as 1.6-2EHA-Zn except that the amount of 2-ethylhexanoic acid was changed to 2.0 mol, and a transparent uniform liquid was obtained. . The obtained liquid was set to 2.0-2EHA-Zn.

Alkylene oxide compound 1: Epoxy-polyether modified silicone oil (X-22-4741, manufactured by Shin-Etsu Chemical Co., Ltd.)
Alkylene oxide compound 2: Polyether-modified silicone oil (X-22-6266, manufactured by Shin-Etsu Chemical Co., Ltd.)
Alkylene oxide compound 3: PTMG (weight average molecular weight: 2000)
Alkylene oxide compound 4: PEG (manufactured by NOF Corporation, weight average molecular weight: 200)

As is clear from the results shown in Table 1 above, it was found that Examples I to IV had high transmittance and excellent transparency and excellent adhesion. Moreover, it was excellent also in sulfidation resistance and heat-resistant coloring stability.
On the other hand, the comparative examples (I-1 and 2, II-1 and 2, III-1 and 2, and IV-1 to 3) which do not contain the alkylene oxide compounds 1 to 4 are inferior in adhesion. I understood.
Moreover, the cloudiness was seen in the comparative examples (I-3, II-3, III-3, and IV-4) in which the content of the alkylene oxide compounds 1 to 4 exceeds the upper limit of the range of the present invention.

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)

For 100 parts by mass of curable silicone resin composition (A),
0.01-5 parts by mass of the zinc compound (B),
0.01 to 5 parts by mass of a compound (C) having a polyalkylene oxide chain;
Containing a silicone resin composition. The curable silicone resin composition (A) is
An organopolysiloxane (a) having at least two hydrolyzable groups bonded to a silanol group or a silicon atom, and at least selected from the group consisting of hydrolyzable silane, hydrolyzate thereof, and hydrolyzate condensate thereof Either one or both of one kind of silane compound (b),
A condensation catalyst (c);
The silicone resin composition according to claim 1, comprising: The curable silicone resin composition (A) is
An organopolysiloxane (d) having at least two alkenyl groups bonded to silicon atoms;
A polyorganohydrogenpolysiloxane (e) having at least two hydrogen atoms bonded to silicon atoms;
A hydrosilylation catalyst (f),
The silicone resin composition of Claim 1 or 2 whose quantity of the said hydrogen atom is 0.1-5.0 mol per mol of said alkenyl groups. The curable silicone resin composition (A) is
Organopolysiloxane (g) having two or more (meth) acryloyl groups in one molecule;
A thermal polymerization initiator and / or a photopolymerization initiator (h);
The silicone resin composition according to any one of claims 1 to 3, comprising: The curable silicone resin composition (A) is
The silicone resin composition in any one of Claims 1-4 containing the organopolysiloxane (i) which has an epoxy 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: