JP2012056251A - Method for preventing corrosion of metallic layer, sulphurization-resistant laminate, semiconductor light emitting device and silicone resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for preventing corrosion of a metallic layer which can inhibit corrosion (e.g., discoloration) of a metallic layer by making the metallic layer highly sulphurization-resistant.SOLUTION: The method for preventing corrosion of the metallic layer is to inhibit corrosion of the metallic layer by the following procedures: The metallic layer which can be obtained from a metal belonging to the Group 11 of the periodic table, is covered with a silicone resin layer which is available from a silicone resin composition. This silicone resin composition contains (A) 100 pts.mass of organopolysiloxane with at least not less than 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 carboxyl group and a phenol group, in one molecule; and (B) 0.01 to 5 pts.mass of zinc compound. Thus, the metallic layer is made corrosion-inhibitive.

Description

  The present invention relates to a method for preventing corrosion of a metal layer, a laminate having resistance to sulfidation, a semiconductor light emitting device, and a silicone resin composition.

  Organopolysiloxane elastomers are highly gas permeable due to their structural characteristics, and compositions containing organopolysiloxane elastomers are used as light-emitting device sealing materials (for example, Patent Documents 1 to 3).

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

However, when a device having a sealing material or a coating agent formed using a composition containing an organopolysiloxane elastomer is placed in a corrosive gas (especially hydrogen sulfide) atmosphere, the organopolysiloxane elastomer Since the air permeability of the composition is high, the composition allows the corrosive gas to permeate, and the adherend or the substrate that is sealed or covered with the composition is corroded (for example, discolored).
In particular, when a composition containing an organopolysiloxane elastomer is used as a sealing material in a semiconductor light-emitting device, the silver-plated reflector in the semiconductor light-emitting device is easily discolored over time due to hydrogen sulfide in the air, As a result, the inventors of the present application have found that the luminance of the semiconductor light emitting device is lowered.

The inventors of the present invention have disclosed that a silicone resin composition containing a zinc compound captures corrosive gas (for example, hydrogen sulfide, amines) having an unshared electron pair and prevents corrosion of a metal (for example, resistance to resistance). And the present invention was completed.
That is, the present invention provides a metal layer corrosion prevention method capable of suppressing the corrosion (for example, discoloration) of the metal layer, and a silicone resin excellent in sulfide resistance and transparency. A composition, a laminate using the composition, and a semiconductor light emitting device are provided as follows.

1. A metal layer obtained using a Group 11 metal,
(A) 100 parts by mass of an organopolysiloxane having at least one reactive functional group selected from epoxy group, (meth) acryloyl group, amino group, carbinol group, mercapto group, carboxyl group and phenol group in one molecule And (B) a silicone resin layer obtained by using a silicone resin composition containing 0.01 to 5 parts by mass of a zinc compound,
A method for preventing corrosion of a metal layer, which prevents corrosion of the metal layer.
2. On the metal layer, the silicone resin composition is applied to a thickness of 1 mm and cured to obtain a laminate having the metal layer and the silicone resin layer,
A sulfidation test is performed in which the laminate is placed in 560 ppm hydrogen sulfide gas at 23 ° C., and the spectral reflectance of the laminate is measured before the sulfidation test and 24 hours after the start of the sulfidation test. Measured using a spectral reflectometer and calculated by fitting the spectral reflectance to the formula [spectral reflectance maintenance ratio = (spectral reflectance after sulfidation test / spectral reflectance before sulfidation test) × 100]. 2. The method for preventing corrosion of a metal layer according to 1 above, wherein the spectral reflectance maintenance factor is 80% or more.
3. 3. The method for preventing corrosion of a metal layer according to 1 or 2 above, wherein the zinc compound is a zinc salt and / or a zinc complex.
4). 4. The method for preventing corrosion of a metal layer according to any one of 1 to 3, wherein the zinc compound is represented by the following formula (1) and / or the following formula (2).
Zn (O—CO—R ¹ ) ₂ (1)
[In Formula (1), R < ¹ > is a C1-C18 alkyl group and an aryl group. ]
Zn (R ² COCHCOR ³ ) ₂ (2)
Wherein ^{(2), R 2, R} 3 are the same or different monovalent hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group. ]
5. 5. The method for preventing corrosion of a metal layer according to any one of 1 to 4 above, wherein the Group 11 metal is at least one selected from the group consisting of copper, silver and gold.
6). (A) 100 parts by mass of an organopolysiloxane having at least one reactive functional group selected from epoxy group, (meth) acryloyl group, amino group, carbinol group, mercapto group, carboxyl group and phenol group in one molecule And (B) a silicone resin composition containing 0.01 to 5 parts by mass of a zinc compound,
On the metal layer obtained using a Group 11 metal, the silicone resin composition is applied to a thickness of 1 mm and cured to form a laminate having the metal layer and the silicone resin layer,
A sulfidation test is performed in which the laminate is placed in 560 ppm hydrogen sulfide gas at 23 ° C., and the spectral reflectance of the laminate is measured before the sulfidation test and 24 hours after the start of the sulfidation test. Measured using a spectral reflectometer and calculated by fitting the spectral reflectance to the formula [spectral reflectance maintenance ratio = (spectral reflectance after sulfidation test / spectral reflectance before sulfidation test) × 100]. A silicone resin composition having a spectral reflectance maintenance factor of 80% or more.
7). 7. The silicone resin composition as described in 6 above, which is used to seal a reflector and a semiconductor light emitting device obtained using a Group 11 metal.
8). A metal layer obtained using a Group 11 metal;
A laminate having a silicone resin layer obtained by using the silicone resin composition described in 6 or 7 above.
9. 9. The laminate according to 8 above, having a semiconductor light emitting element between the metal layer and the silicone resin layer.
10. A semiconductor light emitting element, a frame having a recess, and a sealing material;
The semiconductor light emitting device is disposed at the bottom of the recess,
The frame includes a reflector obtained using a Group 11 metal on a side surface and / or a bottom surface of the recess,
The sealing material seals the semiconductor light emitting element and the reflector,
8. A semiconductor light-emitting device, wherein the sealing material is obtained using the silicone resin composition according to 6 or 7 above.

According to the method for preventing corrosion of a metal layer of the present invention, the metal layer can be excellent in sulfidation resistance, and corrosion (for example, discoloration) of the metal layer can be suppressed.
The silicone resin composition of the present invention and the laminate of the present invention are excellent in sulfidation resistance and transparency.
The semiconductor light-emitting device of the present invention is excellent in sulfidation resistance and transparency, and can maintain excellent luminance.

FIG. 1 is a cross-sectional view schematically showing an example of the laminate of the present invention. FIG. 2 is a cross-sectional view schematically showing another example of the laminate of the present invention. FIG. 3 is a cross-sectional view schematically showing an example of the semiconductor light emitting device of the present invention. FIG. 4 is a cross-sectional view schematically showing another example of the semiconductor light emitting device of the present invention. FIG. 5 is a cross-sectional view schematically showing another example of the semiconductor light emitting device of the present invention. FIG. 6 is a diagram schematically showing an example of an LED display using the silicone resin composition of the present invention and / or the semiconductor light emitting device of the present invention.

  Hereinafter, the method for preventing corrosion of a metal layer, the laminate of the present invention, a semiconductor light emitting device and a silicone resin composition will be described in detail.

First, the method for preventing corrosion of a metal layer according to the present invention will be described.
The method for preventing corrosion of a metal layer according to the present invention includes:
A metal layer obtained from a Group 11 metal,
(A) 100 parts by mass of an organopolysiloxane having at least one reactive functional group selected from epoxy group, (meth) acryloyl group, amino group, carbinol group, mercapto group, carboxyl group and phenol group in one molecule And (B) a silicone resin layer obtained from a silicone resin composition containing 0.01 to 5 parts by mass of a zinc compound,
This is a method for preventing corrosion of the metal layer.

The inventors of the present application have found that the zinc compound contained in the silicone resin layer captures the corrosive gas contained in the air and maintains the corrosion resistance of the metal (for example, sulfidation resistance and amine resistance). . In the present invention, when the silicone resin layer contains a zinc compound, the silicone resin layer has sufficient corrosion resistance (especially sulfidation resistance) without increasing its hardness.
In the present invention, the silicone resin layer is between the outside air and the metal layer, and corrosive gases in the air (for example, unshared electron pairs such as hydrogen sulfide and amines) as the air permeates the silicone resin layer. The present inventor considers that the zinc compound in the silicone resin layer can catch the gas) and prevent the corrosive gas from corroding (for example, discoloring) the metal layer.
In addition, the said mechanism is a presumption of this inventor, and even if a mechanism is a thing other than the above, it is in the scope of the present invention.

The silicone resin composition used in the method for preventing corrosion of a metal layer of the present invention is a reaction selected from (A) an epoxy group, a (meth) acryloyl group, an amino group, a carbinol group, a mercapto group, a carboxyl group, and a phenol group. 100 parts by mass of an organopolysiloxane having at least one or more functional functional group in one molecule and 0.01 to 5 parts by mass of (B) zinc compound.
The silicone resin composition used in the method for preventing corrosion of a metal layer of the present invention is the same as that used for the laminate of the present invention and the semiconductor light emitting device of the present invention. Since the silicone resin composition used in the method for preventing corrosion of a metal layer of the present invention has the same composition as the silicone resin composition of the present invention, the silicone resin composition used in the method of preventing corrosion of a metal layer of the present invention Is described below as a silicone resin composition of the present invention.

  The organopolysiloxane contained in the silicone resin composition (silicone resin composition of the present invention) is composed of (A) epoxy group, (meth) acryloyl group, amino group, carbinol group, mercapto group, carboxyl group and phenol group. It is a silicone having at least one reactive functional group selected per molecule and having an organopolysiloxane skeleton.

The hydrocarbon group that the organopolysiloxane has is not particularly limited. Examples thereof include an aromatic group such as a phenyl group; an alkyl group; and an alkenyl group.
The organopolysiloxane may be, for example, any of silicone oil, silicone rubber, and silicone resin. One preferred embodiment of the organopolysiloxane is a diorganopolysiloxane.
The main chain of the organopolysiloxane may be linear, branched or three-dimensional.
Examples of the organopolysiloxane include an organo group having at least one reactive functional group selected from epoxy group, (meth) acryloyl group, amino group, carbinol group, mercapto group, carboxyl group and phenol group in one molecule. Polydialkylsiloxane is mentioned.
From the viewpoint of excellent curability, the organopolysiloxane is preferably an organopolydialkylsiloxane having two or more reactive functional groups.
The reactive functional group can be bonded to the end or both ends of the organopolysiloxane, and can be bonded as a side chain. The reactive functional group can be bonded to the organopolysiloxane via an organic group. The organic group is not particularly limited. For example, a divalent aliphatic hydrocarbon group (including a chain and a branch), an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof can be given. The carboxyl group as the reactive functional group includes an acid anhydride group such as a succinic anhydride group and a maleic anhydride group.
Examples of the organopolysiloxane include those represented by the following formula (3).

(Wherein R ⁴ 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, a (meth) acryloyl group, an amino group, a carbyl group; It represents a reactive functional group selected from a nor group, a mercapto group, a carboxyl group and a phenol group, and the reactive functional group may be bonded to a silicon atom via an organic group. In this case, X ¹ , X ² and X ³ are Each may contain an organic group, n is an integer of 1 or more, m is an integer of 0 or more, m + n is an integer of 1 or more, and a, b, and c are each an integer of 0 or more, a + b + c is an integer of 1 or more.)

In formula (3), examples of the alkyl group having 1 to 18 carbon atoms represented by R ⁴ 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. Is mentioned. Examples of the aryl group represented by R ⁴ include a phenyl group and a naphthyl group. The aryl group can have 18 or less carbon atoms. Of these, the group represented by R ⁴ is preferably a methyl group or a phenyl group, and more preferably a methyl group. R ⁴ may be the same or different.
Moreover, in Formula (3), n can be made into the numerical value corresponding to the weight average molecular weight of organopolysiloxane. From the viewpoint of excellent workability and crack resistance, m + n is preferably an integer of 10 to 15,000.

The organopolysiloxane is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.
The molecular weight of the organopolysiloxane is 500 to 1,000,000 from the viewpoint of excellent heat-resistant coloring stability, curing time and pot life having an appropriate length, excellent curability, and excellent cured product properties. Is preferable, and it is more preferable that it is 6,000-100,000. In addition, in this invention, the molecular weight of polysiloxane shall be the weight average molecular weight of polystyrene conversion by the gel permeation chromatography (GPC) which uses chloroform as a solvent.

The organopolysiloxanes can be used alone or in combination of two or more.
When combining two or more types of organopolysiloxanes, the two or more types of organopolysiloxanes may have the same reactive functional group or different reactive functional groups.
In addition, an organopolysiloxane having a reactive functional group that reacts with the reactive functional group and acts as a curing agent can be combined with an organopolysiloxane having one kind of reactive functional group. For example, an organopolysiloxane having an epoxy group-containing organopolysiloxane and at least one reactive functional group selected from (meth) acryloyl group, amino group, carbinol group, mercapto group, carboxyl group and phenol group in one molecule Combinations with siloxanes: Combinations of (meth) acryloyl group-containing organopolysiloxanes and mercapto group-containing organopolysiloxanes.

  When an organopolysiloxane having a reactive functional group reacts with the reactive functional group and the organopolysiloxane having a reactive functional group acting as a curing agent is combined, the reactive function acting as a curing agent is combined. The amount of the organopolysiloxane having a group is such that the reactive functional group is 0.1 to 2 equivalents relative to the reactive functional group of the organopolysiloxane having one kind of reactive functional group. can do.

The zinc compound contained in the silicone resin composition (silicone resin composition of the present invention) will be described below.
The zinc compound is not particularly limited as long as it is a compound containing zinc. Examples thereof include zinc salts; zinc complexes; zinc alcoholates; zinc oxides such as zinc white and zinc stannate. Of these, zinc salts and / or zinc complexes are preferred from the viewpoint of superior sulfidation resistance and transparency. The zinc salt is not particularly limited as long as it is a salt formed from zinc and an acid (including inorganic acid and organic acid). 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 include those represented by the following formulas (1) and (2), a zinc complex of a salicylic acid compound, and a zinc complex of a diamine compound.
The zinc compound represented by the formula (1) is as follows.
Zn (O—CO—R ¹ ) ₂ (1)
In formula (1), R ¹ is an alkyl group having 1 to 18 carbon atoms, an aryl group. A C1-C18 alkyl group and an aryl group are synonymous with the above. CO in the formula is a carbonyl group (C═O).
When the zinc compound represented by the formula (1) is a salt, examples of the zinc salt include the following formula (1 ′).

In the above formula (1 ′), R ¹ is the same as in formula (1).
Examples of the zinc compound represented by the formula (1) include zinc acetate, zinc 2-ethylhexanoate, zinc octoate, zinc neodecanate; zinc acetyl acetate; zinc (meth) acrylate; and carboxylate such as zinc salicylate. Can be mentioned.

The zinc compound represented by Formula (2) is as follows.
Zn (R ² COCHCOR ³ ) ₂ (2)
In formula (2), R ² and R ³ are the same or different monovalent hydrocarbon groups having 1 to 18 carbon atoms and alkoxy groups. R ² COCHCOR ³ in the formula is
R ² —C (—O—) ═CH—C (═O) —R ³ or R ² —C (═O) —CH═C (—O —) — R ³ . R ² COCHCOR ³ is C—O— bonded to zinc (C—O—Zn).
When the zinc compound represented by the formula (2) is a complex, examples of the zinc complex include the following formula (2 ′).

In the above formula ^{(2 '), R 2,} R 3 is the same as equation ^{(2), R 2, R} 3 , which are in the same (R ² COCHCOR ³⁾ may be interchanged.
Examples of the monovalent hydrocarbon group having 1 to 18 carbon atoms include an alkyl group having 1 to 18 carbon atoms and an aryl group. A C1-C18 alkyl group and an aryl group are synonymous with the above.
Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.
Examples of the zinc compound represented by the formula (2) include bis (acetylacetonato) zinc complex, 2,2,6,6,6 tetramethyl-3,5-heptanedionate zinc complex, and the like.

The zinc compound is represented by the formula (1) or the formula (2) from the viewpoint that the sulfidation resistance of the metal layer is more excellent and corrosion (for example, discoloration) of the metal layer can be further suppressed. These are preferably used in combination, such as zinc acetate, zinc 2-ethylhexanoate, zinc octoate, zinc neodecanate, zinc acetyl acetate, zinc (meth) acrylate, zinc salicylate, bis (acetylacetonate) zinc complex, 2 2,6,6,6 tetramethyl-3,5-heptanedionate zinc complex is more preferred.
Zinc compounds can be used alone or in combination of two or more.

In this invention, the quantity of a zinc compound is 0.01-5 mass parts with respect to 100 mass parts of organopolysiloxane. In such a range, it is excellent in sulfidation resistance and transparency.
From the viewpoint of better resistance to sulfidation and transparency, the amount of the zinc compound is preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the organopolysiloxane.

The silicone resin composition (silicone resin composition of the present invention) can further contain a curing agent. The curing agent is not particularly limited. It can select suitably according to the kind of reactive functional group which organopolysiloxane has.
Examples of the curing agent include polyamine compounds, polyamide compounds, dicyandiamide, acid anhydrides, carboxylic acid compounds, and phenol resins. Specific examples of curing agents for epoxy group-containing organopolysiloxanes include aliphatic amines such as ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid-modified ethylenediamine, N-ethylaminopiperazine, and isophoronediamine. Metaphenylenediamine, paraphenylenediamine, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenolsulfone, 4,4′-diaminodiphenolmethane, 4,4′-diaminodiphenol ether Aromatic amines such as mercaptopropionate, mercaptans such as terminal mercapto compounds of epoxy resins; bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol Nord 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 novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak, etc. Phenol resins obtained by hydrogenating the aromatic ring of the phenol resins; polyazeline acid anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexa Drophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, methyl -Alicyclic acid anhydrides such as norbornane-2,3-dicarboxylic acid anhydride; aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride; 2-methylimidazole, 2- Imidazoles such as ethyl-4-methylimidazole and 2-phenylimidazole and their salts, the above aliphatic amines, aromatic amines, and / or amine adducts obtained by reacting imidazoles with epoxy resins; adipic acid Hydrazines such as dihydrazide; dimethylbenzylamine, 1,8-diazabicyclo [5,4,0] un Ca 7 tertiary amines such as ene; organic phosphines such as triphenylphosphine; dicyandiamide, and the like.

  Curing of organopolysiloxane having at least one reactive functional group selected from epoxy group, (meth) acryloyl group, amino group, carbinol group, mercapto group, carboxyl group and phenol group in one molecule. It can be used as an agent.

  From the viewpoint of excellent curability, the amount of the curing agent (the total amount when the organopolysiloxane is used as the curing agent) is 0 in the functional group of the curing agent with respect to the reactive functional group of the organopolysiloxane. It is preferable that the amount is from 1 to 2 equivalents.

In addition to the above components, the silicone resin composition (silicone resin composition of the present invention) can further contain additives as necessary within a range that does not impair the purpose and effect of the present invention.
Examples of the additive include a compound containing zinc other than a zinc compound, a metal compound containing a metal other than zinc, and a binary metal compound [such as Zn-M-OCOR. M is a metal other than zinc, and R is a hydrocarbon group. 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, Dispersant, 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, surface activity Agent, storage stability improver, ozone anti-aging agent, thickener, plasticizer, radiation blocking agent, nucleating agent, coupling agent, conductivity-imparting agent, phosphorus peroxide decomposing agent, pigment, metal deactivation Agents and physical property modifiers. Various additives are not particularly limited. For example, a conventionally well-known thing is mentioned.

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

The silicone resin composition (silicone resin composition of the present invention) is mentioned as one of the preferred embodiments that does not substantially contain water from the viewpoint of excellent storage stability. In the present invention, “substantially free of water” means that the amount of water in the silicone resin composition is 0.1% by mass or less.
Moreover, from the viewpoint that the silicone resin composition is excellent in work environment properties, it is mentioned as one of preferable embodiments that substantially does not contain a solvent. In the present invention, the phrase “substantially containing no solvent” means that the amount of the solvent in the silicone resin composition is 1% by mass or less.

The production of the silicone resin composition (silicone resin composition of the present invention) is not particularly limited. For example, it can be produced by mixing an organopolysiloxane and a zinc compound with a curing agent and an additive that can be used as necessary.
The silicone resin composition can be manufactured as a one-pack type or a two-pack type.

Examples of the adherend to which the silicone resin composition (silicone resin composition of the present invention) can be applied include, for example, metals (for example, Group 11 metals), glass, plastics, rubbers, and semiconductors (for example, semiconductor light emitting devices). Element). The silicone resin layer obtained from the silicone resin composition can be adhered to the adherend.
The Group 11 metal is preferably at least one selected from the group consisting of copper, silver and gold.

In the method for preventing corrosion of a metal layer of the present invention, a metal layer obtained from a Group 11 metal is covered with a silicone resin layer obtained from a silicone resin composition (silicone resin composition of the present invention).
The metal layer obtained from the Group 11 metal by the method for preventing corrosion of a metal layer of the present invention is covered with a silicone resin layer obtained from a silicone resin composition (silicone resin composition of the present invention). It is the same as the laminate.
Hereinafter, by explaining the method for preventing corrosion of a metal layer according to the present invention, the laminated body according to the present invention, the manufacturing method thereof; the semiconductor light emitting device according to the present invention, and the manufacturing method thereof will be described.

In the method for preventing corrosion of a metal layer of the present invention, the silicone resin layer may directly cover the metal layer. Further, for example, another transparent layer (for example, a resin layer, a glass layer, an air layer) or a semiconductor light emitting element may be provided between the silicone resin layer and the metal layer.
In the method for preventing corrosion of a metal layer of the present invention, the method for covering the metal layer with a silicone resin layer is not particularly limited. For example, a silicone resin composition is applied to a metal layer, and the metal layer to which the silicone resin composition is applied is heated and / or irradiated with light to cure the silicone resin composition to form a silicone resin layer. The method of obtaining the laminated body of invention is mentioned.

  In the method for preventing corrosion of a metal layer of the present invention (the laminate of the present invention, the semiconductor light emitting device of the present invention), the method for applying the silicone resin composition to the metal layer is not particularly limited. Examples thereof include a method using a dispenser, a potting method, screen printing, transfer molding, and injection molding.

  In the method for preventing corrosion of the metal layer of the present invention (the laminate of the present invention, the semiconductor light emitting device of the present invention), the temperature at which the silicone resin composition is heated is curable (for example, curable in a closed system), Excellent balance between adhesiveness, heat-resistant coloring stability, transparency and adhesive strength, curing time and pot life can be set to appropriate lengths, and alcohol as a by-product due to condensation reaction is foamed. From the viewpoint that the cured product can be further suppressed, cracks of the cured product can be suppressed, and the smoothness, moldability, and physical properties of the cured product are excellent, curing is preferably performed at about 80 ° C. to 150 ° C., and more preferably about 150 ° C.

  In the method for preventing corrosion of a metal layer of the present invention (the laminate of the present invention, the semiconductor light emitting device of the present invention), the light used for curing the silicone resin composition by light irradiation is not particularly limited. Examples thereof include ultraviolet rays and electron beams.

  In the method for preventing corrosion of a metal layer of the present invention (laminated body of the present invention, semiconductor light emitting device of the present invention), curing is performed under substantially anhydrous conditions from the viewpoint of excellent curability and transparency. it can. In the present invention, the phrase “curing is performed under substantially anhydrous conditions” means that the atmospheric humidity of the environment in heating and / or light irradiation is 10% RH or less.

The silicone resin composition (the silicone resin composition of the present invention) used in the method for preventing corrosion of a metal layer of the present invention (the laminate of the present invention, the semiconductor light-emitting device of the present invention),
On the metal layer, the silicone resin composition is applied to a thickness of 1 mm and cured to obtain a laminate having the metal layer and the silicone resin layer,
A sulfidation test is performed in which the laminate is placed in 560 ppm hydrogen sulfide gas at 23 ° C., and the spectral reflectance of the laminate is measured before the sulfidation test and 24 hours after the start of the sulfidation test. Spectral reflectance measured by using a spectral reflectometer and calculated by fitting the spectral reflectance to the formula [spectral reflectance maintenance rate = spectral reflectance after sulfidation resistance test / spectral reflectance before sulfurization resistance × 100]. The rate maintenance rate is preferably 80% or more.

In the present invention, the spectral reflectance maintenance factor was measured by the following method.
<Production of laminate>
That is, first, the silicone resin composition was applied to a thickness of 1 mm on the metal layer and sufficiently cured to obtain a laminate having the metal layer and the silicone resin layer. Two samples of the same laminate were produced. When the silicone resin composition is a thermosetting type or contains a thermal radical initiator, the laminated body is heated at 150 ° C. for 3 hours. In the case where the silicone resin composition is cured by light irradiation, it is assumed that the curing is performed by light irradiation with an integrated light amount of 8,000 mJ / cm ² under irradiation conditions of a high-pressure mercury lamp. When the silicone resin composition is polymerized by cationic polymerization, the curing is performed by heating at 150 ° C. for 3 hours.
<Sulfurization resistance test>
Next, a sulfidation resistance test was performed using one laminate of the samples and placing it in 560 ppm hydrogen sulfide gas at 23 ° C.
Details of the sulfidation resistance test are as follows.
Sulfur resistance test: Place 10 g of powdered iron sulfide (a large excess with respect to 0.5 mmol of hydrochloric acid) on the bottom of a 10-liter desiccator and place it above the iron sulfide so that it does not come into contact with the iron sulfide. (Having through-holes) was mounted in a desiccator, and the laminate (cured sample) was placed on the eye plate. Next, 0.25 mmol of hydrogen sulfide (concentration: 560 ppm) was generated by dropping 0.5 mmol of hydrochloric acid into a large excess of iron sulfide (reaction formula: FeS + 2HCl → FeCl ₂ + H ₂ S).
In the present invention, the concentration of hydrogen sulfide in the sulfidation resistance test is a theoretical value. In the sulfidation resistance test, 0.5 mmol of hydrochloric acid is added, so that 0.25 mmol (0.25 mmol × 22.4 liters = 5.6 ml) of hydrogen sulfide is generated. Therefore, the concentration of hydrogen sulfide is [5.6 ml / 10 liter (desiccator volume)] × 10 ⁶ = 560 ppm.
It becomes.
<Measurement of spectral reflectance>
And the spectral reflectance of the said laminated body was measured using the spectral reflectometer before the said sulfidation resistance test and 24 hours after the said sulfidation resistance test start (hydrogen sulfide generation | occurrence | production start).
<Evaluation method>
The obtained spectral reflectance after the sulfuration resistance test and spectral reflectance before the sulfuration resistance test are expressed by the formula [spectral reflectance maintenance ratio = (spectral reflectance after sulfurization test / spectral reflectance before sulfurization test) × 100] and the spectral reflectance maintenance factor was calculated.
When the calculated spectral reflectance maintenance factor was 80% or more, it was evaluated that the sulfide resistance was good.

In the present invention, the evaluation of sulfidation resistance by discoloration of the metal layer was performed as follows.
First, similarly to the measurement of the spectral reflectance maintenance rate, a laminate was prepared and a sulfuration resistance test was performed. The discoloration of the metal layer covered with the silicone resin layer 24 hours after the start of the sulfidation test was visually confirmed.
24 hours after the start of the sulfidation test, “○” indicates that the surface of the metal layer of the laminate subjected to the sulfidation test was not discolored compared to the laminate not subjected to the sulfidation test, It was set as “x”.

  A cured product [silicone resin layer, sealing material] (when the thickness of the cured product is 2 mm) obtained using the silicone resin composition (silicone resin composition of the present invention) is an ultraviolet ray according to JIS K0115: 2004. The transmittance measured at a wavelength of 400 nm using a visible absorption spectrum measuring apparatus (manufactured by Shimadzu Corporation, the same shall apply hereinafter) is preferably 80% or more, and more preferably 85% or more.

  Moreover, the cured product [silicone resin layer, sealing material] obtained using the silicone resin composition is subjected to a heat resistance test after initial curing [cured product after initial curing (thickness: 2 mm) at 100 ° C. The test is conducted for 500 hours], and the cured product thereafter has a light transmittance of preferably 80% or more measured at a wavelength of 400 nm using an ultraviolet / visible spectrum measuring apparatus in accordance with JIS K0115: 2004, and 85% The above is more preferable.

  The cured product [silicone resin layer, sealing material] obtained using the silicone resin composition has a light transmission retention ratio (light transmittance after heat resistance test / light transmittance during initial curing × 100). It is preferably 70 to 100%, and more preferably 80 to 100%.

The silicone resin composition (silicone resin composition of the present invention) can be used, for example, as an adhesive, a primer, or a sealing material (for example, for a semiconductor light emitting device). Examples of the semiconductor light emitting device to which the silicone resin composition (silicone resin composition of the present invention) can be applied include a light emitting diode (LED), an organic electroluminescent device (organic EL), a laser diode, and an LED array. . Examples of the LED chip include a high power LED, a high luminance LED, and a general luminance LED.
The silicone resin composition (silicone resin composition of the present invention) includes, for example, 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. It can be used for such applications.

The laminated body of this invention is demonstrated below.
The laminate of the present invention is
A metal layer obtained from a Group 11 metal;
It is a laminated body which has a silicone resin layer obtained using the silicone resin composition of this invention.

The silicone resin composition used for the laminate of the present invention is not particularly limited as long as it is the silicone resin composition of the present invention.
The metal layer used in the laminate of the present invention is the same as the metal layer used in the method for preventing corrosion of the metal layer of the present invention.
The laminated body of this invention is mentioned as one of the aspects with preferable having a semiconductor light-emitting device between a metal layer and a silicone resin layer. The semiconductor light emitting device is not particularly limited. For example, the same thing as the above is mentioned.

The laminated body of this invention is demonstrated below using attached drawing.
FIG. 1 is a cross-sectional view schematically showing an example of the laminate of the present invention.
In FIG. 1, the laminate 100 includes a metal layer 120 and a silicone resin layer 102.

FIG. 2 is a cross-sectional view schematically showing another example of the laminate of the present invention.
In FIG. 2, the laminate 200 includes a metal layer 220, a semiconductor light emitting element 203, and a silicone resin layer 202. The laminated body 200 can further include a transparent layer (not shown) between the semiconductor light emitting element 203 and the silicone resin layer 202. Examples of the transparent layer include a resin layer, a glass layer, and an air layer.

The semiconductor light emitting device of the present invention will be described below.
The semiconductor light emitting device of the present invention is
A semiconductor light emitting element, a frame having a recess, and a sealing material;
The semiconductor light emitting device is disposed at the bottom of the recess,
The frame includes a reflector obtained from a Group 11 metal on the side and / or bottom of the recess,
The sealing material seals the semiconductor light emitting element and the reflector,
The sealing material is a semiconductor light emitting device obtained using the silicone resin composition of the present invention.

The silicone resin composition used in the semiconductor light emitting device of the present invention is not particularly limited as long as it is the silicone resin composition of the present invention.
The reflector used in the semiconductor light emitting device of the present invention is the same material as the metal layer used in the method for preventing corrosion of a metal layer of the present invention.

The semiconductor light emitting device of the present invention will be described below with reference to the accompanying drawings.
FIG. 3 is a cross-sectional view schematically showing an example of the semiconductor light emitting device of the present invention.
In FIG. 3, the semiconductor light emitting device 300 includes a semiconductor light emitting element 303, a frame 304 having a recess 302, and a sealing material 308, and the semiconductor light emitting element 303 is on the bottom (not shown) of the recess 302. The frame body 304 includes a reflector 320 obtained from a Group 11 metal on the side surface and / or bottom surface (not shown) of the recess 302, and the sealing material 308 seals the semiconductor light emitting element 303 and the reflector 320. To do.
The sealing material 308 is obtained by curing the silicone resin composition of the present invention. The recessed portion 302 may be filled up to the shaded portion 306 with the silicone resin composition of the present invention. Alternatively, the portion denoted by reference numeral 308 may be another transparent layer, and the hatched portion 306 may be a sealing material included in the semiconductor light emitting device of the present invention. The sealing material can contain a fluorescent substance or the like.
Each semiconductor light emitting device can have one or a plurality of semiconductor light emitting elements. The semiconductor light emitting device may be disposed in the frame with the light emitting layer (the surface opposite to the surface in contact with the mount member) facing up.
The semiconductor light emitting element 303 is disposed on the bottom (not shown) of the recess 302 formed from the frame 304 and the substrate 310, and is fixed by the mount member 301.
When the end portions 312 and 314 included in the frame body 304 are integrally coupled to form a bottom surface, a side surface, and a bottom portion, the semiconductor light emitting element can be disposed on the bottom portion of the reflector.
The reflector 320 may have a tapered opening end (not shown) whose sectional dimension increases as the distance from the bottom (not shown) of the recess 302 increases.
Examples of the mounting member include silver paste and resin. Each electrode (not shown) of the semiconductor light emitting element 303 and the external electrode 309 are wire bonded by a conductive wire 307.

In the semiconductor light emitting device 300, the recess 302 can be sealed with a sealing material 308, 306, or 302 (a portion in which the portion 308 and the portion 306 are combined).
By sealing the semiconductor light emitting device in this way, the resistance to sulfidation is enhanced and corrosion (for example, discoloration, specifically, discoloration of silver) of the reflector (metal layer, particularly silver, silver plating layer) can be suppressed. And the luminance and transparency of the semiconductor light emitting device are not lowered.
In addition, by sealing the recess with the sealing material, the sealing material has low hardness and small curing shrinkage, so that the sealing material can be prevented from peeling from the recess or breaking the wire due to curing shrinkage. it can.

FIG. 4 is a cross-sectional view schematically showing another example of the semiconductor light emitting device of the present invention.
In FIG. 4, a semiconductor light emitting device 400 has a lens 401 on the semiconductor light emitting device 300 shown in FIG. The lens 401 may be formed using the silicone resin composition of the present invention.

FIG. 5 is a cross-sectional view schematically showing another example of the semiconductor light emitting device of the present invention.
In FIG. 5, a semiconductor light emitting device 500 includes a semiconductor light emitting element 503, a substrate 510 including a frame (not shown) having a recess (not shown), and a sealing material 502. The element 503 is disposed at the bottom (not shown) of the recess, and the frame includes a reflector 520 obtained from a Group 11 metal on the side and / or bottom (not shown) of the recess. Encapsulates the semiconductor light emitting element 503 and the reflector 520, and has a substrate 510 and inner leads 505 inside a resin 506 having a lamp function, and the encapsulant 502 is obtained from the above-described silicone resin composition, and is resistant to sulfidation. A semiconductor light emitting device having
In FIG. 5, a frame (not shown) and the substrate 510 can be integrally formed.
The semiconductor light emitting element 503 is fixed on the substrate 510 with a mount member 501. Examples of the mount member include silver paste and resin.
Each electrode (not shown) of the semiconductor light emitting element 503 is wire-bonded by an inner lead 505 and a conductive wire 507.
Resin 506 can be formed using the silicone resin composition of the present invention.

  The case where the silicone resin composition of the present invention and / or the semiconductor light emitting device of the present invention is used for an LED display will be described with reference to the accompanying drawings.

FIG. 6 is a diagram schematically showing an example of an LED display using the silicone resin composition of the present invention and / or the semiconductor light emitting device of the present invention.
In FIG. 6, an LED display 600 includes a semiconductor light emitting device 601 arranged in a matrix inside a housing 604, the semiconductor light emitting device 601 is sealed with a sealing material 606, and a light shielding member is formed on a part of the housing 604. 605 is arranged. The silicone resin composition of the present invention can be used for the sealing material 606. Further, the semiconductor light emitting device of the present invention can be used as the semiconductor light emitting device 601.

  Applications of the semiconductor light emitting device of the present invention include, for example, automotive lamps (head lamps, tail lamps, directional lamps, etc.), household lighting fixtures, industrial lighting fixtures, stage lighting fixtures, displays, signals, and projectors. .

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
1. Production of organopolysiloxane Polydimethylsiloxane having silanol groups at both ends (weight average molecular weight 28,000, trade name ss70, manufactured by Shin-Etsu Chemical Co., Ltd.) 100 parts by mass, methacryloxypropyltrimethoxysilane (trade name KBM503, Shin-Etsu Chemical Co., Ltd.) 4 parts by mass) and 0.01 part by mass of tin 2-ethylhexanoate (manufactured by Kanto Chemical Co., Ltd.) as a catalyst were 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.
Let the obtained polydimethylsiloxane be (A) polysiloxane 4.
(A) The weight average molecular weight of polysiloxane 4 was 35,000 in terms of polystyrene by gel permeation chromatography (GPC) using chloroform as a solvent (hereinafter the same).

2. Evaluation Spectral reflectance maintenance factor, sulfidation resistance (evaluation of discoloration of metal), and transparency were evaluated by the following methods. The results are shown in Table 1.
2.1. Spectral reflectance maintenance rate Hardened sample preparation: The silicone resin composition manufactured as follows is applied onto silver plating so that the thickness is about 1 mm, the silicone resin composition is cured under the following curing conditions, and a cured sample is prepared. Produced.

Curing conditions-When the silicone resin composition (polysiloxane) has an epoxy group: 3 hours at 150 ° C-When the silicone composition contains a thermal radical initiator: 3 hours at 150 ° C

Sulfur resistance test: Place 10 g of powdered iron sulfide (a large excess with respect to 0.5 mmol of hydrochloric acid) on the bottom of a 10-liter desiccator and place it above the iron sulfide so that it does not come into contact with the iron sulfide. (Having through-holes) was mounted in a desiccator, and the cured sample was placed on the eye plate. Next, 0.25 mmol of hydrogen sulfide (concentration theoretical value: 560 ppm) was generated by dropping 0.5 mmol of hydrochloric acid into a large excess of iron sulfide (reaction formula: FeS + 2HCl → FeCl ₂ + H ₂ S). . The temperature in the sulfidation resistance test is 23 ° C.
Spectral reflectance measurement: The spectral reflectance of the laminate was measured before the sulfurization resistance test and 24 hours after the start of the sulfurization resistance test (starting generation of hydrogen sulfide). URE-30) was measured under the condition of 475 nm.
Evaluation method: The obtained spectral reflectance after the anti-sulfurization test and the spectral reflectance before the anti-sulfurization test are expressed by the formula [spectral reflectance maintenance ratio = (spectral reflectance after the anti-sulfurization test / spectral reflection before the anti-sulfurization test]. Ratio) × 100], and the spectral reflectance maintenance factor was calculated.
The case where the calculated spectral reflectance maintenance factor is 95% or more is “◎”, the case where it is 80% or more and less than 95% is “◯”, the case where it is 65% or more and less than 80% is “Δ”, 65% The case where it was less than "x" was evaluated.

2.2. Sulfide resistance (evaluation of discoloration of metals)
First, similarly to the measurement of the spectral reflectance maintenance rate, a laminate was prepared and a sulfuration resistance test was performed. The discoloration of the metal layer covered with the silicone resin layer 24 hours after the start of the sulfidation test was visually confirmed.
The case where the color change was not confirmed visually after 24 hours from the start of the test was “◯”, and the case where the color change was visually confirmed 24 hours after the start of the test was indicated as “X”.

2.2. Transparency (light transmittance evaluation test)
In the light transmittance evaluation test, an initial cured product obtained by curing the silicone resin composition obtained as described below at 150 ° C. for 12 hours, and a heat resistance test (the initial cured product was further cured at 150 ° C. A test of heating for 10 days under the conditions.) For each of the cured products (both having a thickness of 2 mm), a wavelength of 400 nm using an ultraviolet / visible absorption spectrum measuring apparatus (manufactured by Shimadzu Corporation) according to JIS K0115: 2004, respectively. The transmittance was measured. Moreover, the retention with respect to the initial light transmittance of the light transmittance after the heat resistance test was obtained by the following formula.
Light transmittance holding ratio (%) = [(light transmittance after heat resistance test) / (initial light transmittance)] × 100
Table 1 shows the light transparency retention ratio (%) obtained as described above as the evaluation result of transparency.

3. Production 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.

The details of each component shown in Table 1 are as follows.
Polysiloxane 1: x-22-163C (epoxy modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd.), weight average molecular weight 5,400, average number of functional groups 2 polysiloxane 2: X-22-169B (epoxy modified silicone, Shin-Etsu Chemical) ), Weight average molecular weight 3,400, average number of functional groups 2-polysiloxane 3: x-22-161A (amino-modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd.), weight average molecular weight 1,600, average number of functional groups 2 Polysiloxane 4: methacrylated silicone prepared as described above, weight average molecular weight 35,000, average number of functional groups 2 polysiloxane 5: KF-2001 (mercapto-modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd.), weight average molecular weight 6,000 , Average functional group number 3 ・ Polysiloxane 6: x-22-3701E (carboxyl-modified silicone, Koshi Chemical Co., Ltd.), weight average molecular weight 30,000, average number of functional groups 7 ・ Polysiloxane 7: DMS-Z21 (both ends succinic anhydride-modified silicone, manufactured by Gelest), polysiloxane represented by the following structural formula, Weight average molecular weight 700, average number of functional groups 2

(B) Zinc metal compound 1: zinc complex, Zn bisacetylacetonate (manufactured by Kanto Chemical)
(B) Zinc metal compound 2: zinc salt, bis (ethylhexanoic acid) Zn, (Hope Pharmaceutical)
-(E) Aluminum compound: Al acetylacetonate-(E) Magnesium compound: bis (2-ethylhexanoic acid) Mg (trade name: Nikka Octix Magnesium, manufactured by Nippon Kagaku Sangyo Co., Ltd.)
-Radical initiator: thermal radical initiator, compound name 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, trade name perocta O (manufactured by NOF Corporation)
・ Amine compound: Special amine, manufactured by San Apro

4). Results As is apparent from the results shown in Table 1, a metal layer obtained from a Group 11 metal covered with a silicone resin layer obtained using the compositions of Comparative Examples 1 to 7 not containing a zinc compound. Was discolored and had low sulfidation resistance.
On the other hand, the metal layer obtained from the metal of Group 11 covered with the silicone resin layer obtained using the compositions of Examples 1 to 7 has no discoloration and has high sulfidation resistance. Moreover, the silicone resin layer obtained using the composition of Examples 1-7 was excellent in transparency.
Moreover, when the state was visually confirmed about the silicone resin layer obtained using the composition of Examples 1-7, generation | occurrence | production of the crack was not found in the silicone resin layer.
Further, the spectral reflectance maintenance ratio was evaluated in the same manner as in Examples 1 to 7, except that the thickness of the silicone resin layer of the cured sample used in the evaluation of the spectral reflectance maintenance ratio was changed from 1 mm to 0.8 mm. In this case, the same results as in Examples 1 to 7 were obtained.

As described above, according to the method for preventing corrosion of a metal layer of the present invention, corrosion (for example, discoloration) of the metal layer can be suppressed. It is possible to maintain and suppress a decrease in luminance of the light source (for example, a semiconductor light emitting device). Moreover, the silicone resin layer obtained in the method for preventing corrosion of a metal layer of the present invention is excellent in transparency and does not lower the luminance of the light source, for example. In addition, the silicone resin layer obtained by the method for preventing corrosion of a metal layer according to the present invention is suitable in hardness and hardly cracks, and does not break, for example, a wire in a semiconductor light emitting device.
The laminated body of the present invention, the semiconductor light emitting device of the present invention, and the silicone resin composition of the present invention can achieve the same effects as the corrosion prevention method for a metal layer of the present invention.

100, 200 Laminated body 102, 202 Silicone resin layer 120, 220 Metal layer 203 Semiconductor light emitting element 300, 400, 500 Semiconductor light emitting device 301, 501 Mounting member 302, 502 Recess, Silicone resin layer 303, 503 Semiconductor light emitting element 304 Frame body 306 Shaded area (silicone resin layer)
307, 507 Conductive wire 308 Silicone resin layer (other transparent layers)
309 External electrode 312, 314 End 310, 510 Substrate 320, 520 Reflector 401 Lens 505 Inner lead 506 Resin 600 LED display 601 Semiconductor light emitting device 604 Housing 605 Light shielding member 606 Sealing material

Claims (10)

A metal layer obtained using a Group 11 metal,
(A) 100 parts by mass of an organopolysiloxane having at least one reactive functional group selected from epoxy group, (meth) acryloyl group, amino group, carbinol group, mercapto group, carboxyl group and phenol group in one molecule And (B) a silicone resin layer obtained by using a silicone resin composition containing 0.01 to 5 parts by mass of a zinc compound,
A method for preventing corrosion of a metal layer, which prevents corrosion of the metal layer. On the metal layer, the silicone resin composition is applied to a thickness of 1 mm and cured to obtain a laminate having the metal layer and the silicone resin layer,
A sulfidation test is performed in which the laminate is placed in 560 ppm hydrogen sulfide gas at 23 ° C., and the spectral reflectance of the laminate is measured before the sulfidation test and 24 hours after the start of the sulfidation test. Measured using a spectral reflectometer and calculated by fitting the spectral reflectance to the formula [spectral reflectance maintenance ratio = (spectral reflectance after sulfidation test / spectral reflectance before sulfidation test) × 100]. The method for preventing corrosion of a metal layer according to claim 1, wherein the spectral reflectance maintenance factor is 80% or more.   The method for preventing corrosion of a metal layer according to claim 1 or 2, wherein the zinc compound is a zinc salt and / or a zinc complex. The method for preventing corrosion of a metal layer according to any one of claims 1 to 3, wherein the zinc compound is represented by the following formula (1) and / or the following formula (2).
Zn (O—CO—R ¹ ) ₂ (1)
[In Formula (1), R < ¹ > is a C1-C18 alkyl group and an aryl group. ]
Zn (R ² COCHCOR ³ ) ₂ (2)
Wherein ^{(2), R 2, R} 3 are the same or different monovalent hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group. ]   The method for preventing corrosion of a metal layer according to any one of claims 1 to 4, wherein the Group 11 metal is at least one selected from the group consisting of copper, silver and gold. (A) 100 parts by mass of an organopolysiloxane having at least one reactive functional group selected from epoxy group, (meth) acryloyl group, amino group, carbinol group, mercapto group, carboxyl group and phenol group in one molecule And (B) a silicone resin composition containing 0.01 to 5 parts by mass of a zinc compound,
On the metal layer obtained using a Group 11 metal, the silicone resin composition is applied to a thickness of 1 mm and cured to form a laminate having the metal layer and the silicone resin layer,
A sulfidation test is performed in which the laminate is placed in 560 ppm hydrogen sulfide gas at 23 ° C., and the spectral reflectance of the laminate is measured before the sulfidation test and 24 hours after the start of the sulfidation test. Measured using a spectral reflectometer and calculated by fitting the spectral reflectance to the formula [spectral reflectance maintenance ratio = (spectral reflectance after sulfidation test / spectral reflectance before sulfidation test) × 100]. A silicone resin composition having a spectral reflectance maintenance factor of 80% or more.   The silicone resin composition of Claim 6 used in order to seal the reflector and semiconductor light-emitting device which are obtained using a group 11 metal. A metal layer obtained using a Group 11 metal;
The laminated body which has a silicone resin layer obtained using the silicone resin composition of Claim 6 or 7.   The laminated body of Claim 8 which has a semiconductor light-emitting device between the said metal layer and the said silicone resin layer. A semiconductor light emitting element, a frame having a recess, and a sealing material;
The semiconductor light emitting device is disposed at the bottom of the recess,
The frame includes a reflector obtained using a Group 11 metal on a side surface and / or a bottom surface of the recess,
The sealing material seals the semiconductor light emitting element and the reflector,
The semiconductor light-emitting device obtained by using the silicone resin composition of Claim 6 or 7 for the said sealing material.