JP5609444B2 - Method for preventing corrosion of metal layers - Google Patents

Description

  The present invention relates to a method for preventing corrosion of a metal layer.

Conventionally, silicone resins have been used in sealants and the like (Patent Documents 1 and 2).
However, although silicone resin is excellent in heat resistance, it has higher gas permeability than epoxy resin and the like, and therefore, a device (for example, semiconductor light emitting device) having a silver (including silver plating) member sealed or coated with silicone resin. When a lighting device such as a device is placed in a hydrogen sulfide atmosphere, the silicone resin permeates a corrosive gas such as hydrogen sulfide in the air, causing silver to discolor over time, resulting in a decrease in the brightness of the device. There is a case.
As a measure against discoloration of silver over time, means for copolymerizing a silicone resin and a resin having a high gas barrier property is disclosed. (Patent Document 3).

Japanese Patent Laid-Open No. 11-5901 JP 2000-319632 A JP 2003-188503 A

  However, even when a silicone resin and a resin having a high gas barrier property are copolymerized, it has been insufficient to suppress silver discoloration over time.

As a result of intensive studies to solve the above problems, the present inventors have found that a silicone resin composition containing a metal compound having at least one selected from the group consisting of nickel, copper and gallium has an unshared electron pair. The present invention was completed by discovering (for example, hydrogen sulfide, amines) and preventing corrosion of metals (for example, exhibiting resistance to sulfur to suppress discoloration of silver).
That is, the present invention provides a method for preventing corrosion of a metal layer that can improve the sulfidation resistance of the metal layer and suppress corrosion of the metal layer (for example, discoloration of silver) as follows.

1. A metal layer obtained from a Group 11 metal,
(A) A silicone resin composition comprising an organosiloxane having at least one reactive functional group in one molecule and (B) a metal compound having at least one selected from the group consisting of nickel, copper and gallium. Cover with a silicone resin layer obtained from
A method for preventing corrosion of a metal layer, which prevents corrosion of the metal layer.
2. 2. The metal compound according to the above 1, wherein the metal compound is at least one selected from the group consisting of a metal carboxylate or metal complex represented by the following formula (1) and a metal complex represented by the following formula (2): A method for preventing corrosion of metal layers.
M (—O—CO—R ¹ ) _n (1)
[In the formula (1), M is at least one selected from the group consisting of nickel, copper and gallium. When M is nickel or gallium, n is 3, and when M is copper, n is 2 or 3. R ¹ is a hydrocarbon group having 1 to 18 carbon atoms which may contain a hetero atom. ]
M (R ² COCHCOR ³ ) _n (2)
[In formula (2), M is at least one selected from the group consisting of nickel, copper and gallium, n is 3 when M is nickel or gallium, and n is 2 or 3 when M is copper. And R ² and R ³ are the same or different, a C 1-18 hydrocarbon group which may contain a hetero atom, and a C 1-18 alkoxy group. ]
3. The method for preventing corrosion of a metal layer according to 1 or 2, wherein the amount of the metal compound is 0.01 to 5 parts by mass with respect to 100 parts by mass of the organosiloxane.
4). The reactive functional group comprises a silanol group, an alkoxysilyl group, a vinyl group, a hydrosilyl group, an epoxy group, a (meth) acryloyl group, a polyether group, a carboxyl group, a carbinol group, an amino group, a mercapto group, and a phenol group. 4. The method for preventing corrosion of a metal layer according to any one of 1 to 3, which is at least one selected from the 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.

In addition, the present invention provides a silicone resin composition excellent in sulfidation resistance and transparency, a laminate using the same, and a semiconductor light emitting device as follows.
6). A metal layer obtained from a Group 11 metal;
(A) Silicone containing 100 parts by mass of an organosiloxane having at least one reactive functional group in one molecule and (B) a metal compound having at least one selected from the group consisting of nickel, copper and gallium The laminated body which has a silicone resin layer obtained from a resin composition, and has sulfidation resistance.
7). 7. The laminate according to 6 above, having a semiconductor light emitting element between the metal layer and the silicone resin layer.
8). 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 encapsulant is (A) an organosiloxane having at least one reactive functional group in one molecule, and (B) a metal compound having at least one selected from the group consisting of nickel, copper and gallium. Obtained from a silicone resin composition containing,
A semiconductor light emitting device having resistance to sulfuration.
9. (A) an organosiloxane having at least one reactive functional group in one molecule, and (B) a metal compound having at least one selected from the group consisting of nickel, copper and gallium, A silicone resin composition that is used for sealing reflectors and semiconductor light-emitting devices obtained from these metals and that has resistance to sulfidation.
The silicone resin composition and laminate described in the present specification are excellent in sulfidation resistance and transparency.
The semiconductor light emitting device described in this specification has excellent resistance to sulfidation and transparency, and can maintain excellent luminance.

  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.

FIG. 1 is a cross-sectional view schematically showing an example of a laminate in the present invention. FIG. 2 is a cross-sectional view schematically showing another example of the laminate in the present invention. FIG. 3 is a cross-sectional view schematically showing an example of a semiconductor light emitting device according to the present invention. FIG. 4 is a cross-sectional view schematically showing another example of the semiconductor light emitting device in the present invention. FIG. 5 is a sectional view schematically showing another example of the semiconductor light emitting device in the present invention. FIG. 6 is a diagram schematically showing an example of an LED display using a semiconductor light emitting device that is considered to be one application of the silicone resin composition of the present invention and / or the silicone resin composition of the present invention. FIG. 7 is photographic data showing the evaluation results of sulfidation resistance 2.

  Hereinafter, the method for preventing corrosion of a metal layer, a laminate, a semiconductor light emitting device and a silicone resin composition of the present invention 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) A silicone resin composition comprising an organosiloxane having at least one reactive functional group in one molecule and (B) a metal compound having at least one selected from the group consisting of nickel, copper and gallium. Cover with a silicone resin layer obtained from
This is a method for preventing corrosion of a metal layer, which prevents corrosion of the metal layer.

The inventors of the present application provide a metal compound having at least one selected from the group consisting of nickel, copper and gallium contained in the silicone resin layer, trapping the corrosive gas contained in the air, and preventing the corrosion resistance of the metal ( For example, it has been found that sulfidation resistance and amine resistance are maintained. In the present invention, the silicone resin layer contains a metal compound having at least one selected from the group consisting of nickel, copper, and gallium, so that the silicone resin layer has sufficient corrosion resistance even if its hardness is not increased ( In particular, it has sulfidation resistance.
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. Gas) having a metal compound having at least one selected from the group consisting of nickel, copper and gallium in the silicone resin layer to catch the corrosive gas from corrosion (for example, discoloration) of the metal layer. This inventor thinks that it can do.
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 comprises (A) an organosiloxane having at least one reactive functional group in one molecule, and (B) nickel, copper and gallium. And a metal compound having at least one selected from the group.
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 in the laminate described in this specification and the semiconductor light-emitting device described in this specification. The silicone resin composition used in the method for preventing corrosion of a metal layer of the present invention is the same as the silicone resin composition described in the present specification.

The organosiloxane contained in the silicone resin composition (the silicone resin composition described in the present specification) has at least one reactive functional group in one molecule, and has a siloxane bond [(—Si—O—) _n. , N is an integer of 2 or more. If it is a polysiloxane compound which has], it will not restrict | limit in particular. For example, silicone oligomer, silicone resin, organopolysiloxane, and diorganopolysiloxane can be used.

The hydrocarbon group which organosiloxane has is not particularly limited. Examples thereof include an aromatic group such as a phenyl group; an alkyl group; and an alkenyl group.
The main chain of the organosiloxane may be either linear or branched.
The reactive functional group is a group consisting of silanol group, alkoxysilyl group, vinyl group, hydrosilyl group, epoxy group, (meth) acryloyl group, polyether group, carboxyl group, carbinol group, amino group, mercapto group and phenol group. It is preferably at least one selected from the group consisting of
Examples of the organosiloxane include those represented by the following formula (3).

X ¹ —SiR ⁴ ₂ —O— [SiR ⁴ ₂ —O] _n —SiR ⁴ ₂ —X ² (3)
Wherein R ⁴ is the same or different and represents an alkyl group or aryl group having 1 to 18 carbon atoms, X ¹ and X ² each independently represent a reactive functional group, and n is an integer of 1 or more. .)

In formula (3), the alkyl group having 1 to 18 carbon atoms represented by R ⁴ includes a chain (including a straight chain and a branched chain), a cyclic (cycloalkyl group), and a combination thereof. Examples of the alkyl group having 1 to 18 carbon atoms represented by R ⁴ include chain groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group. An alkyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group. Examples of the aryl group represented by R ⁴ include a phenyl group and a naphthyl group. 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 organosiloxane. From the viewpoint of excellent workability and crack resistance, n is preferably an integer of 10 to 15,000.

The organosiloxane is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.
The molecular weight of the organosiloxane is 1,000 to 1,000,000 from the viewpoints of excellent heat-resistant coloring stability, appropriate curing time and pot life, excellent curability, and excellent cured product properties. Of 6,000 to 100,000 is more preferable. In the present invention, the molecular weight of the organosiloxane is a weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) using chloroform as a solvent.

The organosiloxanes can be used alone or in combination of two or more.
When combining 2 or more types of organosiloxane, 2 or more types of organosiloxane may have the same reactive functional group mutually, and may have a different reactive functional group.
In addition, an organosiloxane having a reactive functional group that reacts with the reactive functional group and acts as a curing agent can be combined with an organosiloxane having one kind of reactive functional group. For example, an epoxy group-containing organosiloxane and an organosiloxane having 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 A combination of (meth) acryloyl group-containing organosiloxane and mercapto group-containing organosiloxane; vinyl group-containing organosiloxane and hydrosilyl group-containing organosiloxane.

  When an organosiloxane having a reactive functional group is combined with an organosiloxane having a reactive functional group that reacts with the reactive functional group and acts as a curing agent, the reactive functional group that acts as a curing agent is The amount of the organosiloxane possessed can be such that the reactive functional group is 0.1 to 10 equivalents relative to the reactive functional group possessed by the organosiloxane having one kind of reactive functional group. .

  The silicone resin composition can further contain a silane compound having a reactive functional group. The silane compound that can be further contained in the silicone resin composition is not particularly limited as long as it is a compound having one silicon atom and having a functional functional group bonded to the silicon atom directly or via an organic group. One silane compound has 1 to 4 reactive functional groups. The hydrocarbon group that one silane compound can have in addition to the reactive functional group is not particularly limited. For example, an aliphatic hydrocarbon group (including linear, branched, and alicyclic), an aromatic hydrocarbon group, and a combination thereof can be given. The hydrocarbon group can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. A reactive functional group is synonymous with the reactive functional group which organosiloxane has. Examples of the silane compound include alkyl alkoxy silanes; tetraalkoxy silanes; silane coupling agents such as hydroxy silane, amino silane, mercapto silane, (meth) acryl silane, and vinyl silane.

The metal compound contained in the silicone resin composition (silicone resin composition described in the present specification) will be described below.
In the present invention, the metal compound is a compound having at least one metal selected from the group consisting of nickel, copper and gallium. The metal compound is not particularly limited as long as it is a compound containing at least one metal selected from the group consisting of nickel, copper and gallium. For example, salt; complex; alcoholate; oxide. Among these, from the viewpoint of being superior in resistance to sulfidation, for example, a metal compound having a hetero atom such as a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom is preferable, and a metal carboxylate and / or a metal complex is preferable. More preferably.

The metal carboxylate is not particularly limited as long as it is a salt formed from a metal and an organic carboxylic acid. The metal complex is not particularly limited as long as it is a chelate compound formed from a metal and a ligand.
Examples of the metal compound include a metal carboxylate or metal complex represented by the following formula (1) and a metal complex represented by the formula (2).

M (—O—CO—R ¹ ) _n (1)
[In the formula (1), M is at least one selected from the group consisting of nickel, copper and gallium. When M is nickel or gallium, n is 3, and when M is copper, n is 2 or 3. R ¹ is a hydrocarbon group having 1 to 18 carbon atoms which may contain a hetero atom. ]

  Examples of the hydrocarbon group having 1 to 18 carbon atoms include alkyl groups; unsaturated aliphatic hydrocarbon groups such as vinyl groups and allyl groups; and aryl groups. A C1-C18 alkyl group and an aryl group are synonymous with the above. The hydrocarbon group having 1 to 18 carbon atoms may contain a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.

M (R ² COCHCOR ³ ) _n (2)
[In formula (2), M is at least one selected from the group consisting of nickel, copper and gallium, n is 3 when M is nickel or gallium, and n is 2 or 3 when M is copper. And R ² and R ³ are the same or different, a C 1-18 hydrocarbon group which may contain a hetero atom, and a C 1-18 alkoxy group. ]
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, an aryl group, and a hetero atom are synonymous with the above.
Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.

When Formula (1) is a metal salt, the metal salt can be represented in detail by the following Formula (1-1). When Formula (1) is a metal complex, the metal complex can be represented in detail by the following Formula (1-2).
The metal complex represented by the formula (2) can be represented in detail by the following formula (2-1).

M, n, and R ^{1 to} R ³ in the formula are as defined above.

  Examples of the nickel compound include carboxylates such as nickel acetate, nickel 2-ethylhexanoate, nickel octoate, nickel neodecanate, nickel acetyl acetate, nickel (meth) acrylate, nickel salicylate; Acetonato) nickel complex, nickel (II) hexafluoropentanedionate, nickel (II) 2,2,6,6-tetramethyl-3-5-heptanedionate, nickel (II) trifluoropentanedionate Complex.

  Examples of copper compounds include carboxylates such as copper acetate, copper 2-ethylhexanoate, copper octoate, copper neodecanate, copper acetyl acetate, copper (meth) acrylate, copper salicylate; di (acetylacetonate) copper complex , Tri (acetylacetonato) copper complex, copper (II) allyloxyethoxytrifluoroacetoacetate, copper (II) benzoylacetonate, copper (II) benzoyltrifluoroacetonate, 1,3-diphenyl-1,3- Propanedionate, copper (II) ethyl acetoacetate, 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate, copper (I) hexafluoro Pentandionate-2 butylene complex, copper (I) hexafluoropentanedionate vinyl Complexes such as Rimechirushiran complex, copper (II) ethoxide, copper (II) methoxyethoxy ethoxide, alkoxides such as copper (II) dimethylamino ethoxide.

  Examples of the gallium compound include carboxylic acid salts such as gallium acetate, gallium 2-ethylhexanoate, gallium octoate, gallium neodecanate, gallium acetyl acetate, gallium (meth) acrylate, and gallium salicylate; Acetonato) gallium complexes, gallium ethoxide, alkoxides such as gallium isopropoxide.

The metal compound is at least one selected from the group consisting of the metal carboxylate or metal complex represented by the formula (1) and the metal complex represented by the formula (2) from the viewpoint of being superior in resistance to sulfidation. Of these, tri (acetylacetonato) nickel complex, di (acetylacetonato) copper complex, tri (acetylacetonato) copper complex, tri (acetylacetonato) gallium complex, and diacetylacetonatocopper complex are more preferred.
A metal compound can be used individually or in combination of 2 types or more, respectively.
The combination of the organosiloxane and the metal compound is preferably a combination of the organosiloxane and the metal compound having copper from the viewpoint of being superior in sulfur resistance.

  The amount of the metal compound is preferably 0.01 to 5 parts by mass, preferably 0.1 to 0.5 parts by mass with respect to 100 parts by mass of the organosiloxane, from the viewpoint of being excellent in sulfidation resistance and excellent in transparency. More preferably.

The silicone resin composition (silicone resin composition described in the present specification) 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 organosiloxane 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 organosiloxanes 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, etc. Aromatic amines; mercaptans such as mercaptopropionic acid esters and terminal mercapto compounds of epoxy resins; bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, biphenol, dihydroxynaphthalene, 1,1,1-tris (4-hydroxyphenyl) methane, 4, 4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol, phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak, etc. Phenol resins in which aromatic rings of the phenol resins are hydrogenated; polyazeline acid anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydride Phthalic 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-ethyl Imidazoles such as -4-methylimidazole and 2-phenylimidazole and salts thereof, amine adducts obtained by reaction of the above aliphatic amines, aromatic amines, and / or imidazoles with epoxy resins; adipic acid dihydrazide Hydrazines such as dimethylbenzylamine, 1,8-diazabicyclo [5,4,0] undeca Tertiary amines 7-ene and the like; organic phosphines such as triphenylphosphine; dicyandiamide; tris (pentafluorophenyl) organic boranes borane and the like.

  Curing agent for organosiloxane having at least one reactive functional group selected from the group consisting of epoxy group, (meth) acryloyl group, amino group, carbinol group, mercapto group, carboxyl group and phenol group in one molecule. Can be used as

  From the viewpoint of excellent curability and adhesiveness, the amount of the curing agent (the total amount when the organosiloxane is used as the curing agent) is the functional group that the curing agent has relative to the reactive functional group that the organosiloxane has. The amount can be 0.1 to 10 equivalents.

The silicone resin composition (silicone resin composition described in the present specification) may further contain a catalyst. The catalyst is not particularly limited. It can select suitably according to the kind of reactive functional group which organosiloxane has. Examples of the catalyst include a condensation catalyst, a hydrosilylation catalyst, a Lewis acid, and a Lewis base.
For example, when the reactive functional group is a combination of a vinyl group and a hydrosilyl group, an addition-type curing catalyst can be used. The addition type curing catalyst is not particularly limited. For example, a conventionally well-known thing is mentioned. Specific examples include hydrosilylation catalysts.
When the reactive functional group is a silanol group, an alkoxysilyl group, a mercapto group, or a phenol group, a condensation catalyst can be used.
The condensation catalyst that can be further contained in the silicone resin composition is not particularly limited as long as it can hydrolyze and condense a hydrolyzable group-containing silyl group or silanol group. For example, a metal compound or a boron compound containing a metal such as a lanthanoid metal such as tin, aluminum, titanium, zirconium, hafnium, calcium, barium, or cerium can be given. Especially, it is preferable that it is at least 1 sort (s) chosen from the group which consists of a zirconium compound, a hafnium compound, and a tin compound from a viewpoint that it is excellent by sulfidation resistance, and is excellent in transparency and surface curability. Examples of the condensation catalyst include a combination of a zirconium compound or a hafnium compound and a tin compound. Examples of the metal compound include a metal alkoxide compound, a metal chelate compound, and a metal alkyl compound.

Examples of the zirconium compound include a zirconium metal salt represented by the following formula (I).

(In the formula, n is an integer of 1 to 3, R ¹ is a hydrocarbon group having ^{1 to} 16 carbon atoms, and R ² is a hydrocarbon group having 1 to 18 carbon atoms.)
In the formula (I), when n is 2 or more, the plurality of R ¹ may be the same or different. Further, a plurality of R ² when n is 1-2 may be the same or different.
In the zirconium metal salt represented by the formula (I), the hydrocarbon group as R ^{1 has 1} to 16 carbon atoms. In R ¹ , the number of carbon atoms is from 3 to 16 from the viewpoint of being excellent in sulfidation resistance, excellent in transparency, heat-resistant coloring stability, thin film curability, and excellent in compatibility (for example, compatibility with curable silicone resin). It is preferable that it is 4 to 16, more preferably.
Examples of the hydrocarbon group for R ¹ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof. The hydrocarbon group may be linear or branched. The hydrocarbon group can have an unsaturated bond. The hydrocarbon group can have, for example, a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
R ¹ preferably has a cyclic structure from the viewpoints of transparency and sulfidation resistance, heat resistant coloration stability, thin film curability, and compatibility. Examples of the cyclic structure that R ¹ can have include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. R ¹ can have, for example, an aliphatic hydrocarbon group in addition to the cyclic structure. In addition, the hydrocarbon group in R ¹ is preferably an alicyclic hydrocarbon group or an aliphatic hydrocarbon group from the viewpoint of excellent heat-resistant coloring stability and thin film curability, and excellent compatibility.

Examples of the alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; a naphthene ring (a cycloparaffin ring derived from naphthenic acid); Examples thereof include condensed ring hydrocarbon groups such as an adamantyl group and a norbornyl group.
Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and azulene.
Examples of the aliphatic hydrocarbon group 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, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, and an undecyl group. Is mentioned.
Of these, alicyclic hydrocarbon groups and aromatic hydrocarbon groups are preferred from the viewpoints of transparency and sulfidation resistance, heat resistant coloration stability, thin film curability, and compatibility, and cyclopropyl groups and cyclopentyls. Group, cyclohexyl group, adamantyl group, naphthene ring (naphthate group as R ¹ COO—) and phenyl group are more preferable, and cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group and naphthene ring are more preferable.

In the present invention, the hydrocarbon group as R ² has 1 to 18 carbon atoms. In R ² , the number of carbon atoms is preferably 3 to 8 from the viewpoints of excellent heat-resistant coloring stability, thin film curability, and compatibility.
Examples of the hydrocarbon group for R ² include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof. The hydrocarbon group may be linear or branched. The hydrocarbon group can have an unsaturated bond. The hydrocarbon group can have, for example, a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. The hydrocarbon group in R ² is preferably an aliphatic hydrocarbon group from the viewpoint of being excellent in sulfidation resistance, excellent in transparency, heat-resistant coloring stability, thin film curability, and excellent compatibility.

Examples of R ² O— (alkoxy group) having an aliphatic hydrocarbon group include methoxy group, ethoxy group, propoxy group (n-propoxy group, isopropoxy group), butoxy group, pentyloxy group, hexyloxy group, An octyloxy group is mentioned.
Of these, methoxy group, ethoxy group, propoxy group (n-propoxy group, isopropoxy group), butoxy are superior in terms of transparency and sulfidation resistance, heat resistance coloring stability, thin film curability, and compatibility. And a pentyloxy group is preferred.
Among these, zirconium tributoxy mononaphthate, zirconium trichloride are preferred from the viewpoint of superior sulfidation resistance, transparency, heat-resistant coloration stability, thin film curability, suppression of heat loss, and excellent compatibility. Butoxy monoisobutyrate and zirconium tributoxy mono 2-ethylhexanoate are preferred.
A zirconium compound can be used individually or in combination of 2 or more types, respectively.

As a manufacturing method of a zirconium compound, for example, Zr (OR ² ) ₄ [zirconium tetraalkoxide. R ² is a hydrocarbon group having 1 to 18 carbon atoms. R ² has the same meaning as R ² in formula (I). The carboxylic acid represented by R ¹ —COOH with respect to 1 mole [R ¹ is a hydrocarbon group having ^{1 to} 16 carbon atoms, respectively. R ¹ has the same meaning as R ¹ in formula (I). ] 1 mol or more and less than 4 mol can be produced by stirring under a condition of 20 to 80 ° C. in a nitrogen atmosphere.
Regarding the reaction between Zr alcoholate and carboxylic acid, see D.C. C. Reference can be made to Bradley's “Metal alcoholide” Academic Press (1978).

Examples of Zr (OR ² ) ₄ that can be used to produce a zirconium compound include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetranormal propoxide, zirconium tetrapropoxide, and zirconium tetranormal butoxide. It is done.

  Carboxylic acids that can be used to produce zirconium compounds include, for example, aliphatic carboxylic acids such as acetic acid, propionic acid, isobutanoic acid, octylic acid, 2-ethylhexanoic acid, nonanoic acid, lauric acid; Examples thereof include alicyclic carboxylic acids such as acid, cyclopropane carboxylic acid, cyclopentane carboxylic acid, cyclohexyl carboxylic acid (cyclohexane carboxylic acid), adamantane carboxylic acid and norbornane carboxylic acid; and aromatic carboxylic acids such as benzoic acid.

The hafnium compound as the condensation catalyst is not particularly limited as long as it is a compound having a hafnium atom and an organic group. Examples of the hafnium compound include a compound represented by the following formula (I) and a compound represented by the following formula (II).

[In formula (I), n is an integer from 1 to 4, R ¹ is a hydrocarbon group, R ² is an alkyl group having 1 to 18 carbon atoms. ]

[In the formula (II), m is an integer of 1 to 4, R ² is an alkyl group having 1 to 18 carbon atoms, and R ³ and R ⁴ are the same or different hydrocarbons having 1 to 18 carbon atoms. Group or alkoxy group. ]

The hafnium compound represented by the formula (I) will be described below.

[In formula (I), n is an integer from 1 to 4, R ¹ is a hydrocarbon group, R ² is an alkyl group having 1 to 18 carbon atoms. ]

Examples of the hydrocarbon group in R ¹ include an aliphatic hydrocarbon group having 1 to 18 carbon atoms (an alkyl group; including an unsaturated aliphatic hydrocarbon group such as an allyl group), an alicyclic hydrocarbon group, and an aryl group. (Aromatic hydrocarbon group) and combinations thereof. The hydrocarbon group may be linear or branched. The hydrocarbon group can have an unsaturated bond. The hydrocarbon group can have, for example, a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
The hydrocarbon group in R ¹ preferably has a cyclic structure from the viewpoint of being superior in resistance to sulfurization, and more preferably an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. R ¹ can have, for example, an aliphatic hydrocarbon group in addition to the cyclic structure.

Examples of the alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; a naphthene ring (a cycloparaffin ring derived from naphthenic acid); Examples thereof include condensed ring hydrocarbon groups such as an adamantyl group and a norbornyl group.
Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and azulene.
Examples of the aliphatic hydrocarbon group 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, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, and an undecyl group. Is mentioned.
Of these, alicyclic hydrocarbon groups and aromatic hydrocarbon groups are preferred from the viewpoint of superior sulfidation resistance. Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, naphthene ring , An adamantyl group, a norbornyl group, a phenyl group, a naphthyl group, and an azulene, but more preferably a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a naphthene ring (as R ¹ COO- A naphthate group) and a phenyl group, and a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a naphthene ring are particularly preferable.

In the formula (I), R ² is an alkyl group having 1 to 18 carbon atoms. In R ² , the number of carbon atoms is preferably 3 to 8 from the viewpoint of being excellent in resistance to sulfidation.

Examples of R ² include a methyl group, an ethyl group, a propyl group (n-propyl group, isopropyl group), a butyl group, a pentyl group, a hexyl group, and an octyl group.
Of these, a methyl group, an ethyl group, a propyl group (n-propyl group, isopropyl group), a butyl group, and a pentyl group are preferable from the viewpoint of superior sulfurization resistance.

Examples of the hafnium compound having an alicyclic hydrocarbon group as a cyclic structure include, for example, hafnium alkoxy (mono-tri) cyclopropanecarboxylate, hafnium tetracyclopropanecarboxylate,
Hafnium alkoxy (mono-tri) cyclopentanecarboxylate, hafnium tetracyclopentanecarboxylate,
Hafnium alkoxy (mono-tri) cyclohexanecarboxylate, hafnium tetracyclohexanecarboxylate,
Hafnium alkoxy (mono-tri) adamantane carboxylate, hafnium tetraadamantane carboxylate,
Hafnium alkoxy (mono-tri) naphthate and hafnium tetranaphthate can be mentioned.

As a hafnium compound having an aromatic hydrocarbon group as a cyclic structure, for example,
Examples include hafnium alkoxy (mono-tri) benzene carboxylate and hafnium tetrabenzenecarboxylate.

As a hafnium compound having an aliphatic hydrocarbon group, for example,
Hafnium alkoxy (mono-tri) butyrate, hafnium tetrabutyrate,
Hafnium alkoxy (mono-tri) 2 ethyl hexanoate, hafnium tetra 2 ethyl hexanoate,
Examples include hafnium alkoxy (mono-tri) neodecanate and hafnium tetraneodecanate.
In the present specification, “(mono to tri)” means any one of mono, di and tri.

The hafnium compound represented by the formula (II) will be described below.

[In the formula (II), m is an integer of 1 to 4, R ² is an alkyl group having 1 to 18 carbon atoms, and R ³ and R ⁴ are the same or different hydrocarbons having 1 to 18 carbon atoms. Group or alkoxy group. ]
Alkyl group having 1 to 18 carbon atoms has the same meaning as R ² (alkyl group having 1 to 18 carbon atoms) in the formula (I).
The hydrocarbon group having 1 to 18 carbon atoms is the same as that in which R ¹ (hydrocarbon group) in formula (I) has 1 to 18 carbon atoms.
Examples of the alkoxy group include those having 1 to 18 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group.
R ³ and R ⁴ may have a halogen such as a chlorine atom, a bromine atom or a fluorine atom.
In formula (II), R ³ and R ⁴ may be interchanged.

As the hafnium compound represented by the formula (II), for example,
Examples include hafnium alkoxide (mono-tri) 2,4-pentadionate, hafnium-2,4-pentadionate, hafnium alkylpentadionate, and hafnium fluoropentadionate.

  The tin compound as the condensation catalyst is not particularly limited. An example is 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. The tin compound can have an acyl group as an ester bond.

Examples of the tetravalent tin compound include those represented by the formula (II), bis type and polymer type represented by the formula (II).
_{^{R 3 a -Sn- [O-CO}} -R 4] 4-a (II)
In the formula, R ³ is an alkyl group, R ⁴ is a hydrocarbon group, and a is an integer of 1 to 3.

Examples of the alkyl group include those having 1 or more carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and an octyl group.
The hydrocarbon group is not particularly limited. Examples thereof include an aliphatic hydrocarbon group such as a methyl group, an ethyl group, and a 2-ethylpentyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof. The hydrocarbon group may be linear or branched. The hydrocarbon group can have an unsaturated bond. The hydrocarbon group can have, for example, a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.

Examples of the tin compound include dialkyltin compounds such as dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dioctyltin diacetate, and dioctyltin maleate [wherein a is 2 represented by the above formula (II) Dibutyltin oxyacetate dibutytin oxyoctylate, dibutyltin oxylaurate dibutyltin bismethylmalate, dialkyltin dimer such as dibutyltin oxyoleate; or dibutyltin malate polymer, dioctyltin malate polymer; monobutyltin And tris (2-ethylhexanoate) [wherein a is 1 represented by the above formula (II)].
Among these, from the viewpoints of superior sulfidation resistance, transparency, heat resistant color stability, and thin film curability, dibutyltin diacetate, dibutyltin dioleate, dibutyltin dilaurate, dibutyltin oxyacetate dibutyltin oxyoctylate, dibutyltin oxy Laurate and monobutyltin tris (2-ethylhexanoate) are preferred.
The condensation catalyst is not particularly limited for its production. The condensation catalysts can be used alone or in combination of two or more.

  From the viewpoint that the amount of the condensation catalyst is superior in sulfidation resistance, transparency, curability in a closed system, adhesion, heat-resistant coloring stability, and a balance between transparency and adhesive strength, and excellent surface curability. , 0.001 to 1 part by mass, preferably 0.01 to 1 part by mass with respect to 100 parts by mass of organosiloxane (the total of the organosiloxane and the silane compound when the silicone resin composition further contains a silane compound) More preferably, it is part.

  In the case where a zirconium compound or a hafnium compound and a tin compound are used in combination, the amount of the tin compound is superior in terms of transparency and resistance to sulfidation, excellent in heat-resistant coloring stability and thin film curability, and can suppress loss of heat. The amount is preferably 0.1 mol or more and less than 4 mol, and more preferably 0.5 to 1.5 mol, per 1 mol of the zirconium compound or hafnium compound.

The silicone resin composition (silicone resin composition described in the present specification) can further contain additives as necessary within a range not impairing the object and effect of the present invention, in addition to the above components.
Examples of additives include radical initiators (including thermal radical initiators and photoradical initiators), metal compounds other than nickel, copper and gallium, inorganic fillers, antioxidants, lubricants, ultraviolet absorbers, and heat light. Stabilizers, dispersants, antistatic agents, polymerization inhibitors, antifoaming agents, curing accelerators, solvents, fluorescent substances (including inorganic and organic substances), anti-aging agents, radical inhibitors, adhesion improvers, flame retardants , Surfactant, storage stability improver, ozone anti-aging agent, thickener, plasticizer, radiation blocker, nucleating agent, coupling agent, conductivity-imparting agent, phosphorus peroxide decomposer, pigment, metal An inactivating agent and a physical property adjusting agent are listed. 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 described in the present specification) is not particularly limited in its production. For example, it can be produced by mixing an organosiloxane, a metal compound, and 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 described in the present specification) can be applied include, for example, metal (for example, Group 11 metal), glass, plastic, rubber, semiconductor (for example, , Semiconductor light emitting device). 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 described in the present specification).
What covered the metal layer obtained from the metal of Group 11 with the silicone resin layer obtained from the silicone resin composition (silicone resin composition described in the present specification) by the method for preventing corrosion of the metal layer of the present invention, It is the same as the laminated body described in this specification.
Hereinafter, by explaining the method for preventing corrosion of a metal layer according to the present invention, the laminate described in the present specification, a method for producing the same, and a semiconductor light-emitting device described in the present specification, which is considered to be one application of the silicone resin composition The manufacturing method 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. And a method of obtaining a laminate described in the specification.

  In the method for preventing corrosion of a metal layer of the present invention (laminated body described in the present specification, semiconductor light-emitting device described in the present specification), 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 a metal layer of the present invention (laminated body described in the present specification, semiconductor light-emitting device described in the present specification), the temperature at which the silicone resin composition is heated is curable (for example, a sealed system). Is a by-product due to a condensation reaction, and has an excellent balance between transparency and adhesive strength, and can have a suitable curing time and pot life. From the viewpoint that alcohol can be further suppressed from foaming, cracks in the cured product can be suppressed, and the smoothness, moldability and physical properties of the cured product are excellent, it is preferably cured at around 80 ° C to 150 ° C, and around 150 ° C. Is more preferable.

  In the method for preventing corrosion of a metal layer of the present invention (laminated body described in the present specification, semiconductor light-emitting device described in the present specification), the light used when the silicone resin composition is cured by light irradiation is not particularly limited. Examples thereof include ultraviolet rays and electron beams.

A cured product obtained by curing a silicone resin composition (silicone resin composition described in the present specification) has resistance to sulfurization.
In the present invention, the sulfidation resistance based on the spectral reflectance maintenance factor was evaluated as follows. First, the silicone resin composition is applied onto silver plating so as to have a thickness of about 1 mm and sufficiently cured to obtain a cured sample. Next, about 10 g of iron sulfide ground in powder form (large excess with respect to 0.5 mmol of hydrochloric acid) is placed on the bottom of a 10 L desiccator, and the eye plate is placed above the iron sulfide so as not to contact the iron sulfide. (With through-holes) is installed in a desiccator, the cured sample is placed on the eye plate, and 0.5 mmol of hydrochloric acid is added dropwise to a large excess of iron sulfide to give 0.25 mmol of hydrogen sulfide (concentration: approx. 500 ppm) is generated (reaction formula: FeS + 2HCl → FeCl ₂ + H ₂ S).
About the cured sample before the sulfidation test and after the sulfidation test (24 hours after the generation of hydrogen sulfide), the spectral reflectance at 475 nm is measured using a spectral reflectometer, URE-30 manufactured by USHIO INC. At the time of measurement before and after the sulfidation test, the spectral reflectance was measured using the metal layer (silver plating) remaining after peeling the silicone resin layer from the cured sample.
Spectral reflectance maintenance ratio was calculated by applying the spectral reflectance before and after the sulfurization resistance test to the following equation.
Spectral reflectance maintenance factor = (Spectral reflectance after anti-sulfurization test / Spectral reflectance before anti-sulfurization test) × 100
The spectral reflectance maintenance factor is preferably 80% or more, and more preferably 90% or more.

  Further, as an evaluation of the sulfidation resistance in the present invention, in the above sulfidation resistance test, 24 hours after the generation of hydrogen sulfide was evaluated visually to confirm the discoloration of silver in the cured sample. It is preferable that no discoloration is confirmed after 24 hours from the generation of hydrogen sulfide.

  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 described in the present specification) is JIS K0115: 2004. The transmittance measured at a wavelength of 400 nm using an ultraviolet / visible absorption spectrum measuring device (manufactured by Shimadzu Corporation, the same shall apply hereinafter) is preferably 80% or more, 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 transmittance of 80% or more, preferably 85% or more, measured at a wavelength of 400 nm using an ultraviolet / visible spectrum measuring device in accordance with JIS K0115: 2004. It is more preferable that

  The cured product [silicone resin layer, sealing material] obtained by using the silicone resin composition has a permeability retention rate (transmittance after heat resistance test / transmittance at initial curing × 100) of 70 to 100. % Is preferable, and 80 to 100% is more preferable.

The silicone resin composition (silicone resin composition described in the present specification) 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 described in the present specification) can be applied include a light emitting diode (LED), an organic electroluminescent device (organic EL), a laser diode, and an LED array. Is mentioned. Examples of the LED chip include a high power LED, a high luminance LED, and a general luminance LED.
Silicone resin compositions (silicone resin compositions described in the present specification) include, for example, display materials, optical recording medium materials, optical equipment materials, optical component materials, optical fiber materials, optical / electronic functional organic materials, and semiconductor integration. It can be used for applications such as circuit peripheral materials.

The laminate will be described below.
The laminate described in this specification is
A metal layer obtained from a Group 11 metal;
(A) Silicone containing 100 parts by mass of an organosiloxane having at least one reactive functional group in one molecule and (B) a metal compound having at least one selected from the group consisting of nickel, copper and gallium It is a laminate having a silicone resin layer obtained from the resin composition and having sulfur resistance.

The silicone resin composition used in the laminate described in the present specification is the same as the silicone resin composition (silicone resin composition described in the present specification) used in the metal layer corrosion prevention method of the present invention. .
The metal layer used in the laminate described in the present specification is the same as the metal layer used in the method for preventing corrosion of a metal layer of the present invention.
One of the aspects of the laminate described in this specification is to have a semiconductor light emitting element between the metal layer and the 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 described in the present specification will be described below with reference to the accompanying drawings. The present invention is not limited to the attached drawings.
FIG. 1 is a cross-sectional view schematically showing an example of a laminate in 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 in 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 will be described below.
The semiconductor light emitting device described in this specification 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 encapsulant is (A) an organosiloxane having at least one reactive functional group in one molecule, and (B) a metal compound having at least one selected from the group consisting of nickel, copper and gallium. Obtained from a silicone resin composition containing,
This is a semiconductor light-emitting device having sulfidation resistance.

The silicone resin composition used in the semiconductor light emitting device described in the present specification is the same as the silicone resin composition (silicone resin composition described in the present specification) used in the method for preventing corrosion of a metal layer of the present invention. is there.
The reflector used in the semiconductor light emitting device described in this specification has the same material as the metal layer used in the metal layer corrosion prevention method of the present invention.

The semiconductor light-emitting device described in this specification will be described below with reference to the accompanying drawings.
FIG. 3 is a cross-sectional view schematically showing an example of a semiconductor light emitting device in 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 described in this specification. The recessed portion 302 may be filled with the silicone resin composition described in this specification up to the shaded portion 306. Alternatively, the portion denoted by reference numeral 308 can be another transparent layer, and the hatched portion 306 can be a sealing material included in the semiconductor light emitting device described in this specification. 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.
The end portions 312 and 314 included in the frame body 304 may be integrally coupled, and the reflector may form the side surface and the bottom portion. In this case, the semiconductor light emitting element can be disposed on the bottom 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, it is possible to increase the resistance to sulfidation and suppress corrosion (for example, discoloration, specifically, discoloration of silver) of the reflector (metal layer, particularly silver plating layer). The brightness and transparency of the semiconductor light emitting device are not reduced.
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 in 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 described in this specification.

FIG. 5 is a cross-sectional view schematically showing another example of the semiconductor light emitting device according to 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, the frame body is provided with a reflector 520 obtained from a Group 11 metal on the side surface (not shown) of the recess, and the sealing material 502 is a semiconductor light emitting element. 503 and the reflector 520 are sealed, a substrate 510 and an inner lead 505 are provided inside a resin 506 having a lamp function, and the sealing material 502 is obtained from the above-described silicone resin composition, and is a semiconductor light emitting device having sulfidation resistance. Device.
In FIG. 5, a frame (not shown) and the substrate 510 can be integrally formed.
The reflector 520 may be formed integrally with the side surface and the bottom (not shown) of the recess.
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 a conductive wire 507.
Resin 506 can be formed using the silicone resin composition described herein.

  The case where the silicone resin composition described in the present specification and / or the semiconductor light-emitting device described in the present specification 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 a semiconductor light-emitting device that is considered to be one application of the silicone resin composition in the present invention and / or the silicone resin composition in 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 described in this specification can be used for the sealing material 606. In addition, the semiconductor light emitting device described in this specification can be used as the semiconductor light emitting device 601.

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

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
1. Production of organosiloxane 1.1. Organosiloxane 2
A 500 mL three-necked flask equipped with a stirrer and a reflux condenser and a polysiloxane having silanol groups at both ends (polydimethylsiloxane-α, ω-diol, weight average molecular weight 49,000, trade name ss10, manufactured by Shin-Etsu Chemical Co., Ltd.) The same applies hereinafter.) 100 parts by weight, 10 parts by weight of tetramethoxysilane, and 0.1 parts by weight of acetic acid were added, and the reaction was carried out under a nitrogen atmosphere at 100 ° C. for 6 hours. The disappearance of the silanol group possessed by ss10 was confirmed by ¹ H-NMR analysis. The obtained organosiloxane was designated as organosiloxane 2. The main structure of organosiloxane 2 is represented by the following formula. The weight average molecular weight of organosiloxane 2 (weight average molecular weight expressed in terms of polystyrene by gel permeation chromatography (GPC) using chloroform as a solvent. The same applies hereinafter) was 55,000.

1.2. Organosiloxane 3
A 500 mL three-necked flask equipped with a stirrer and a reflux condenser, 100 parts by weight of polysiloxane (ss10) having silanol groups at both ends, and a partial hydrolysis-condensation product of methyltrimethoxysilane (KC-89, Shin-Etsu Chemical Co., Ltd.) 10 parts by weight and 0.1 part by weight of acetic acid were added and reacted under a nitrogen atmosphere at 140 ° C. for 15 hours. The disappearance of the silanol group possessed by ss10 was confirmed by ¹ H-NMR analysis. The obtained organosiloxane was designated as organosiloxane 3. The main structure of organosiloxane 3 is represented by the following formula. The weight average molecular weight of organosiloxane 3 was 60,000.

1.3. Organosiloxane 6
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, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 mass Part, and 0.01 parts by mass of 2-ethylhexanoate (manufactured by Kanto Chemical Co., Inc.) 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.
The obtained polydimethylsiloxane having methacryloxypropyldimethoxysilyl groups at both ends is referred to as (A) organosiloxane 6 (M-ss70).
(A) The weight average molecular weight of organosiloxane 6 was 35,000.

2. Evaluation of sulfidation resistance 1
Sulfuration resistance (spectral reflectance maintenance factor, sulfidation resistance 1) was evaluated by the method described below. The results are shown in Tables 1 to 3.
2.1. Preparation of cured sample: A silicone resin composition produced as described below was applied onto silver plating so as to have a thickness of about 1 mm, and the silicone resin composition was cured under the following curing conditions to prepare a cured sample.

2.2. Curing conditions-When the silicone composition contains the condensation catalyst 1: Heated for 24 hours under conditions of 150 ° C-When the silicone composition contains the condensation catalyst 2: heated for 24 hours under conditions of 150 ° C-Silicone composition When containing an addition-type curing catalyst: heated for 6 hours under conditions of 150 ° C. When the silicone composition contains radical initiator 1: heated for 3 hours under conditions of 150 ° C. • silicone composition is a radical initiator When 2 is contained: Irradiated with a cumulative light amount of 8,000 mJ / cm ² under irradiation conditions of a high-pressure mercury lamp • When the silicone composition contains a cationic polymerization initiator: Heated at 150 ° C. for 3 hours

2.3. Sulfide resistance test: Place about 10 g of powdered iron sulfide (large excess with respect to 0.5 mmol of hydrochloric acid) at the bottom of a 10 L desiccator, and keep it from contacting iron sulfide above this iron sulfide. An eye plate (having a through hole) was mounted in the desiccator, and the cured sample was placed on the eye plate. Next, 0.25 mmol hydrogen sulfide (concentration: about 500 ppm) was generated by dropping 0.5 mmol hydrochloric acid into a large excess of iron sulfide (reaction formula: FeS + 2HCl → FeCl ₂ + H ₂ S).

2.4. Spectral reflectance maintenance factor: Sulfurization resistance was evaluated by spectral reflectance maintenance factor. Using a spectral reflectometer, URE-30 manufactured by Ushio Electric Co., Ltd., the spectral reflectance at 475 nm was measured for the cured samples before the sulfuration resistance test and after the sulfurization resistance test (24 hours after generation of hydrogen sulfide). When measuring the cured samples before and after the sulfidation resistance test, the spectral reflectance was measured using the remaining metal layer (silver plating) after peeling the silicone resin layer from the cured sample.
Spectral reflectance maintenance ratio was calculated by applying the spectral reflectance before and after the sulfurization resistance test to the following equation.
Spectral reflectance maintenance factor = (Spectral reflectance after anti-sulfurization test / Spectral reflectance before anti-sulfurization test) × 100
When the spectral reflectance maintenance ratio was 80% or more, it was evaluated that the resistance to sulfidation was excellent.

2.5. Evaluation criteria for sulfidation resistance 1: In the above sulfidation resistance test, the discoloration of silver in the cured sample was visually confirmed 24 hours after the generation of hydrogen sulfide.
In Table 1, “◯” indicates that no color change was observed after 24 hours from the start of the test, and “X” indicates that the color change was confirmed after 24 hours from the start of the test.

3. Production of silicone resin composition 1
The components shown in Tables 1 to 3 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 Tables 1 to 3 are as follows.

Organosiloxane 1: polydimethylsiloxane-α, ω-diol, weight average molecular weight 49,000, reactive functional group silanol group, average number of functional groups 2. Organosiloxane 2: weight average molecular weight 55,000, reactive functional group 6 having an average functional group having a methoxysilyl group, organosiloxane 3: weight average molecular weight 60,000, 14 having an average functional group having a methoxysilyl group as a reactive functional group, organosiloxane 4: silanol dimethyl silicone at both ends Oil, weight average molecular weight of 4,000, having silanol groups as reactive functional groups, average number of functional groups: 2 • Organosiloxane 5: Polysiloxane having vinyl group and polysilyloxane having hydrogensilyl group • Organosiloxane 6: Both Methacryloxy at the end Polydimethylsiloxane having propyldimethoxysilyl group, weight average molecular weight 35,000, reactive functional methacryloxy group, average number of functional groups 2 Organosiloxane 7: Polysiloxane containing epoxy groups at both ends, weight average molecular weight 5,400, Two functional groups having an epoxy group as a reactive functional group. Organosiloxane 8: Silicone alkoxy oligomer, reactive functional group alkoxysilyl group, average functional group number 0 <n <2 [R _m Si (OR ′) _n O _{(4-mn) / 2 wherein} R is an alkyl group having 1 to 6 carbon atoms, an alkenyl group or an aryl group, R ′ is an alkyl group having 1 to 6 carbon atoms, and m is 0 < m <2, n is m + n is 0 <m + n ≦ 3). Weight average molecular weight 6,000. Product name x-40-9246, manufactured by Shin-Etsu Chemical Co., Ltd.
Condensation catalyst 1: The condensation catalyst 1 is a mixture of tributoxynaphthenic acid Zr (0.03 parts by mass) and dibutyltin diacetate (manufactured by Nitto Kasei Co., Ltd., 0.02 parts by mass) in detail.
Condensation catalyst 3: Condensation catalyst 3 is a mixture of tributoxy hafnium naphthate (a reaction product of naphthenic acid and hafnium ratrabutoxide, 0.03 parts by mass) and dibutyltin diacetate (0.02 parts by mass).

The production of tributoxynaphthenic acid Zr is as follows.
17.5 g (0.026 mol) of zirconium tetrabutoxide having a concentration of 87.5% by mass (manufactured by Kanto Chemical Co., Inc.) 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) of neutralization value 220 mg, the same applies hereinafter) was put into a three-necked flask and stirred at room temperature for about 2 hours in a nitrogen atmosphere to obtain a target compound.
The neutralization value of naphthenic acid is the amount of KOH required to neutralize 1 g of naphthenic acid.
The qualitative properties of the synthesized product were analyzed 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 ^{1 in} the naphthate group (R ¹ COO—) of tributoxynaphthenic acid Zr is 15.

4). Results As is apparent from the results shown in Tables 1 to 3, obtained using the compositions of Comparative Examples 1 to 8 not containing a metal compound having at least one selected from the group consisting of nickel, copper and gallium. The metal layer obtained from the Group 11 metal covered with the obtained silicone resin layer was discolored and had low sulfidation resistance. Moreover, it is obtained using the composition of Comparative Examples 9-11 which does not contain the metal compound which has at least 1 sort (s) chosen from the group which consists of nickel, copper, and gallium but contains a boron compound, a magnesium compound, or an aluminum compound instead. The metal layer obtained from the Group 11 metal covered with the silicone resin layer was discolored and had low sulfidation resistance.
On the other hand, the 11th covered with the silicone resin layer obtained using the composition of Examples (Ni) 1-4, Examples (Cu) 1-6, Examples (Ga) 1-4. A metal layer obtained from a group metal has no discoloration and is highly sulfide resistant.
Moreover, the generation | occurrence | production of a crack did not occur in the silicone resin layer obtained using the composition of Example (Ni) 1-4, Example (Cu) 1-6, and Example (Ga) 1-4.

5. Evaluation of sulfidation resistance 2
Using the composition obtained in Production 2 of the silicone resin composition shown below, sulfidation resistance was evaluated by the following method. The results are shown in Table 5, attached drawing (FIG. 7). In Table 5, sulfidation resistance evaluated by the following method is shown as sulfidation resistance 2.
5.1. Preparation of cured sample: A silicone resin composition produced as described below was applied onto silver plating so as to have a thickness of about 1 mm, and the silicone resin composition was cured under the following curing conditions to prepare a cured sample.

5.2. Curing conditions The obtained composition (containing an addition-type curing catalyst) was cured by heating at 150 ° C. for 6 hours.

5.3. Sulfur resistance test: Sulfur resistance test was performed in the same manner as described above.
5.4. Evaluation of sulfidation resistance 2: In the sulfidation resistance test, the discoloration of silver was confirmed in a cured sample 24 hours after the generation of hydrogen sulfide. In the attached drawing (FIG. 7), the state of each cured sample 24 hours after the generation of hydrogen sulfide is shown as photographic data. In the evaluation of sulfidation resistance 2, a photograph was taken of the cured sample without peeling off the silicone resin layer. In FIG. 7 (I), the silicone resin layer was partially peeled from the cured sample, and a photograph was taken.

6). Production of silicone resin composition 2
The components shown in Table 5 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 5 are as follows.
-(A) Organosiloxane 5: Same as (A) Organosiloxane 5 in Table 1-Cu Compound 1: Same as Cu Compound 1 in Table 2-Ga Compound 1: Same as Ga Compound 1 in Table 3-Boron Compound 1: Same as boron compound 1 in Table 1. Ti compound 1: tetraacetylacetonate titanium Zr compound 1: tetra-2-ethylhexanoate zirconium Co compound 1: triacetylacetonate cobalt Fe compound 1: tri Acetylacetonate iron ・ Catalyst 1: Addition-type curing catalyst, trade name CAT-RG, manufactured by Shin-Etsu Chemical Co., Ltd.

7). Results FIG. 7 is photographic data showing the evaluation results of sulfidation resistance 2.
FIGS. 7A to 7H are photographs of the entire cured sample taken with the resin layer facing up. 7A to 7H, the resin layer is overlaid on the silver plating layer.
FIG. 7 (I) shows the surface of the silver plating layer from which the resin layer was peeled off partially from the cured sample in the cured sample photographed in FIG. 7 (F) (occupies the upper half in the photograph). It is the photograph which image | photographed the back surface (lower half in a photograph) of the resin layer which peeled and the white part. In FIG. 7 (I), the surface 12 (portion occupying the upper half in the photograph) of the silver plating layer from which the resin layer 14 was peeled from the cured sample 10 was white, and there was no silver discoloration.
As is apparent from the results shown in FIG. 7, it does not contain a metal compound having at least one selected from the group consisting of nickel, copper, and gallium, but instead contains no additive, boron compound, titanium compound, zirconium compound, cobalt compound In Comparative Examples 12 to 17 [FIGS. 7A to 7D, (G) and (H)] containing an iron compound, discoloration of silver was observed.
On the other hand, Example (Cu) -7 is excellent in sulfidation resistance with no discoloration on the surface of the silver plating layer from which the resin layer has been peeled, as is apparent from the results shown in FIG. As is clear from the results of FIG. 7E, Example (Ga) -5 has no discoloration in the entire cured sample and is excellent in sulfur resistance.

Thus, according to the method for preventing corrosion of a metal layer according to the present invention, corrosion (for example, discoloration) of the metal layer can be suppressed, so that, for example, light reflectivity due to corrosion of the metal layer can be maintained over time. It can suppress that the brightness | luminance of a light source (for example, semiconductor light-emitting device) falls. 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 laminate, the semiconductor light emitting device, and the silicone resin composition described in the present specification can achieve the same effects as those of the metal layer corrosion prevention method of the present invention.

DESCRIPTION OF SYMBOLS 10 Hardened sample 12 Surface of silver plating layer 14 Resin layer 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 Mount member 302, 502 Recessed part, Silicone resin layer 303, 503 Semiconductor light emitting element 304 Frame body 306 Shaded portion (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 506 Resin 600 LED display 601 Semiconductor light emitting device 604 Housing 605 Light shielding member 606 Sealing material

Claims (4)

A metal layer obtained from a Group 11 metal, (A) at least one selected from the group consisting of an organosiloxane having at least one reactive functional group in one molecule and (B) nickel, copper and gallium A method for preventing corrosion of a metal layer, which is covered with a silicone resin layer obtained from a silicone resin composition containing a metal compound, and which prevents corrosion of the metal layer .
At least one metal carboxylate or metal complex selected from the group consisting of nickel and gallium, wherein the metal compound is represented by the following formula (1-i):
A copper metal complex represented by the following formula (1-ii):
A metal complex represented by the following formula (2), and
At least one selected from the group consisting of alcoholates having at least one selected from the group consisting of nickel, copper and gallium ;
The method for preventing corrosion of a metal layer, wherein the Group 11 metal is at least one selected from the group consisting of copper, silver and gold .
M (—O—CO—R ¹ ) _n (1-i)
[In formula (1), M is at least one selected from the group consisting of nickel and gallium, n is 3, and R ¹ is a hydrocarbon group having 1 to 18 carbon atoms which may contain a hetero atom. . ]
M (—O—CO—R ¹ ) _n (1-ii)
[In Formula (1), M is copper, n is 2 or 3, and R < ¹ > is a C1-C18 hydrocarbon group which may contain a hetero atom. ]
M (R ² COCHCOR ³ ) _n (2)
[In formula (2), M is at least one selected from the group consisting of nickel, copper and gallium, n is 3 when M is nickel or gallium, and n is 2 or 3 when M is copper. And R ² and R ³ are the same or different, a C 1-18 hydrocarbon group which may contain a hetero atom , and a C 1-18 alkoxy group. ] The method for preventing corrosion of a metal layer according to claim 1, wherein the amount of the metal compound is 0.01 to 5 parts by mass with respect to 100 parts by mass of the organosiloxane. The reactive functional group comprises a silanol group, an alkoxysilyl group, a vinyl group, a hydrosilyl group, an epoxy group, a (meth) acryloyl group, a polyether group, a carboxyl group, a carbinol group, an amino group, a mercapto group, and a phenol group. The method for preventing corrosion of a metal layer according to claim 1 or 2 , which is at least one selected from the group. A silicone resin composition used in the method for preventing corrosion of a metal layer according to any one of claims 1 to 3,
  (A) an organosiloxane having at least one reactive functional group in one molecule, and (B) a metal compound having at least one selected from the group consisting of nickel, copper and gallium,
At least one metal carboxylate or metal complex selected from the group consisting of nickel and gallium, wherein the metal compound is represented by the following formula (1-i):
  A copper metal complex represented by the following formula (1-ii):
  A metal complex represented by the following formula (2), and
  A silicone resin composition which is at least one selected from the group consisting of alcoholates having at least one selected from the group consisting of nickel, copper and gallium.
M (-O-CO-R ¹ ) _n       (1-i)
[In the formula (1), M is at least one selected from the group consisting of nickel and gallium, n is 3, R ¹ Is a hydrocarbon group having 1 to 18 carbon atoms which may contain a hetero atom. ]
M (-O-CO-R ¹ ) _n       (1-ii)
[In Formula (1), M is copper, n is 2 or 3, R ¹ Is a hydrocarbon group having 1 to 18 carbon atoms which may contain a hetero atom. ]
M (R ² COCHCOR ^Three ) _n       (2)
[In formula (2), M is at least one selected from the group consisting of nickel, copper and gallium, n is 3 when M is nickel or gallium, and n is 2 or 3 when M is copper. Yes, R ² , R ^Three Are the same or different, a C1-C18 hydrocarbon group which may contain a hetero atom, and a C1-C18 alkoxy group. ]