JP2012256648A - Kit for forming metal electrode protection film, metal electrode protection film and formation method therefor, and semiconductor light-emitting device and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a kit for forming a metal electrode protection film which can prevent discoloration or blackening of a metal electrode, exhibits excellent atmospheric stability while retaining gas barrier properties, and exhibits excellent transparency causing no yellow discoloration or white turbidity or the like over time, and to provide a formation method therefor, and a semiconductor light-emitting device which can have a high luminance and a long life by using the metal electrode protection film.SOLUTION: The kit for forming a metal electrode protection film at least has an alkoxysilane compound, an A liquid the content of which is 0.0001-0.005 molar equivalent for the alkoxysilane, and a B liquid containing a polymer which contains at least vinyl alcohol as a constitutional unit. The A liquid and the B liquid are mixed when used.

Description

  The present invention relates to a metal electrode protective film production kit used for producing a metal electrode protective film for protecting a metal electrode in a semiconductor light emitting device, a metal electrode protective film produced using the metal electrode protective film production kit, and The present invention relates to a manufacturing method thereof, a semiconductor light emitting device using the same, and a manufacturing method thereof.

  Conventionally, as an electrode in a semiconductor light emitting device using a light emitting diode (hereinafter sometimes referred to as an LED) as a light source, a metal electrode having excellent electrical conductivity and reflectivity, particularly a silver plated electrode is used. From the viewpoint of excellent durability in recent years, it is known to use a silicone-based resin as a sealing resin in the semiconductor light-emitting device. A disadvantage of the silicone resin is that the gas permeability is very high.

The silver-plated electrode is sulfurized by a sulfur compound contained in a very small amount in the air, causing discoloration and / or blackening, resulting in a problem that the LED light quantity is reduced.
Therefore, for the purpose of solving such problems, a protective film is formed by heating a material containing a polymer containing a silane compound and vinyl alcohol as a structural unit and an acid catalyst on a metal electrode, A semiconductor light emitting device that can prevent blackening of a metal electrode has been proposed (see, for example, Patent Document 1).
However, in this case, not only is there still insufficient points regarding the yellowing of the protective film over time during heating, but also white turbidity is very likely to occur, and the transparency of the protective film, which is a particular problem for the LED application described above. There is a serious problem of being inferior. Further, since the protective film contains a silane compound, the gas barrier property is not maintained, and the protective film is deteriorated by absorbing moisture contained in the atmosphere in the solution state before the formation of the metal electrode protective film. There is also a problem in that it is inferior in atmospheric stability.

  Therefore, the metal electrode protective film can prevent discoloration and blackening of the metal electrode, has excellent atmosphere stability while maintaining gas barrier properties, and does not cause yellowing or cloudiness over time. At present, there is a strong demand for rapid development of semiconductor light-emitting devices using the same.

JP 2008-274272 A

  An object of the present invention is to solve the above problems and achieve the following object. That is, the present invention can prevent discoloration and blackening of the metal electrode, is excellent in atmospheric stability while maintaining gas barrier properties, and is excellent in transparency without causing yellowing or cloudiness over time. It aims at providing the kit for metal electrode protective film preparation for producing a metal electrode protective film, the said metal electrode protective film, and its manufacturing method. It is another object of the present invention to provide a semiconductor light emitting device and a method for manufacturing the same that can increase the luminance and extend the life by using the metal electrode protective film of the present invention.

As a result of intensive studies to achieve the above object, the present inventors have found that the acid catalyst in the metal electrode protective film containing a polymer containing a silane compound and vinyl alcohol as a structural unit and an acid catalyst, When the content in the metal electrode protective film is a conventionally used content, white turbidity is very likely to occur in the solution state before the protective film is formed. We found that there is a new problem that changes will occur.
Thus, when white turbidity or yellowing occurs in the metal electrode protective film, discoloration or blackening of the metal electrode cannot be prevented over a long period of time, and it is possible to increase the brightness and life of the semiconductor light emitting device. I found that there was a problem that I could not do.
Therefore, discoloration of the metal electrode can be achieved by using, as a metal electrode protective film, a heat-cured material having a content of the acid catalyst of 0.0001 molar equivalent or more and 0.005 molar equivalent or less with respect to the alkoxysilane compound. It has been found that the metal electrode protective film can be prevented from being blackened, has excellent atmosphere stability while maintaining gas barrier properties, and has excellent transparency without causing yellowing or cloudiness over time. The present invention has been completed.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> A liquid containing at least an alkoxysilane compound and an acid catalyst having a content with respect to the alkoxysilane of 0.0001 molar equivalent or more and 0.005 molar equivalent or less, and a polymer containing at least vinyl alcohol as a constituent unit. A metal electrode protective film preparation kit for mixing and using the A liquid and the B liquid.
<2> A liquid containing at least an alkoxysilane compound, B liquid containing a polymer containing at least vinyl alcohol as a constituent unit, and C liquid containing at least an acid catalyst, the A liquid, the B liquid, and It is a metal electrode protective film preparation kit for using the said C liquid by mixing so that the said acid catalyst may be 0.0001 molar equivalent or more and 0.005 molar equivalent or less with respect to the said alkoxysilane compound.
<3> The metal electrode protective film preparation kit according to any one of <1> to <2>, wherein the content of the acid catalyst with respect to the alkoxysilane compound is 0.0001 molar equivalent or more and 0.001 molar equivalent or less. is there.
<4> The metal electrode protective film preparation kit according to any one of <1> to <3>, wherein the acid catalyst is at least one of hydrochloric acid and acetic acid.
<5> The metal electrode protective film preparation kit according to any one of <1> to <4>, wherein the metal electrode is an electrode containing silver.
<6> A metal electrode protective film formed using the metal electrode protective film preparation kit according to any one of <1> to <5>.
<7> Mass of solid content derived from polymer containing vinyl alcohol as constituent unit (M1), Mass of solid content derived from polymer containing vinyl alcohol as constituent unit (M1), and solid content derived from alkoxysilane compound The metal electrode protective film according to <6>, wherein the ratio [M1 / (M1 + M2)] of the total mass (M2) to the total mass (M1 + M2) is 0.2 to 0.9.
<8> An alkoxysilane compound, an acid catalyst having a content with respect to the alkoxysilane of 0.0001 molar equivalent or more and 0.005 molar equivalent or less, and a polymer containing at least vinyl alcohol as a constituent unit are mixed and cured. A method for producing a metal electrode protective film comprising a step of forming a metal electrode protective film.
<9> A method for manufacturing a semiconductor light emitting device, comprising: a metal electrode; a semiconductor chip electrically connected to the metal electrode; and a metal electrode protective film protecting at least a part of the metal electrode and the semiconductor chip. A semiconductor light emitting device comprising a step of mixing and curing the metal electrode protective film preparation kit according to any one of <1> to <5> to form the metal electrode protective film It is a manufacturing method.
<10> A semiconductor light emitting device comprising a metal electrode, a semiconductor chip electrically connected to the metal electrode, and a metal electrode protective film protecting at least a part of the metal electrode and the semiconductor chip, The metal electrode protective film is a metal electrode protective film according to any one of <6> to <7>.

  According to the present invention, it is an object to solve the above problems and achieve the following object. That is, the present invention can prevent discoloration and blackening of the metal electrode, is excellent in atmospheric stability while maintaining gas barrier properties, and is excellent in transparency without causing yellowing or cloudiness over time. A metal electrode protective film production kit for producing a metal electrode protective film, the metal electrode protective film, and a method for producing the metal electrode protective film can be provided. In addition, by using the metal electrode protective film of the present invention, it is possible to provide a semiconductor light emitting device capable of increasing the luminance and extending the lifetime, and a method for manufacturing the same.

FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor light emitting device before coating of a kit for preparing a metal electrode protective film. FIG. 2 is a cross-sectional view schematically showing an example of a semiconductor light emitting device during coating of the metal electrode protective film preparation kit. FIG. 3 is a cross-sectional view schematically showing an example of a semiconductor light emitting device cured after coating of the kit for preparing a metal electrode protective film. FIG. 4 is a cross-sectional view schematically showing an example of a semiconductor light-emitting device before coating of the metal electrode protective film preparation kit. FIG. 5 is a cross-sectional view schematically showing an example of a semiconductor light emitting device during coating of the metal electrode protective film preparation kit. FIG. 6 is a cross-sectional view schematically showing an example of a semiconductor light emitting device cured after coating of the kit for preparing a metal electrode protective film.

(Metal electrode protective film production kit)
In one embodiment, the kit for preparing a metal electrode protective film of the present invention is a kit for preparing a metal electrode protective film used by mixing, and at least an alkoxysilane compound and a content of 0.0001 molar equivalent or more with respect to the alkoxysilane. It is a two-component composition comprising a liquid A containing an acid catalyst of 0.005 molar equivalent or less and a liquid B containing a polymer containing at least vinyl alcohol as a structural unit, and preferably contains a solvent, Furthermore, other components are included as necessary.

  The metal electrode protective film preparation kit of the present invention in another embodiment is a metal electrode protective film preparation kit used by mixing, and contains at least liquid A containing an alkoxysilane compound and at least vinyl alcohol as constituent units. A three-component composition comprising a liquid B containing a polymer and a C liquid containing an acid catalyst having a content of at least 0.0001 molar equivalents and not more than 0.005 molar equivalents relative to the alkoxysilane. It is preferable to contain, and also other components are included as necessary.

<Alkoxysilane compound>
The alkoxysilane compound is a compound that constitutes the metal electrode protective film, and is used when the metal electrode protective film is formed by being cured by a sol-gel reaction with a polymer containing vinyl alcohol as a constituent unit to be described later. Compound.

The alkoxysilane compound is not particularly limited as long as it is a compound having silicon and an alkoxy group bonded thereto, and can be appropriately selected according to the purpose. The compound represented by the following general formula (I) Is preferred. These may be used individually by 1 type and may use 2 or more types together.
However, in said general formula (I), R < ¹ > may mutually be the same and may differ, and shows the monovalent organic group which does not contain an alkoxy group or a fluorine (however, four R ^At least one of 1 is an alkoxy group).

  There is no restriction | limiting in particular as said alkoxy group, According to the objective, it can select suitably, For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned.

  Examples of the organic group include a hydrocarbon group that may contain at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom. Examples of the hydrocarbon group include an alkyl group, an aryl group, an alkenyl group, and an acyl group. Examples of the alkyl group include a methyl group, an ethyl group, and an isopropyl group. Examples of the aryl group include a phenyl group, a benzyl group, a tolyl group, and the like. Examples of the alkenyl group include a vinyl group, a propenyl group, and a butenyl group. Examples of the acyl group include formyl group, acetyl group, propionyl group, and the like. Among these, a methyl group is preferable because it is more excellent in heat resistance and transparency.

  The average number of alkoxy groups or siloxane bonds in the alkoxysilane compound is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 or more and 4 or less per silicon atom. 5 or more and 4 or less are more preferable.

The alkoxysilane compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include tetraethoxysilane, tetramethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrisilane. Methoxysilane, methyltriethoxysilane, methyltrin-propoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrin-propoxysilane, ethyltriisopropoxysilane, ethyltributoxy Silane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriet Sisilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyl Triacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, β-cyanoethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dimethyldichlorosilane, diphenyl Dichlorosilane, methylphenyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, methyltrichlorosilane, γ-aminopropi Rutriethoxysilane, 4-Acinobutyltriethoxysilane, p-aminophenyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, aminoethylaminomethylphenethyltrimethoxysilane, 3-glycid Xylpropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, N- (6- Aminohexyl) aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrichlorosilane, (p-chloromethyl) phenyltrimethoxysilane, 4-chlorophenyltrimethoxysilane, 3-methacryl Xylpropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, styrylethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrichlorosilane, vinyltris (2-methoxyethoxy) silane And trifluoropropyltrimethoxysilane. These may be used individually by 1 type and may use 2 or more types together.
Among these, tetraethoxysilane is preferable in terms of excellent crosslink density after curing, stability in the air environment, and safety of by-products.

  As said alkoxysilane compound, what was synthesize | combined suitably may be used and a commercial item may be used. As said commercial item, tetraethoxysilane (made by Tokyo Chemical Industry Co., Ltd.) etc. are mentioned, for example.

  The mass average molecular weight of the alkoxysilane compound is not particularly limited and may be appropriately selected depending on the intended purpose. However, the curing time and the pot life are appropriate lengths, and the viewpoint that the curability and compatibility are excellent. From the viewpoint of polystyrene measured by gel permeation chromatography (GPC), 160 to 100,000 is preferable, and 200 to 2,000 is more preferable.

  There is no restriction | limiting in particular as content in the A liquid of the said metal electrode protective film preparation kit (2 liquid composition) of the said alkoxysilane compound, Although it can select suitably according to the objective, 1 mass%- 90 mass% is preferable, 10 mass%-80 mass% is more preferable, 20 mass%-70 mass% is especially preferable. When the content is less than 1% by mass, a film thickness sufficient for protecting the metal electrode may not be secured at the time of curing, and when it exceeds 90% by mass, the compatibility with the liquid B is lacking. There is. On the other hand, when the content is within the preferable range, it is advantageous in that the compatibility with the liquid B is good and the metal electrode protective film has an appropriate thickness.

  There is no restriction | limiting in particular as content in the A liquid of the said metal electrode protective film preparation kit (three-component composition) of the said alkoxysilane compound, Although it can select suitably according to the objective, 1 mass%- 90 mass% is preferable, 10 mass%-80 mass% is more preferable, 20 mass%-70 mass% is especially preferable. When the content is less than 1% by mass, a film thickness sufficient for protecting the metal electrode may not be secured at the time of curing. When the content exceeds 90% by mass, the phases of the B liquid and the C liquid It may lack solubility. On the other hand, when the content is within the preferable range, the compatibility with the liquid B and the liquid C is good, and it is advantageous in that the metal electrode protective film has an appropriate thickness.

<Acid catalyst>
The acid catalyst is a catalyst in a hydrolysis and dehydration condensation reaction during a sol-gel reaction when producing the metal electrode protective film.

The acid catalyst is not particularly limited and may be appropriately selected depending on the intended purpose. For example, inorganic acids such as hydrochloric acid, hydrogen bromide, hydrogen iodide, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, phosphorous acid, etc. Acid; Carboxylic acids (formic acid, acetic acid, propionic acid, butyric acid, succinic acid, cyclohexanecarboxylic acid, octanoic acid, maleic acid, 2-chloropropionic acid, cyanoacetic acid, trifluoroacetic acid, perfluorooctanoic acid, benzoic acid, pentafluoro Benzoic acid, phthalic acid, etc.), sulfonic acids (methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, pentafluorobenzenesulfonic acid, etc.), phosphoric acid / phosphonic acids (phosphoric acid dimethyl ester, phenylphosphonic acid) Etc.), Lewis acids (boron trifluoride etherate, scandium triflate, And the like; Rukiruchitan acid and aluminate), heteropoly acids (phosphomolybdic acid, an organic acid of phosphotungstic acid) and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, hydrochloric acid and acetic acid are preferable because they are easily available and do not volatilize and remain in the metal electrode protective film.

  A commercial item may be used as the acid catalyst, and examples of the commercial item include acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.).

  The content of the acid catalyst is not particularly limited as long as it is 0.0001 molar equivalent or more and 0.005 molar equivalent or less with respect to the alkoxysilane compound, and can be appropriately selected according to the purpose. It is preferably 0.0001 molar equivalent or more and 0.001 molar equivalent or less. When the content is less than 0.0001 molar equivalent, the hydrolysis of the alkoxysilane is not sufficient, and the crosslink density of the metal electrode protective film may be insufficient, and when the content exceeds 0.005 molar equivalent. The metal electrode protective film is liable to be yellowed or clouded, resulting in poor transparency. On the other hand, when the content is in the preferred range, the hydrolysis of alkoxysilane proceeds to form the metal electrode protective film excellent in crosslink density, and it is difficult to cause yellowing at a high temperature and to prevent white turbidity. This is advantageous in that a protective film having excellent properties can be formed.

<Polymer containing vinyl alcohol as a structural unit>
The polymer containing vinyl alcohol as a structural unit is a resin that constitutes the metal electrode protective film, and is used when the metal electrode protective film is formed by being cured by a sol-gel reaction with the alkoxysilane compound. Resin.

The polymer containing the vinyl alcohol as a structural unit is not particularly limited and may be appropriately selected according to the purpose. For example, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, methyl methacrylate / vinyl alcohol copolymer may be selected. Examples thereof include modified polyvinyl alcohols such as polymers and acrylamide / vinyl alcohol copolymers. The saponification degree of polyvinyl alcohol may be several tens of percent (partial saponification), 99% or more (complete saponification), or any saponification degree. The copolymerization ratio of the modified part of the modified polyvinyl alcohol copolymer may be any ratio.
Among these, polyvinyl alcohol is preferable in terms of excellent gas barrier properties.

  As the polymer containing vinyl alcohol as a structural unit, an appropriately synthesized polymer may be used. Examples of the synthesis method include polymerizing a vinyl acetate monomer and saponifying the obtained polyvinyl acetate. The method etc. are mentioned.

  As the polymer containing vinyl alcohol as a structural unit, a commercially available product may be used. Examples of the commercially available product include Poval (manufactured by Kuraray), Eval (manufactured by Kuraray), and Gohsenol (Nippon Synthetic Chemical Industry). And Soarnol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

  There is no restriction | limiting in particular as content in the B liquid of the said metal electrode protective film preparation kit (two-component composition) containing the said vinyl alcohol as a structural unit, According to the objective, it can select suitably. However, 0.000001 mass%-30 mass% are preferable, 0.00001 mass%-3 mass% are more preferable, 0.0001 mass%-1 mass% are especially preferable. When the content is less than 0.000001% by mass, a film thickness sufficient for protecting the metal electrode may not be secured during curing. When the content exceeds 30% by mass, the solution has a high viscosity and is handled as a solution. May be difficult. On the other hand, when the content is within the preferable range, it is advantageous in terms of easy handling as a solution and an appropriate thickness of the metal electrode protective film.

  There is no restriction | limiting in particular as content in the B liquid of the said metal electrode protective film preparation kit (three-component composition) which contains the said vinyl alcohol as a structural unit, According to the objective, it can select suitably. However, 0.000001 mass%-30 mass% are preferable, 0.00001 mass%-3 mass% are more preferable, 0.0001 mass%-1 mass% are especially preferable. When the content is less than 0.000001% by mass, a film thickness sufficient for protecting the metal electrode may not be secured during curing. When the content exceeds 30% by mass, the solution has a high viscosity and is handled as a solution. May be difficult. On the other hand, when the content is within the preferable range, it is advantageous in terms of easy handling as a solution and an appropriate thickness of the metal electrode protective film.

<Solvent>
The solvent is used as a solvent for a sol-gel reaction in producing the metal electrode protective film.
The solvent mixes each component in the sol liquid uniformly, and adjusts the solid content of the composition contained in the metal electrode protective film, and at the same time, can be applied to various coating methods to stabilize the dispersion of the composition. Improve the stability and storage stability.

  There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, primary alcohol, such as methanol, ethanol, n-propanol, n-butanol, isopropanol (IPA), isobutanol, sec -Secondary alcohols such as butyl alcohol, tertiary alcohols such as tert-butyl alcohol (t-butanol), tert-amyl alcohol, various alcohol solvents such as methoxymethanol, methoxyethanol, ethoxymethanol, 2-ethoxyethanol Aromatic solvents such as toluene, xylene, 2-phenoxyethanol, benzyl alcohol and phenol; ketone solvents such as acetone and methyl ethyl ketone; β-diketones such as acetylacetone (2,4-pentanedione) and 2,4-hexanedione Solvents; ester solvents such as ethyl acetate and methyl acetate; ketoester solvents such as ethyl acetoacetate and methyl acetoacetate; haloalkane solvents such as chloroform, dichloromethane and carbon tetrachloride; ether solvents such as dimethyl ether, diethyl ether and tetrahydrofuran; Water etc. are mentioned. These may be used alone or in combination of two or more.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, inorganic fillers, inorganic phosphors and the like are preferable, and anti-aging agents, radical inhibitors, ultraviolet absorption Agent, adhesion improver, flame retardant, surfactant, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, coupling agent, antioxidant, antiseptic, heat stabilizer , Conductivity imparting agents, antistatic agents, radiation blocking agents, nucleating agents, phosphorus peroxide decomposing agents, lubricants, pigments, metal deactivators, physical property modifiers and the like. These may be used individually by 1 type and may use 2 or more types together.

  The inorganic filler is not particularly limited as long as the optical properties are not deteriorated, and can be appropriately selected according to the purpose. For example, alumina, aluminum hydroxide, fused silica, crystalline silica, ultrafine amorphous silica, Hydrophobic ultrafine silica, flat mica, talc, calcium carbonate, barium sulfate and the like can be mentioned. These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as said inorganic fluorescent substance, According to the objective, it can select suitably, For example, YAG type | system | group fluorescent substances, such as yttrium, aluminum, garnet, etc. which are widely utilized for LED; ZnS type fluorescent substance; Examples thereof include Y ₂ O ₂ S-based phosphors; red-emitting phosphors; blue-emitting phosphors; green-emitting phosphors; quantum dot-based phosphors formed of nanoparticles such as CdSe and InP. These may be used individually by 1 type and may use 2 or more types together.

<Usage pattern>
There is no restriction | limiting in particular as a usage form of the said preparation kit for metal electrode protective films, According to the objective, it can select suitably, For example, after mixing the said preparation kit for metal electrode protective films with a mixer, 48 It is preferable to use (apply) within the time.
Further, in producing the metal electrode protective film, it is not always necessary to use a two-component, three-component, etc. kit. For example, at least the alkoxysilane compound, the acid catalyst, and the vinyl alcohol are configured. A composition for forming a metal electrode protective film containing a polymer as a unit, wherein the content of the acid catalyst with respect to the alkoxysilane compound is 0.0001 molar equivalent or more and 0.005 molar equivalent or less (one-pack type) May be used.

<Application>
By using the metal electrode protective film preparation kit of the present invention, it is possible to prevent discoloration or blackening of the silver-plated electrode, particularly as a metal electrode, and it has excellent atmospheric stability, yellowing, cloudiness while maintaining gas barrier properties. Thus, it is possible to provide a metal electrode protective film excellent in transparency that does not cause the above.

(Metal electrode protective film)
As one embodiment of the metal electrode protective film of the present invention, the metal electrode protective film preparation kit is used.
As another embodiment of the metal electrode protective film of the present invention, it contains at least an alkoxysilane compound, an acid catalyst, and a polymer containing at least vinyl alcohol as a constituent unit, and the acid catalyst is contained in the alkoxysilane compound. The metal electrode protective film-forming composition (one-component type) having an amount of 0.0001 molar equivalent or more and 0.005 molar equivalent or less is formed.

  The metal electrode protective film is formed by putting a dehydrated condensate obtained by mixing the metal electrode protective film preparation kit or the metal electrode protective film preparation composition into a mold having a desired shape, Can be obtained by heating or drying. In addition, the metal electrode protective film of the present invention can be directly formed at a target site by heating or drying in a state where the dehydration condensate is applied to the target site.

  There is no restriction | limiting in particular as a formation site | part of the said metal electrode protective film, According to the objective, it can select suitably, For example, as shown in FIGS. 1-3, the said metal electrode protection is carried out on the metal electrode and reflector 5 The metal electrode protective film 7 may be formed by applying a film preparation kit 6. As shown in FIGS. 4 to 6, the metal electrode is formed on the sealing material 8 formed on the metal electrode / reflector 5. The metal electrode protective film 7 may be formed by applying an electrode protective film preparation kit 6. Since the metal electrode protective film is excellent in gas barrier properties, even if it is formed on the sealing material, sulfidation (discoloration and / or blackening) of the metal electrode can be prevented.

<< Principle of hardening of protective film in manufacturing metal electrode protective film >>
The principle of curing the protective film when manufacturing the metal electrode protective film will be described.
When the alkoxysilane compound is reacted in the presence of the acid catalyst, the alkoxy group of the alkoxysilane compound is de-alcoholated by hydrolysis to become a hydroxyl group, and the hydrogen in the polymer containing the hydroxyl group and the vinyl alcohol as constituent units. A hydrogen bond is formed with the bond forming group, or a stable siloxane bond is formed by dehydration condensation to form a metal electrode protective film (cured product) formed by three-dimensional condensation.

The metal electrode protective film is not particularly limited and may be appropriately selected depending on the intended purpose, but has a polymer containing tetraethoxysilane and vinyl alcohol as structural units in terms of reactivity, brittleness, and gas barrier properties. A protective film is preferred.
It should be noted that the solvent used in the reaction and the water produced by the dehydration condensation reaction are considered to be vaporized and removed by the heating or drying, but the solvent and the water are not necessarily vaporized. The dehydration condensate having fluidity is included in the curing phenomenon in that it loses fluidity.

  There is no restriction | limiting in particular as an average film thickness of the said metal electrode protective film, Although it can select suitably according to the objective, 0.1 micrometer or more and 10 micrometers or less are preferable, and 0.3 micrometer or more and 5 micrometers or less are more preferable. When the average film thickness is less than 0.1 μm, the step coverage of the protective film is inferior, and the barrier property may not be exhibited. When the average film thickness exceeds 10 μm, cracks are likely to occur or the film is transparent due to coloring at high temperatures. Sexuality may be lost. On the other hand, when the average film thickness is in the preferred range, it is advantageous in terms of the coverage of the protective film, cracklessness and transparency.

  The mass (M1) derived from a polymer containing the vinyl alcohol as a structural unit in the metal electrode protective film, the mass (M1) derived from a polymer containing the vinyl alcohol as a structural unit, and the alkoxysilane The ratio [M1 / (M1 + M2)] of the total mass (M1 + M2) of the mass (M2) of the solid content derived from the compound is not particularly limited and can be appropriately selected according to the purpose, but 0.2 or more 0.9 or less is preferable, and 0.6 or more and 0.8 or less is more preferable. If the ratio [M1 / (M1 + M2)] is less than 0.2, cracks may occur in the protective film. If the ratio [M1 / (M1 + M2)] exceeds 0.9, the barrier property against the increase in humidity may be deteriorated, or at a high temperature. The coloring may become prominent. On the other hand, when the ratio [M1 / (M1 + M2)] is within the preferable range, it is advantageous in terms of cracklessness, retention of barrier properties against humidity, and transparency at high temperatures.

<< Method for Producing Metal Electrode Protective Film >>
The method for producing the metal electrode protective film comprises the kit for producing the metal electrode protective film or the composition for producing the metal electrode protective film (the content of the alkoxysilane compound and the alkoxysilane is 0.0001 molar equivalent or more. A solution containing an acid catalyst having a 005 molar equivalent or less and a polymer containing at least vinyl alcohol as a structural unit) and curing to form a metal electrode protective film.

-Process for forming metal electrode protective film-
The step of forming the metal electrode protective film is performed by enclosing or applying to a target site using a dehydration condensate obtained by mixing the metal electrode protective film preparation kit or the metal electrode protective film preparation composition. Coating means for curing, and curing means for curing the coated dehydrated condensate.

--Coating means--
The coating means is means for encapsulating or applying to a target site using a dehydration condensate obtained by mixing the metal electrode protective film preparation kit or the metal electrode protective film preparation composition.

  The method for mixing the metal electrode protective film preparation kit or the metal electrode protective film preparation composition is not particularly limited and can be appropriately selected according to the purpose. For example, in the case of a two-component type, A method in which the liquid A and the liquid B are collectively charged into a reaction vessel and mixed, and in the case of the three-liquid type, a method in which the liquid A, the liquid B and the liquid C are charged in a reaction vessel and mixed. In the case of the one-pack type, the method for preparing the metal electrode protective film preparation composition in a reaction vessel in a lump and mixing, the method of mixing while adding the other liquid to one liquid intermittently or continuously, etc. Is mentioned. The mixing can be performed using, for example, a mixer (manufactured by Shinky Co., Ltd. Awatori Nertaro), a stirrer, and a stirrer.

The method for coating the dehydration condensate is not particularly limited and can be appropriately selected depending on the purpose. For example, application and / or injection may be performed depending on the shape of the light emitting device to which the dehydration condensate is adapted. And a method of enclosing and applying the solution (see FIG. 2), a method of applying the dehydrated condensate to the surface of the sealing material (see FIG. 5), and the like. And an inkjet method. Specific examples include a coating method by a spray coating method, a dip coating method, a spray coating method, a roll coating method, a spin coating method, and the like.
There is no restriction | limiting in particular as a method of enclosing the said dehydration condensate, According to the objective, it can select suitably, For example, the method of enclosing with an injection needle, a micropipette etc. is mentioned.
There is no restriction | limiting in particular as application | coating thru | or enclosure amount of the said dehydration condensate, Although it can select suitably according to the objective, The quantity added so that it may become the target average film thickness is preferable.

-Curing means-
The curing means is means for curing the coated dehydrated condensate.
The method for curing is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method of curing by air drying and a method of curing by heating.

--- Air-dry ---
There is no restriction | limiting in particular as said air drying, According to the objective, it can select suitably, For example, the method of air-drying with room temperature standing, a dryer etc. is mentioned.

--- Heating ---
There is no restriction | limiting in particular as said heating, According to the objective, it can select suitably, For example, it heats in the 1st heating heated in the area | region of 50 to 100 degreeC, and the area of 100 to 180 degreeC. Second heating.

--First heating--
The first heating is heating of the metal electrode protective film preparation kit or the metal electrode protective film preparation composition in a region of 50 ° C. or higher and lower than 100 ° C., and the alcohol generated by the hydrolysis is removed. Heating to prevent foaming due to residual solvent and dissolved water vapor. The dehydration condensation reaction may be partially advanced by the first heating.

  There is no restriction | limiting in particular as heating temperature in said 1st heating, Although it can select suitably according to the objective, 50 to 100 degreeC is preferable, 60 to 95 degreeC is more preferable, 70 to 95 degreeC is more preferable. A temperature of less than 0C is particularly preferred. When the heating temperature is less than 50 ° C., the solvent or the like does not evaporate sufficiently and curing may be insufficient. When the heating temperature is 100 ° C. or more, the shape of the metal electrode protective film tends to deteriorate, It is easy to produce. Further, the heat energy required for heating is large, which is not preferable from the viewpoint of energy saving, and may increase the cost. On the other hand, when the heating temperature is within the particularly preferable range, it is advantageous in that the solvent is sufficiently evaporated.

  The heating time in the first heating is not generally determined depending on the thickness of the applied or injected dehydrated condensate, but is preferably 10 minutes to 24 hours, more preferably 30 minutes to 12 hours, and more preferably 1 hour to 6 hours. Time is particularly preferred. If the heating time is less than 10 minutes, the solvent or the like may not evaporate sufficiently, and hardness and heat resistance may not be obtained. If the heating time exceeds 24 hours, the thermal energy required for heating increases, and the viewpoint of energy saving This is not preferable and may increase the cost. On the other hand, when the heating time is within the particularly preferable range, it is advantageous in that the solvent is sufficiently evaporated.

--- Second heating-
The second heating is a step of heating in a region of 100 ° C. or higher and 180 ° C. or lower, and is a step for curing the dehydrated condensate. After curing at a low temperature in the first heating, additional curing at a high temperature in the second heating evaporates residual moisture in the film, and internal stress is unlikely to occur in the resulting metal electrode protective film, resulting in cracks. And a metal electrode protective film with reduced peeling is produced.

  There is no restriction | limiting in particular as heating temperature in said 2nd heating, Although it can select suitably according to the objective, 100 to 180 degreeC is preferable, 110 to 150 degreeC is more preferable, 120 to 140 degreeC is more preferable. A temperature of not higher than ° C is particularly preferred. When the heating temperature is less than 100 ° C., evaporation of the solvent may be insufficient. When the heating temperature exceeds 180 ° C., the metal electrode protective film preparation kit or the metal electrode protective film preparation composition is cured when cured. There is a possibility that a member (for example, an LED chip) heated together with an object may be deteriorated by heat. On the other hand, when the heating temperature is within the particularly preferable range, it is advantageous in that internal stress is hardly generated in the obtained metal electrode protective film and cracks and peeling can be prevented.

  There is no restriction | limiting in particular as the heating time in said 2nd heating, Although it can select suitably according to the objective, 10 minutes-24 hours are preferable, 30 minutes-12 hours are more preferable, 1 hour-6 hours Particularly preferred. When the heating time is less than 10 minutes, uneven curing may occur, and when it exceeds 24 hours, the metal electrode protective film may be fragile. On the other hand, when the heating time is within the particularly preferable range, it is advantageous in that internal stress is hardly generated in the obtained metal electrode protective film, and cracks and peeling can be prevented.

<Application>
By using the metal electrode protective film of the present invention, the metal electrode protective film preparation kit or the metal electrode protective film preparation composition is used. Semiconductor light-emitting device that can prevent blackening, has excellent atmospheric stability, and maintains transparency without causing yellowing, cloudiness, etc. while maintaining gas barrier properties. Can be provided.

(Semiconductor light-emitting device)
The semiconductor light emitting device of the present invention has a metal electrode, a semiconductor chip electrically connected to the metal electrode, and the metal electrode protective film that protects at least part of the metal electrode and the semiconductor chip, Furthermore, it has other members, such as a sealing material, as needed.

<Metal electrode protective film>
As the metal electrode protective film, the above metal electrode protective film is used.

<Metal electrode>
There is no restriction | limiting in particular as said metal electrode, Although it can select suitably according to the objective, A silver plating electrode (electrode plated with silver) is cheaper than gold | metal | money, and is excellent in electrical conductivity and a reflectance. This is preferable. As said metal electrode, you may have a form like the metal electrode and reflector 5 shown in FIGS.

<Semiconductor chip>
The semiconductor chip is not particularly limited and may be appropriately selected according to the purpose. Any semiconductor chip that emits light of any wavelength from ultraviolet to infrared may be used. For example, a gallium nitride based semiconductor chip Etc. A commercially available product can be used as the semiconductor chip, and examples of the commercially available product include sapphire and gallium nitride (GaN) blue LED chips (manufactured by Genelite). There is no restriction | limiting in particular as a form of the said semiconductor chip, According to the objective, it can select suitably, For example, as shown in FIGS. 1-6, it fixes to the LED package 2 with the silicone type die bonding paste 3. FIG. The semiconductor chip 4 may have a form connected by a gold bonding wire 1.

  As the semiconductor chip, one mounted in a package can be used together with the metal electrode. The package is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a ceramic material, a circular shape having a circular recess, and the like, and further an inner side of the package. A heat sink may be fitted into the. As the package, a commercially available product can be used. Examples of the commercially available product include KD-LA6F70 and KD-V93B95-B (manufactured by Kyocera Corporation).

<Encapsulant>
There is no restriction | limiting in particular as said sealing material, According to the objective, it can select suitably, For example, although a silicone type resin, an acrylic resin, an epoxy resin etc. are mentioned, the said sealing material and the said metal electrode protection From the viewpoint of good adhesion at the interface with the film, a sealing material composed of terminal silanol group polydimethylsiloxane (PDMS) and tetraethoxysilane (TEOS) is preferable.

(Method for manufacturing semiconductor light emitting device)
The method of manufacturing a semiconductor light emitting device according to the present invention includes the metal electrode, a semiconductor chip electrically connected to the metal electrode, and the metal electrode protective film protecting at least a part of the metal electrode and the semiconductor chip. A method of manufacturing a semiconductor light-emitting device having at least a step of forming the metal electrode protective film, and further including other steps as necessary. These steps may be performed before the semiconductor light emitting device is singulated (diced), or may be performed individually after being mounted on the substrate.

<Process for forming metal electrode protective film>
As the step of forming the metal electrode protective film, the step of forming the metal electrode protective film described above is used.

<Other processes>
Examples of the other steps include a step of molding a sealing material (sealing resin) after enclosing and / or air-drying the metal electrode protective film preparation kit or the metal electrode protective film preparation composition, and the heating step. The process of performing various post-processing as needed with respect to the semiconductor light-emitting device obtained after is mentioned.

Examples of the sealing resin injection method in the step of molding the sealing material include a pressure injection method and an inkjet method. Examples of the application method include a spray coating method, a dip coating method, a roll coating method, Examples include spin coating.
As the post-processing step, for example, a surface treatment step for improving adhesion with the transparent sealing resin (sealing material) portion, a step of forming an antireflection film, and an improvement in light extraction efficiency Examples include a process for producing a fine uneven surface.

  The semiconductor light-emitting device of the present invention can prevent discoloration and blackening of the metal electrode, is excellent in atmospheric stability while maintaining gas barrier properties, and excellent in transparency without causing yellowing, cloudiness, etc. High brightness and long life can be improved.

  Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example.

(Examples 1-16 and Comparative Examples 1-16)
<Formation of metal electrode protective film (two-component type)>
In the examples and comparative examples shown below, the liquid A and the liquid B prepared so that the total mass of the alkoxysilane-derived cured product and the polymer-derived cured product containing vinyl alcohol as a constituent unit are the same amount are protected with metal electrodes. Used as a membrane preparation kit. Moreover, the glass sample for evaluation and the base film sample for evaluation in which a metal electrode protective film is formed by coating a mixture of the liquid A and the liquid B on a base film, glass, and an LED package, followed by heat curing. The LED package sample for evaluation (semiconductor light-emitting device sample for evaluation) was produced.

-Preparation of solution A-
While adding alkoxysilane and 2-propanol shown in Table 1 to a glass vial bottle at 25 ° C. in an atmospheric environment and stirring (300 rpm) using a rotor, the glass vial was filled with water shown in Table 1 using a micropipette. Added to the jar. Furthermore, the acid catalyst shown in Table 1 was added to the said glass vial bottle, and it stirred for 1 hour (300 rpm) using the rotor, and prepared A liquid.

-Preparation of solution B-
A polymer containing the vinyl alcohol shown in Table 1 as a structural unit while adding water and 2-propanol shown in Table 1 to a glass vial bottle at 25 ° C. in an atmospheric environment and stirring (300 rpm) using a rotor. The solution was added to a glass vial with a dropper and stirred for 1 hour (300 rpm) using a rotor to prepare solution B.
In addition, the polymer solution (7 mass%) containing the said vinyl alcohol as a structural unit was prepared in the following procedures. First, 7.28 g of PVA-124C (manufactured by Kuraray Co., Ltd.) was weighed and added to a glass vial. Subsequently, 32.92 g of 2-propanol and 63.71 g of water were added, and the mixture was stirred for 2 hours while heating in an 80 ° C. water bath.

-Mixing of liquid A and liquid B-
The solution B was added to the solution A and stirred for 2 hours (300 rpm) using a rotator to prepare an evaluation glass and an evaluation base film coating material.
Moreover, the coating material of the LED package for evaluation added water and 2-propanol so that the total mass of the cured product derived from alkoxysilane and the cured product derived from polymer containing vinyl alcohol as a constituent unit would be 3% by mass. Then, it obtained by stirring (300 rpm) for 2 hours using a rotor. The mass ratio of water and 2-propanol at that time was 65:35. The coating thickness at the time of drying was 6 μm to 7 μm as a calculated value.

-Preparation of glass samples for evaluation-
Using a glass (Eagle XG, manufactured by Corning) with the surface subjected to oxygen plasma treatment (O ₂ : 70 sccm, 80 W, 60 sec, 100 Pa), the coating material for the evaluation glass was used using an applicator (manufactured by YOSHIMITSU SEIKI). It was applied so that the film thickness was 500 μm in a wet state. The glass coated with the evaluation glass coating material is placed in an oven, heated at 85 ° C. for 2 hours, and then heated at 150 ° C. for 4 hours, whereby an evaluation glass sample having a metal electrode protective film formed thereon is obtained. Produced.

-Preparation of evaluation base film sample-
A base film (ZEONOR film, manufactured by Nippon Zeon Co., Ltd.) whose surface was subjected to oxygen plasma treatment (O ₂ : 70 sccm, 80 W, 60 sec, 100 Pa) was coated with a coating material for the evaluation base film using a wireless bar equivalent to # 12 ( D-bar, manufactured by OSG) was applied so that the film thickness was 27.5 μm in a wet state. The base film coated with the evaluation base film coating material was placed in an oven and heated at 120 ° C. for 30 minutes to prepare an evaluation base film sample on which a metal electrode protective film was formed.

-Preparation of LED package samples for evaluation-
A commercially available silver-plated electrode LED package (KD-LA9R48, manufactured by Kyocera Corporation) was used as the LED package for mounting the light emitting element, and a commercially available 610 μm square blue LED chip (B2424CCD0, manufactured by Genelites) was used as the light emitting element. . The light emitting element and the package were fixed with a silicone die bond material and then connected with a gold bonding wire (see FIG. 1).
The coating material of the LED package for evaluation is applied to the recess of the LED package on which the light emitting element is mounted, and the liquid crystal when the LED package is viewed from the horizontal direction using the tip of a micropipette chip for 1,000 μL. An appropriate amount was dropped (potted) so that the surface was the same height as the upper surface of the package (see FIG. 2). Then, after leaving at room temperature for 30 minutes, the LED package coated with the coating material for the LED package for evaluation is placed in an oven, heated at 85 ° C. for 2 hours, and then heated at 150 ° C. for 4 hours to protect the metal electrode. An LED package sample for evaluation (semiconductor light-emitting device sample for evaluation) on which a film was formed was produced (see FIG. 3).

(Comparative Example 17)
<Metal electrode protective film not formed (other company's two-component silicone resin only)>
Using a commercially available two-component thermosetting resin (silicone resin) (KER-2500 manufactured by Shin-Etsu Chemical Co., Ltd.), a mixture of liquid A and liquid B in KER-2500 of the same mass was used for various evaluation glasses and evaluations. As a coating material for a base film and an LED package for evaluation, the base film, the glass, and the LED package were coated and then heat-cured at 100 ° C. for 1 hour and at 150 ° C. for 5 hours. Similarly, an evaluation glass sample on which a resin film was formed, an evaluation base film sample, and an evaluation LED package sample (evaluation semiconductor light-emitting device sample) were produced.

(Comparative Example 18)
<Formation of metal electrode protective film (only B liquid)>
An evaluation glass sample in which a metal electrode protective film was formed in the same manner as in Example 1 except that the coating material for the evaluation glass, the evaluation base film, and the evaluation LED package was prepared using only the liquid B. An evaluation base film sample and an evaluation LED package sample (evaluation semiconductor light-emitting device sample) were prepared.

(Comparative Example 19)
<Metal electrode protective film not formed, sealing resin not formed>
Only the LED package sample for evaluation (semiconductor light-emitting device sample for evaluation) was produced.

In Table 1, TEOS represents tetraethoxysilane, TMOS represents tetramethoxysilane, and PVA represents a polymer solution containing vinyl alcohol as a structural unit.

(Examples 17-19 and Comparative Examples 20-21)
<Formation of metal electrode protective film (3 liquid type)>
In the examples and comparative examples shown below, A liquid, B liquid, and C liquid prepared so that the total mass of the alkoxysilane-derived cured product and the polymer-derived cured product containing vinyl alcohol as a constituent unit is the same amount. Was used as a metal electrode protective film preparation kit. A glass sample for evaluation having a metal electrode protective film formed by coating a mixture of the liquid A, the liquid B, and the liquid C on a base film, glass, and an LED package, followed by heat curing. A base film sample for evaluation and an LED package sample for evaluation (semiconductor light-emitting device sample for evaluation) were produced.

-Preparation of solution A-
While adding alkoxysilane and 2-propanol shown in Table 2 to a glass vial bottle at 25 ° C. in an atmospheric environment and stirring (300 rpm) using a rotor, the glass vial was filled with water shown in Table 2 using a micropipette. After adding to a bottle, it stirred for 1 hour (300 rpm) using the rotor, and prepared the A liquid.

-Preparation of solution B-
Water, 2-propanol and an acid catalyst shown in Table 2 were added to a glass vial bottle at 25 ° C. in an atmospheric environment, and stirred for 1 hour (300 rpm) using a rotor to prepare solution B.

-Preparation of solution C-
A polymer solution containing the vinyl alcohol shown in Table 2 as a constituent unit was weighed, added to a glass vial, and stirred for 1 hour (300 rpm) using a rotor to prepare solution C. In addition, the polymer solution (7 mass%) containing the said vinyl alcohol as a structural unit was prepared with the following procedures. First, 7.28 g of PVA-124C (manufactured by Kuraray Co., Ltd.) was weighed and added to a glass vial. Subsequently, 32.92 g of 2-propanol and 63.71 g of water were added, and the mixture was stirred for 2 hours while heating in an 80 ° C. water bath.

-Mixing of liquid A, liquid B and liquid C-
The liquid B is added to the liquid A, stirred for 1 hour (300 rpm) using a rotor, then the liquid C is added and stirred for 2 hours (300 rpm), and the evaluation glass and the evaluation base film are mixed. A coating material was prepared.
Moreover, water and 2-propanol were added to the coating material of the evaluation LED package so that the total mass of the cured product derived from alkoxysilane and the polymer-derived cured product containing vinyl alcohol as a structural unit was 1% by mass. Thereafter, it was obtained by stirring (300 rpm) for 2 hours. The mass ratio of water and 2-propanol at that time was 65:35.

-Preparation of evaluation glass sample, evaluation base film sample, and evaluation LED package sample-
An evaluation glass sample on which a metal electrode protective film was formed and evaluated in the same manner as in Example 1 except that the three-component glass for evaluation, the base film for evaluation, and the coating material for the LED package for evaluation were used. A base film sample for evaluation and an LED package sample for evaluation (semiconductor light-emitting device sample for evaluation) were produced.

In Table 2, TEOS represents tetraethoxysilane, and PVA represents a polymer solution containing vinyl alcohol as a structural unit.

(Evaluation)
Examples About the glass samples for evaluation, the base film samples for evaluation, and the LED package samples for evaluation (semiconductor light-emitting device samples for evaluation) produced in Examples 1 to 19 and Comparative Examples 1 to 21, Characteristics were evaluated. The results are shown in Table 3.

<Transparency>
The transparency of the liquid was evaluated 1 hour after preparation of the liquid A and 2 hours after mixing the liquid A and the liquid B.
[Evaluation]
○: Transparent ×: Cloudiness or phase separation (including some gelled)

<Heat resistance>
The glass sample for evaluation was heated in an oven at 170 ° C. for 12 hours to evaluate heat resistance. For the evaluation, an ultraviolet-visible spectroscope (manufactured by JASCO Corporation, V-560) was used, and after measuring the absorbance at a wavelength of 450 nm, the film thickness was measured with a stylus-type step gauge (Dektak 150 Veeco), and per 1 μm. The transmittance was calculated.
[Evaluation]
◎: 95% or more ○: 80% or more and less than 95% △: 70% or more and less than 80% ×: less than 70%

<Gas barrier properties>
The base film sample for evaluation was evaluated for oxygen permeability with an oxygen permeability measuring device (registered trademark “OX-TRAN” 2/21 manufactured by MOCON).
[Evaluation]
○: Less than 0.3 cc / m ² · day · atm ×: Impossible to measure (equipment overflow, 300 cc / m ² · day · atm or more)

<LED characteristics>
-Initial light emission amount-
The LED package sample for evaluation was measured for an intensity of 450 nm when a current of 10 mA was applied with an external quantum efficiency measurement device (C9920-12, manufactured by Hamamatsu Photonics). In addition, the intensity | strength without the coating material of the said LED package for evaluation was normalized as 1. FIG.
[Evaluation]
◎: 0.95 or more ○: 0.8 or more and less than 0.95
Δ: 0.7 or more and less than 0.8 ×: less than 0.7

-Heat resistance during mounting-
The LED package sample for evaluation was heated in a 170 ° C. oven for 12 hours after the initial light emission amount measurement, and the heat resistance was evaluated. For the evaluation, the external quantum efficiency measuring device was used to measure the strength of each sample after heating. The initial light emission amount in each sample was normalized as 1, and the light emission amount in each sample after heating was calculated.
[Evaluation]
◎: 0.95 or more ○: 0.8 or more and less than 0.95 △: 0.7 or more and less than 0.8 ×: Less than 0.7

−Sulfur barrier property during mounting−
The LED package sample for evaluation was heated at 80 ° C. for 15 hours using an oven (DK340S (volume 20 L), manufactured by Yamato Kagaku Co., Ltd.) in which 6 g of sulfur powder was encapsulated after the initial light emission amount was measured. Was evaluated. For the evaluation, the external quantum efficiency measuring device was used to measure the strength of each sample after heating. The initial light emission amount in each sample was normalized as 1, and the light emission amount in each sample after heating was calculated.
[Evaluation]
○: 0.8 or more △: 0.6 or more and less than 0.8 ×: Less than 0.6

From the above, the metal electrode protective film produced using the metal electrode protective film production kit in the example can prevent discoloration and blackening of the metal electrode, and is excellent in atmospheric stability while maintaining gas barrier properties. It was found that the film was excellent in transparency without causing yellowing or cloudiness with time. It has also been found that the use of the metal electrode protective film as a protective film for a metal electrode plate of a semiconductor light emitting device makes it possible to increase the brightness and life of the semiconductor light emitting device.
In addition to the two-component and three-component metal electrode protective film preparation kits described above, even when a one-component metal electrode protective film preparation composition is used, the content of the acid catalyst is not limited to the alkoxysilane. It has been found that the same result can be obtained if it is 0.0001 molar equivalent or more and 0.005 molar equivalent or less with respect to the compound.

  The metal electrode protective film formed using the kit for preparing a metal electrode protective film of the present invention is particularly useful as a protective film for a metal electrode plate in a semiconductor light-emitting device, and can prevent discoloration and blackening of the metal electrode. In order to maintain excellent properties, it has excellent atmospheric stability, transparency that does not cause yellowing over time, white turbidity, etc., so display materials, optical recording medium materials, optical equipment materials, optical component materials, optical fiber materials, It can also be suitably used for applications such as optical / electronic functional organic materials and semiconductor integrated circuit peripheral materials.

DESCRIPTION OF SYMBOLS 1 Bonding wire 2 LED package 3 Die bonding paste 4 Semiconductor chip 5 Metal electrode and reflector 6 Metal electrode protective film preparation kit 7 Metal electrode protective film 8 Sealing material

Claims (10)

A liquid containing at least an alkoxysilane compound and an acid catalyst having a content with respect to the alkoxysilane of 0.0001 molar equivalent or more and 0.005 molar equivalent or less,
B liquid containing a polymer containing at least vinyl alcohol as a structural unit,
A kit for preparing a metal electrode protective film for mixing and using the liquid A and the liquid B. A liquid containing at least an alkoxysilane compound;
B liquid containing a polymer containing at least vinyl alcohol as a structural unit;
C liquid containing at least an acid catalyst,
Metal electrode protection for using the liquid A, the liquid B and the liquid C by mixing them so that the acid catalyst is 0.0001 molar equivalent or more and 0.005 molar equivalent or less with respect to the alkoxysilane compound. Membrane preparation kit.   The metal electrode protective film preparation kit according to claim 1, wherein the content of the acid catalyst with respect to the alkoxysilane compound is 0.0001 molar equivalent or more and 0.001 molar equivalent or less.   The metal electrode protective film preparation kit according to any one of claims 1 to 3, wherein the acid catalyst is at least one of hydrochloric acid and acetic acid.   The metal electrode protective film preparation kit according to any one of claims 1 to 4, wherein the metal electrode is an electrode containing silver.   A metal electrode protective film, which is formed using the metal electrode protective film preparation kit according to claim 1.   The mass (M1) derived from a polymer containing vinyl alcohol as a structural unit, the mass (M1) derived from a polymer containing vinyl alcohol as a structural unit, and the mass of a solid derived from an alkoxysilane compound (M1) The metal electrode protective film according to claim 6, wherein a ratio [M1 / (M1 + M2)] of the total mass (M1 + M2) of M2) is 0.2 to 0.9.   An alkoxysilane compound, an acid catalyst having a content with respect to the alkoxysilane of 0.0001 molar equivalent or more and 0.005 molar equivalent or less, and a polymer containing at least vinyl alcohol as a constituent unit are mixed and cured, and a metal electrode The manufacturing method of the metal electrode protective film characterized by including the process of forming a protective film. A semiconductor light emitting device manufacturing method comprising: a metal electrode; a semiconductor chip electrically connected to the metal electrode; and a metal electrode protective film that protects at least a part of the metal electrode and the semiconductor chip,
A method for manufacturing a semiconductor light-emitting device, comprising the steps of mixing and curing the metal electrode protective film preparation kit according to claim 1 to form the metal electrode protective film. A semiconductor light emitting device comprising: a metal electrode; a semiconductor chip electrically connected to the metal electrode; and a metal electrode protective film protecting at least a part of the metal electrode and the semiconductor chip,
A semiconductor light emitting device, wherein the metal electrode protective film is the metal electrode protective film according to claim 6.