JP2001332222A - Glass for electric bulb, and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide glass for electric bulb with general glass material and superior wear resistance, without using such a special glass as crystallized glass or reinforced glass, and to provide its manufacturing method. SOLUTION: The glass for electric bulb with a metal oxide film is readily provided, by attaching a composite for metal oxide film with zirconium oxide as a major component on the surface of a base material for the bulb glass and by crystallizing it. This composite has a zirconium component and other metal components. This zirconium component is a salt of zirconium complex or zirconium salt, formed from amino-polycarboxylic acid and a zirconium compound with amine, and the zirconium component is contained by 70 to 98 mol% converted in terms of zirconium oxide in the whole metallic components of this composite. It is obtained by using a composite such as the glass for electric bulb with superior chemical stability, heat stability and mechanical strength.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass for a bulb and a method for producing the same. More specifically, the present invention relates to a glass for an electric bulb reinforced with a metal oxide thin film containing zirconium oxide as a main component, which is excellent in abrasion resistance, and a method for producing the glass.

[0002]

2. Description of the Related Art In general, lighting fixtures such as fluorescent lamps and incandescent lamps are widely used in various applications such as general lighting, street lights, flashlights, and automobile lights. They are,
They are collectively called light bulbs or lamps. The bulb emits light through a fluorescent tube in the case of a fluorescent lamp and through a bulb in the case of an incandescent lamp. This fluorescent tube or bulb is
It is formed of a glass material such as hard glass such as borosilicate glass and aluminosilicate glass or soft glass such as soda lime glass and lead glass.

[0003] These light bulbs are in a situation where they are scratched in the room, such as when dust is swept away with a brush during cleaning or the surface of the light bulb is wiped with a cloth or the like. The surface appearance of the bulb is impaired due to the increase of the fine scratches. In addition, in the outdoor, for example, fine sand and dust caused by the wind and rain, pebbles rolled up by a gust such as a typhoon, and a part of a natural tree are exposed to an environment where various damages such as abrasion or destruction are caused by contact. . In addition, when replacing these bulbs, indoors and outdoors, they may be damaged by impact such as dropping.

Conventionally, various coating agents have been proposed to make glass materials used for fluorescent tubes, bulbs and the like less susceptible to the above-mentioned damage, and a surface having high abrasion resistance has been proposed. Cured glass has also been proposed.

As a coating agent, for example, a coating agent containing colloidal silica by adding silica sol has been proposed. However, the film obtained by applying and curing this coating agent generates interference fringes,
There is a problem that the appearance of the glass material surface is impaired. Further, a coating agent containing colloidal tin oxide by adding a tin oxide sol has been proposed. However, tin oxide sols have low compatibility with organosilicon compounds such as silane coupling agents and silicon-containing substances such as hydrolysates, and have poor stability. There is a problem that the resulting film has insufficient water resistance. Further, a coating agent containing colloidal titanium oxide by adding a titanium oxide sol has been proposed. However, titanium oxide sol has low compatibility with organosilicon compounds such as silane coupling agents and silicon-containing substances such as hydrolysates, and also has poor stability. The resulting film has problems that the water resistance is not sufficient and the color changes to blue upon irradiation with ultraviolet rays.

On the other hand, crystallized glass and tempered glass have been proposed as surface hardened glass having high abrasion resistance. The crystallized glass is a polycrystal obtained by reheating the glass under controlled conditions and uniformly depositing and growing many fine crystals. The properties (including abrasion resistance) of crystallized glass are determined by the type of precipitated crystals (such as β-quartz and β-spodumene), their size and amount, and the nature of the residual glass phase. These factors are determined by the glass composition and the reheating conditions. When compared with similar compositions, the crystals are stronger than glass, and are less likely to cause scratches that cause damage. Furthermore, when strong crystals precipitate in the glass, the generated cracks do not go straight,
Proceeding around the crystal grains, the crack path is long and the fracture toughness increases.

[0007] The tempered glass suppresses the generation of scratches that cause destruction by applying compressive stress to the glass surface layer. In this case, the fracture toughness increases, but the wear resistance itself does not always increase.

However, the above-mentioned conventional crystallized glass has a large difference in hardness between the precipitated crystal phase and the residual glass phase.
By performing crystallization, a macro increase in hardness can be realized, but there is a problem that wear resistance is reduced. The cause is that, when the crystallized high hardness particles lose their support of the remaining glass phase and detach, the sliding surfaces become extremely rough and promote the progress of wear. Further, with respect to tempered glass, there is a problem that an increase in fracture toughness and an improvement in wear resistance do not always correspond.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to use a general glass without using special glasses such as crystallized glass and tempered glass. An object of the present invention is to provide a glass for a light bulb, which uses a base material and has excellent wear resistance, and a method for producing the same.

[0010]

SUMMARY OF THE INVENTION The present invention is directed to a glass for a light bulb having a metal oxide thin film containing a zirconium component and a metal component other than zirconium on the surface of the lamp glass base material, wherein the thin film comprises: A zirconium complex formed from a polycarboxylic acid and a zirconium compound or a salt of a zirconium salt and an amine, wherein the metal component other than zirconium is a compound containing a metal other than zirconium, and the total metal component of the composition The zirconium component is 70 mol% in terms of zirconium oxide.
Metal component other than the zirconium is contained in an amount of 2 mol% to 30 mol% in terms of an oxide of the metal.
A film derived from the composition, which is contained in a proportion of mol%; a solid solution of zirconium oxide and an oxide of a metal other than zirconium; and the oxide of the metal other than zirconium as a component of the solid solution, It is glass for electric bulbs, which is contained at a ratio of 2 mol% to 30 mol%. The problem described above is solved by using the glass for a light bulb.

[0011] In a preferred embodiment, the zirconium compound is at least one selected from the group consisting of zirconium alkoxides and zirconium salts of organic acids or inorganic acids.

[0012] In a preferred embodiment, the composition is a liquid composition containing the zirconium component and a metal component other than zirconium in a polar solvent.

[0013] In a preferred embodiment, the metal component other than zirconium is at least one selected from the group consisting of compounds containing Y, Mg, Ca, Sc, Ce or Sr.

Further, the present invention provides a method for manufacturing a light-emitting glass substrate, comprising:
A method for producing a bulb glass having a metal oxide thin film containing a zirconium component and a metal component other than zirconium, comprising a zirconium complex formed from an aminopolycarboxylic acid and a zirconium compound or a salt of a zirconium salt and an amine Wherein the metal component other than zirconium is a compound containing a metal other than zirconium, and among all metal components of the composition, the zirconium component is 70 mol% to 98 mol% in terms of zirconium oxide.
And the metal component other than zirconium is contained at a ratio of 2 mol% to 30 mol% in terms of an oxide of the metal. And forming a coating film; and by crystallizing the composition of the coating film formed on the bulb glass substrate, a metal oxide thin film containing a zirconium component and a metal component other than zirconium is formed. Forming.

In a preferred embodiment, the composition is applied onto the bulb glass substrate by spin coating, dip coating, or spray coating.

In a preferred embodiment, the crystallization is performed by heat-treating, light-treating, or chemically treating the bulb glass substrate having the coating.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The lamp glass of the present invention has a metal oxide thin film containing a zirconium component and a metal component other than zirconium on the surface of the bulb glass substrate.

The light bulb glass substrate used in the present invention is a glass used for a light irradiating portion of a lighting device such as a fluorescent lamp, an incandescent lamp, a sodium lamp, a halogen lamp, a helium lamp, a neon lamp, an argon lamp, a xenon lamp. Material. Examples of the lighting equipment include general lighting equipment, street lights, flashlights, and lamps for vehicles such as automobiles and motorcycles. In addition, as a light bulb glass substrate used in those lighting devices, is not particularly limited,
For example, a fluorescent tube and a bulb (irradiation part of an incandescent lamp) may be mentioned.

In the present invention, a metal oxide thin film is formed on the surface of the bulb glass substrate. Here, the surface of the bulb glass substrate may be either the outer surface of the bulb glass substrate or both the outer surface and the inner surface. The thickness of the metal oxide thin film applied to the surface of the bulb glass substrate is not particularly limited, but is preferably from 10 nm to 3 nm.
00 nm, more preferably 40 nm to 140 nm. If the thickness of the metal oxide thin film is less than 10 nm, the effect of wear resistance may not be sufficient. On the other hand, even if the thickness of the metal oxide film exceeds 300 nm, there is a possibility that no remarkable improvement in the effect can be seen. Further, there is a risk that the bulb glass substrate is colored as a result of the interference color of the metal oxide thin film.

The metal oxide thin film is formed by using a composition for forming a metal oxide thin film, which is a strength improving agent for a glass substrate.

The zirconium component contained in the composition for forming a metal oxide thin film used in the present invention comprises, as described above, a zirconium complex or a zirconium salt formed from an aminopolycarboxylic acid and a zirconium compound;
It is a salt with an amine.

The aminopolycarboxylic acids include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
1,2-propanediaminetetraacetic acid, 1,3-propanediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, N, N′-dihydroxyethylethylenediaminediacetic acid, 2-hydroxy-1,3-propanediaminetetraacetic acid, Triethylenetetramine hexaacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, carboxyethyliminodiacetic acid, carboxyethyliminodipropionic acid, iminodiacetic acid, iminodipropionic acid, hydroxyethyliminodiacetic acid, hydroxyethyliminodipropionic acid,
Methoxyethyl iminodiacetic acid, alanine-N, N-diacetate, serine-N, N-diacetate, isoserine-N, N-diacetate, aspartic acid-N, N-diacetate, glutamic acid-N, N-diacetic acid Examples include, but are not limited to, acetic acid.

The zirconium compound is preferably a zirconium alkoxide or a zirconium salt of an organic or inorganic acid. Among these, zirconium alkoxides include tetramethoxy zirconium, tetraethoxy zirconium, tetraisopropoxy zirconium, tetra-n-propoxy zirconium, tetraisobutoxy zirconium, tetra-n-butoxy zirconium, tetra-sec-butoxy zirconium, tetra-t -Butoxy zirconium and the like, and zirconium salts of organic acids or inorganic acids include zirconium acetate, zirconium propionate, zirconium acetylacetonate, zirconium stearate, zirconium oxychloride octahydrate, zirconium oxynitrate dihydrate , Zirconium sulfate, zirconium sulfate tetrahydrate, zirconium oxyacetate, and the like, but are not limited thereto.

Examples of the amine include methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine,
t-butylamine, pentylamine, hexylamine,
Heptylamine, octylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, amylamine, diamylamine, dibutylamine,
Di-sec-butylamine, di-t-butylamine, ethylbutylamine, ethylpropylamine, dihexylamine, dioctylamine, benzylamine, aniline, dimethylaniline, phenylmethylamine, phenylethylamine, aminopyridine, dimethylaminopyridine and the like. Are not limited to these. These may be used alone or in combination of two or more.

The metal component other than zirconium contained in the metal oxide thin film forming composition used in the present invention is a compound containing a metal other than zirconium (hereinafter sometimes referred to as other metal compound). Metals contained in such compounds include yttrium (Y), magnesium (Mg), calcium (Ca), scandium (S
c), cerium (Ce), strontium (Sr) and the like. Alkoxides and carboxylate salts containing such metals are preferably used. Such compounds include trimethoxy yttrium, triethoxy yttrium, tri-isopropoxy yttrium, yttrium carbonate, yttrium acetate, yttrium oxalate,
Dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, diisopropoxy magnesium, diisobutoxy magnesium, dibutoxy magnesium, magnesium acetate, magnesium carbonate, dimethoxy calcium, diethoxy calcium, diisopropoxy calcium, dipropoxy calcium, diisobutoxy calcium, Di-sec-butoxycalcium, di-
t-butoxycalcium, calcium carbonate, calcium acetate, scandium oxalate, scandium hydroxide, cerium carbonate, cerium oxalate, dimethoxystrontium, diethoxystrontium, diisopropoxystrontium, di-n-butoxystrontium, strontium carbonate, oxalic acid Examples include, but are not limited to, strontium and strontium nitrate.

The composition used in the present invention is preferably a liquid composition containing the zirconium component and a metal component other than zirconium in a polar solvent. The salt of a zirconium complex or a zirconium salt, which is the zirconium component, with an amine is formed by the aminopolycarboxylic acid, a zirconium compound, and an amine. Specifically, the liquid composition is a solution obtained by heating the aminopolycarboxylic acid, the zirconium compound, and the amine in a polar solvent (a solution of a zirconium component), and a metal compound other than zirconium. Obtained by mixing. Alternatively, it is also preferable to mix a solution obtained by heating a metal compound other than zirconium together with an aminopolycarboxylic acid and an amine in a polar solvent and a solution of a zirconium component. Alternatively, a metal compound other than zirconium is reacted with an aminopolycarboxylic acid to form a complex or salt of the metal, which is isolated, and obtained by heating the complex or salt and an amine in a polar solvent. A solution may be used. If necessary, an oxidizing agent may be added to these solutions.

As the above-mentioned polar solvent, methanol, ethanol, propanol, isopropanol, butanol, water and the like are preferably used, but not limited thereto. These polar solvents may be used alone or in combination of two or more. The liquid composition of the present invention containing the above components in such a polar solvent is preferably transparent.

In the composition used in the present invention, a zirconium component contains 70 to 9 of all metal components of the composition.
8 mol% (in terms of zirconium oxide) and a metal component other than zirconium in a proportion of 2 to 30 mol% (in terms of oxide of the metal). When the above components are contained at such a ratio, when a metal oxide thin film derived from this composition is prepared, the thin film is formed of a solid solution of zirconium oxide and an oxide of a metal other than zirconium, and Is contained in the thin film as a solid solution component in the above ratio.

If the amount of the metal component other than zirconium is excessive, an oxide of a metal other than zirconium is mixed in the formed thin film without forming a solid solution. A bulb glass substrate having such a thin film has poor chemical stability, thermal stability, and mechanical strength.

If necessary, an oxidizing agent such as hydrogen peroxide or ozone is added to the composition used in the present invention.

The glass for building materials of the present invention is manufactured as follows.

In order to produce a bulb glass having a metal oxide thin film on the surface of a bulb glass substrate by the method of the present invention, first, the obtained polar solvent solution is applied to the outside or outside of the bulb glass substrate. It is applied (applied) to the inside. There is no limitation on the method of application, and when a person skilled in the art produces a metal oxide thin film, an application method appropriately selected and used according to the form and shape of the substrate, for example, a spin coating method, a dip coating method, a spray coating method And the like.

Next, the bulb glass substrate provided with the composition used in the present invention is treated by heat treatment, light treatment, chemical treatment or the like, whereby crystallization of the composition proceeds. As a result, a metal oxide thin film containing zirconium oxide as a main component is formed on the surface of the bulb glass substrate. These processes may be performed alone or in combination of two or more.

The above-mentioned heat treatment is a treatment for giving heat at a temperature higher than the temperature at which the organic matter burns. Preferably, in general,
This is a heat treatment at about 400 ° C. to 1200 ° C., which is performed at a temperature not higher than the heat resistant temperature of the base material to be used.

The light treatment is a treatment such as laser irradiation or ultraviolet irradiation, and is a treatment method which is not affected by the heat resistant temperature of the substrate.

The chemical treatment is a method including a treatment with an acid or a base and a treatment with steam, and a treatment at a relatively low treatment temperature.

The above-mentioned crystallization method is an example, and the present invention is not limited thereto.

The thin film of the glass for a bulb having the metal oxide thin film thus obtained is mainly composed of zirconium oxide, and the oxide of a metal other than zirconium contains 2%.
It is a solid solution contained at a ratio of 30 mol%. Since such a thin film has a stabilized crystal structure, it is excellent in chemical stability, thermal stability, mechanical strength, and the like. This allows the bulb glass to also have excellent wear resistance.

[0039]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Production Example 1) Preparation of a salt (zirconia precursor) of an amine with a metal complex formed from an aminopolycarboxylic acid and a zirconium compound 53.03 g of ethanol and 4.65 g of nitrilotriacetic acid were placed in a 100 ml four-necked flask. While charging and stirring, zirconium-n-butoxide (purity 87%) 10.7
4 g were added dropwise. Subsequently, 3.56 g of butylamine was added dropwise, and the reaction was carried out at reflux temperature for 1 hour. And 40 ℃
After cooling, 3.04 g of 30% aqueous hydrogen peroxide was added dropwise,
The reaction was carried out at the reflux temperature for 1 hour to obtain a red-orange transparent solution (zirconia precursor) containing the title salt. Zirconium (Z) in this zirconia precursor
r) The content was 2.96% by weight.

(Production Example 2) Preparation of a salt of a metal (calcium) compound other than zirconium and a complex of an aminopolycarboxylic acid with an amine (calcia precursor) (1) 300 ion-exchanged water was placed in a 500 ml four-necked flask.
g and heated to 75-80 ° C. Subsequently, after adding 6.31 g of ethylenediaminetetraacetic acid, 3.81 g of calcium acetate monohydrate was slowly added. The dissolution progressed by the addition of calcium acetate, and after a while, it became colorless and transparent. After stirring at 75-80 ° C for 1 hour, ethanol 2 was added.
5 g was slowly added, and the mixture was allowed to cool to room temperature. The precipitated white solid was collected by filtration, washed successively with 10 g of ion-exchanged water and 5 g of ethanol, and dried with a blow dryer at 40 ° C. to obtain calcium ethylenediaminetetraacetate dihydrate. Yield 6.03 g. (2) 5.13 g of the ethylenediaminetetraacetate calcium dihydrate obtained in the item (1) and 62.72 g of ethanol were placed in a 100 ml four-necked flask, and 2.15 g of butylamine was added with stirring. Then, the mixture was stirred at the reflux temperature for 6 hours to obtain a colorless and transparent solution. The calcia precursor thus obtained was subjected to ICP emission analysis (inductively coupled plasma emission analysis). As a result, the calcium (Ca) content in the precursor was 0.80% by weight.
Met. The calcia precursor was stored at room temperature for one year and was stable.

(Production Example 3) Preparation of magnesia precursor In a 100 ml four-necked flask, 58.5 g of ethanol was added.
7.1 g of nitrilotriacetic acid and 4.2 g of magnesium ethoxide were added, and dibutylamine 4.8 was added with stirring.
g was added. This was stirred at the reflux temperature for 4 hours to obtain a magnesia precursor. The magnesia precursor thus obtained was analyzed by ICP emission spectroscopy. As a result, magnesium (M
g) The content was 1.27% by weight. The magnesia precursor was stored at room temperature for one year and was stable.

(Production Example 4) Preparation of Strontia Precursor (1) Synthesis of Sr-EDTA Salt A 500 ml four-necked flask was charged with 250 g of ion-exchanged water, heated to 80 ° C., and treated with strontium acetate hemihydrate 6 0.5 g was added with stirring to obtain a clear solution. Next, 8.8 g of ethylenediaminetetraacetic acid was added, and the mixture was stirred at 80 ° C. for 1 hour, concentrated using an evaporator, and the precipitated crystals were collected by filtration. The crystals thus obtained were washed with ethanol and dried to obtain 11.0 g of strontium ethylenediaminetetraacetate. (2) Synthesis of Strontia Precursor 3.45 g of ethylenediaminetetraacetate strontium salt obtained in (1) and 4.0 g of methanol were placed in a 50 ml eggplant-shaped flask, and butylamine 1.2 was added with stirring.
3 g were added. Then, the solution was refluxed for 2 hours to obtain a transparent solution. ICP emission analysis of the thus obtained strontium precursor revealed that the strontium (Sr) content in the solution was 6.26% by weight. The Strontia precursor was stored at room temperature for one year and was stable.

Comparative Production Example 1 Production of Zirconia Sol by Sol-Gel Method 80.09 g of ethanol was placed in a 100 ml four-necked flask, and zirconium-n-butoxide (8
7%) 8.35 g was dropped, and then 0.52 g of 60% nitric acid.
A mixture of and 0.39 g of ion-exchanged water was added dropwise at room temperature. Then, zirconia sol was obtained by stirring at room temperature for 2 hours. The zirconium (Zr) content in the sol was 1.93% by weight. When this solution was stored at room temperature for 1 day, it became a milky white solution, and a precipitate formed after 3 days.

(Comparative Production Example 2) Production of calcia sol 7.54 g of ethanol and 0.149 g of calcium acetate monohydrate were placed in a 30 ml eggplant-shaped flask, and 0.12 g of 60% nitric acid was added dropwise with stirring. By stirring at room temperature for 1 hour, a colorless and transparent calcia sol was obtained. The calcium (Ca) content in the sol was 0.44% by weight.

Example 1 The zirconia precursor and the calcia precursor prepared in Production Examples 1 and 2 were mixed at the ratio shown in Table 1 to prepare a coating solution. The state of the obtained coating liquid and the state after storage at room temperature for one day (storage stability) were evaluated. ：: No precipitation occurred after storage at room temperature for one day. ×: Precipitation occurred after storage at room temperature for one day. This coating solution was applied on a quartz glass substrate by spin coating, heated from 100 ° C. to 800 ° C. at a rate of 10 ° C./min, and baked at 800 ° C. for 30 minutes. As a result, a glass member whose base material was coated with a thin film mainly composed of zirconium oxide was obtained. This member was evaluated for the following items.

(1) Abrasion Resistance Test The abrasion resistance of the thin film on the substrate was evaluated by a Taber abrasion test. The wear wheel is a Taber type no. Using CS-10F, the force applied to the test specimen of each wear wheel was 4.90 N. The appearance of the film at each rotation speed shown in Table 1 was visually evaluated. ：: The film remains. Δ: The film is peeled by 50% or more. ×: The film is completely peeled. The results of the above evaluation are summarized in Table 1. Table 1 also shows the results of Examples 2 to 6 described below.

Examples 2 to 6 The proportions of the zirconia precursor prepared in Production Example 1 and the calcia precursor, magnesia precursor, and strontium precursor prepared in Production Examples 2 to 4 are shown in Table 1. To prepare a coating solution. Hereinafter, the operation is performed in accordance with Example 1, a coating solution is applied to the base material shown in Table 1, and baked at the firing temperature and time shown in Table 1, and the base material is a thin film containing zirconium oxide as a main component. A coated member was obtained. Evaluation of the obtained member was performed in the same manner as in Example 1.

(Comparative Examples 1 to 3) The zirconia precursor (Preparation Example 1), calcia precursor (Preparation Example 2), zirconium solution (Comparative Coating Solution 1), and calcium solution (Comparative Coating Solution 2) prepared above were prepared. Either one or two or more were mixed at a ratio shown in Table 2 to prepare a coating solution. Hereinafter, the operation is performed in accordance with Example 1, the coating liquid is applied on the base material shown in Table 2, and baked at the firing temperature and time shown in Table 2, and the base material is a thin film containing zirconium oxide as a main component. A coated member was obtained. Evaluation of the obtained member was performed in the same manner as in Example 1.

[0050]

[Table 1]

[0051]

[Table 2]

As is clear from Tables 1 and 2, the coating solutions of Examples 1 to 6 are transparent and do not precipitate even after storage for one day. On the other hand, although the coating solution of Comparative Example 1 was transparent at the time of preparation, it was found that if it was left at room temperature for 1 day, it became milky white or precipitated and lacked stability.

When the coating solutions of Examples 1 to 6 were stored for a longer period of time, it was clear that no change was observed even after storage for one year.

As a result of the abrasion resistance test, Examples 1 to 6
It can be seen that the member having sufficient abrasion resistance. In contrast, a member having a thin film formed by the sol-gel method of Comparative Example 1, a member having a thin film containing a single crystal of Comparative Example 2,
It can be seen that the member having a zirconium oxide thin film containing excessive calcium oxide of Comparative Example 3 lacks abrasion resistance.

(Example 7) In the same manner as in Example 1 except that the quartz glass substrate used in Example 1 was replaced with a glass substrate molded for a 60 W white light bulb, the outside of the glass substrate was changed. A metal oxide thin film is formed on the surface. When the obtained glass for electric bulbs is evaluated in the same manner as described above, it is shown that the glass has excellent strength and abrasion resistance.

[0056]

According to the present invention, excellent mechanical strength and wear resistance are provided. The glass for a light bulb of the present invention has more chemical stability and thermal stability than a metal oxide thin film member containing zirconium oxide as a main component produced by a sol-gel method, which is said to provide a uniform film. Excellent mechanical strength. This allows the glass for a light bulb to also have excellent wear resistance.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Yoshiaki Sakashita 5-41 Senmon, Itami-shi, Hyogo Teikoku Chemical Industry Co., Ltd. Itami Plant (72) Inventor Mitsumi Sato 2-29 Bessho, Hachioji-shi, Tokyo 4 Estrase Nagaike −501 (72) Inventor Riichi Nishiide 2-21-5 Honcho, Koriyama-shi, Fukushima Prefecture First Palace III 307

Claims (7)

[Claims] 1. A glass for a light bulb having a metal oxide thin film containing a zirconium component and a metal component other than zirconium on a surface of a lamp glass base material, wherein the thin film comprises: an aminopolycarboxylic acid and a zirconium compound. A zirconium complex or a salt of a zirconium salt and an amine to be formed, wherein the metal component other than zirconium is a compound containing a metal other than zirconium, and among the total metal components of the composition, the zirconium component is zirconium oxide. A film derived from a composition, which is contained at a ratio of 70 mol% to 98 mol% in terms of conversion and a metal component other than the zirconium is contained at a ratio of 2 mol% to 30 mol% in terms of an oxide of the metal. A solid solution of zirconium oxide and an oxide of a metal other than zirconium; and an oxide of a metal other than zirconium As a component of the solid solution, is contained at 2 mol% to 30 mol%, the glass bulb. 2. The glass for an electric lamp according to claim 1, wherein the zirconium compound is at least one selected from the group consisting of zirconium alkoxides and zirconium salts of organic acids or inorganic acids. 3. The glass for a light bulb according to claim 1, wherein the composition is a liquid composition containing the zirconium component and a metal component other than zirconium in a polar solvent. 4. The metal component other than zirconium,
The bulb glass according to any one of claims 1 to 3, wherein the glass is at least one selected from the group consisting of compounds containing Y, Mg, Ca, Sc, Ce, or Sr. 5. A method for producing a glass for a light bulb having a metal oxide thin film containing a zirconium component and a metal component other than zirconium on the surface of the bulb glass base material, comprising: an aminopolycarboxylic acid and a zirconium compound. A zirconium complex or a salt of a zirconium salt and an amine, wherein the metal component other than zirconium is a compound containing a metal other than zirconium, and among the total metal components of the composition, the zirconium component is converted to zirconium oxide. And a metal component other than the zirconium in a ratio of 2 mol% to 30 mol% in terms of an oxide of the metal. Applied to the outside or outside and inside,
Forming a coating film; and forming a metal oxide thin film containing a zirconium component and a metal component other than zirconium by crystallizing the composition of the coating film formed on the bulb glass substrate. A method comprising: 6. The method according to claim 5, wherein the composition is applied on the bulb glass substrate by a spin coating method, a dip coating method, or a spray coating method. 7. The method according to claim 5, wherein the crystallization is performed by heat-treating, light-treating, or chemically treating the bulb glass substrate having the coating.