JP3153056B2 - Staining agent for fog lamp and method for producing fog lamp lens or glass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colorant for a vehicle fog lamp and a method for producing a colorant for obtaining chromaticity within European standards, and a method for producing a fog lamp lens using the colorant.

[0002]

2. Description of the Related Art Conventionally, as a glass used for a fog lamp, a color glass obtained by mixing a coloring agent at the time of glass molding or a glass obtained by applying an enamel coat or a vapor-deposited film has been used.

[0003] However, colored glass tends to have a variation in color, so that the productivity is extremely poor, and cadmium used for coloring also has an adverse effect on human bodies and the like. Enamel-coated glass has poor water resistance, and glass coated with a vapor-deposited film has a drawback that the color of reflected light becomes pale and causes a problem.

Therefore, recently, a method for exchanging alkali ions on the surface of a glass material with copper ions and coloring the glass material yellow has been proposed for a glass for fog lamps. A paste containing copper ions is applied to the glass surface, and a liquid of the paste is applied. After removing a portion by heating at 150 ° C. for 10 minutes,
It was baked at a temperature of 0 ° C. for 80 minutes to give a color that was within the specification.

[0005]

However, when only the copper ions are ion-exchanged with the alkali ions on the glass surface as described above, there are the following disadvantages.

[0006] Unless it is fired at a temperature of 1.580 to 600 ° C, it is impossible to obtain a color that meets the standard.

Since the glass is fired at a temperature of 2.580 to 600 ° C., the surface of the glass is deteriorated, and the glass is clouded.

The present invention has been made in view of the above circumstances, and has as its object to lower the firing temperature and obtain a good surface after ion exchange.

[0009]

SUMMARY OF THE INVENTION In order to solve the problems, the present invention provides 10 to 65% by weight of copper salt and 10 to 50% by weight.
Alkali metal sulfate and 5 to 60% by weight of chromium oxide
And a powder obtained by mixing 3 to 10% by weight of a silver salt with an organic solvent.
A mixing agent with a kneading oil such as
You.

Also, 10 to 65% by weight of copper salt and 10 to 5 %
A step of mixing 0% by weight of an alkali metal sulfate, 5 to 60% by weight of chromium oxide and 3 to 10% by weight of a silver salt, wet-milling and drying to obtain a powder having a uniform particle size; This is a method for producing a staining agent, comprising: a step of kneading a kneading oil such as a solvent to form a paste; a step of allowing the mixture to stand for a predetermined time after kneading; and a step of kneading the left paste again.

A step of applying the stain agent to the lens or glass, a step of drying the kneading oil of the stain agent applied to the lens or glass, and a step of baking the lens or glass after drying and gradually cooling the lens or glass. And a step of washing and drying the lens or glass.

[0012]

[Function] By containing a copper salt and a silver salt, it is possible to obtain a yellow color which falls within the specification when heated, and by containing an alkali metal sulfate, an ion of an alkali ion and a copper ion in glass can be obtained. Exchange can be promoted, and by containing chromium oxide, the dispersibility of the contained material can be improved and uneven coloring after firing can be prevented.
Further, by mixing the kneading oil, the performance of applying the mixture of the above substances to the substrate is improved.

The most important feature of the present stain agent is that chromium oxide is added. The reason is that it is possible to improve the dispersibility of the substance containing the stain agent and prevent uneven coloring after firing. Although the basis for this is not clear, chromium oxide is softer and easier to pulverize than copper salts, alkali metal salts and silver salts. Therefore, when these components are mixed and pulverized, the particles of chromium oxide become the finest. In addition, since chromium oxide is easily compatible with the kneading oil, the chromium oxide tends to be uniformly dispersed in the kneading oil. Due to the properties of these chromium oxides, when the above-ground components and the kneading oil are mixed, the chromium oxide particles uniformly dispersed in the kneading oil enter between the other component particle groups. It is presumed that the contained material is uniformly dispersed in the mixture.

Next, the mixture of copper salt, alkali metal sulfate, and chromium oxide is wet-pulverized to reduce the particle size, and by uniforming the particle size, the contents are uniformly dispersed in the paste. When the mixture is left for a certain time after kneading, the silver salt can be adapted to the paste.

Here, the content of each substance will be described. Percentages used herein mean weight percent.

The copper salt is desirably contained in an amount of 10 to 65%. This is because if the content of the copper salt is less than 10%, ion exchange into the glass is insufficient and coloring becomes difficult, and if it exceeds 65%, the content of other components is reduced, resulting in unevenness after coloring.

The silver salt is desirably contained at 3 to 10% . This is because if the amount of silver salt is less than 3%, it is impossible to produce a color that can be within the standard, and if it exceeds 10%, the color is too dark to be within the standard.

It is desirable that the content of the alkali metal sulfate is 10 to 50%. This is because if the content of the alkali metal sulfate is less than 10%, ion exchange cannot be promoted, and if the content exceeds 50%, the alkali roughens the glass surface and causes cloudiness during firing.

Chromium oxide is desirably contained at 5 to 60%. This is because if the content of chromium oxide is less than 5%, the contained material cannot be uniformly dispersed, and if it exceeds 60%, silver ions are oxidized and the color after coloring becomes brown.

[0020]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described with reference to FIGS.

The stain agent for fog lamps of the present invention comprises a kneading oil such as a copper salt, an alkali metal sulfate, chromium oxide, and an organic solvent, and a silver salt. Hereinafter, these constituent substances will be described.

Copper salt: As the copper salt, copper sulfate, copper sulfide, copper oxide, copper chloride, copper nitrate and the like can be used. Among them, copper sulfate is excellent in coloring. Because, the sulfate ion (SO ₄
^-2 ) is to facilitate replacement of alkali ions near the glass surface with copper ions. In addition, since the above-mentioned copper salt is subjected to a heat treatment at the time of coloring, it may be an anhydride or a hydrate.

The mixing amount of the copper salt is 10 to 65 in terms of anhydride.
%, And the reasons for limitation are as follows. When the mixing amount is less than 10%, coloring becomes difficult because the amount of copper ions is small. On the other hand, when the mixing amount is more than 65%, the amount of the other mixture becomes small, and coloring unevenness occurs after coloring.

Alkali metal sulfate: As the alkali metal sulfate, sodium sulfate, sodium thiosulfate, potassium sulfate, potassium hydrogen sulfite, potassium disulfite, potassium disulfate, etc. can be used. Is excellent. The above-mentioned alkali metal sulfate has excellent adhesion to the glass surface and promotes exchange of alkali ions and copper ions.

The mixing amount of the alkali metal sulfate is 10 to 5
It is in the range of 0%, and the reasons for limitation are as follows. 10%
When the mixing amount is smaller, ion exchange becomes difficult to be promoted. Conversely, when the mixing amount is more than 50%, a large amount of alkali ions is contained, so that the surface of the glass becomes rough and causes cloudiness.

Chromium oxide: Mixing chromium oxide makes the mixture smooth and improves the dispersibility of the mixture when the mixture is made into a paste. Thereby, since the coating performance is improved, the paste can be uniformly applied to the glass surface, and color unevenness is prevented. Even when screen printing is performed using the paste, the screen is not clogged.

Further, since the viscosity of the paste can be easily adjusted, the thickness of the applied paste can be adjusted. Because the degree of coloring due to staining is related to the thickness of the paste applied,
By adjusting the thickness of the paste applied, the color tone can be controlled. At that time, when alumina, zircon, kaolin, loess, zinc oxide, etc. are used in combination, the adjusting effect is increased and the finish is beautiful.

The mixing amount of chromium oxide is in the range of 5 to 60%, and the reasons for limitation are as follows. When the mixing amount is less than 5%, the effect of uniformly dispersing the mixture is diminished. Conversely, if the mixing amount is larger than 60%, silver ions are oxidized and the color after coloring becomes brown.

Silver salt: As a silver salt, silver nitrate, silver sulfide, silver chloride, silver acetate, silver sulfate, silver perchlorate and the like can be used. Among them, silver nitrate is excellent in the following points. The above silver salt,
The yellow color created by copper ions can be deepened.

The mixing amount of the silver salt is in the range of 3 to 10 % by weight, and the reasons for the limitation are as follows. When the mixing amount is less than 3% , the glass must be fired at 580 ° C. to 600 ° C., and in this temperature range, the glass surface is whitened, and when the mixing amount is more than 10%, the coloring color is deep. It becomes out of the standard range of the fog lamp too much.

Kneading oil such as an organic solvent: As the kneading oil, terpineol, cellulose, ethylcellosolob, butyl carbitol, pine oil, rosin and the like are mixed and used. Among them, a mixture of terpineol, cellulose, and ethyl cellosolov makes it easier to apply the mixture of the above substances to a glass substrate surface.

Example 1 60 g of anhydrous copper sulfate, 20 g of sodium thiosulfate, 18 g of chromium oxide and 5 g of silver nitrate were mixed with 200 ml of ethanol to form a paste, and the paste was ground in a pot mill for 50 hours. The paste-like substance was dried with a thermostatic drier equipped with a duct facility, and a powder having a particle size of 20 μm or less was obtained through a 100-mesh sieve.

The kneading oil was a mixture of terpineol: cellulose: ethylcellosolob at a ratio of 7: 2: 1. The kneading oil and the powder were kneaded at a ratio of 3: 7 with an automatic kneader for several hours for 5 hours to form a paste. After the kneading, the mixture was allowed to stand for 24 hours to adjust the silver nitrate to the paste, and then kneaded for another 5 hours to obtain a stain agent for fog lamps. Here, by leaving the mixture for 24 hours after the kneading, the silver nitrate adapts to the paste, and the coloring unevenness due to the silver nitrate after firing can be prevented.

The lens used for coloring has a coefficient of thermal expansion of 90 ×
It is made of soda-lime glass of 10 ^-7 / ° C. The staining agent produced by the above method was applied to the flat portion of the lens by an application device. As a condition for this coating, using a 200-mesh screen mask,
It is applied at a rate of 400 to 500 g / m ² .

Next, the kneading oil was dried at 150 ° C. for 10 minutes using a dryer equipped with duct equipment, and the lens coated with the stain agent was baked at 520 ° C. for 20 minutes. Thereafter, the lens was gradually cooled, and the residue on the lens flat portion was removed by washing with water to obtain a fog lamp lens.

FIG. 1 shows the spectral transmittance of the lens manufactured by this process. The transmittance is about 90% at a wavelength of 800 nm, and the transmittance also becomes arcuate as the wavelength becomes shorter. The transmittance decreases to about 30% near the wavelength of 500 nm, and shows the lowest transmittance of about 5% near the wavelength of 420 nm.

FIG. 2 shows a chromaticity diagram according to JIS.
The standard is the range enclosed by the straight line shown below.

Y = 1.290x-0.100, y = -x
+0.992, y = 0.580x + 0.138, y =
0.440, y = -x + 0.940 The European standard is a range surrounded by the following linear equation.

Y = 1.290x-0.100, y = -x
+0.992, y = 0.580x + 0.138, y = −
x + 0.966 The above lens has X = 0.5233, Y = 0.4440, which is within the range of the European standard.

Example 2 In this example, a dipping liquid was prepared by mixing a stain agent prepared in the same manner as in Example 1 and ethyl cellosolob at a weight ratio of 2: 1. Using this dipping solution, a cap capable of containing an electric bulb was dipped in the dipping solution for several seconds to apply a stain to the cap.

Next, drying, baking and washing with water were performed in the same manner as in Example 1 to color the cap. The chromaticity at this time is
X = 0.5268, Y = 0.4450, and this coloring shown in FIG. 2 also satisfied the European standard.

(Other Embodiments) Here, Embodiment 3 and
Example 4 will be described. The manufacturing method, the application method, and the coloring method of the stain agent are the same as those in Example 1. Hereinafter, the mixing amounts of the respective compositions are shown in Table 1.

[0043]

[Table 1] These chromaticity of each embodiment as shown in FIG. 2, Example 3
Then, X = 0.5204, Y = 0.4429, Example 4
Then, X = 0.5207 and Y = 0.451. All of these chromaticities satisfied European standards.

[0044]

According to the present invention, the sintering temperature can be lowered from the conventional 580 ° C. to 520 ° C. by mixing the silver salt into the stain agent, so that the deterioration of the glass surface and the cloudiness can be prevented. Can be suppressed. By mixing the chromium oxide into the stain agent, the mixed substance in the stain agent is uniformly dispersed, and the screen printing is performed so that the stain agent is applied evenly and can be uniformly colored without color unevenness.

[Brief description of the drawings]

FIG. 1 is a diagram showing a spectral transmittance of one embodiment of the present invention.

FIG. 2 is a diagram illustrating chromaticity according to an embodiment of the present invention.

FIG. 3 is a conceptual diagram illustrating a method of applying a stain agent according to another embodiment of the present invention.

[Description of Signs ] 1 ... Spectral transmittance curve, 2 ... y = 1.290x-0.10.
0, 3 ... y = -x + 0.992, 4 ... y = 0.580x
+0.138, 5 ... y = 0.440, 6 ... y = -x +
0.940, 7 ... y = -x + 0.966, 8 ... Example 1
Chromaticity of 9, 9 Chromaticity of Example 2, 10 Chromaticity of Example 3,
11 Chromaticity of Example 4 14 Cap 15 Dippi
Liquid

Claims (3)

(57) [Claims] 1 to 10% by weight of a copper salt;
Wt% alkali metal sulfate and 5-60 wt% oxidation
Powder mixed with chromium and 3 to 10% by weight of silver salt;
It is characterized by mixing with kneading oil such as organic solvent
Staining agent for fog lights. 2. 10 to 65% by weight of copper salt and 10 to 50 % by weight
% Of alkali metal sulfate, 5 to 60% by weight of chromium oxide and 3 to 10% by weight of silver salt, and wet-milling and drying to obtain a powder having a uniform particle size. 2. The method for producing a stain agent according to claim 1, comprising: a step of kneading the kneading oil such as a kneading oil to form a paste; a step of allowing the kneading oil to stand for a certain period of time; and a step of kneading the left paste again. 3. A step of applying the stain agent according to claim 1 to a lens or glass, a step of drying a kneading oil of the stain agent applied to the lens or glass, and a step of drying the lens after drying. Firing and cooling down;
A method of manufacturing a lens or glass for a fog lamp, comprising the steps of washing and drying the lens or glass.