JP2000160104A - Treating liquid for coloring fog lamp and production of the fog lamp - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a treating liquid for coloring a fog lamp capable of easily adjusting the related color strength by its coating weight, retaining the transparency of the glass, lessening the burning time and dispensing with being cleaned, and to provide a production method for the fog lamp. SOLUTION: This method for producing a fog lamp whose surface is colored yellow is conducted by applying, onto the glass of the fog lamp, a treating liquid obtained by blending at least silver fine particles, an organic silver compound, organic titanium compound, organic silicon compound, binder resin and organic solvent, followed by burning it at 500 to 700 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing solution for coloring fog lamps and a method for manufacturing fog lamps, and more particularly to a fog lamp mounted on an automobile and colored in yellow, without impairing the transparency of glass at all and in a short time. Can be fired,
The present invention relates to a processing solution for coloring a fog lamp and a method for manufacturing the fog lamp, which can eliminate the need for cleaning the processing solution.

[0002]

2. Description of the Related Art Conventionally, as a method for coloring a glass portion of a fog lamp with yellow, there is baking of a paint containing solder glass as a main component, but it is poor in chemical resistance and transparency. Also,
Other methods include processing of colored glass and production of interference filters, but due to poor productivity, at present, they are colored by an ion exchange method using a staining agent.

[0003] In this ion exchange method, a specific inorganic salt of Ag or Cu is applied to the surface of a glass substrate, then fired, and finally, the salts remaining on the surface of the glass substrate are washed. In the obtained glass substrate, ultrafine particles of Ag or Cu are generated in the glass substrate, and colloidally develops a transparent color.

[0004]

However, in general, the ion exchange method tends to be cloudy, and the ion exchange treatment time is as long as about 1 hour, and it takes time to remove the processing solution residue after coloring. However, there was a problem that productivity became worse.

The present invention has been made to solve the above problems, and the color density can be easily adjusted by the coating amount, the transparency of the glass can be maintained, the firing time can be reduced, and the cleaning of the processing solution can be performed. An object of the present invention is to provide a processing solution for coloring a fog lamp which is unnecessary and a method for manufacturing the fog lamp.

[0006]

That is, the invention according to claim 1 of the present application is a processing solution used for coloring a fog lamp, and includes at least silver fine particles, an organic silver compound, an organic titanium compound, an organic silicon compound, and a binder resin. And a fog lamp coloring solution mixed with an organic solvent.

According to a second aspect of the present invention, there is provided a method of manufacturing a fog lamp for coloring the surface of a fog lamp to yellow, wherein at least silver fine particles, an organic silver compound, an organic titanium compound, an organic silicon compound, a binder resin, and an organic solvent are used. This is a method of manufacturing a fog lamp in which the mixed treatment liquid is applied to a glass portion of a fog lamp and fired at 500 to 700 ° C.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Silver fine particles used in the present invention are:
Silver fine particles having a particle size of 1 to 100 nm, preferably 1 to 50 nm, dispersed in a polymer without agglomeration (composite); or silver having a particle size of 1 to 100 nm, preferably 10 nm or less. Are independently dispersed in a solvent such as α-terpineol or toluene.

One method of dispersing silver fine particles in a polymer is to use a cyano group (-) at the terminal or side chain of the molecule.
CN), amino group (-NH _2), and thiol group (-
A polymer or oligomer having at least one functional group selected from SH) is used. Specifically, the cyano group (-CN) at the terminal or side chain of the molecule, amino (-NH _2), and has at least one functional group selected from a thiol group (-SH), Its backbone is polyethylene oxide, polyethylene glycol,
It is made of polyvinyl alcohol, nylon 11, nylon 6, nylon 66, nylon 6.10, polyethylene terephthalate, polystyrene or the like, and its melting point or softening point is 40 to 100 ° C. The average molecular weight of the oligomer is not particularly limited, but is about 500 to 6000.
The functional group particularly easily forms a covalent bond or a coordination bond with silver atoms on the surface of the fine particles, suppresses grain growth, and enhances the dispersibility of the fine particles.

Then, a container in which the matrix material is placed in a vacuum device is placed on a heating device such as a heater, and the heating device is heated at 70 to 200 ° C. to melt the polymer or oligomer. Maintain a constant viscosity at all times. Then, the vacuum pump is operated, and the inside of the vacuum device is 5 × 10 ^−5.
After the pressure is reduced to torr, silver as an evaporation source is evaporated by resistance heating, and the silver fine particles are dispersed in the matrix material by trapping the silver fine particles in the melt of the polymer or oligomer. Since the matrix material is heated, it is constantly convected, and a large amount of silver fine particles are uniformly dispersed.

A silver fine particle independently dispersed in a solvent is produced by a method called a gas evaporation method disclosed in, for example, JP-A-3-34211. That is, the metal is evaporated by introducing a helium inert gas into the chamber, and cooled and condensed by collision with the inert gas. In this case, α- The surface of the particles is coated by introducing vapor of an organic solvent such as terpineol. The addition amount of the silver fine particles can be selected according to the desired transmittance, and is not particularly limited.

As the organic silver compound, specifically,
Ag acetate, Ag cyanate, and Ag thiocyanate are exemplified.

The amount of each component in the treatment liquid is appropriately determined depending on the coloring method. For example, in the case of a colorant composition for screen printing, the silver atom concentration is 0.001 to 1;
Mol% / kg, and if it is less than 0.001 mol% / kg, a sufficiently deep coloring cannot be obtained, and 1 mol% / k
If it exceeds g, the number of silver atoms in the processing solution is too large,
Easily aggregates and precipitates.

The organic titanium compound used in the present invention includes alkoxides such as ethoxide and propoxide of titanium (Ti), acetylacetone salts, organic acid salts, and various complex salts. Specifically, Ti-propoxide, Ti -Acetylacetone salts and Ti stearate. This organic titanium compound has the effect of improving the alkali resistance and water resistance of the colored film, and must be soluble in the organic solvent in the treatment liquid.

The organic silicon compound is Si (silicon)
Ethoxides, alkoxides such as propoxide, polyorganosiloxane, etc. Specifically, specifically,
Si-propoxide salts and polydimethylsiloxane are exemplified. This organosilicon compound is acid resistant of the colored film,
It has the effect of improving the abrasion resistance and must be soluble in the organic solvent in the treatment liquid like the Ti-organic compound.

Further, the binder resin used in the present invention maintains the viscosity of the processing solution at an appropriate level to maintain good handling of the glass member at the time of application, and to maintain the color film applied on the substrate after drying. It has the function of maintaining strength. This binder resin is preferably decomposed at a low temperature during firing, but is not particularly limited as long as it is soluble in an organic solvent.

As the binder resin, for example, celluloses such as nitrocellulose, ethyl cellulose, cellulose acetate and butyl cellulose are preferable. This amount is determined by printing or coating conditions, and is not limited. When a composite is used, the polymer may be the same as the binder resin.

The organic solvent used in the present invention does not cause silver fine particles to aggregate. Examples thereof include metacresol, carbitol, dimethylformamide, dimethylimidazolidinone, terpinol, diacetone alcohol, ethylene glycol monoethyl ether, and ethylene glycol. It is a high boiling point solvent such as monobutyl ether. This organic solvent dissolves a binder resin or a polymer in which binder resin or silver fine particles are dispersed, and one or more kinds thereof can be used.

The above-mentioned processing solution comprises silver fine particles independently dispersed in a solvent, an organic titanium compound, an organic silicon compound,
A solution obtained by dissolving a binder resin in an organic solvent can be sufficiently stirred to obtain a paste.

The paste-like treatment liquid thus produced is screen-printed on a base glass. This printing procedure places the printed circuit board (glass) under a horizontally placed screen (eg, polyester plain weave, 255 mesh) with a spacing of several millimeters. After the treatment liquid is placed on the screen, the treatment liquid is spread over the entire screen using a squeegee. At this time, the screen and the printed circuit board have an interval. Subsequently, the screen is pressed and moved with a squeegee to such an extent that the screen contacts the printed board. This completes one printing, and thereafter, repeats this.

After that, the printed substrate is left in the air at 100 to 200 ° C. for 10 minutes to remove the organic solvent and dried, or dried while being degassed in a closed container.
Bake by heat treatment at 800 ° C. for several minutes.

As a method of producing a colored film on a base glass, spraying, dipping,
Roll coating, spin coating, flexo printing, and gravure printing can be used.

[0023]

Next, the present invention will be described in more detail with reference to specific examples. The properties of the treatment liquid and the method of evaluating the colored film are as follows.

1. Optical properties The transmittance of the sample was measured using a turbidimeter. The color tone (Lab) of the sample was measured by a color difference meter.

2. Durability The change in transmitted color tone (ΔE) before and after immersing the colored film in boiling water for 4 hours was measured using a color difference meter, and ΔE = (L ² + a ² + b)
² ) Calculated from the formula of ^1/2 .

2. Acid Resistance The sample was immersed in a 3% aqueous solution of H ₂ SO ₄ for 24 hours, and the color tone difference before and after immersion was indicated by ΔE using a color difference meter.

3. Base resistance The sample was immersed in a 3% aqueous sodium hydroxide solution for 24 hours, and the color tone difference before and after immersion was indicated by ΔE.

Examples 1 and 2 and Comparative Examples 1 and 2 Additives consisting of a fine particle component, a fixing agent component, a binder resin component, and an organic solvent component shown in Table 1 were blended.
The mixture was stirred and mixed at 0 ° C. for 60 minutes to obtain a fog lamp coloring treatment liquid. The silver fine particles used herein are silver fine particles previously dispersed in terpineol.

This treatment liquid was applied to a substrate glass (thickness 3 mm, width 50 mm, length 50 mm) by the above-described screen printing.
Soda lime glass) and print it at 150 ° C
For 5 minutes. This sample was placed in an oven at 700 ° C, 5
After baking for a minute, a glass material having a transparent yellow colored film was obtained. Table 1 shows the properties of the treatment liquid and the colored film.

[0030]

[Table 1]

As a result, in this example, the haze ratio was 1 or less, and yellow coloring was obtained without impairing the transparency of the glass at all, and the glass was taken out after 5 minutes in a furnace heated to 700 ° C. Sufficient coloring was possible. And it turns out that the chemical resistance, heat resistance, and light resistance of the selected base material are also excellent. On the other hand, in Comparative Examples 1 and 2, yellow coloring was not obtained because gold fine particles were used, and they were gray and green, respectively, and were not suitable as fog lamps.

[0032]

As described above, in the invention described in the present application, a fog lamp comprising at least a silver fine particle, an organic silver compound, an organic titanium compound, an organic silicon compound, a binder resin, and a processing solution obtained by mixing an organic solvent. And a fog lamp coloring method in which this is applied to the glass part of a fog lamp and baked at 500 to 700 ° C., the color density can be easily adjusted by the application amount, and the transparency of the glass is maintained. This has the effect of shortening the firing time and eliminating the need for cleaning the processing solution.

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Claims (2)

[Claims] 1. A treatment liquid used for coloring a fog lamp, wherein at least silver fine particles, an organic silver compound, an organic titanium compound, an organic silicon compound, a binder resin, and an organic solvent are mixed. Processing liquid. 2. A method for producing a fog lamp in which the surface of the fog lamp is colored yellow, at least silver fine particles,
A treatment liquid obtained by mixing an organic silver compound, an organic titanium compound, an organic silicon compound, a binder resin, and an organic solvent is applied to a glass portion of a fog lamp,
A method for producing a fog lamp, comprising firing at 0 ° C.