JP2000185942A - Coloration of glass vessel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloration method for glass vessels that can color glass in a variety of colors without any damage to the transparency of glass at all with excellent durability and can be fired in a short time, and can make a treatment solution unnecessary to be washed. SOLUTION: In the method for clearly coloring the surface of glass vessels, a treatment solution is prepared by mixing metal fine particles comprising at least one selected from gold fine particles and silver fine particles, an organosilver compound, an organotitanium compound, an organosilicon compound, a binder resin, and an organic solvent, and the glass vessels are coated with this treatment solution and fired at temperatures of 500-700 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for coloring the surface of a glass container transparently and in various colors. More specifically, the present invention relates to a method for coloring a glass container in various colors without impairing the transparency of the glass at all. The present invention relates to a method for coloring a glass container which can be fired in a short time and can eliminate the necessity of washing the treatment liquid.

[0002]

2. Description of the Related Art Conventionally, Au, Ag, Se,
As a method of performing transparent coloring with a unique depth using a metal colloid such as Cd or Cu, a “raw material coloring method” for coloring the entire glass, an “ion exchange method (stain method)” for coloring the glass surface, and a “raster method” And so on.

[0003] In the "raw material coloring method", metal ions are mixed with a raw glass in a molten glass state and cooled and solidified.
A method in which a metal colloid is generated in the presence of a reducing element and colored by the color of the colloid, which has been used for a long time. "Ion exchange method (stain method)" is that, after manufacturing a glass container, an inorganic metal compound is applied to the glass surface and heat-treated, thereby diffusing various metal ions from the glass surface into the glass. In the presence,
This is a method of forming and coloring metal colloid. The "raster method" is a method in which a mixture of a noble metal compound and an organometallic compound is applied to the surface of a glass container and baked, whereby a metal oxide film containing a noble metal colloid is attached to the surface of the glass container and colored.

[0004]

[Problems to be Solved by the Invention] Generally, "raw material coloring method"
Since the entire glass is colored, it is possible to color the glass very darkly and with excellent durability, but has problems such as difficulty in patterning, difficulty in controlling color tone, and poor productivity. The “ion exchange method (stain method)” is different from the “raw material coloring method” in that a treatment liquid is applied to a glass surface and then subjected to ion exchange. be able to. However, the former, such as turbidity, little variation in color tone, the length of time required for ion exchange treatment when trying to color deeply (about 1 hour), removal of treatment liquid after ion exchange, etc. Has a different problem. The "raster method" is a method that solves all the problems of the former two and has good productivity such as color depth, variety of color tones, ease of pattern application, and application and baking only. However, there is a problem that chemical characteristics such as chemical resistance and water resistance and physical characteristics such as abrasion resistance are significantly reduced.

The present invention has been made to solve the above problems, and can be colored in various colors without impairing the transparency of glass at all, has excellent durability, and can be fired in a short time.
It is an object of the present invention to provide a method for coloring a glass container, which can eliminate the need for cleaning the treatment liquid.

[0006]

That is, the invention according to claim 1 of the present application is a method for transparently coloring the surface of a glass container, comprising: a metal fine particle comprising at least one of gold fine particles and silver fine particles; The method is a method for coloring a glass container, in which a treatment liquid obtained by mixing an organic silicon compound, a binder resin, and an organic solvent is applied to a glass container and fired at 500 to 700 ° C.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The fine metal particles of gold or silver used in the present invention have a particle size of 1 to 100 nm, preferably 1 to 100 nm.
What was obtained by dispersing 50 nm metal fine particles without aggregating in a polymer (composite), or having a particle size of 1 to 50 nm
Metal fine particles of 100 nm, preferably 10 nm or less are converted to α
-Independently dispersed in a solvent such as terpineol or toluene.

One of the methods for dispersing the metal fine particles in a polymer is to use a cyano group (—CN), an amino group (—NH ₂ ), and a thiol group (—SH) at the terminal or side chain of the molecule. A polymer or oligomer having at least one selected functional group 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 skeleton is made of polyethylene oxide, polyethylene glycol, polyvinyl alcohol, nylon 11, nylon 6, nylon 66, nylon 6.10, polyethylene terephthalate, polystyrene and 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 gold or 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 a 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, gold or silver as an evaporation source is evaporated by resistance heating, and the gold or silver fine particles are trapped in the polymer or oligomer melt to disperse the gold or silver fine particles in the matrix material. . Since the matrix material is heated, it is always in convection, and a large amount of gold or silver fine particles are uniformly dispersed.

[0010] The fine particles of gold or silver independently dispersed in a solvent are 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 amount of the metal fine particles to be added can be selected according to the desired transmittance, and is not particularly limited. However, the color tone when gold or silver is used alone or the color tone when these are mixed and used are various. Can be changed.

[0011] The amount of each component in the treatment liquid is appropriately determined by the coloring method. For example, in the case of a colorant composition for screen printing, the atomic number concentration of gold or silver is 0.1.
001 to 1 mol% / kg, and 0.001 mol% / k
If the amount is less than 1 g, a sufficiently deep coloring cannot be obtained and 1
If the amount exceeds mol% / kg, the number of atoms of gold or silver in the processing solution is too large, so that the solution easily aggregates and precipitates.

The organic silver compound used in the present invention includes:
Silver thiocyanate, silver cyanate, silver acetate, silver lactate and the like can be mentioned. The organic silver compound has an effect of stably holding fine particles of gold or silver in the colorant.

The organic titanium compound used in the present invention includes alkoxides such as ethoxide and propoxide of titanium (Ti), chelate compounds, organic acid salts, and various complex salts. Specifically, Ti-propoxide, Ti -Acetylacetone salt, Ti-stearate salt and the like.
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 agglomerate fine particles of gold or silver. Examples of the organic solvent include meta-cresol, carbitol, dimethylformamide, dimethylimidazolidinone, terpinol, diacetone alcohol, ethylene glycol monoethyl ether, High boiling solvents such as ethylene glycol monobutyl ether.
This organic solvent dissolves a binder resin or a polymer in which binder resin, gold or silver fine particles are dispersed, and one kind or two or more kinds can be used.

The above-mentioned treatment liquid is obtained by dissolving gold or silver fine particles independently dispersed in a solvent, an organic titanium compound, an organic silicon compound, and a binder resin in an organic solvent and stirring the mixture to obtain a paste. Can be.

The paste-like treatment liquid thus prepared 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.

Thereafter, the printed substrate is left in the air at 100 to 200 ° C. for 10 minutes or dried while being degassed in a closed container, and then heat-treated at 500 to 700 ° C. for several minutes and fired.

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

[0022]

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. Water resistance 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 as ΔE = (L ² + a ² + b ² ).
^It was calculated from the equation of ^1/2 .

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

4. 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.

5. Wear resistance Wear wheel: CS10F, weight 250g, 500 revolutions of Taber abrasion test was carried out, and the transmittance difference before and after the test was △.
Indicated by T.

Examples 1 to 5 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 coloring treatment liquid.
The fine particles of gold or silver used here are particles in which fine particles of gold or silver are dispersed in terpineol in advance.

This treatment liquid was printed on a soda-lime glass cup by the screen printing described above,
Dry at 0 ° C. for 5 minutes. Put this cup in the furnace for 700
C. for 5 minutes to obtain a colored cup. Table 1 shows the properties of the treatment liquid and the colored film.

[0030]

[Table 1]

As a result, in the present embodiment, the haze ratio is 1 or less, the glass can be colored without impairing the transparency of the glass at all, and it can be taken out after 5 minutes in a furnace heated to 700 ° C. Could be colored. And it turns out that the water resistance, chemical resistance, and abrasion resistance of the obtained colored glass cup are also excellent. On the other hand, in Comparative Examples 1 and 2, water resistance, chemical resistance, and abrasion resistance were significantly reduced because a raster was used.

[0032]

As described above, according to the invention claimed in the present application, in a method for transparently coloring the surface of a glass container, metal fine particles comprising at least one of gold fine particles and silver fine particles, an organic titanium compound, and an organic silicon compound. , A binder resin, and a treatment liquid in which an organic solvent is mixed, is applied to a glass container, and is baked at 500 to 700 ° C. in a method of coloring a glass container. Transparency can be maintained, firing time can be reduced, and various shades can be colored.

Claims (1)

[Claims] In a method for transparently coloring the surface of a glass container, metal fine particles comprising at least one of gold fine particles and silver fine particles, an organic silver compound, an organic titanium compound, an organic silicon compound, a binder resin, and an organic solvent are mixed. The treated solution was applied to a glass container, and 500 to 700
A method for coloring a glass container, characterized by firing at a temperature of ° C.