JPH0761834A - Coloring agent for frost-like colored glass - Google Patents

Abstract

PURPOSE:To provide a coloring agent capable of giving frost-like colored glass products having various color tones at a low sintering temperature. CONSTITUTION:A coloring agent capable of coloring the surface of glass into a frosted glass-like color and used for frost-like colored glass comprises a polymer composite material, ceramic powder, glass powder, a binder resin and an organic solvent, the polymer composite material being produced by dispersing novel metal ultrafine particles selected from at least Au, Pt, Pd, Rh, and Ag ultrafine particles in a polymer without coagulating the ultrafine particles.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coloring agent for frosted colored glass, and more particularly to a coloring agent for frosted colored glass capable of coloring the surface of glass in a frosted glass state.

[0002]

2. Description of the Related Art Conventionally, in the case of coloring the surface of a glass substrate, a method of printing a mixture of glass powder and a coloring agent on the surface of the glass substrate, applying the mixture, and then baking the mixture to color the mixture is often used. It was Further, in order to perform color development by colloidal gold, an aqueous solution of chloroauric acid is mixed with glass powder, and the mixed color former is baked at a temperature of 800 ° C or higher to reduce gold ions, which is further heated at 800 ° C. It was colored by growing the reduced gold atoms to colloidal particles by heat treatment at the above temperature. In this method, 800 °
At a heat treatment temperature of C or lower, it was difficult to grow gold particles, and thus it was difficult to develop gold colloid. On the other hand, it is more common than before to process the glass surface by acid treatment or sandblasting to process it into a frosted glass called frosted glass.

[0003]

However, in order to obtain the frosted colored glass by the above method, the design is limited because the surface has to be etched, and a very complicated process is required. . When a glass color former is used to obtain a frost tone, in order to avoid deformation due to softening of the glass base material coated with the color former, in reality, baking is performed at a temperature of 800 ° C or lower, and etching is performed after coloring. Was needed. For this reason, it has been substantially difficult to obtain color development by colloidal gold. Further, in the case of producing a reddish color without using gold colloid, there is a problem that the inorganic pigment used contains Cd and Cr and cannot be put to practical use. The present invention solves such a problem, and an object of the present invention is to provide a coloring agent capable of obtaining frosted colored glass having various color tones by lowering the firing temperature.

[0004]

That is, the feature of the present invention is that at least ultrafine particles of Au, Pt, P are formed.
A polymer composite obtained by dispersing ultrafine particles of a noble metal selected from d, Rh, and Ag in a polymer without aggregating them, a ceramic powder, a glass powder, a binder resin, and an organic solvent. It is a coloring agent for frosted colored glass consisting of. In addition to the above five components, the frosting coloring glass coloring agent may contain a fixing agent composed of an organometallic compound for fixing ultrafine particles of noble metal in the glass. Further, this coloring agent may contain SiO ₂ different from the above ceramic powder.

In the polymer composite used here, a thermodynamically non-equilibrium polymer layer is prepared, and a precious metal selected from Au, Pt, Pd, Rh, and Ag is formed on the surface of the polymer layer. After adhering, the polymer layer is heated to stabilize the polymer layer, whereby the noble metal in the form of ultrafine particles having a particle size of 1 to 50 nm is dispersed in the polymer without agglomeration. It is a thing.

That is, the color former for frosted colored glass of the present invention is basically a polymer composite obtained by dispersing at least a noble metal in a polymer without aggregating it, and SiO ₂ which changes the color tone of frost. It is a paste-like material in which ceramic powder, glass powder, and binder resin that do not contain are uniformly dispersed in an organic solvent. It is also possible to include a fixing agent composed of an organometallic compound for fixing ultrafine particles of a noble metal in glass. Moreover, in order to maintain the strength of the colored film and the transparency of the film, the above-mentioned basic material is made of Si different from that of the ceramic powder.
O ₂ can also be included.

First, when obtaining the above-mentioned polymer composite, it is necessary to form the polymer layer into a thermodynamically non-equilibrium state. Specifically, this is a vacuum deposition method in which a polymer is heated in a vacuum to melt and evaporate to solidify a polymer layer on a substrate, or a polymer is melted at a melting temperature or higher,
In this state, there is a method such as a rapid quenching solidification method in which the polymer layer is immediately put into liquid nitrogen or the like to be rapidly cooled and a polymer layer is attached onto the substrate.

In the case of the vacuum vapor deposition method, a vacuum degree of 10 ⁻⁴ to 10 ⁻⁶ Torr and a vapor deposition rate of 0.1 to 100 μm / min, preferably 0.
At 5 to 5 μm / min, a polymer layer can be obtained on a substrate such as glass. In the melt-quenching and solidification method, a polymer is melted and cooled at a rate equal to or higher than a critical cooling rate specific to the polymer to obtain a polymer layer. The polymer layer thus obtained is placed in a thermodynamically unstable non-equilibrium state, and shifts to an equilibrium state with the passage of time.

The polymer used in the present invention is, for example, nylon 6, nylon 66, nylon 11, nylon 12, nylon 69, polyethylene terephthalate (PET),
Polyvinyl alcohol, polyphenylene sulfide (P
PS), polystyrene (PS), polycarbonate, polymethylmethacrylate, etc., which have a molecular cohesive energy of 2000 cal / mol or more are preferable. This polymer includes a crystalline polymer and an amorphous polymer which are usually called. Regarding the molecular cohesive energy, the Chemical Handbook, edited by the Chemical Society of Japan (edited in 1974)
890, page 890.

Subsequently, the thermodynamically non-equilibrium polymer layer is transferred to the step of bringing the precious metal layer into close contact with the surface of the polymer layer. In this step, the precious metal layer is deposited on the polymer layer by a method such as depositing the precious metal on the polymer layer by a vacuum vapor deposition apparatus or by directly adhering the precious metal foil or the precious metal plate to the polymer layer. Au (gold), Pt as the noble metal
(Platinum), Pd (palladium), Rh (rhodium), A
g (silver) and the like.

The composite in which the noble metal layer and the polymer layer are in close contact with each other is heated at a temperature not lower than the glass transition point of the polymer and not higher than the flow temperature to shift the polymer layer to a stable state. As a result, the metal of the noble metal layer is 100 nm or less and 1 to 10 n
The noble metal particles that have the maximum particle size distribution in the m region become ultrafine particles of the noble metal that diffuse and permeate into the polymer layer, and this state continues until the polymer layer is completely stable. The layer also decreases in its thickness and eventually disappears. The ultrafine particles are distributed in the polymer layer without being aggregated. In this case, the content of the ultrafine particles is 0.01 to 80% by weight, but this content can be adjusted by changing the production conditions of the polymer layer or the thickness of the noble metal layer.

In the present invention, the method for producing the polymer composite is not limited to the above-mentioned method, but includes, for example, a vapor phase method belonging to the melt vaporization method, a liquid phase method belonging to the precipitation method, a solid phase method and a dispersion method. There is a method of producing ultrafine particles and mechanically mixing the ultrafine particles with a polymer composed of a solution or a melt, or a method of simultaneously evaporating the polymer and the noble metal and mixing them in a gas phase.

The obtained polymer composite is mixed and dissolved in a solvent consisting of an organic solvent such as metacresol, dimethylformamide, cyclohexane and formic acid to obtain an ultrafine particle dispersion paste in which ultrafine particles are uniformly dispersed. Since the ultrafine particles have a small particle size and have an interaction with the polymer, separation, precipitation and aggregation of the ultrafine particles do not occur in the paste.

The ceramic powder used in the present invention is Al
N, Al ₂ O ₃ , Si ₃ N ₄ , ZrO, Y ₂ O ₃ , B
N, or C when blocking ultraviolet rays or infrared rays in particular
UCL _2, TiO _2, ZnO, is CuS, etc., the addition amount thereof is 0.01 to 50 wt%, preferably 0.1 to 30
% By weight.

The glass powder has a softening point of 300 ° C. or higher, and the powder diameter is determined by the printing conditions such as the screen hole diameter at the time of screen printing and the pattern accuracy, and is not particularly limited. Specifically, borosilicate glass, lead glass, tin oxide-
There are phosphoric acid glass and the like. The glass powder improves not only the binder that increases the strength of the film but also the chemical durability. The amount added is 20% by weight or more and is not particularly limited.

The above-mentioned binder resin is one which decomposes at a relatively low temperature. For example, celluloses such as nitrocellulose, ethyl cellulose, cellulose acetate and butyl cellulose, polyethers such as polyoxymethylene, polyvinyl such as polybutadiene and polyisoprene. And acrylates such as polybutyl acrylate and polymethyl acrylate.

The fixing agent used in the present invention is, for example, Al, Si, Ti, Cr, Mn, Fe, Co, Ni, C.
u, Y, Zr, Nb, In, Sn, Sb and other ethoxides, propoxide and other alkoxides, naphthenates,
The object of the present invention can be achieved by using organic acid salts such as acetate, organic complex salts such as acetylacetone complex salt, oxine complex salt and the like, and by using glass powder containing these elements in advance.

In particular, when a color former obtained by combining a polymer composite containing ultrafine particles of gold with the above-mentioned organometallic compound is fired, the obtained color tone includes red and Cu in the organometallic compound containing Si. The organometallic compound is pink, the organometallic compound containing Ti is blue, the organometallic compound containing Fe is green, the organometallic compound containing Co is gray, the organometallic compound containing Zr is blue, and the organometallic compound containing Ni is It turns blue. The addition amount is not particularly limited, but it is necessary that the molar ratio to the noble metal fine particles is 0.1 or more.

Further, in the present invention, in order to maintain the strength of the colored film and to impart the transparency of the film, a powder of SiO ₂ different from the above ceramic powder may be included.
The amount added is 0.01 to 50% by weight, preferably 0.1.
Is about 20% by weight.

The organic solvent used in the present invention is selected according to the kind of the polymer composite, ceramic powder, glass powder, binder resin, or fixing agent. Specifically, it is metacresol, dimethylformamide, carbyl. A high boiling solvent such as tall, terpinol, diacetone alcohol, triethylene glycol, and paraxylene is preferable for printing the color former on the glass substrate.

The above-mentioned color former is prepared by mixing the polymer composite with other additives at the same time with an organic solvent and stirring them well to form a paste, or separating them and mixing them with an organic solvent and stirring them well to form a paste. It is also possible to make a shape.

The paste-like color former produced in this manner is screen-printed on a substrate such as a glass plate. In this printing procedure, a printing substrate (glass) is placed under a horizontally placed screen (eg, polyester plain weave, 255 mesh) with a spacing of a few millimeters. After putting the above color former on this screen,
Use a squeegee to spread the color former on the entire screen.
At this time, there is a gap between the screen and the printed board. Then, the squeegee is pressed against the screen so that the screen comes into contact with the printed board, and the screen is moved to perform printing. After that, this is repeated.

[0023]

In the color former of the present invention, Au, Pt, P
It is a paste-like product obtained by mixing and stirring a polymer composite obtained by dispersing ultrafine particles of a noble metal selected from d, Rh, and Ag, ceramic powder, glass powder, and a binder resin with an organic solvent. , When it is adhered to a substrate such as glass and baked, low temperature baking becomes possible, internal distortion does not easily occur in the glass substrate and the baked film, and frosted glass-like frost is generated due to light scattering by unmelted ceramic powder. It is also possible to obtain frosted colored glass of various color tones by using ceramic powder. Further, in the color former of the present invention, the fixing agent agglomerates the ultrafine particles and fixes them in the particles, so that the desired coloring is possible and a baked film having strength is formed. Then, by adding SiO ₂ different from the ceramic powder, the strength of the colored film can be maintained and the transparency of the film can be provided.

[0024]

Next, the present invention will be described in more detail with reference to specific examples. Examples and Comparative Examples Using a vacuum vapor deposition apparatus, 5 g of polymer pellets of nylon 11 were placed in a tungsten board and 10 ⁻⁶ Torr
Depressurize to. Then, a voltage is applied to heat the tungsten board in a vacuum to melt the polymer, and 10 ^-4 to 10 ^-4 is placed on the substrate (glass plate) installed on the upper part of the mounting base.
-Thickness of about 5μ at a speed of about 1μm / min at a vacuum of ⁶ Torr
A polymer layer of the vapor-deposited film of m was obtained. The molecular weight of this polymer layer is about 1/2 to 1/10 of that of the polymer pellet.

Further, the gold chip was placed in a tungsten board, heated and melted, and vapor deposition was performed at a vacuum degree of 10 ^-4 to 10 ^-6 Torr to deposit a gold vapor deposition film on the polymer layer. This was taken out from the vacuum vapor deposition apparatus and left in a constant temperature bath kept at 120 ° C. for 10 minutes to obtain a composite. as a result,
This polymer composite contained about 25% by weight of gold and had an average particle size of 5 nm. The obtained polymer composite and meta-cresol were mixed at a weight ratio of 1: 2 to prepare a polymer composite solution.

Next, a solution prepared by dissolving nickel acetylacetone as a fixing agent in meta-cresol at a weight ratio of 3:17, glass powder (soda glass), ceramic powder, Si.
A solution was prepared by mixing O ₂ powder and ethyl cellulose and terpinol as a binder resin for printing in a weight ratio of 3:37.

Then, the polymer composite solution was mixed with a fixing agent solution, glass powder, ceramics powder, SiO ₂ powder, and a binder resin solution for printing to obtain a color former. The composition ratios of these color formers are shown in Table 1.

The above color former was printed on the glass substrate by the screen printing described above, dried at 120 ° C. for 10 minutes and then baked at 650 ° C. to obtain a glass substrate having a baked film. The characteristics of the fired film are shown in Table 1. The evaluation of the frost tone was performed with the naked eye, and the haze ratio (turbidity) was calculated according to JIS K0101 of the industrial water test method.

[0029]

[Table 1]

As a result, it was possible to produce a frosted colored glass which was fired at a low temperature and had various color tones depending on the type of ceramic powder by screen printing using a color former. Furthermore, it can be seen that the addition of SiO ₂ powder also makes it possible to obtain a semitransparent colored glass having a small haze ratio.

[0031]

As described above, the color former of the present invention is obtained by mixing and stirring a polymer composite obtained by dispersing ultrafine particles of a noble metal, ceramic powder, glass powder, and a binder resin with an organic solvent. It is a paste-like material, and when it is adhered to a substrate such as glass and baked, low temperature baking becomes possible, internal distortion does not easily occur in the glass substrate and baked film, and light scattering by the ceramic powder that does not melt Not only it is possible to obtain frosted colored glass having various color tones by the coloring agent of the present invention, the fixing agent agglomerates the ultrafine particles to fix in it, it is possible to achieve the desired coloring. A fired film having strength can be formed. Further, since it is possible to screen print, various designs can be drawn on glass. Further, by adding SiO ₂ different from the ceramic powder, the strength of the fired film can be maintained and the film can be made transparent.

Front page continuation (72) Inventor Yoshio Yamaguchi 4-1-21, Hamazoe-dori, Nagata-ku, Kobe Mitsuboshi Belt Co., Ltd.

Claims (4)

[Claims] 1. At least ultrafine particles of Au, Pt,
From a polymer composite obtained by dispersing ultrafine particles of a noble metal selected from Pd, Rh, and Ag in a polymer without aggregating them, a ceramic powder, a glass powder, a binder resin, and an organic solvent. A coloring agent for frosted colored glass, which is characterized by 2. The color forming agent for frosted colored glass according to claim 1, further comprising a fixing agent composed of an organometallic compound for fixing the ultrafine particles of the noble metal in the glass. 3. SiO ₂ different from the above ceramic powder
The color former for frosted colored glass according to claim 1 or 2, further comprising: 4. A polymer composite forms a thermodynamically non-equilibrium polymer layer, and Au, P is formed on the surface of the polymer layer.
After adhering a noble metal selected from t, Pd, Rh, and Ag, the polymer layer is heated to stabilize the polymer layer, thereby forming ultrafine particles of the noble metal in the polymer. The color former for frosted colored glass according to claim 1, which is obtained by dispersing without aggregation.