JPS6129911B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of forming a hard polysiloxane film on the surface of ceramics and coloring it with an organic dye, and a dye paste and ceramics used therein.

Traditionally, the surface of ceramics is colored and painted using metals such as iron, copper, cobalt, manganese, chromium, nickel, uranium, antimony, cadmium, lead, tin, gold, and silver, as well as their oxides, carbonates, and bases. A method of drawing a preliminary or overpainting using a colored paint, a method of transferring from transfer paper colored with the same, a method of mixing it with a glaze and using it as a colored glaze, a method of mixing it with makeup clay to make a colored makeup, a method of mixing it with the base material. This is done by coloring using a method such as using it as a pigment base, and baking it for a long time at a high temperature of 700 to 1300°C to achieve color development and fixation (for example, JP-A-51-7005). However, the coloring materials used in these conventional methods include metal compounds such as cadmium that are toxic to the human body, and the color tones are extremely limited, making it impossible to obtain clear primary color tones. Furthermore, the color tone varies depending on the base material, the ingredients of the glaze, the nature of the flame in the kiln, the temperature and its changes, etc., and it is not much different from the days of potter Kakiemon that it is difficult to obtain the desired color. . Furthermore, it requires high-temperature firing of 700 to 1,300 degrees Celsius for a long time, resulting in high costs in terms of production equipment and fuel consumption, and drawbacks have been pointed out, such as damage under harsh manufacturing conditions and poor yields. Furthermore, since the color tone changes significantly before and after high-temperature firing, it was necessary to predict this change when creating the original painting, which required a high degree of skill. Also, since you can't freely add light and shade, and you can't use the blurring method,
It was difficult to make full use of the artist's ideas.

The present inventors have made extensive studies to solve the problems of the prior art as described above, and as a result, have arrived at the present invention described below.

That is, in the present invention, as a first step, a polysiloxane compound consisting of a condensate obtained by hydrolyzing a silicon compound represented by the following general formula () is adhered to the surface of ceramics to form a hard coating, and then a hard coating is formed on the surface of the ceramic. A method for coloring ceramics, characterized in that, as a second step, the coating is colored using an organic dye.

R _x R′ _y Si(OR″) _4-(x+y) () (In the formula, R and R′ are hydrocarbon groups having 1 to 3 carbon atoms,
It represents an organic group containing an amino group, a glycidoxy group, a methacryloxy group, or a mercapto group, R'' represents a hydrocarbon group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, and x and y are 0 and 1, respectively. or 2, and x+y is 0, 1 or 2).

_The hard _{polysiloxane film} of the present invention has _the general formula R represents an organic group containing a group, a glycidoxy group, a methacryloxy group, or a mercapto group, R'' represents a hydrocarbon group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms,
x, y are 0, 1 or 2, respectively, and x+
y is 0, 1 or 2. ), and the silicon compounds specifically include methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. Silane, phenyltrimethoxysilane, phenyltriethoxysilane, N-(trimethoxysilylpropyl)ethylenediamine, aminomethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, γ
-glycidoxypropyltrimethoxysilane, γ
- methacryloxypropyltrimethoxysilane,
Trifunctional silanes such as γ-mercaptopropyltrimethoxysilane, dimethyldimethoxysilane,
Diethyldimethoxysilane, dimethyldibutoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, etc. Examples include difunctional silanes such as difunctional silanes, and tetrafunctional silanes such as tetramethoxysilicon and tetrabutoxysilicon.

A condensation product of a hydrolyzate obtained by adding hydrochloric acid etc. to these alone or a mixture of two or more in a suitable solvent, or a mixture of a condensate of these hydrolysates, alone or polyvinyl butyral, polyamide, epoxy resin, A coating agent suitable for the present invention is prepared by combining appropriate amounts of organic polymers such as (meth)acrylic acid ester copolymers, and further adding curing catalysts, surfactants, etc. as necessary. Among these, particularly preferred are those containing a silane hydrolyzate containing an epoxy group in the molecule, those containing an epoxy compound as an organic polymer, or those containing a compound of a transition metal such as nickel.

The above paint is applied to the surface of the ceramic by a suitable method such as dipping, spinning or spraying, and then hardened by heating and curing. The thickness of the coating film is not particularly limited. It is also possible to improve adhesion and appearance by performing appropriate cleaning and pretreatment prior to coating. Heating curing conditions vary depending on the amount of catalyst added, but usually 10 minutes to 2 hours at 70 to 200°C is sufficient, and compared to conventional ceramic firing conditions,
Compared to overglaze painting, the process is much lower and takes less time.

The above paint blends well with the ceramic surface, and even when heated for a short time at the low temperature mentioned above, it not only crosslinks and cures itself, but also adheres well to the ceramic, forming a film with high surface hardness that is integrated with the substrate. . Of course, it can also be applied to unglazed ceramics, but in view of the strength of the product during use, it is best to apply it to fully fired ceramics.
It doesn't matter if there is a glaze or not, but if the film is thin,
In order to increase gloss and smoothness, it is preferable to apply a glassy glaze. In this case, the use of colored glazes allows for even more diverse expressions. The ceramics to be painted can also be pre-colored using conventional methods. The traditional method, which has a long history, has its own charm that is hard to give up, so if you combine it with the clear and beautiful coloring of the present invention, you can create extremely artistic paintings. This method can also be applied for purposes such as correcting and adding defects in conventional painting.

Furthermore, the paint must be dyeable or have an affinity for dyes. The introduction of an amino group, glycidoxy group, methacryloxy group, or mercapto group is significant in that it becomes compatible with many dyes such as disperse dyes. In addition to the above, it is also effective to introduce a suitable dyeing seat and select a dye that matches it.

For example, coloring can be done by using disperse dyes, acid dyes, basic dyes, anionic dyes, etc. on the polysiloxane film.
This is achieved by coloring with organic dyes such as cationic dyes and chelate-binding disperse dyes, and fixing the dyes through heat treatment. Organic dyes are kneaded in advance with a water-soluble polymer, a surfactant, or a mixture of the two and a medium such as water to form a viscous dye paste in order to improve adhesion or create deep colors. Good to use. In this case, dyes made by simply dissolving organic dyes with a medium lack viscosity, which causes problems such as the dye solution dripping during coloring, the inability to achieve deep coloring, and the dye solution being difficult to adhere to. Further, when the dye is fixed by heat treatment, the dye layer dries and peels off from the painted ceramic surface, resulting in problems such as no dyeing.

Examples of the above-mentioned water-soluble polymers include starch paste, tragacanth gum, CMC, locust bottle gum, sodium alginate paste, mapro rubber, Brittish rubber, etc., and the surfactants include commonly commercially available cationic, anionic, Surfactants such as amphoteric, nonionic, silicone glycol copolymers, preferably liquid themselves;
Alternatively, even in solid form, one with high solubility in water is used.

When preparing dye paste, the mixing ratio of organic dyes, water-soluble polymers, surfactants, or mixtures thereof, and media such as water can be determined freely based on the shade of coloring and work efficiency during coloring. The mixing ratio is preferably in the range of 0.1 to 10% by weight, 1 to 30% by weight, and 10 to 95% by weight, respectively.

Coloring with the dye paste described above can be done by hand-drawing directly onto the surface of ceramics coated with a hard polysiloxane film (in this case, it is easier to draw by temporarily stamping the outline with a rubber stamp, etc.), or by printing using a screen printing method. , or mechanical printing. In particular, collodion-coated paper, separate paper,
Prepare a screen-printed pattern on a flexible substrate such as ceramic transfer paper such as Thermaflat paper, fabric such as cotton cloth, nylon or polyester, or film such as polyethylene, polyester, or polypropylene. Paste the varnish,
Alternatively, ceramics colored with the same pattern can be mass-produced with good reproducibility by applying gelatin liquid or the like to the surface of ceramics, heat-treating, transferring, and dyeing.

It is also possible to use a carrier for dyeing polyester fibers in combination with the dye paste to deepen the dyed pattern and improve fastness. As a carrier,
Examples include P-oxydiphenyl, P-chlorodimethylphenol, etc., and the amount is 0.5 per 100 parts by weight of dye paste.
It is preferable to mix and use up to 20 parts by weight.

Ceramics that have been colored by hand painting, screen printing, mechanical printing, transfer, etc. can be fixed with dyes by heat treatment in dry heat or moist heat at 80 to 300°C for about 10 minutes to 2 hours. After dyeing, excess dye, paste, transfer paper, etc. are removed by washing with water to obtain a product.

In one embodiment of the present invention, the paint that provides the polysiloxane coating film is partially flow-coated onto the ceramic surface in a pattern, or the paint is screen printed in a pattern, heated and cured, and then coated with an organic dye. It is also possible to dye it. In this case, if the material is colored using the so-called dip dyeing method, an artistic pattern similar to that created by flowing colored glazes using the conventional method can also be obtained. In this case, the organic dye is used as a dye bath containing an aqueous solution of 0.5 to 10% by weight, and ceramics coated with polysiloxane are immersed in this bath and dyed at a temperature of 80°C or higher. Various dyeing aids are used in the dyebath to deepen dyeing, level dyeing, and improve fastness.
It is also possible to use a carrier in combination, and high-temperature pressure dyeing at 100 to 150°C is also possible.

In addition, a hard polysiloxane film is pre-cured on the ceramic surface by heat treatment at 40 to 70°C for about 10 minutes, coloring is applied while the film is still uncured, and then the dye is fixed and the polysiloxane film is cured at the same time. By doing this, it is also possible to dye a strong and dark pattern. By employing such a two-stage curing method of pre-curing and main curing of the polysiloxane film, the dye is likely to be fixed in the film, and once fixed, the dye is difficult to detach. The pre-curing conditions in this case depend on the composition of the coating material that provides the hard polysiloxane film, but it is sufficient that the film is dry to the touch after the pre-curing.

Furthermore, by repeating the above series of dyeing operations on the ceramic surface several times, it is possible to obtain ceramics with a pattern with a three-dimensional effect, and by layering a hard polysiloxane film as the top layer, it is possible to obtain ceramics with a solid pattern. It becomes possible to obtain a colored product.

Ceramics colored in the above manner have a pattern with a variety of color tones and are clear, and have much richer fashionability than those made using conventional inorganic pigments. There are many types of organic dyes, and the range of choices for color tone, shade, etc. is greatly expanded. This coloring method is applied to various types of ceramics such as decorative plates, tableware, vases, and urns, making it possible to mass-produce products rich in aesthetic value with high yield. In addition, the patterned portion of the ceramic according to the present invention is covered with a hard polysiloxane coating, so it has excellent scratch resistance and abrasion resistance.
It does not fall off easily. When used as tableware, it will not be damaged by a knife blade, and even if used tableware is processed in an automatic dishwasher, it will not be damaged or penetrated.

Another feature of this coloring method is that it can produce any color from dark to light, including intermediate tones. As a result, compared to conventional drawing methods that tended to resemble line drawings or animations, it has become possible to create highly realistic expressions that incorporate shading techniques. The ability to produce halftones also means that color photographs can be printed on ceramic.
Although this type of product has not existed in the past, it has been pointed out that the color tone is completely poor and the defect is extremely susceptible to scratches.

As is clear from the above explanation, the coloring method of the present invention is extremely simple and can be easily carried out by the general public as long as ceramics coated with a coating can be obtained. recently,
Many people choose to take up pottery as a hobby to use their free time,
It requires a high degree of skill to run the brush freely on the unglazed pottery. In contrast, in the present invention, since the base is made of glazed, fired ceramics, the brush strokes are smooth and anyone can easily color. Moreover, the subsequent fixation can be carried out using a household steamer and does not require a kiln, so it has a wide range of applications.

This ease of coloring is also an advantage for professional ceramic manufacturers. If you prepare plain products in various shapes, you can easily apply the desired coloring and ship quickly according to trends and changes in demand. Inventory management is easy, and the cost of plain base materials is low, so the impact of defective or damaged products during glazing, firing, storage, and other processes is reduced. It is also possible to separate the coloring stage and use it as a cottage industry process with low labor costs.

Next, the present invention will be explained in detail using examples.

Example 1 248 parts by weight of γ-methacryloxypropyltrimethoxysilane, 45 parts by weight of vinyltriethoxysilane, 38 parts by weight of acetic acid and 81 parts by weight of 0.01N hydrochloric acid.
The mixture was placed in a 500ml beaker and stirred vigorously for 2 hours using a magnetic stirrer to form a colorless and transparent solution, which was then aged overnight. To this were added 98 parts by weight of 1,2 dichloroethane, 104 parts by weight of ethanol, 11.6 parts by weight of acetylacetone aluminum salt, and 0.62 parts by weight of a silicone surfactant, and the mixture was stirred at room temperature for 1 hour to prepare a paint. This paint was applied with a brush to a white unglazed ceramic plate, air-dried for 10 minutes at room temperature, and then cured for 2 hours in a hot air circulation oven at 120°C. On the other hand, “Resoline Blue FBL” (disperse dye manufactured by Ciba),
“Celiton Fast Scarlet GF2R” (disperse dye made by BASF), “Celiton Fast Green FFG” (disperse dye made by BASF) 5 parts by weight each, 30 parts by weight each of tragacanth gum, SH190 (silicone glycol copolymer made by Toray Silicone Co., Ltd.) 3 consisting of 0.5 parts by weight each, 5 parts by weight each of P-oxydiphenyl, and 65 parts by weight each of water
Mix colored dye pastes.

A flower pattern was screen printed on the surface of the white plate coated with the hard polysiloxane coating using these three colors of dyeing paste, and then placed in an oven at 150℃ for 30 minutes.
The dye was fixed by processing for a minute, and then taken out and water dyed to remove excess dye paste remaining in the patterned area. The resulting pattern is clear and extremely resistant to abrasion with steel wool and hot water immersion treatment, and we have obtained a decorative plate with a flower pattern that has a surface hardness and smoothness comparable to that of conventional high-temperature fired ceramic plates. Ta.

Example 2 γ-glycidoxypropyltrimethoxysilane
Add 54 parts by weight of a 0.01N aqueous hydrochloric acid solution to 236 parts by weight, and stir on a magnetic stirrer for 1 hour to obtain a hydrolyzate. 50 parts by weight of this hydrolyzate, 25 parts by weight of glycerol polyglycidyl ether (“Denacol EX314” manufactured by Nagase Sangyo Co., Ltd.), 0 m-xylene
parts by weight, 50 parts by weight of ethylene chlorohydrin, 5 parts by weight of acetylacetone aluminum salt, and 0.7 parts by weight of a silicone surfactant were added, stirred until a homogeneous solution was obtained, aged for a day and night, and then filtered to prepare a coating agent. . The viscosity of this coating agent is (20℃) 12 centipoise, solid content concentration (calculated from the remaining amount after heating at 85℃ for 1 hour and 130℃ for 1 hour)
is 51%.

This coating agent was spray coated onto a plain white porcelain vase, and dried and cured for 2 hours in a hot air circulation oven at 120°C.

Separately, a floral pattern was screen-printed onto nylon taffeta using the three colors of dyeing paste used in Example 1.
This was pasted onto the vase coated with the hard polysiloxane film using CMC glue, and heat treated in a dryer at 160°C for 1 hour to transfer the pattern. After the heat treatment, the nylon taffeta was peeled off and the first dyeing of the pattern on the vase was completed. Furthermore, the above-mentioned process of coating with a hard polysiloxane film and transfer printing was repeated three times, and the final film was finished with a clear coat that did not dye, thereby obtaining a vase with a sturdy, three-dimensional floral pattern. . The color tone matched well with that of the original painting.

Example 3 The coating agent used in Example 2 was applied by dipping onto a glazed plain white ceramic sake bottle, air-dried at room temperature for 10 minutes, and then pre-cured for 20 minutes in a hot air circulation dryer at 40°C. . A checkered pattern was screen printed on this using the blue dye paste containing "Resoliue Blue FBL" used in Example 1, and heat treated in a dryer at 130°C for 2 hours to cure the polysiloxane coating and cure the dye. Let's do it. After the heat treatment, the bottle was taken out and the excess dye paste was washed off with water to obtain a sake bottle with a checkered pattern that was clear, extremely durable against alcohol-based organic solvents and hot water, and resistant to scratches even when rubbed with steel wool.

Example 4 222 parts by weight of trimethoxysilane containing amino groups and imino groups represented by the chemical formula H ₂ NCH ₂ CH ₂ NH (CH ₂ ) _{3 Si} (OCH ₃ ) ₃ and 222 parts by weight of ethanol were collected and mixed. 54 parts by weight of water was added dropwise to the mixture to carry out a hydrolysis reaction. Since this reaction is accompanied by some heat generation, the reactant is stirred while being cooled with ice at a temperature of 20° C. during the reaction, and stirring is continued for 30 minutes after the completion of the dropwise addition of water.

The hydrolyzate thus obtained was stirred for 20 minutes.
While cooling to ℃, 346 parts by weight of acetic acid is added dropwise to the mixture to obtain an acetate. This is the chemical formula Denacol is a tetrafunctional epoxy resin represented by
Mix and dissolve 85 parts by weight of "EX-612" (manufactured by Nagase Sangyo Co., Ltd.), and further mix 100 parts by weight of ethanol and 25 parts by weight of xylene to obtain a paint. Pour this paint into a plain white pot. Paint and air dry for 10 minutes at room temperature.
Cure for 1 hour in a hot air circulation oven at 100°C. Meanwhile Alizarine Fast Green 2GW
An immersion bath consisting of a 5% by weight aqueous solution of (acid dye manufactured by Ciba) was prepared in advance. By heating this dye bath to 80℃ and soaking the vase coated with the above paint for 30 minutes, only the hard paint film is dyed in a complicated flowing striped pattern, and then the green glaze is poured and fired. I got an artistic vase like the one I made.

Claims (1)

[Claims] 1. As a first step, a polysiloxane compound consisting of a condensate obtained by hydrolyzing a silicon compound represented by the following general formula () is adhered to the surface of the ceramic to form a hard film, A method for coloring ceramics, characterized in that, as a second step, the coating is colored using an organic dye. R _x R′ _y Si(OR″) _4-(x+y) () (In the formula, R and R′ are hydrocarbon groups having 1 to 3 carbon atoms,
It represents an organic group containing an amino group, a glycidoxy group, a methacryloxy group, or a mercapto group, R'' represents a hydrocarbon group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, and x and y are 0 and 1, respectively. or 2, and x+y is 0, 1 or 2.) 2 The second step is by printing or textile printing with a dye paste containing a water-soluble polymer or surfactant or a mixture thereof, an organic dye and a medium. The method for coloring ceramics according to claim 1, characterized in that the steps include patterning and then heat treatment. 3. The second step is a flexible base material patterned with an organic dye. The method for coloring ceramics according to claim 1, characterized in that the first step is a step of applying a paste to the surface of the ceramic and heat-treating it to transfer the pattern.4. The method for coloring ceramics according to claim 1, characterized in that the step is to form a coating in a pattern.5 The second step is to color the hard coating using an organic dye, and further to color the surface of the hard coating. 6. A method for coloring ceramics according to claim 1, which comprises forming a hard polysiloxane film on a ceramic material. 6. A method for coloring ceramics according to claim 1, characterized in that the organic dye is a disperse dye. 7. The method for coloring ceramics according to claim 1, wherein the hard coating in the first step is semi-cured polysiloxane.