JPS6159237B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a method of forming an alumina film or a silica film on the surface of an inorganic material or a metal material, and heat transfer printing a character pattern made of a sublimable coloring agent on this film (Japanese Patent Application No. 150137, patent application 1977-
88124).

That is, the above invention can be applied under extremely severe conditions.
In particular, there were problems with chemical resistance and steam resistance when used in the presence of organic solvents or in steam for long periods of time. Furthermore, when a coloring agent with poor light resistance was used, there was also a problem in fastness.

The present invention aims to improve these drawbacks, and is characterized by coating the transfer surface with colloidal alumina and/or colloidal silica containing a water-soluble resin capable of making it waterproof, and then drying and curing the transfer surface. This is a method for improving heat transfer materials that have excellent chemical resistance and weather resistance, especially weather resistance.

Conventionally, when coloring glass etc., the method of manufacturing colored products by adding a coloring agent to a batch of glass has been used, but when a colored glass product with multiple colors is desired, or when this product is partially If it is colored, there are problems in manufacturing.

In addition, methods for printing on inorganic materials include the silk screen method and slide transfer method, but these have complicated printing processes and require a long baking time of 1 to 3 hours after printing, reducing production efficiency. The coloring agents were mostly opaque pigments.

On the other hand, as a method to improve the above-mentioned drawbacks, there are methods of coating glass, ceramics, porcelain, slate, concrete, etc. with a synthetic resin film, and dyeing this film with dyes or thermal transfer printing. Due to poor abrasion resistance, heat resistance, nonflammability, and surface smoothness, it is difficult to form a thin film, and the types of synthetic resins are limited due to the adhesive strength between the film and the base material. It is in.

Therefore, the present inventors coated an inorganic material or a metal material with colloidal alumina or colloidal silica, dried and fired it, and contained a sublimable and coloring agent on the obtained alumina or silica film. Abrasion resistance, heat resistance, nonflammability, surface smoothness, and thin film formation characterized by overlapping transfer foils with character designs formed with ink and pressurizing and heating to form character designs on alumina or silica film. Although we have disclosed a heat transfer printing method that provides decorative materials with excellent properties, the degree of coloration may be affected when the transfer material is used in extremely harsh environments, especially when used in the presence of organic solvents or in steam for long periods of time. There were also problems with fastness when colorants with poor light fastness were used.

Prior to carrying out the present invention, inorganic materials such as glass, enamel, ceramics, slate, and concrete, and metal materials such as iron, zinc, copper, and aluminum are coated with colloidal alumina or colloidal silica, dried, and fired. After forming an alumina or silica film, heat transfer is performed using a transfer foil containing a sublimable colorant, and then top coating is applied to the transfer surface.

Colloidal alumina as a top coating material may be a sol made of boehmite obtained by hydrolyzing basic aluminum chloride or aluminum acetate, or a sol made by peptizing a gel. Further, it is acceptable even if some gel is mixed in, but in cases where coating workability, thin film forming properties, and film uniformity are important, a low-viscosity material containing almost no gel content is preferable. Conversely, for the purpose of increasing viscosity, an alkali or salt solution can be added as long as it does not impair film-forming properties. The colloidal silica used as the top coating material may be a sol prepared by any method such as acid decomposition of water glass, electrolytic dialysis, hydrolysis, gel peptization, or ion exchange. Colloidal alumina or colloidal silica can be used alone or in a mixture. However, when mixing, it is necessary to pay attention to the charge and pH of the particles and to avoid rapid gelation. The mixing ratio is 1 to 99% colloidal alumina and 99 to 1% colloidal silica, and they can be used in any proportion.

The water-soluble resin to be mixed with colloidal alumina, colloidal silica, or a mixture of colloidal alumina and colloidal silica must be capable of being made water-resistant by drying or by adding a hardening agent. By adding a resin, drying or curing can be carried out at a relatively low temperature, preventing any influence on the colorant, and also imparting chemical resistance and weather resistance, making it possible to produce a tough film.

Furthermore, thick films that cannot be achieved using colloidal alumina or colloidal silica alone can be produced.

The water-soluble resin that can be used in the present invention is an emulsion obtained by emulsion polymerization of vinyl unsaturated monomers such as vinyl acetate-ethylene copolymer emulsion, vinyl acetate-acrylic acid ester emulsion, acrylic resin emulsion, etc. Polymer types, emulsified resin types obtained by emulsifying resins such as alkyd resins and epoxy resin esters in water with an emulsifier, or emulsifying easily emulsifiable resins in water, alkyd resins, melamine resins, and urea. Hydrophilic groups are introduced into the core of resin, aminoalkyd resin, aminoacrylic resin, etc.
Examples include water-soluble aqueous solutions.

In addition, polyol/blocked isocyanate emulsions known as reactive emulsions and emulsions made by adding polymerizable carboxylic acids to acrylic acid or methacrylic esters and subjecting them to emulsion polymerization can also be used.
It is said to be extremely effective when a high degree of boiling water resistance is desired.

Furthermore, water-soluble resins that crystallize by heating and drying, such as polyvinyl alcohol resins, can also be used.

Among these, melamine resin is preferred in terms of its excellent weather resistance, chemical resistance, and surface hardness.
Here, melamine resin refers to monomethylolmelamine, dimethylolmelamine, trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine, which is a reaction product of 2,4,6-triamino-1,3,5-triazine and formaldehyde, Part or all of the methylol groups of hexamethylolmelamine and the above methylolmelamine can be replaced by an alcohol C _o H _n OH (n=1 to
4, m=3 to 9), and may be alkoxylated with a plurality of alcohols. Also included are alkoxylated compounds that are sparingly soluble in water but can be made into aqueous emulsions or suspensions.

In addition, the said water-soluble resin may be individual or may be a mixture consisting of two or more types of water-soluble resins.

The amount of water-soluble resin added varies somewhat depending on the type of resin, but generally it exceeds 20 parts by weight and 10,000 parts by weight per 100 parts by weight (solid content) of colloidal alumina and/or colloidal silica. The amount is less than parts by weight (in terms of solid content), preferably 60 to 2000 parts by weight (in terms of solid content), and more preferably 100 to 900 parts by weight (in terms of solid content). If the amount added exceeds 20 parts by weight, particularly improved weather resistance can be achieved. Also, when top coating with 100% water-soluble resin, depending on the type of resin, cracks may occur or peeling may occur between the resin film surface and the transfer surface. In order to improve adhesive strength, it is necessary to add at least 1% or more of a water-soluble resin. For water-soluble resins that require the addition of a curing agent, the required amount of curing agent is added.

It is also possible to add small amounts of stabilizers, radiation absorbers, dyes, pigments, lubricants, viscosity modifiers, etc. to the top coating material.

An appropriate top coating method should be selected depending on the size, flatness, curved surface, surface roughness, etc. of the base material, and generally speaking, casting method, spray method,
A roll coating method, a dipping method, a brush coating method, a screen printing method, an electrostatic coating method, etc. can be adopted.

After top coating, drying and curing are performed, and the temperature varies depending on the type and amount of water-soluble resin added, and is usually about 50 to 220°C.

The top coat film can be produced with a thickness of about 0.5 to 100 μm, but even with a thickness of about 0.5 to 10 μm, the transfer surface can be improved to have excellent chemical resistance, weather resistance, and abrasion resistance.

The thus obtained transfer material can be used in a wide variety of applications such as interior materials and exterior materials.

Furthermore, since the film is uniform and can be made thin, the refractive index is constant, and the quality of the surface of the base material is directly reflected, making it suitable for decorative applications.

Next, the present invention will be specifically explained with reference to Examples.

Example 1 Colloidal alumina (boehmite, solid content 10% by weight PH4) prepared by peptizing alumina gel was applied to a glass plate, dried at 75°C, and then fired at 550°C for 1 hour, resulting in a thickness of 5 μm. A transparent γ-alumina film was obtained.

Next, disperse dye manufactured by Sumitomo Chemical Co., Ltd. (TS-W)
The printed side of the transfer paper printed with BLUE 603) and the alumina film side were overlapped at a pressure of 0.5Kg/cm ² and a temperature of 200℃.
A transparent color print was obtained by pressing for 1 minute at .degree.

Next, the solid content of colloidal silica is 100
Epoxy emulsion EP made by Toto Kasei in the weight part
266 in terms of solid content and 245 parts by weight in terms of solid content of Toto Kasei's curing agent KP-131 were mixed, and this was coated on the transfer surface and dried at 150°C for 60 minutes, resulting in a thickness of 9 μm. A cured film was obtained.

No change in color was observed even when this was exposed to a light fastness tester, Fedmeter, for 20 hours, in steam at 120°C for 1 hour, or immersed in toluene at 50°C for 24 hours.

Example 2 Colloidal alumina (boehmite, solid content 10% by weight, PH4) prepared by peptizing alumina gel was applied to a glass plate, dried at 75°C, and then fired at 550°C for 1 hour. A transparent γ-alumina film of 5 μm was obtained.

Next, disperse dye manufactured by Sumitomo Chemical Co., Ltd. (TS-
The printed side of the transfer paper printed with WBlue 603) and the alumina film side were overlapped at a pressure of 0.5 kg/cm ² and a temperature of 200 ml.
A transparent color print was obtained by pressing for 1 minute at .degree.

Next, in terms of solid content of colloidal alumina,
Water-soluble methylated melamine resin manufactured by Sumitomo Chemical Co., Ltd. (2 methylol groups, 3 methoxy groups) was added to 100 parts by weight.
900 parts by weight (in terms of solid content) were mixed, and this was coated on the transfer surface and dried at 160°C for 60 minutes, resulting in a cured film with a thickness of 8 μm. this,
20 hours or 120 hours on lightfastness tester Fedometer
There was no change in color even when exposed to steam at a temperature of 50°C for 1 hour, and no change in color was observed even when immersed in toluene at a temperature of 50°C for 24 hours.

Example 3 Colloidal alumina (boehmite, solid content 10% by weight, PH4) prepared by peptizing alumina gel was applied to a glass plate, dried at 75°C, and then fired at 550°C for 1 hour. A transparent γ-alumina film of 5 μm was obtained.

Next, disperse dye manufactured by Sumitomo Chemical Co., Ltd. (TS-W)
The printed side of the transfer paper printed with Blue 603) and the alumina film side were overlapped at a pressure of 0.5Kg/cm ² and a temperature of 200℃.
A transparent color print was obtained by pressing for 1 minute at .degree.

Next, 100 parts by weight of a water-soluble methylated melamine resin (one methylol group, two methoxy groups) manufactured by Sumitomo Chemical Co., Ltd. was added to 100 parts by weight of the above colloidal alumina in terms of solid content. After mixing, this was coated on the transfer surface and dried at 170°C for 60 minutes, resulting in a cured film with a thickness of 5 μm and a pencil hardness of 8H. Add this to the light fastness tester FEDOMETER for 20 minutes.
There was no change in color even when exposed to steam at 120°C for 1 hour, and no change in color was observed even when immersed in toluene at 50°C for 24 hours.

Example 4 Colloidal silica (PH9.5, solid content 20% by weight)
was applied to a porous absorption plate and dried at 90℃ for 2 hours.
It was baked at ℃ for 30 minutes.

Next, disperse dye manufactured by Sumitomo Chemical Co., Ltd. (TS-W)
Layer the printed side of the transfer paper printed with Blue 603) and the silica film side at a pressure of 0.5 kg/cm ² and a temperature of 200 ml.
When pressed for 1 minute at ℃, a color print was obtained.

Next, 100 parts by weight (in terms of solid content) of colloidal silica was mixed with 400 parts by weight in terms of solid content of the water-soluble methylated melamine used in Example 3, this was coated on the transfer surface, and the mixture was heated at 150°C. After drying for 30 minutes, a cured film with a thickness of 7 μm was obtained.

There was no change in color in the same toluene resistance test as in Example 1 and methanol resistance test in which it was immersed in methanol at a temperature of 30°C for 24 hours, and in the weather test, there was no change in color even after 100 hours of irradiation. It wasn't recognized.

Example 5 The colloidal alumina obtained by the method of Example 1 was applied on a tile degreased with trichlene, air-dried, and then baked at 600°C for 30 minutes to form a transparent γ film with a thickness of 6 μm.
- An alumina film was obtained.

Next, disperse dye manufactured by Sumitomo Chemical Co., Ltd. (TS-W)
Red 603) printed surface of the transfer paper and the alumina film surface were overlapped at a temperature of 220℃ and a pressure of 0.1Kg/
After pressing for 2 minutes at cm ² , clear color prints were obtained.

Next, 70 parts by weight of colloidal alumina used in Example 1 in terms of solid content, 30 parts by weight of colloidal silica (PH4) in terms of solid content, and Example 3
In terms of water-soluble methylated melamine solid content used in
560 parts by weight was mixed, coated on the transfer surface of the above transfer body, and dried at 170℃ for 60 minutes, resulting in a thickness of 10μ.
A cured film of m was obtained.

No change in color was observed even after the same toluene resistance and weather tests as in Example 1 were carried out by irradiation for 100 hours.

Claims (1)

[Scope of Claims] 1. In a method for thermally transferring characters and designs onto an alumina film or a silica film obtained from colloidal alumina or colloidal silica, after the heat transfer using a transfer foil containing a sublimable colorant, Colloidal alumina and/or colloidal silica
A method for improving a thermal transfer body, characterized by applying a solution containing a mixture of more than 20 parts by weight and less than 10,000 parts by weight of a water-soluble resin capable of making it waterproof per 100 parts by weight, and drying and curing the transfer surface. . 2. The method for improving a thermal transfer body according to claim 1, wherein the water-soluble resin is a melamine resin.