JPS6239275A - Production of decorating water transfer paper for ceramic ware or the like - Google Patents

Abstract

PURPOSE:To mass-produce the titled water transfer paper, by a method wherein an ink having a composition in which particles of water-soluble high molecular weight substance having a diameter in a specified range or swollen particles thereof are suspended in a mixed solvent of an organic solvent and water is applied to a water-absorptive raw paper as a releasable layer by screen printing, an ink layer is provided thereon by printing, and a cover coat layer is provided thereon by printing. CONSTITUTION:An ink having a composition in which particles of a water-soluble high molecular weight substance having a diameter of 5-50mum or swollen particles thereof are suspended in a mixed solvent of an organic solvent and water is applied to a water-absorptive raw paper as a releasable layer by screen printing, then an ink layer for decorating a ceramic ware or the like is provided thereon by printing, and a cover coat layer is provided thereon by printing. The water-soluble high molecular weight substance may be a polyacrylic acid, a derivative thereof, a mixture thereof or a sodium or amino salt thereof, polyvinyl alcohol or the like. The high molecular weight substance is suspended in an alcohol solvent, a hydrocarbon solvent, an aromatic solvent or a mixed solvent thereof to prepare an ink for screen printing. Accordingly, it is possible to facilitate the step of decorating a ceramic ware or the like by the water transfer method.

Description

[Detailed description of the invention]

-1 J The present invention relates to water transfer paper used for painting on ceramics and the like. 11 Good 1 The well-known water transfer paper, which has traditionally been used as a means of large-scale production on an industrial scale for painting on ceramics, etc., is a water-absorbing base paper coated with a water-soluble resin as a release layer. Supply it to the printing factory. It is necessary to keep a large amount of stock to match the printing scale of the printing factory, and quality changes (curling, cracking, etc.) occur during storage. In printing, it causes printing unevenness and printing misalignment. During transfer, there are drawbacks such as sliding failure. The well-known water-absorbent base paper referred to in this text is a highly water-absorbent base paper made from evergreen pulp and does not contain clay fillers, and calendered on one or both sides. Next, as a release layer,
A water-soluble polymer (starch, dextran, cellulose, polyacrylic resin, polyethylene oxide, pectin, carrageenan, etc.) is coated for 1 to 3 days. Coating: This is done using a roll coater, knife coater, etc. before cutting the long paper into sheets. Match this with a printing press (currently, screen printing and ifsesoto printing are mainly done), and print 20 to 100 centimeters.
Cut into m paperboard (square or rectangle). Printing is done on this paperboard at a printing factory. The (7)-7' process involves printing the flux-containing ink, patterning, and then cover-coating the support film to give a sliding effect. In the painting process, a necessary portion of the paper laminated and printed on the water-absorbent base paper with the above-mentioned water-absorbent base paper, release layer, pattern, and support film cover coat is cut out and immersed in water. After 10 to 120 seconds of immersion, take it out, slide the paper, pattern, and supporting film parallel to each other with a release layer, and transfer and paste it onto an object such as ceramics. After that, the printed design is heat-fused to the ceramic by firing,
The adhesive of the release layer and the support film for the slide are thermally decomposed, carbonized,
Let it vaporize. Fire excretion and fortune-telling J2 ↓ Lae [presentation] ll harvest 1

[The well-known water transfer paper manufacturing method has the following problems. 1. In particular, problems may arise in the final product obtained after applying the box-shaped layer, such as markings H+J, slides with pictures, pasting, and firing. As a solution to this problem, it is often necessary to change the release layer. At this time, changing the water-soluble polymer lake in the release layer and adjusting the water absorption are easy because they are produced by integrated production at a paper mill or mass coating at a processed paper mill. I can't. 2. Water-absorbent base paper coated with a release layer made of water-soluble polymer glue is easily affected by humidity and temperature;
Depending on the temperature conditions, curling (curving) and cracking of the release layer may occur due to the difference in the degree of expansion and contraction between the front and back sides. Curling makes it impossible to print on the transfer paper, and cracking is a fatal drawback in that it impedes sliding when using water transfer paper. 3. For mass production processing, it is necessary to constantly prepare tens to hundreds of thousands of sheets of water-absorbent base paper coated with a box-shaped layer that is easily affected by humidity and temperature, ensuring dimensional stability. Therefore, careful attention must be paid to humidity and temperature control during storage. We, the research group, took up this problem, conducted extensive research, and established the water transfer paper manufacturing method of the present invention. Question 1. In the present invention, water-absorbing base paper is made by a conventional method, cut to a rated value,
After confirming dimensional stability, we have made it possible to implement on an industrial scale a water transfer paper production method in which the composition of the present invention, which will become a release layer, is applied only to the necessary areas using a printing method immediately before the screen printing process. . By applying the final method, water transfer paper can be made, coated with a release layer, then humidity controlled to ensure dimensional stability, and decorative ink can be printed without the need for long-term storage. The process of painting should be simplified. In other words, it is only necessary to prepare a water-absorbing base paper, print a release layer of a water-washing composition immediately before painting on ceramics, etc., and then print a painted ink cover coat. Examples of ink compositions having a mold release effect that are suitable for t: and y of the present invention include the following. Organic solvents include aromatic solvents such as benzene, toluene, and xylene; hydrocarbon solvents such as cuben, kerosene, gasoline, and liquid paraffin; alcohols such as methacol, glycerin, and ethylene glycol; ketones, esters, and carbonized halides. Hydrogen solvents, etc. alone or in mixtures. A composition formed by suspending particles of a water-soluble polymer compound alone and fine particles swollen with water or the above-mentioned organic solvent is used as a coating ink. Unlike known aqueous solutions of hydrophilic polymer compounds, fine particles of a water-soluble polymer compound suspended in a solvent have a low viscosity at the time of printing or coating in the powder method, and have a viscosity of 10% of their own weight during water transfer.
Use a composition that absorbs ~100 times more water and swells or dissolves. Known water-soluble polymer coating solutions have been used in the form of aqueous solutions. This coating liquid cannot be processed unless it has medium to low viscosity and no particles (less than 5 microns). Therefore, it is not possible to prepare a highly concentrated liquid, and the processing of the actual product is
Two or three coats of medium to low density ink were used to achieve this goal. On the other hand, in the screen printing method, it is possible to print one page with a particle size of 5 to 50 microns. The ink composition of the invention in which fine particles of a water-soluble polymer of 5 to 50 microns or swollen particles thereof are suspended can contain a high concentration of a high-viscosity hydrophilic substance. Compounds that can be used as fine particles or swollen particles of water-soluble polymers include the following. Polyacrylic acid and its derivatives alone or in mixtures, their sodium or amine salts, polyvinyl alcohol, polyacrylamide, polymaleic acid. Cellulose, starch derivatives (carboxymethyl cellulose, carboxymethyl starch, hydroquinoethyl cellulose, hydroquinopropyl cellulose, etc.) Microparticles of polymers that absorb several to several hundred times their own weight are generally called water-absorbing polymers. You can mix it up. (Example, starch-polyacrylonitrile crosslinked product, starch-polyacrylonitrile crosslinked product,
Polyacrylate crosslinked products, polyvinyl polymer crosslinked products,
partially cross-linked water-soluble polymers, etc.). In addition, water-soluble polymer glues such as locust bean gum and its derivatives, guar gum, gum arabic, and sodium alginate can be used. These water-soluble polymers are suspended in an alcoholic solvent, a hydrocarbon solvent, an aromatic solvent, or a mixture thereof, and atomized in a mill to obtain a screen printing ink. For products that are difficult to atomize using only these two components, a technique is used in which water is added to make the water-soluble polymer absorb water and swell, making it easier to atomize. Among the water-soluble polymer compounds, the water-absorbing polymers referred to in -a are particularly effective as those having a large sliding and mold-releasing effect for the decorative printing coating of the present invention. Particles of 5 to 50 microns, which have a water-absorbing swelling effect of 10 to 100 times the weight of the water-absorbing polymer, are added to the powdered ink.
Add 0% (weight). The ink composition of the present invention solves this problem by incorporating a water-absorbing pot into a flexible ink and fixing it to the casing, but deteriorating its function often impedes such use. The following industrially useful auxiliary components are also blended. Hydrophilic surfactants (nonionic surfactants, anionic surfactants, etc.) to increase water absorption. Contains a resin (water-soluble polymer) that adjusts the viscosity of the ink during printing. In addition, smoothing agents (dextrin, gum arabic,
An aqueous solution such as a vinyl water-soluble polymer lake can be blended. The main purpose of the present invention is water transfer for painting on ceramics, but it can also be used as a water transfer paper for painting on glass, enamel, etc. by using the same fired painting ink as the ink for painting on ceramics. It can also be used for painting on soaps, candles, plastics, metals, etc., which are currently being used for water transfer. Example 1゜Water-absorbent base paper (Shikoku Paper Co., Ltd. AQ Susu--), size 640
cm x 490 cm paper, leaving 2 cm of each outer edge,
The water-soluble glue of Formulation Example 1 was applied to an area of 638<em>X 4 B 8 cm by screen printing (ink size: 70 microns) and dried. Next, print the design with ceramic painting ink, acrylic 41
[(Cover coat resin LO-1 manufactured by Rohm and Hass Co., Ltd.
80HR) to prepare a water transfer paper. The degree of curl due to humidity of paper before printing for pottery painting is measured by applying water-based glue (polyacrylamide 2g/m') to conventional long rolling paper.
, dextrin 20 g/m' double-layer coated paper) compared to humidity (80%, 25 °C), 60 °C after 24 hours3
When left in the drying room for 0 minutes, the conventional product curled inward and could not be printed. This prescription product caused no problems in printing, with only slight waving. Suspension ink formulation example of water-soluble glue (ffi amount%) water
40 isopropyl alcohol
423GP polymer (Henkel Corporation product) 1
0 (passed through 200 ITIesh, diameter 20-70 microns) Octyl alcohol 2 Polyvinyl alcohol 5 (degree of polymerization 500, degree of saponification 97) Alkylbenzenesulfone soda 1 The above mixture was processed in a Miki roll mill (with a roll spacing of 0.05 m,
Subsequently, the ink was subjected to finishing kneading with a roll interval of 0.02 cylinders. The viscosity of the ink can be adjusted by adding water during printing. Example 2 Water-soluble glue suspension ink formulation (% by weight) Keronone 31 Sorbitan oleate (98% purity) 4 Carbogynomethyl cellulose 10 Dextrin
2゜water
28 glycerin
5 Realyl sulfosacunnate 2 The above formulation was atomized using a triple roll to form a water-soluble glue swelling particle suspension ink of 5 to 50 microns. The ink viscosity during printing was adjusted by adding water and using a high-speed homomixer to make W10 ink. This was made into water transfer paper using the same process as in [Example], and when ceramics were painted, the printability, sliding properties, adhesion to ceramics, and firing quality were the same as with conventional water transfer paper. I got something. This manufacturing method is extremely advantageous in terms of shortening the process and preventing paper from curling. Example 3 Suspension ink formulation of water-soluble polymer glue (wt%) Mineral spirit 35 Nisben (
Toyojun Yoko Co., Ltd. products)] Tsurupon 580
(Toho Chemical Industry Co., Ltd. product) 4 water
18 Sumikagel S50 5 (Fine powder of 44 microns, manufactured by Sumima Kagaku Kogyo Co., Ltd.) Polyethylene oxide 2 (Produced by Seitetsu Kagaku Co., Ltd., average degree of polymerization 600,000) Dextrin
3 The above was made into ink, and as in Example 1, a circular water-based glue with a diameter of 15+m was screen printed on water-absorbing base paper. Next, the decorative ink was printed on the water-based glue in a circular pattern with a diameter of 10 (t), and the cover coat resin ink was applied as a support film in a circular pattern with a diameter of 12 ma+diameter. This paper was cut out (a square cut of about 2 cIT+ centered around the circle design), thrown into water, taken out after 30 seconds, and examined for sliding properties. As a result, there was no problem in the areas where the release layer was not applied, and the length was 12+ m. The film could be transferred to ceramics. This formulation uses less water-based glue and is more economical than conventional water transfer paper in which a water-based glue is applied as a release layer over the entire surface. or,
It was recognized that the paper does not curl during printing and does not require special humidity control during paper storage. Example 4 Suspension ink formulation of water-soluble polymer glue (% by weight) Ethylene glycol 10 Isopropyl alcohol 35 Water
3
6 Polyacrylamide 14 (
Harikyu Kasei Kogyo Co., Ltd. product, Harifloc N200) Ultra-high polymer water-soluble polymer polyacrylamide is conventionally 1
The limit was to prepare an aqueous solution with a concentration of ~2%, and a highly concentrated solution could not be obtained. By suspending the above formulation as swollen particles in a mixed solvent of an organic solvent and water, a coating liquid with high concentration and good fluidity can be obtained. To adjust the viscosity, increasing the alcohol component will lower the viscosity, and adding more water will increase the viscosity. Absorb the above ink on the entire surface of base paper (paper size 470cnn
670e+n (Wi), dried, and then printed with decorative ink (oil-based) to create water transfer paper. This example has water-soluble glue applied to the entire surface like conventional water transfer paper, but since the process from obtaining the water-absorbing base paper to creating the designer's water transfer paper is short, Curling occurred during hot air drying after application of the release layer, but it could be corrected to a flat surface by adjusting the humidity before printing the design. Conventionally, in order to prevent curling and obtain dimensional stability, curling occurred in a controlled room (warehouse). There is no longer a need for processes that had to be preserved and managed for several months.

[Brief explanation of the drawing]

Fig. 1 shows the composition of a conventional water transfer paper. Fig. 2 shows the basic composition 1 of the water transfer paper of the present invention, a cover coat 1152, a decorative ink pattern 3a, a release layer 3b coated on the entire surface, and a screen-printed release layer. Mold layer 4, water absorbent base paper Figure 1

Claims (3)

[Claims] (1) Composed of water-soluble polymer particles with a diameter of 5 to 50 microns or swollen particles thereof suspended in a mixed solvent of an organic solvent and water.The ink is used as a release layer and screened onto water-absorbing base paper. A method for producing water transfer paper for painting on ceramics, etc., which comprises printing on a desired area, and then laminating and printing an ink layer for painting on ceramics, etc. and a cover coat layer. (2) For painting on ceramics, etc., inks made of glass, metals, and metal oxides are applied, and for transferring the design, the laminated printing layer released from water-absorbing base paper is attached to the ceramics, etc., and the painting is applied by firing. A method for producing a water transfer paper for painting according to claim (1), which is characterized by carrying out the following. (3) The picture according to claim (1), characterized in that a combination of compatible solvents or an incompatible emulsion-like mixed solvent is used as the mixed solvent with the organic solvent and water. Manufacturing method of water transfer paper.