JPH0636958Y2 - Thermosensitive reversible color change pattern transfer sheet for ceramic products - Google Patents

Description

[Detailed Description of the Invention] Industrial Application Field of the Invention The present invention is capable of easily forming a pattern on the surface of ceramic products such as ceramics, enamel or glass, which is sensitive to temperature changes and reversibly changes in color. The present invention relates to a novel temperature-sensitive reversible color change pattern transfer sheet for ceramic products, which can be firmly fixed by various operations.

Conventional technology and its problems Conventionally, ceramic products such as porcelain, enamel or glass are formed with a normal colorant by a water-transfer slide transfer method using transfer paper or a direct screen printing method using printing ink. It is done by doing.

By the way, in recent years, various thermochromic substances have been developed, and in particular, an acid-developing substance excellent in coloring power is used in combination with an acidic substance and a solvent to produce a pressure-sensitive thermosensitive copying paper and a pressure-sensitive thermosensitive copying desensitizer. It is disclosed that the findings are effective as, further, for example, an acid color-developing substance in US Pat.
The fact that a coexisting mixture of three components of an acidic substance and a solvent can reversibly change the color due to temperature change in the outside world has been disclosed, and the specific color change behavior using the mixture is today a doll. , Toys such as stuffed animals, daily necessities such as sponges and buckets, and products such as accessories such as towels, T-shirts and clothing. Further, as disclosed by the applicant in Japanese Utility Model Publication No. 62-50999 and Japanese Utility Model Publication No. 62-51149, such a thermochromic function is utilized in ceramics and glass.

The invention of the above-mentioned ceramics and glass is to prepare a three-component mixture of an acid-developing substance, an acidic substance and a solvent in a microcapsule encapsulated with a thermosetting resin, and further coat the surface with a hydrophilic polymer compound. A printing ink containing the temperature-sensitive color-changing granules is used to form a color-changing pattern on the surface of ceramics or glass.The density at the time of color development is high, and the hue and color-changing temperature can be selected clearly. Although it has the characteristic of permanently exhibiting the excellent thermochromic function,
Since the picture is directly attached by screen printing, there are various problems as described below.

1) In the printing of a pattern having a large number of discoloring colors, pattern matching is difficult, and the efficiency of printing work is extremely poor.

2) The sharpness of the picture is poor, and fine line patterns and complicated patterns cannot be obtained.

3) Discoloration pattern cannot be applied to the flat or cylindrical side surface of ceramic products.

4) When a handle such as a mug or mug is targeted, printing cannot be performed around the handle, the position of the pattern is limited, and the efficiency of printing work is low.

Further, Japanese Utility Model Publication No. 61-19040 discloses a transfer printing sheet having the same temperature-sensitive color changing function as described above. However, when this sheet is applied to a ceramic product, the adhesiveness is poor, and the hardness of the transfer layer surface is low, so that the sheet is easily scratched, so that it cannot be applied at all.

Further, the thermochromic substance is weak against heat and loses its function at high temperature. Therefore, even if an attempt is made to form a temperature-sensitive color-changing pattern on a ceramic product by using the temperature-sensitive color-changing substance or this microcapsule-encapsulated substance to form a water-coated slide-transfer sheet, sufficient adhesion will be obtained after the slide transfer. In order to obtain the property and surface hardness, baking at a high temperature of about 600 ° C. is required, and at that time, the thermochromic function is lost.

The above has hindered the spread of products in which ceramics are provided with a thermochromic pattern.

Means for Solving the Problems The present invention aims to provide a temperature-sensitive reversible discolorable transfer sheet for ceramic products which can solve or alleviate the problems of the direct screen printing method. Further, the present invention is capable of imparting a thermosensitive color-changing pattern pattern having excellent adhesiveness, surface hardness, and abrasion resistance by baking at a relatively low temperature, and the pattern is sensitive to temperature change and the color is reversible. An object of the present invention is to provide a temperature-sensitive reversible color-changeable transfer sheet for ceramic products that changes dynamically.

That is, the present invention is an adhesive that is directly provided on the release layer (2) for water-bonding slide transfer provided on the entire surface or a specific portion of the base sheet (1) with a contour that can be enlarged from the desired pattern. Layer (3), a granular material on which the three components of an acid-developing substance, an acidic substance and a solvent are co-encapsulated with a thermosetting resin on the adhesive layer (3) directly or through another layer A color-changing pattern layer (4) comprising a thermosensitive color-changing granular material further surface-coated with a hydrophilic polymer compound, and the color-changing pattern layer (4)
A protective layer (5), which is formed so as to match the contour of the adhesive layer (3) on which an ultraviolet absorber is contained, directly or through another layer, and the protective layer (5) A cover coat layer (6) formed on the top of the protective layer (5) by a printing ink containing a polymeric elastic resin and a plasticizer having a poor compatibility with the protective layer (5) and having a contour that is enlarged. ) A thermosensitive reversible discolorable pattern transfer sheet for a ceramic product, wherein the adhesive layer (3), the discolored pattern pattern layer (4) and the protective layer (5) are a silane coupling agent and a heat, respectively. The present invention relates to a temperature-sensitive reversible discolorable pattern transfer sheet for ceramic products, which is formed by a printing ink containing a curable resin.

According to the study by the present inventor, as described above, the adhesive layer (3), the color change pattern layer (4) and the protective layer (5) in the transfer sheet are printed by using a silane coupling agent and a thermosetting resin. When formed with ink, the temperature-sensitive reversible discoloration pattern has excellent adhesion to ceramic products even when baked at a relatively low temperature of 120 to 220 ° C, and also has a high surface hardness of the transfer layer and excellent abrasion resistance. It has been found that patterns can be applied to ceramic products.

The excellent effect as described above can be obtained only when the silane coupling agent and the thermosetting resin are used in the above three layers, and the silane coupling agent or the thermosetting resin is used in any one layer. You can't get it if there are no layers.

In the temperature-sensitive reversible color change pattern transfer sheet for ceramic products of the present invention, a printing sheet having good water absorption is most suitable as the base sheet (1).

The release layer (2) allows the base sheet (1) to be peeled off during the transfer by the water-bonding slide transfer method so that the base sheet can be extracted. Examples of the releasable substance forming the release layer (2) include water-soluble pastes such as starch, dextrin, gum arabic, wheat flour and polyvinyl alcohol. The release layer (2) can be formed by appropriately applying these to the entire surface of the base sheet (1) or a specific portion.

The adhesive layer (3) adheres well to the ceramic products by water-bonding slide transfer, and firmly adheres by the subsequent heat treatment. The adhesive layer (3) is one or more thermosetting resins such as epoxy resin, melamine resin, benzoguanamine resin and urea resin, or the thermosetting resin and polyolefin resin, halogenated olefin resin, polyacryl. A silane cup such as a methoxysilane-based or acetoxysilane-based resin that is used in combination with one or more polymer elastic resins such as acid ester resin, saturated polyester resin, nylon resin, amino acid resin, polyurethane resin, and fatty acid vinyl resin. It can be formed by applying it as a printing ink in the form of a solvent solution, an emulsion or a melt together with a ring agent onto the release layer (2).

The temperature-sensitive color-changing particles contained in the color-changing pattern layer (4) are particles obtained by encapsulating a three-component mixture of an acid-developing substance, an acidic substance and a solvent in a microcapsule with a thermosetting resin. Since the surface is coated with the hydrophilic polymer compound, the coating film of the granular material containing the three components is tough and is excellent in heat resistance, solvent resistance and the like. Therefore, it is completely unaffected by heat treatment (about 120 to 220 ° C) when fixing various solvents or plasticizers or the sheet of the present invention to ceramic products, and the constant ratio system of acid components is completely preserved, and the coloring density is maintained. Highly effective, it permanently exhibits the thermochromic function of repeating coloring and decoloring with sharpness. The color-changing pattern layer (4) is formed by applying a desired pattern with the same printing ink as that used in the temperature-sensitive color-changing granular material and the adhesive layer (3).

Examples of the acid-developing substance include benzoyl leuco methylene blue, crystal violet lactone, and rhodamine carbinol hydrochloride, and examples of the acidic substance include:
Dibenzotriazole, 4-phenyltriazole, amidophenol, β-oxynaphthoic acid methyl ester,
Examples thereof include phenol resins, and examples of the solvent include higher fatty acid alcohols, acid amides, high boiling point esters, azomethine, and the like.

These three-component mixture is a known microencapsulation method such as an interfacial polymerization method or an in situ polymerization method using one or two or more kinds of thermosetting resins such as melamine resin, urea resin, alkyd resin, and epoxy resin as a wall film substance. In the present invention, the thermosensitive discoloration in the present invention is obtained by coexisting and encapsulating to form a granular material, and further by applying a surface coating with a hydrophilic polymer compound such as polyvinyl alcohol, polyacrylate, gelatin, methylcellulose, and alginate. Granulated.

As the protective layer (5), the discolored pattern layer (4) is attached to the adhesive layer (3).
It is fixed so as to be wrapped between and, so that the color change pattern layer (4) is shielded from ultraviolet rays, solvent, hot water, etc., and the adverse effect of friction is eliminated, so the color change property of the color change pattern layer (4) The function is less likely to deteriorate during manufacturing and subsequent use, and the commercial value is further enhanced. Protective tank (5)
Is formed on the discolored pattern layer (4) by the same printing ink as that used in the adhesive layer (3) with an ultraviolet absorber added, which matches the contour of the adhesive layer (3). . Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylic acid-based, cyanoacrylate-based and the like. Further, by adding a leveling agent to the protective layer (5), the gloss and smoothness of the surface of the discolored pattern pattern layer (4) can be further improved.

The cover coat layer (6) prevents deformation due to stretching of each layer below when the sheet of the present invention is adhered to a ceramic product by a slide transfer method and then adhered by a rubber cage or the like. Since it is poorly compatible with 5), it is temporarily adhered but does not adhere, so that it can be easily peeled off before heat treatment for fixing to ceramic products. Therefore, it is not necessary to burn the cover coat layer (6) at the time of heat treatment, the heat treatment temperature can be set to a relatively low temperature, and the thermoreversible color-changing function of the thermochromic granules can be favorably maintained. The cover coat layer (6) contains, on the protective layer (5), a polymer elastic resin and a plasticizer having a contour that is larger than the shape of the protective layer (5) and poor in compatibility with the protective layer (5). It is formed by the printing ink. Examples of the polymeric elastic resin include polymethacrylic acid ester, polystyrene, vinyl chloride, and cellulosic resin. The cover coat layer (6) can be formed with a printing ink in which this and a phthalate ester-based, phosphate ester-based, or fluorine-based release agent are used in combination.

In the sheet of the present invention, a printing ink similar to that used in the adhesive layer (3) with a non-color-changing colorant added between the adhesive layer (3) and the protective layer (5), if necessary. The non-color-changing pattern pattern layer (8) may be formed, whereby a variety of pattern patterns can be expressed.

Further, it is optional to form the concealing layer (7) between the adhesive layer (3) and the color-changing pattern pattern layer (4), and the color of the color-changing pattern pattern layer (4) can be further sharpened. it can. This effect is particularly remarkable when painted on a transparent substrate such as glass. Examples of the hiding substance forming the hiding layer (7) include titanium oxide, zinc white, calcium carbide, barium sulfate, ammonium silicate and the like, which are mixed with the same printing ink as used in the adhesive layer (3). Used.

Incidentally, in the above-mentioned granular material and in each layer, usual chemical agents such as extender pigments, surfactants, viscosity modifiers, plasticizers, ultraviolet absorbers, antioxidants, cross-linking agents, catalysts, water repellents, defoamers. Addition of agents, fats, waxes, antistatic agents, etc. does not depart from the gist of the present invention.

By drying the laminate thus formed and removing unnecessary volatile components, the temperature-sensitive reversible color change pattern transfer sheet for ceramic products of the present invention can be obtained.

Since the transfer sheet of the present invention uses a silane coupling agent and a thermosetting resin for the adhesive layer (3), the color-changing pattern layer (4) and the protective layer (5), it functions as a thermochromic substance. It is firmly fixed to the ceramic products by heat treatment at a relatively low temperature without damage, and the discolored pattern obtained has a high surface hardness and excellent abrasion resistance.

The transfer sheet of the present invention is used, for example, as follows.

That is, first, the transfer sheet of the present invention is soaked in water, and then it is attached to a desired position of ceramic products of various shapes such as ceramics, enamel or glass by the slide transfer method and brought into close contact with a rubber cage or the like. Next, after allowing the water to evaporate sufficiently by natural drying, the cover coat layer (6) on the surface of the pattern is peeled off, and finally heat treatment is carried out at about 120 to 220 ° C for 5 to 60 minutes to give a stable and robust feeling. A thermochromic pattern can be applied.

Specific examples of the present invention will be described below.

Example 1 This example will be described based on 1 in FIG. 2 and 2 in FIG.

First, a dextrin aqueous solution was glued on the surface of a printing paper [base sheet (1)] having high water absorption, dried and moisture-conditioned, and then mirror-finished to form a release layer (2).

Next, 100 parts of epoxy screen printing ink (epoxy resin urea melamine formalin condensate, manufactured by Seiko Advance Co., Ltd.), 1 part of silicone SH6040 (methoxysilane-based silane coupling agent, manufactured by Toray Silicone Co., Ltd.) and silicone TSA720 (antifoam). Agent, manufactured by Toshiba Silicone Co., Ltd.), and prepared a clear ink (hereinafter, the same composition) consisting of 0.3 part, and using a die having a contour reduced to 2 mm inward from the release layer (2), the release layer (2) An adhesive layer (3) was formed on top.

In addition, 100 parts of clear ink is mixed with 0.1 to 1% of a general pigment to print the girl and balloon parts in FIG. 2 in multicolor on the adhesive layer (3) to obtain a non-changing color pattern layer ( 8) was formed.

Furthermore, 100 parts of clear ink, chromic color S-45
A bee with a printing ink consisting of 20 parts of first black (temperature-sensitive color-changing granular material [manufactured as described above; the same applies hereinafter] [black colorless], manufactured by Matsui Pigment Chemicals Co., Ltd.),
Bee orbital point and printing of tree, leaf and nut outline (4a), 100 parts of clear ink, chromic color S-45
Printing leaves (4b) with a printing ink consisting of 10 parts of green (thermosensitive granules [colorless], manufactured by Matsui Pigment Chemicals Co., Ltd.), 100 parts of clear ink, chromic color S-45 brown (temperature-sensitive discoloration) Granular material (brown colorless),
Printing of tree trunk (4c) with 10 parts of printing ink, and 100 parts of clear ink, Chromic Color S-45 Vermillion (thermochromic granules, vermilion colorless), Matsui Printing of tree nuts (4d) with a printing ink consisting of 10 parts of Dye-Chemical Industry Co., Ltd. was performed on the adhesive layer (3) or the non-color-changing pattern pattern layer (8), and a multicolor color-changing pattern pattern layer ( 4) was formed.

Next, with 100 parts of clear ink, 0.5 parts of TINUVIN 328 (UV absorber, manufactured by Ciba Geigy) was added to the printing ink, and a protective layer was formed on the entire surface with the same plate as that used for the adhesive layer (3). (5) was formed.

Lastly, DIANAR BR-107 (polymethacrylic acid ester copolymer resin, Mitsubishi Rayon Co., Ltd.) 40 parts, epoxy fatty acid ester plasticizer 20 parts, xylene 40 parts, silicone
SH-200 (silicone release agent, manufactured by Toray Relecon Co.) 0.5
2m from the contour of the protective layer (5) with printing ink consisting of parts
m After forming the cover coat layer (6) with a die having an enlarged contour, it was naturally dried for 24 hours to obtain a transfer sheet of the present invention.

The transfer sheet was soaked in water, picture-painted on the prismatic surface of an octagonal prism mug by a slide transfer method, and sufficiently adhered by contacting with a rubber cage, and then naturally dried for about 12 hours to completely evaporate the water content. .

Next, the cover coat layer (6) was peeled off, and heat treatment was carried out at 180 ° C. for 15 minutes, whereby the pattern of the discoloring multicolored pattern “Girl's Tree Climbing” was firmly adhered to the side surface of the prism of the mug.

At room temperature, the bee is flying and the girl is climbing on the tree at room temperature, but when the temperature of the beer and the tree reached about 45 ° C by pouring coffee or the like, the bee and the tree disappeared, and the girl left the balloon and became a pattern. .
This change could be repeated any number of times by changing the temperature.

Example 2 This example will be described with reference to FIG.

First, starch was glued onto the surface of a printing paper [base sheet (1)] having high water absorption, dried and moisture-conditioned, and then mirror-finished to form a release layer (2).

Next, 85% ethyl cellosolve acetate solution of 35% Byron 300 (saturated polyester resin, manufactured by Toyobo Co., Ltd.), Epicoat 1001 (epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd.)
7 parts, Super Beckamine J820-20 (butylated methylol melamine resin, manufactured by Dainippon Ink and Chemicals, Inc.) 8 parts, Silicone TSA720 0.3 parts, Silicone SH6075 (acetoxysilane-based silane coupling agent, manufactured by Toray Silicone Co., Ltd.) 1 part A base clear consisting of (hereinafter, the same composition) was used to form an adhesive layer (3) having a contour that was 2 mm larger than the balloon boat pattern to be applied later.

Next, a concealing layer (7) was formed on the entire surface of the adhesive layer (3) with a printing ink consisting of 100 parts of base clear and 20 parts of titanium JR-701 (titanium oxide, manufactured by Teikoku Chemical Co., Ltd.).

Furthermore, 100 parts of the base clear is mixed with 0.1 to 1% of a general pigment to print children and baskets in multiple colors, and only the outlines of the balloons are printed in black. ) Was formed on the hiding layer (7).

Next, 100 base clear, chromic color S-17
The leftmost balloon (4e) made of printing ink consisting of 20 parts of yellow (thermochromic granules [yellow colorless], manufactured by Matsui Dye Chemical Industry Co., Ltd.) and 0.3 parts of Hoster Palm Pink E (pink organic pigment, manufactured by Hoechst) ) Printing, base clear 100 copies,
Printing the central balloon (4f) with a printing ink consisting of 25 parts of chromic color S-10 green (temperature-sensitive discolorable granular material [green colorless], Matsui Dye Chemicals Co., Ltd.) and 0.3 parts of Hoster Palm Pink E, Also, with a printing ink consisting of 100 parts of base clear, 25 parts of chromic color S-5 turkis blue (thermochromic granules [blue colorless], manufactured by Matsui Pigment Chemicals Co., Ltd.), and 0.3 parts of Hoster Palm Pink E. The balloon (4 g) at the right end was printed on the adhesive layer (3) or the non-color changing pattern pattern layer (8) to form a multicolor color changing pattern pattern layer (4).

Next, 100 parts of base clear, 0.5 parts of silicone ST90PA (leveling agent, manufactured by Toray Silicone Co., Ltd.), and seesaw 102
(UV absorber, manufactured by Shiraishi Calcium Co., Ltd.) A protective layer (5) was formed on the entire surface with the same plate as that used for the adhesive layer (3) with 0.5 parts of a printing ink.

Finally, 75 parts of Dyanal BR-107, 25 of DHP (plasticizer)
Part of silicone SH-200 0.5 part, a cover ink layer (6) with a contour 2 mm larger than the contour of the protective layer (5) was formed with a printing ink, and then the sheet was naturally dried for 1 day to obtain the transfer sheet of the present invention. Obtained.

The transfer sheet was dipped in water, picture-painted on a curved surface of a wine glass by a slide transfer method, and brought into close contact with a rubber cage so as to be sufficiently adhered thereto, and then naturally dried for about 12 hours to completely evaporate water.

Next, the cover coat layer (6) was peeled off, and heat treatment was performed at 180 ° C. for 15 minutes, whereby the handle of the “balloon ship” was firmly fixed to the curved surface of the wine glass.

Balloons (4e), (4f), and (4g) are all pink at room temperature of 25 ° C, but when wine with a liquid temperature of 10 to 17 ° C is poured, only the leftmost balloon (4e) changes color and becomes orange. When a wine with a liquid temperature of 5 to 10 ° C is poured, the balloon in the center changes color to black, and when wine with a liquid temperature of 5 ° C or less is poured, the balloon at the right end also changes to blue, and what is the change? It can be reversibly repeated even once, and it senses the optimum temperature for drinking wine while enjoying the change in the design.

Comparative Example 1 As in Example 2, except that the formation of the protective layer was omitted, a pattern was applied to the curved surface of the wine glass, and the qualities were compared as shown in Table 1.

Comparative Example 2 The curved surface of the wine glass was patterned in the same manner as in Example 2 except that the temperature-sensitive color-changing granules used in Example 2 were used without the hydrophilic polymer surface coating.
The quality was compared as shown in Table 2.

Comparative Example 3 The adhesive layer (3) and the discolored pattern layer (4) in Comparative Example 2
Also, a transfer sheet was obtained in the same manner as in Example 2 except that the protective layer (5) was replaced with that of the example of Japanese Utility Model Publication No. 61-19040, that is, with the following composition, and fixed to a wine glass. The quality is shown in Table 4. The heat treatment is 180 ℃, 5
It was performed under the conditions of second, 180 ° C., and 15 minutes.

Adhesive layer Denka vinyl (vinyl chloride resin, manufactured by Nippon Zeon Co., Ltd.) 30 parts Butyl cellosolve acetate 30 parts Xylol 40 parts Discolored pattern layer Piperon # 30 (chlorosulfonated polyethylene rubber,
Showa Neoprene Co., Ltd.) 20 parts Temperature-sensitive color-changing granules 30 parts Aerosil (silica gel, Nippon Aerosil Co., Ltd.) 2 parts Xylol 48 parts The temperature-sensitive color-changing granules are 2.8 parts of crystal violet lactone, 8.5 parts of dibenzotriazole, 42.8 parts of Calcol # 20 (lauryl alcohol, manufactured by Kao Corporation),
Epicoat # 828 (epoxy resin, Yuka Shell Epoxy Co., Ltd.) 28.5 parts, Epicure U8.7 parts and Epicure Z
(Curing agent for epoxy resin, Yuka Shell Epoxy Co., Ltd.
8.7 parts of melted emulsified oil droplets are solidified in ice water, and then 2 parts using 80 parts of polyvinyl alcohol, 20 parts of Stylite HS-1 (styrene maleic acid resin, manufactured by Daido Industry Co., Ltd.) and 100 parts of sodium alginate. After separating the layers, gelation was performed with 25 parts of borax, precipitation was performed in saturated sodium sulfate, and decantation was performed.

Protective layer Pandex (thermoplastic polyurethane resin, manufactured by Dainippon Ink and Chemicals, Inc.) 20 parts Xylene 50 parts Butyl cellosolve acetate 30 parts Comparative Example 4 In Example 2, a silane coupling agent was added to the discolored pattern layer and the protective layer. A transfer sheet was obtained in the same manner except that it was not used and was fixed to a wine glass. The quality is shown in Table 4.

Comparative Example 5 A transfer sheet was obtained in the same manner as in Example 2 except that the silane coupling agent was not used for the adhesive layer, the discolored pattern layer and the protective layer, and the sheet was fixed to a wine glass. The quality is shown in Table 4.

Table 4 shows the test results of the adhesiveness, surface hardness and abrasion resistance of the discolored pattern patterns applied to the wine glasses in Example 2 and Comparative Examples 4 to 6.

Adhesiveness: Cellophane tape was applied on 100 squares with a 1 mm interval formed on a 1 cm ² discolored pattern, and the number of squares that were peeled off when the tape was peeled off was checked.

Surface hardness: Pencil hardness test.

Friction resistance: Compliant with JIS-L-0849.

Effect of the Invention According to the transfer sheet of the present invention, there is no misalignment, sharp edges, high coloring density, and high coloring density on various curved surfaces of ceramic products including those with handles such as mugs and coffee cups. A thermo-reversible discoloration pattern with a sharp and permanent color function and excellent durability can be easily obtained by performing heat treatment at a relatively low temperature once regardless of the number of colors and the complexity of the pattern. It can be applied and its industrial utility is enormous.

[Brief description of drawings]

FIG. 1 is an enlarged sectional view showing one embodiment of the present invention.
1 and 2 of FIG. 2 show another embodiment of the present invention, in which the former shows a pattern when coloring and the latter shows a pattern when erasing. FIG. 3 shows a pattern in coloration according to still another embodiment of the present invention. In the drawings, (1) is a base sheet, (2) is a release layer, and (3)
Is an adhesive layer, (4) is a discolored pattern layer, (5) is a protective layer,
(6) is a cover coat layer, (7) is a concealing layer, and (8) is a non-discolored pattern layer.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Bibliographic references Sho 61-19040 (JP, Y2) Actual application 54-172179 (Actual development 56-88563) A microfilm (JP, U) of which the contents were photographed. A microfilm (JP, U, U) of which the detailed description and drawings attached to the application of Japanese Patent Application No. 48-67994 (No. )

Claims (2)

[Scope of utility model registration request] 1. A release layer (2) for water-bonded slide transfer, which is provided on the entire surface or a specific portion of a base sheet (1),
An adhesive layer (3) provided directly with a contour that can be enlarged from a desired pattern, and on the adhesive layer (3), directly or through another layer, an acid-developing substance, an acidic substance and a solvent. A color-changing pattern layer (4) comprising a temperature-sensitive color-changing granular substance in which a granular substance capable of co-encapsulating a component with a thermosetting resin is further coated with a hydrophilic polymer compound, and the color-changing pattern layer A protective layer (5) formed on the (4) so as to match the contour of the adhesive layer (3) containing the ultraviolet absorber, directly or through another layer, and the protective layer. A cover coat formed on the (5) with a contour that expands from the shape of the protective layer (5) and containing a polymeric elastic resin and a plasticizer having poor compatibility with the protective layer (5). A temperature-sensitive reversible discolorable pattern transfer sheet for a ceramic product, comprising a layer (6), the contact sheet comprising: Layer (3), discoloration design pattern layer (4)
The thermosensitive reversible color-changeable pattern transfer sheet for ceramic products, wherein the protective layer (5) and the protective layer (5) are formed by a printing ink containing a silane coupling agent and a thermosetting resin, respectively. 2. A thermosensitive reversible color change for a ceramic product according to claim 1, which is formed by a printing ink containing a polymer elastic resin in addition to a silane coupling agent and a thermosetting resin. Sex pattern transfer sheet.