JPH06234297A - Thermally color-changeable water slide transfer paper, its production, and decorated container using it - Google Patents

Abstract

PURPOSE:To obtain a thermally color-changeable water slide transfer paper having a picture pattern layer capable of keeping such functions as sufficient anchoring properties, frictional resistance, and water resistance after the transfer to a base material with respect to water slide transfer paper provided with a thermally color-changeable picture pattern layer requiring a pigment content higher than a normal picture pattern layer and containing a relatively small amount of anchoring agent. CONSTITUTION:Title paper is formed by laminating a water-soluble glue layer, an adhesive layer made of a thermosetting resin, a thermally color-changeable picture pattern layer containing a solvent-free thermosetting resin curing at a temperature lower than the thermosetting temperature of the thermosetting resin and a thermally color-changeable pigment, and a cover coating layer over a surface of base paper, successively. At the time of producing the transfer paper, before the lamination of the cover coating layer, the laminate is cured at a temperature enough to thermoset only the thermally color-changeable picture pattern layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water slide transfer paper carrying a pattern whose color reversibly changes with temperature, a method for producing the same, and a ceramic or glass container transferred and decorated using the transfer paper. Regarding

[0002]

2. Description of the Related Art Conventionally, there are a high temperature baking transfer method and a low temperature baking method as a method for painting and transferring to ceramics, glass, enamel products and metal products. The high-temperature baking transfer method involves printing a pattern on a water slide base paper with an ink containing an inorganic pigment as a colorant, and then laminating a cover coat layer for the purpose of facilitating the transfer operation to the substrate, and swelling it with water. The peeled transfer part is attached to the base material, baked in a high-temperature furnace for ceramics to burn all organic materials, and only the inorganic pigment is fused with the glass material of the base material. A painting effect can be obtained. However, in the transfer by this method, the transfer target is glass,
It is limited to those with high heat resistance such as ceramics and enamel, and moreover, it requires a baking facility for the ceramic industry, which imposes a heavy burden on the facility.
Further, the composition of the pattern is limited to the heat-resistant inorganic pigments, and there is a drawback that any organic pigments or colorants cannot be applied. On the other hand, a so-called low-temperature printing transfer method has also been widely developed in which a pattern printing layer using an organic pigment is adhered to a transfer target through an adhesive layer. The basic structure of this transfer paper is (A) on a base paper coated with water-soluble glue, and (B)
An adhesive layer made of a thermosetting resin is provided, (C) a pattern is printed with a thermosetting resin-based printing ink mainly composed of an organic pigment, and (D) a cover coat layer necessary for a transfer operation. It is stacked. However, the layer (B) may be omitted in some cases. As the painting transfer operation, after dipping the transfer paper in water to swell the sizing agent and sticking the peeled transfer portion onto the transfer target, only the cover coat layer is peeled off,
The adhesive layer and the pattern layer remaining on the transferred material are adhered to the transferred material by thermosetting the resin of the adhesive layer or the resin of the pattern layer together at a temperature of about 100 ° C to 240 ° C. This method has the advantage that transfer products can be obtained easily, but in products that require repeated washing, such as glass containers and ceramics, water resistance, abrasion resistance, and strong adhesiveness of the pattern part are required. However, few have sufficient practical strength. Recently, many reinforcing measures have been proposed in which a protective layer is further provided on the design layer to cover the weakness of the design layer.
Even though this is initially effective, physical deterioration of the pattern layer due to long-term use was unavoidable. Further, a reversible thermochromic material consisting of an electron-donating color-developing organic compound, an electron-accepting compound and a polar organic compound is encapsulated in a microcapsule or a thermochromic pigment made into resin solid solution particles is kneaded with a vehicle to form a base material. Ceramics with a thermochromic pattern that is printed directly on the surface and thermoset are also provided, but glass containers or metal containers are also provided, but with this method of production, it is difficult to match patterns with a large number of colors and production efficiency is high. There were problems that it was extremely bad, that it could not handle complicated shapes, and that the printing process took too long for mass production. Further, since the thermochromic pigment has a considerably low color density of the pigment itself as compared with the general pigment, it is necessary to compensate for it by increasing the pigment content in the ink, and especially in a pattern that hides the rough background, the content is higher. The amount is required. Therefore, in water slide transfer for ceramics and glass containers, a thermochromic water slide transfer paper with high concentration and excellent coating strength, gloss of the coating, and strong adhesiveness to the transfer target is desired. It was rare.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to a low temperature transfer paper having a practical problem in terms of physical strength, and relates to a low temperature baking water slide having a thermochromic pattern layer satisfying the practical strength without providing a protective layer. It is intended to provide transfer paper. In general, the material composition of the adhesive layer for low-temperature baking transfer paper is a resin in which an epoxy resin, an acrylic resin, or the like and a methylol group-containing urea-based or melamine-based resin are combined. Thermal crosslinking and curing reaction are carried out at a temperature between about 100 ° C. and about 240 ° C. to impart adhesiveness to a transfer target such as ceramics and glass. The ink for the adhesive layer is usually of a type in which a solid resin is dissolved in a solvent. Therefore, the resin content in the ink is usually 50%.
It is a degree. Since the adhesive layer normally does not contain a pigment, even if the adhesive layer is made of such an ink, there is no problem in its film strength and adhesiveness. However, when the vehicle of the adhesive layer is applied to the ink for the pattern layer, the decrease in the strength of the film is avoided due to the problem of the content of the additive for dispersing the pigment, the auxiliary agent for imparting printability and the pigment content. I couldn't do it. Further, when the above-mentioned thermochromic pigment is used, since the concentration is lower than that of general pigments, it is necessary to add a larger amount of the pigment component. Therefore, when the pattern layer is formed with the solvent solution type ink, the resin solid content ratio is increased. Inevitably, the film is fragile and has poor adhesion, which makes it unusable as a ceramic or glass container. The present inventors intend to improve the above-mentioned drawbacks by examining the constitution of the resin necessary for forming the thermochromic pattern layer into a tough film and, in connection with it, the treatment of the pattern layer during the production of transfer paper. is there.

[0004]

The thermochromic water slide transfer paper of the present invention has a water-soluble adhesive layer, an adhesive layer made of a thermosetting resin, and a temperature lower than the thermosetting temperature of the thermosetting resin on one side of the base paper. The thermosetting resin thermosetting resin, a pattern layer containing a thermochromic pigment, and a cover coat layer are sequentially laminated, and when the transfer paper is manufactured, after the pattern layers are laminated, the thermosetting property of the adhesive layer is set. It is characterized in that the resin of the pattern layer is thermally cured at a temperature lower than the thermosetting temperature of the resin and then the cover coat layer is laminated. Particularly in the present invention, a high pigment content,
Specifically, it is characterized by the constitution of a pattern printing ink containing 15 to 25% by weight of a thermochromic pigment in the ink and its heat treatment. Generally, the ratio of the pigment to the fixed resin is ceramics, glass or metal containers unless the weight ratio of the resin is 3 or more with respect to the pigment 1 on the assumption of good gloss, adhesion of the pigment and adhesion of the coating film. It was found that excellent performance as a coating film of the above can not be obtained. Therefore, for example, in the case of a solvent solution type ink, if the content of the thermochromic pigment in the ink is 15% by weight, the amount of resin required is 45%, and the remaining 40% is the solvent. The ink having such a ratio is slightly different depending on the type of resin, but in general, the ink viscosity is too high and is not suitable for screen printing. Further, if the content of the thermochromic pigment is 30%, the required amount of resin is 90%, and there is no room for calculation of the solvent. For the above reasons, the thermochromic pigment should be 15-25
In the high pigment content ink containing wt%, the solvent solution type ink is basically not suitable for a coating film requiring fastness. As a result of studying the above-mentioned problems, the inventors of the present invention configured the ink for thermochromic pattern layer containing a large amount of thermochromic pigment with a substantially solvent-free vehicle so that the content of the thermochromic pigment was ink. In the range of 15 to 25% by weight, it has been found that necessary conditions for obtaining excellent gloss, adhesion and fastness as a coating film on the surface of a ceramic, glass or metal container. Furthermore, by appropriately selecting the resin composition of the substantially solvent-free vehicle, a thermochromic pattern layer having better strength can be obtained. After laminating the solventless thermochromic pattern layer, it is necessary to provide a cover coat layer, but the solventless ink has a viscous printing layer even after printing, and the cover coat layer is directly formed thereon. It cannot be printed. For this reason, the thermochromic pattern layer is thermally cured, but depending on the heating conditions at this time, the thermosetting resin of the adhesive layer is also thermally cured and the function of the adhesive layer is lost. In order to avoid such a situation, the thermosetting temperature of the thermosetting resin of the thermochromic pattern layer is selected to be lower than the thermosetting temperature of the resin of the adhesive layer, and the temperature lower than the thermosetting temperature of the resin of the adhesive layer is selected. And heat cure. As a result, the thermochromic pattern layer is cured to allow printing of the cover coat layer while maintaining the reaction activity of the adhesive layer, and the transfer paper is finished by stacking the layers.

The construction and manufacturing method of the thermochromic water slide transfer paper of the present invention will be described in detail below. An adhesive layer is formed on the entire surface or a part of the water slide base paper having a water-soluble glue layer on the surface with an ink composed of a solvent-soluble thermosetting resin having a thermosetting temperature of 100 ° C or higher, and after the layer is dried, it is substantially Printing a thermochromic pattern layer with an ink in which a thermochromic pigment is dispersed in a solventless liquid thermosetting resin (having a thermosetting temperature lower than that of the adhesive layer resin) within the range of the adhesive layer To do. The thermochromic pattern layer is quickly heat-set at a temperature lower than the heat-setting temperature of the adhesive layer. Then, the cover coat layer is printed in an area larger than that of the adhesive layer to obtain the thermochromic water slide transfer paper of the present invention. Next, the transfer method will be described. The thermochromic water slide transfer paper is immersed in water to swell or dissolve the water-soluble glue layer, and only the water slide transfer paper is peeled off. A laminated film consisting of an adhesive layer, a thermochromic pattern layer and a cover coat layer is attached by a conventional method of a water slide transfer method so that the adhesive layer is in contact with the surface of a ceramic or glass or metal container, and a rubber squeegee or the like is sufficient. In close contact with. After drying the water, remove the cover coat layer,
By performing heat treatment at a temperature of 00 ° C. for about 15 to 30 minutes, a thermochromic pattern layer having a practically sufficient color density and film strength is formed on the container surface.

Each part of the above structure and each step of the manufacturing method will be described in detail. The base paper is one side of printing paper with good water absorption,
As the water-soluble sizing agent, those coated with a sizing agent such as starch, dextrin, polyvinylpyrrolidone, polyvinyl alcohol, gum arabic, and water-soluble acrylic resin are used. Commercially available products of this type of water slide base paper can also be obtained. The adhesive layer is a thermosetting resin mainly composed of a hard epoxy resin having an alcoholic hydroxyl residue, an acrylic resin, and a urethane resin, in which a urea resin, a melamine resin, a benzoguanamine resin, and a resin having an active methylol group are mixed. A so-called one-component or two-component curable thermosetting resin composed of a solvent and a solvent is applied. The resin solution for the adhesive layer is printed by screen printing to be slightly larger than or the same shape as the contour of the thermochromic pattern layer, and the solvent content is evaporated and dried at low temperature or at room temperature. The ink for the thermochromic pattern layer is composed of 15 to 25% by weight of the thermochromic pigment and 75 to 85% by weight of a thermosetting resin which is liquid at room temperature. The following solvents may be added. Further, in order to enhance the printing effect, a slight amount of an antifoaming agent, a leveling agent, an ultraviolet absorber or the like may be added for the purpose of improving the light resistance of the thermochromic pigment. This pattern layer ink is printed within the range of the adhesive layer, and then subjected to a thermosetting treatment at a temperature lower than the thermosetting temperature of the adhesive layer, and the thermochromic pattern layer while potentially retaining the reaction activity of the adhesive layer. Only is heat set. As the thermosetting resin which is liquid at room temperature, a resin composition composed of a hard type liquid epoxy resin and a liquid curing agent is suitable. As the curing agent, aliphatic amines or their modified adduct amines that can be thermally cured at room temperature or a relatively low temperature are used. An acid anhydride-based curing agent or an aromatic amine-based curing agent whose curing reaction does not proceed unless the temperature is 100 ° C. or higher is unsuitable. The epoxy resin and the curing agent are mixed at the time of use in a ratio according to the reaction equivalent. Usually, the thermochromic pigment is dispersed in a liquid epoxy resin and mixed with a curing agent during printing to obtain a printing ink for the thermochromic pattern layer. The features of the present invention are exhibited here with respect to the temperature at which the thermochromic pattern layer is cured. That is, the thermochromic pattern layer can be cured at a temperature of room temperature or higher, but it is preferable to heat it in order to accelerate the curing. By curing at a heating temperature lower than the thermosetting temperature of the adhesive layer, usually 90 ° C. or less, only the thermochromic pattern layer can be cured without losing the reaction activity of the adhesive layer. Next, the thermochromic pigment contained in the thermochromic pattern layer will be described. The thermochromic pigment is obtained by microencapsulating a reversible thermochromic material consisting of an electron-donating color-developing organic compound, an electron-accepting compound, and a homogeneous compatible solution of an organic compound having a polar sensitizing group by a known encapsulation method. can get. For the thermochromic material, see JP-B-51-4470.
6, JP-B-51-44707, JP-B-51-4470
The materials disclosed in Japanese Patent Publication No. 9-29398 and Japanese Patent Publication No. 4-17154 can be used. The thermochromic pigment is generally colored on the lower temperature side than the color changing temperature and colorless or light color on the higher temperature side. It is also possible to develop a discoloration from colored (A) to colored (B) by appropriately using a non-discoloring general pigment in combination therewith. Further, by combining a plurality of thermochromic pigments having different color changing temperatures and hues, a multi-step color changing pattern due to temperature change can be revealed. Next, the cover coat layer will be described.
The covercoat layer is printed in a continuous area including the adhesive layer. As a material for the ink for the cover coat layer, a solvent solution of a thermoplastic resin containing a release agent or a plasticizer is used. As the thermoplastic resin, acrylic ester resin, methyl methacrylate ester, vinyl chloride resin, vinyl acetate resin,
Cellulosic resins and copolymer resins thereof are used,
As the releasing agent or plasticizer, various plasticizers for soft vinyl chloride, silicone oil, and fluorine compounds are used. The cover coat layer is used for the purpose of transferring the adhesive layer and the thermochromic pattern layer in the water slide transfer operation to the transfer target without losing the shape, and after drying the water, only the cover coat layer peels off,
To be removed. The release agent or plasticizer is used to facilitate this peeling operation. Generally, a thermochromic pattern is often provided with a non-color-changing pattern portion. In such a case, by adding a non-color-changing pigment to the medium constituting the adhesive layer, the pigment can be easily used together. The non-discolored picture portion may be laminated on a colorless adhesive layer, or the adhesive layer itself may be colored and used.

[0007]

[Function] Regarding the thermochromic pattern layer, which is an important component in the construction of the thermochromic water slide transfer paper, the vehicle of the thermochromic ink forming the layer is substantially a solventless liquid thermosetting resin. By this, the ratio of the thermochromic pigment to the binder resin can be set to 1: 3 or more, whereby the performance of both the color density and the film strength of the thermochromic pattern layer is satisfied. Further, for the solventless liquid thermosetting resin,
By selecting the thermosetting temperature to be lower than the thermosetting temperature of the adhesive layer, at the time of manufacturing, the thermochromic pattern layer is thermoset at a temperature lower than the thermosetting temperature of the adhesive layer before laminating the cover coat layer. Without losing the reaction activity of the adhesive layer, adverse effects due to solvent attack at the time of laminating the cover coat layer can be avoided.

[0008]

【Example】

Example 1 An aqueous dextrin solution as a water-soluble sizing agent was applied to one side of a water-absorbent printing paper and dried to prepare a water slide base paper. The outline of the letter A of the thermochromic pattern layer to be printed later on the coated surface of the water slide base paper with a one-component epoxy-melamine-based medium low temperature thermosetting resin (curing temperature 120 ° C. or higher) ink using a 250 mesh screen plate After printing in a slightly enlarged shape, it was dried with warm air to form an adhesive layer. Then 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindole-3
-Yl) -4-Azaphthalide, bisphenol A, myristyl alcohol, a thermochromic microcapsule pigment that encapsulates a reversible thermochromic material consisting of decyl myristate in an epoxy resin film (colored blue at approximately 10 ° C or lower, approximately 15 ° C 30 parts by weight (hereinafter simply referred to as "part"), 5 parts of a silane coupling agent, 4 parts of an ultraviolet absorber and 1 part of an antifoaming agent,
A thermochromic ink obtained by adding 35 parts of a room-temperature-curing type aliphatic polyamine-based curing agent to a composition which is kneaded and dispersed in 100 parts of a hard type liquid epoxy resin and uniformly mixed (at room temperature or (Curable at 20 ° C or higher)
The letter A was printed on the adhesive layer with a 0 mesh screen plate, and then heat-treated at 70 ° C. for 1 hour to form a thermochromic pattern layer. Finally, cover coat resin (Cover coat resin LO-316, product name of Kyokai Kagaku Co., Ltd.) is printed on a 80-mesh screen plate of a punch die that is 5 mm larger than the contour of the adhesive layer, then dried with warm air and thermochromic water. A slide transfer paper was obtained. The thermochromic water slide transfer paper was soaked in water and the base paper was peeled off. The laminated film was sufficiently adhered to the surface of the glass cup with a rubber squeegee and left overnight, and then only the cover coat layer was peeled off. Heat treated for minutes. When cold water was poured into the obtained cup, the blue letter A was revealed from the plain surface, and after a while after the water was drained, the letter A was discolored and returned to the original plain state.

Example 2 An aqueous solution containing dextrin and polyvinyl alcohol as a water-soluble sizing agent was applied to one side of a water-absorbent printing paper and dried to prepare a water slide base paper. A 250-mesh screen plate was used on the coated surface of the water slide base paper to print a heart mark shape with a one-liquid acrylic-epoxy medium-low temperature thermosetting resin (curing temperature of 140 ° C. or higher), and then dried by warm air to bond Layers were formed. Next, the letter A was printed on the adhesive layer with a 250 mesh screen plate using a non-color-changing ink in which a light pink pigment was kneaded in the resin. Further, a thermochromic microcapsule pigment containing a reversible thermochromic material composed of 1,2-benz-6-diethylaminofluorane, bisphenol A, stearyl alcohol and stearyl laurate in an epoxy resin film (pink color at about 36 ° C or lower 30 parts, silane coupling agent 5 parts, ultraviolet absorber 4 parts, and defoaming agent 1 part are kneaded into 100 parts of a hard type liquid epoxy resin,
A thermochromic ink (curable at room temperature or higher) obtained by uniformly mixing 35 parts of a room temperature curing type aliphatically modified amine curing agent with the dispersed composition was used, and a little more than the adhesive layer with a 110 mesh screen plate. After printing the reduced heart mark pattern covering the letter A, it was heat-treated at 70 ° C. for 1 hour to form a thermochromic pattern layer. Finally, the cover coat resin was printed and laminated on a 80-mesh screen plate of a punching die that was enlarged by 5 mm from the contour of the adhesive layer, and dried with warm air to obtain a thermochromic water slide transfer paper. After immersing the thermochromic water slide transfer paper in water and peeling off the base paper, stick the laminated film to the side of the cup of the pottery with a rubber squeegee and leave it overnight,
Peel off only the cover coat layer and pour a cup of water at 150 ° C for 30
Heat treatment was performed for minutes. When hot water was poured into the obtained teacup, the pink heart mark disappeared and the letter A of the background was revealed, and when the temperature of the water dropped, the original heart mark pattern was restored.

Comparative Example The thermochromic property used in Example 1 was applied to 100 parts of a one-component epoxy-melamine type low temperature thermosetting resin (resin solid content 50%) on the coated surface of a water slide base paper coated with a dextrin aqueous solution. A thermochromic ink in which 30 parts of microcapsule pigment, a silane coupling agent, a defoaming agent, and an ultraviolet absorber are kneaded and dispersed, and the letter A is printed using a 109 mesh screen plate and dried with warm air to produce a thermochromic pattern. Layers were formed. Next, a cover coat layer was provided to obtain a thermochromic water slide transfer paper. The thermochromic water slide transfer paper is soaked in water to remove the base paper, and the laminated film is adhered to the surface of the glass cup with a rubber squeegee and left overnight, and then only the cover coat layer is peeled off, and the cup is kept at 150 ° C. for 30 minutes. It heat-processed and the cup with a thermochromic pattern was obtained. Next, with respect to the samples of Examples 1 and 2 and Comparative Example, the color density and surface gloss of the transferred thermochromic pattern layer were visually observed, and after dipping in hot water at 50 ° C. for 60 minutes, the pattern coating film was subjected to a cross-cut test. The adhesive strength was examined. The test results are shown in Table 1.

[Table 1]

[0011]

EFFECTS OF THE INVENTION According to the thermochromic water slide transfer paper of the present invention, not only can highly accurate thermochromic patterns be painted on containers, tableware, and ornaments having complicated shapes, but also transfer products The thermochromic pattern part can be extremely strongly adhered to the transferred surface, and the thermochromic pattern layer itself has excellent surface gloss without providing any protective layer and has a tough film strength. Ceramics, glass, metal It is possible to provide a high quality unprecedented thermochromic water slide transfer painting for such products, and its industrial applicability is great.

Claims (4)

[Claims] 1. A water-soluble glue layer, an adhesive layer made of a thermosetting resin, a thermochromic pattern layer made of a thermosetting resin containing a reversible thermochromic pigment, and a cover coat layer are sequentially laminated on one surface of a base paper. In the thermochromic water slide transfer paper, the thermosetting resin of the thermochromic pattern layer is a solventless thermosetting resin that is thermoset at a temperature lower than the thermosetting temperature of the thermosetting resin of the adhesive layer. Thermochromic water slide transfer paper characterized by. 2. The thermochromic water slide transfer paper according to claim 1, wherein the thermosetting resin of the thermochromic pattern layer is a liquid epoxy resin and a liquid curing agent. 3. A water-soluble glue layer, an adhesive layer, and a thermochromic pattern layer are sequentially laminated on one surface of the base paper, and then the thermochromic pattern layer is heated at a temperature lower than the thermosetting temperature of the thermosetting resin of the adhesive layer. The method for producing a thermochromic water slide transfer paper according to claim 1 or 2, wherein a cover coat layer is laminated after curing. 4. A container made of ceramics or glass, which is transferred and decorated using the thermochromic water slide transfer paper according to claim 1 or 2.