JPH06116064A - Thermal transfer sheet for forming under coated ceramic coloring layer and formation of under coated ceramic coloring layer using this thermal transfer sheet - Google Patents

Abstract

PURPOSE:To provide a thermal transfer sheet and a method for forming a ceramic coloring layer using the thermal transfer sheet capable of saving the glazing process of a ceramic coloring layer and the calcining process being a preceding stage to a sintering process in the methods by using conventional thermal transfer sheets, in the forming process of an under coated ceramic coloring layer. CONSTITUTION:This thermal transfer sheet for forming under coated ceramic coloring layer is formed with a base material sheet whose surface is a releasable one, a peelable layer containing a hydrophilic resin formed on the releasable surface of the base material and a coloring layer containing a pigment for calcining formed on the surface of the peelable layer as a coloring agent. The under coated ceramic coloring layer is formed by applying a transparent water- based glazing after transferring the transfer layer of the thermal transfer sheet on the surface of the base material and sintering it as it is.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer sheet used when a ceramic colored layer is formed as an undercoat on the surface of a ceramic molded body, a metal molded body or the like, and an underpainted ceramic colored sheet using the thermal transfer sheet. A method for forming a layer.

[0002]

2. Description of the Related Art As a means for forming a ceramic colored layer on a surface of a substrate made of a ceramic molded body, a metal molded body or the like by using a thermal transfer sheet by underprinting, it is disclosed in, for example, JP-A-53-54211. As
A base material sheet having a release surface, a release layer formed on the release surface of the base sheet, and a baking pigment formed on the surface of the release layer as a colorant. Utilizing a thermal transfer sheet having a coloring layer, thermally transferring a coloring layer containing a baking pigment, which is a transfer layer of the thermal transfer sheet as a coloring agent, and a peeling layer to the surface of the substrate, and then performing preliminary baking. There is a method in which the resin vehicle is removed from the colored layer on the surface of the substrate by sublimation or burning, followed by applying a transparent aqueous glaze and further performing main baking.

[0003]

In the method of forming the undercoating ceramic colored layer on the surface of the substrate formed of a ceramic molded body, a metal molded body or the like by using the above-mentioned thermal transfer sheet, after the transfer layer is transferred by the thermal transfer sheet, However, if the aqueous glaze is applied without prebaking, the aqueous glaze is repelled by the liquid repellency of the transfer layer, and it is not possible to form a uniform glaze layer.

Therefore, after the transfer of the transfer layer, the pre-baking step of the first stage is carried out, and further, the main baking step of the latter stage is carried out after the application of the aqueous glaze, and the two-step firing is carried out. It is complicated and this is a factor of cost increase.

On the other hand, the present invention is a thermal transfer sheet which can omit the firing step in the step of forming the undercoating ceramic coloring layer in the case of using the conventional thermal transfer sheet, and the undercoating ceramic coloring using the thermal transfer sheet. A method of forming a layer is provided.

[0006]

According to a first aspect of the present invention, there is provided a thermal transfer sheet for forming an undercoating ceramic colored layer, comprising a base sheet having a release surface, and a release surface of the base sheet. The peeling layer is formed, and the coloring layer containing the pigment for baking formed on the surface of the peeling layer as a coloring agent is provided, and the peeling layer is a resin layer containing a hydrophilic resin. .

A thermal transfer sheet for forming an undercoating ceramic colored layer according to a second aspect of the present invention is the thermal transfer sheet according to the first aspect of the present invention, wherein the release layer comprises a resin layer containing 10% by weight or more of a hydrophilic resin.

A thermal transfer sheet for forming an undercoating ceramic colored layer according to a third aspect of the present invention is the thermal transfer sheet according to the first or second aspect, wherein the hydrophilic resin in the release layer is a polyethylene glycol methacrylate resin.

According to a fourth aspect of the present invention, there is provided a method for forming an undercoating ceramic colored layer using a thermal transfer sheet, the base sheet having a release surface, and the release surface of the base sheet. A thermal transfer sheet comprising a release layer comprising a resin layer containing a hydrophilic resin and a coloring layer containing a baking pigment formed as a colorant on the surface of the release layer is used. After thermally transferring a coloring layer containing a baking pigment, which is a transfer layer of a sheet, as a colorant and a peeling layer onto the surface of a substrate, applying a transparent aqueous glaze on the transfer layer subjected to heat transfer, and baking this. To obtain a ceramic colored layer.

In the thermal transfer sheet for forming the undercoating ceramic colored layer of the present invention having the above-mentioned structure, the substrate sheet has releasability between the substrate sheet and a transfer layer comprising a colored layer and a release layer. A sheet having good properties is used, for example, paper such as high-quality paper, thin paper, glassine paper, or a plastic film having a thickness of about 5 to 200 μm is used. As a plastic film,
For example, polyester resin films such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymers, polyolefin resin films such as polyethylene, polypropylene and polymethylpentene, polyvinyl fluoride, polyvinylidene fluoride, poly 4 Polyfluorinated ethylene resin film made of ethylene fluoride, ethylene / tetrafluoroethylene copolymer, etc., polyamide resin film made of nylon-6, nylon-6,6, etc., polyvinyl chloride, vinyl chloride-vinyl acetate copolymer Vinyl resin film such as polymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol,
Cellulose films made of cellulose triacetate, cellophane, etc., acrylic resin films made of polymethyl methacrylate, polyethyl methacrylate, polybutyl acrylate, etc., resin films made of polystyrene, polycarbonate, polyarylate, polyimide, etc. are used.

On the release surface of the base material sheet, that is, on the surface on which the release layer is formed, a release treatment such as forming a release layer for enhancing the releasability between the transfer layer and the transfer layer is carried out, if necessary. Is given. For example, a coating agent may be formed by adding a release agent such as a fluororesin, various waxes, or silicones to a paint whose vehicle is an acrylic resin, a fibrin resin, a vinyl resin, or the like, or The release layer is formed by a means such as forming an extruded film of a release resin such as a fluorine resin, silicone, melamine resin, epoxy resin, polyester resin, or ionizing radiation crosslinkable polyfunctional acrylate resin. To be done.

The release layer formed on the release surface of the substrate sheet is composed of a resin layer containing a hydrophilic resin and serves as a transfer layer together with a coloring layer containing a baking pigment as a coloring agent. It is preferably formed as a mixed resin layer with a hydrophobic resin for the purpose of imparting flexibility to itself. However, when the content ratio of the hydrophilic resin in the release layer is less than 10% by weight, the degree of hydrophilicity on the surface of the release layer becomes low and the initial purpose cannot be achieved. It is preferably 10% by weight or more in the layer.

The release layer is usually formed to have a thickness of about 1 to 10 .mu., And the hydrophilic resin in the release layer is, for example, polyethylene glycol resin, polyethylene glycol methacrylate resin, viscose, polyvinyl alcohol resin. , Polyvinyl amine resin, polyvinyl methoxy acetal resin, polyacrylic acid resin,
Polyvinylpyrrolidone resin, sodium polyacrylate resin, etc. are used.

Among these hydrophilic resins, the antiglare property of the aqueous glaze, coating properties, printability, foaming and discoloration of the glaze layer due to gas generated by sublimation or combustion in the main baking step are involved. Polyethylene glycol methacrylate resin is most preferable from the viewpoint of suppressing chemical reaction.
If the content of the polyethylene glycol methacrylate resin in the vehicle is less than 10% by weight, the effect of preventing the liquid repellency of the release layer becomes insufficient. Further, since the polyethylene glycol methacrylate resin is hard and brittle, if it exceeds 50% by weight in the vehicle, cracks are likely to occur in the release layer during the transfer sheet manufacturing process or the transfer sheet transfer process. Therefore, the polyethylene glycol methacrylate resin is preferably used within the range of 10 to 50% by weight in the vehicle.

Hydrophobic resins mixed with these hydrophilic resins include acrylic ester resins, methacrylic ester resins, copolymer resins thereof, butyral resins, alkyd resins, phenol resins, urea resins, melamine resins. , Polyester resin, melamine-alkyd resin, vinyl chloride resin, etc. are used.

The colored layer formed on the surface of the release layer made of a resin layer containing a hydrophilic resin is formed by an ink containing a vehicle that sublimes or burns by firing, a solvent for adjusting the viscosity of the ink, and a firing pigment. can get.

Vehicles that sublime or burn upon firing include, for example, acrylic acid ester resins, methacrylic acid resins, copolymer resins thereof, butyral resins, cellulose resins, alkyd resins, polyethylene oxide resins, phenol resins, Urea resin, melamine resin,
Polyester resin, melamine / alkyd resin, vinyl resin, maleic acid resin, etc. are used.

The solvent for adjusting the viscosity of the ink is, for example, pentane, hexane, heptane, octane, or a mixture thereof such as gasoline, petroleum, benzine,
Aliphatic hydrocarbons such as mineral spirits and petroleum naphtha, benzene, toluene, xylene, cyclohexane,
Aromatic hydrocarbons such as ethylbenzene, halogenated hydrocarbons such as trichloroethylene, perchloroethylene, chloroform, carbon tetrachloride, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol,
Monohydric alcohols such as amyl alcohol, benzyl alcohol and diacetone alcohol, polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cyclohexanone, isophorone and other ketones, Ethyl ether, isopropyl ether, ethylene glycol mono-methyl ether, ethylene glycol mono-ethyl ether,
Ethers such as diethylene glycol mono-methyl ether, diethylene glycol mono-ethyl ether, diethylene glycol mono-butyl ether, diethylene glycol di-butyl ether, ethylene glycol mono-methyl ether acetate, ethylene glycol mono-ethyl ether acetate, Acetates such as diethylene glycol mono-methyl acetate, diethylene glycol mono-ethyl ether acetate, diethylene glycol mono-butyl ether acetate, and esters such as butyrate,
Nitrohydrocarbons, nitriles, amines, other acetals, acids, furans, etc., alone or as a mixed solvent, are used.

Further, as the pigment for firing, for example, oxides of Fe, Cr, Zn ... Brown oxides of Zn, Co, Al, Si ... Blue Ti , Zn, Co, Ni, Cr oxides ・ ・ ・ ・ ・ ・ Green oxides of Ti, Ba, Ni, Pb, Sb ・ ・ ・ ・ ・ ・ Yellow Cd, Se, S oxides ・···· Red oxides of Fe, Cu, Mn, Cr, Co ···· Ordinary ceramics made of oxides of transition metals such as CdS, CaO, etc. in addition to black, etc. The pigment used for underpainting is used.

Particularly for high temperature firing, blue (Co),
Green (Cr), brown (Fe, Ni, Cr, Co, Sb), yellow (Ti, Sb), black (Fe, Mn), etc. are used.

Further, as the glass quality added to the firing pigment as desired, for example, PbO ... 78%, S
_{iO 2 ···· 10%, B 2} O 3 ···· consisting 12% or low-melting glass, PbO-S ₂ O ₃ system, PbO-B ₂ O ₃ -S
iO ₂ system, PbO-ZnO-B ₂ O ₃ system, SnO ₂ -T
A particle size of 2 to 2 based on iO ₂ —SiO ₂ —PbO—CdO system, etc.
The one having a size of about 30 μ is used.

The pigment for firing used for forming the colored layer does not mean the pigment obtained by firing, but
It is a pigment that is fixed on the surface of a substrate by being subjected to a firing process and has a function of exhibiting a desired color.

The colored layer containing the above-mentioned baking pigment as a colorant may be in the form of a print pattern or may be in a uniform solid state over the entire surface. It may be composed of two layers of a colored layer, for example, a printed pattern-shaped colored layer directly formed on the surface of the peeling layer, and a concealing colored layer formed on the colored layer in a completely solid state. This colored layer is formed by various printing methods such as guavia and silk screen.

When a colored layer containing a baking pigment as a coloring agent is formed by an ink mixed with glass, it is necessary to avoid the formation of the colored layer by the gravure printing method, but the gravure printing method is used. When using a coloring layer forming means and when it is desired to form a coloring layer having a vitreous surface, vitreous is added as an aqueous glaze applied after the step of forming the transfer layer by the thermal transfer sheet. You should use an aqueous glaze.

An adhesive layer is formed on the colored layer of the thermal transfer sheet, if necessary. This adhesive layer is a heat-sensitive type that melts by heating to develop adhesiveness, or a pressure-sensitive adhesive type that adheres by pressure, and is formed from a substance having a property of subliming or burning by firing as a main component, and usually, It is formed of an acrylic resin or a resin mainly composed of an acrylic resin. However, when the adhesive layer is formed only by the acrylic resin, the sublimation rate of the adhesive layer is too fast, and the colored layer containing the firing pigment as the colorant is pierced to cause pattern omission. Sometimes. Therefore, it is preferably formed as a mixed resin layer with another resin having a slow sublimation rate that is compatible with the acrylic resin.

If the thickness of the adhesive layer becomes too thick, shrinkage occurs in the firing process, so that the thickness of the adhesive layer is 1-10.
It is desirable to be formed to a thickness of about 0 μ. Furthermore, a glass frit may be added to the adhesive layer for the purpose of preventing coating film cracking due to shrinkage in the firing step.

The method for forming an undercoating ceramic colored layer of the present invention comprises the steps of transferring the transfer layer in the thermal transfer sheet for forming an undercoating ceramic colored layer to the surface of a substrate by a thermal transfer method, and then transferring the transferred thermal transfer. It consists of applying a clear aqueous glaze on top of the layer and then calcining it as it is.

The aqueous glaze used here has the property of vitrifying by vitrification and at the same time fusing to form a glass layer. Lead-containing frit glaze, lead-free frit glaze, ash glaze,
Lime glaze, talc glaze, Ba type glaze, reduction type glaze, etc. are used,
The main component is one in which most of the components become vitreous by melting, to which a colloidal raw material such as kaolin is added, crushed, and further water is applied in the form of a suspension. The baking step after application of the aqueous glaze is performed in the same manner as in the case of ordinary glaze treatment.

The substrate on which the ceramic colored layer is exposed is, for example, an unglazed ceramic plate or a metal plate, but generally, it is heat resistant so as not to deteriorate during the firing step in the process of forming the ceramic pattern. There is no particular limitation as long as it has Further, an adhesive layer is formed on the surface of the substrate on which the ceramic colored layer is exposed, that is, the surface of the thermal transfer sheet to which the transfer layer is transferred, if necessary. In particular, when a thermal transfer sheet having no adhesive layer is used, it is preferable to form an adhesive layer on the surface of the substrate and place it.

[0030]

EXAMPLES A specific structure of a thermal transfer sheet for forming an undercoating ceramic coloring layer of the present invention and a method for forming an undercoating ceramic coloring layer using the thermal transfer sheet will be described based on Examples.

[Example 1] An acrylic resin "Showa Ink Co., Ltd .: SLM-C Primer A" 5 was formed on the surface of a biaxially stretched polyethylene terephthalate film having a thickness of 25 μm.
A coating agent containing a mixed resin of 0 part by weight and 35 parts by weight of polyethylene glycol methacrylate resin as a coating film forming component was applied by a gravure printing method to give a thickness of 3 μm.
Was uniformly formed on the entire surface.

Next, an acrylic ink "Showa Ink Co., Ltd .: SL" containing a baking pigment on the release layer.
Gravure printing pattern is formed by "MC", and acrylic adhesive "Showa Ink Co., Ltd .: SLM-" is further formed on it.
CHS "was uniformly applied to the entire surface to form an adhesive layer having a thickness of 10 μm, and a thermal transfer sheet for forming an undercoating ceramic colored layer, which is an example of the present invention, was obtained.

[Example 2] The surface of the substrate made of unglazed porcelain was brought into contact with the surface of the adhesive layer of the thermal transfer sheet obtained in Example 1 described above, and then the heat was applied by pressing with a heated silicone rubber roller. The transfer layer in the thermal transfer sheet, that is, the transfer layer composed of "adhesive layer-gravure printing pattern layer containing pigment for firing-release layer" was transferred.

Thereafter, 100 g (dry) / m of PbO-based transparent glaze mixed with 5% by weight of ZnO ₂ was applied to the surface of the release layer in the transfer layer transferred to the surface of the unglazed ceramic plate.
Apply at a rate of ² and then at 1000-1200 ° C for 1
By firing for a period of time, a ceramic colored layer was formed on the surface of the unglazed porcelain plate.

[0035]

The thermal transfer sheet for forming the undercoating ceramic coloring layer of the present invention comprises a base sheet having a release surface and a peeling formed on the release surface of the base sheet. And a colored layer containing a baking pigment formed on the surface of the release layer as a colorant, wherein the release layer is a resin layer containing a hydrophilic resin.

In the method of forming a ceramic colored layer on the surface of a substrate by using the thermal transfer sheet for forming the undercoating ceramic colored layer of the present invention having the above-mentioned structure, the repelling of the transfer layer formed on the surface of the substrate is performed. Since the liquid performance is suppressed, the pre-baking step after the transfer of the transfer layer of the thermal transfer sheet can be omitted as compared with the case of using the conventional thermal transfer sheet for forming the undercoating ceramic coloring layer.

That is, in the step of forming a ceramic coloring layer using a conventional thermal transfer sheet for forming a rough-colored ceramic coloring layer, since the transfer layer transferred to the surface of the substrate is liquid repellent, this transfer layer surface When the aqueous glaze is directly applied to the glaze layer, a glaze layer having a uniform thickness cannot be obtained and an orderly ceramic colored layer cannot be formed. For this reason, a step of pre-baking the transfer layer before applying the aqueous glaze was necessary, but in the method for forming a colored layer using the thermal transfer sheet for forming the undercoating ceramic colored layer of the present invention, the transfer layer Since a uniform aqueous glaze coating layer can be formed on the surface of the product, it is possible to omit the pre-baking step before applying the aqueous glaze, and there is no trouble for that, and the formation of the undercoating ceramic coloring layer is easy. Can be done.

Further, the method of forming the undercoating ceramic colored layer utilizing the thermal transfer sheet of the present invention makes full use of the characteristics of the thermal transfer sheet of the present invention, and the firing step in forming the undercoating ceramic colored layer. Is only required for the main firing step after the application of the aqueous glaze, and compared with the conventional method for forming the undercoating ceramic colored layer using a thermal transfer sheet, the troublesomeness of performing the firing step in two steps is not required. The formation of the undercoating ceramic coloring layer on the substrate can be carried out easily and inexpensively.

Claims (4)

[Claims] 1. A base sheet having a release surface as a surface, and a release layer formed on the release surface of the base sheet,
A thermal transfer sheet for forming an undercoating ceramic coloring layer, comprising a coloring layer containing a firing pigment as a coloring agent formed on the surface of the peeling layer, wherein the peeling layer is a resin layer containing a hydrophilic resin. A thermal transfer sheet for forming a ceramic coloring layer for undercoating, which comprises: 2. The thermal transfer sheet for forming an undercoating ceramic colored layer according to claim 1, wherein the release layer is a resin layer containing 10% by weight or more of a hydrophilic resin. 3. The thermal transfer sheet for forming an undercoating ceramic colored layer according to claim 1, wherein the hydrophilic resin in the release layer is a polyethylene glycol methacrylate resin. 4. A base sheet having a release surface, a release layer formed of a resin layer containing a hydrophilic resin formed on the release surface of the base sheet, and a release layer comprising: A thermal transfer sheet for forming an undercoating ceramic colored layer comprising a coloring layer containing a baking pigment formed on the surface as a coloring agent is used, and the baking pigment that is the transfer layer of the thermal transfer sheet is used as the coloring agent. After the heat transfer of the contained coloring layer and release layer to the surface of the substrate, a transparent aqueous glaze is applied on the heat-transferred transfer layer, and further firing is performed. Method for forming colored layer.