JPH11105493A - Transfer sheet and printing method of toner image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer sheet which has a toner image and a resin film and causes neither void nor nonuniformity in printing in a pattern printed on the surface of a heat-resistant solid, and a printing method of the toner image. SOLUTION: In a transfer sheet having on a substrate a toner image constituted of toner containing thermoplastic resin and being colored after burning and a resin film, the ashing temperature of the resin film is lower than that of the thermoplastic resin contained in the toner. The toner image and the resin film of the transfer sheet are peeled off from the substrate and stuck on the surface of a heat-resistant solid by bringing the toner image side into close contact with the surface, and then the heat-resistant solid having the toner image and the resin film is heated to or above the ashing temperature of the thermoplastic resin contained in the toner.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer sheet having a toner image obtained by developing an electrostatic latent image with a toner which is colored after baking, and more particularly, to a transfer sheet having a color after baking by a dry electrophotographic method or the like. A toner image obtained by developing an electrostatic latent image with a certain toner is used for porcelain, glass, enamel,
The present invention relates to a transfer sheet for painting which is useful for transferring and baking to a heat-resistant solid surface such as a tile or a stone, and a method for printing a toner image.

[0002]

2. Description of the Related Art As a method of forming a pattern on a heat-resistant solid surface of a ceramic product or the like, a pattern is directly handwritten on a heat-resistant solid surface with a brush or the like using a paint made of an inorganic pigment and a glaze component. Is usually baked at 750 ° C. to 1300 ° C. According to this method, by baking, the incinerated components in the paint are ashed, the glaze component in the paint is dissolved, and then when cooled to room temperature, the inorganic pigment is fixed on the heat-resistant solid surface by the glaze component And a hand-drawn pattern is formed on the heat-resistant solid surface. According to this method, skilled workers are required even for simple patterns in order to obtain a plurality of ceramic products having the same pattern.

In order to manufacture a large number of ceramic products having the same pattern, a pattern is formed on transfer paper by a screen printing method, and then the pattern is peeled from the transfer paper and attached to the ceramic product surface. Is generally performed. This method is described in, for example, Japanese Patent Application Laid-Open No. 49-354.
As disclosed in JP-A-07-07, an image is formed on a transfer paper having a water-soluble adhesive layer on a substrate by an ink containing an inorganic pigment or the like by a screen printing method, and then a vinyl-based image is formed on the ink image. Alternatively, after forming a cellulose-based water-insoluble resin film, the transfer paper is immersed in water to dissolve the adhesive layer of the transfer paper, and the resin film holding the ink image is peeled from the transfer paper to retain the ink image. This is a method in which the obtained resin film is attached to the surface of a ceramic product, for example, the surface of a dish or the like, and is baked. A large number of transfer papers with the same pattern of ink images are created by screen printing, and the ink images are attached to a number of ceramic product surfaces and baked to obtain a large number of ceramic products with the same pattern. it can.

However, in the case of the screen printing method, there are a plurality of steps for preparing a plate for forming an ink image for a picture, which requires enormous time and labor, not only lacks immediacy but also reduces the number of lots. However, there is a drawback in that a unit price per product is high when a variety of products are manufactured. In addition, since an organic solvent is used for printing, there are disadvantages such as a poor working environment. As a method for solving such a problem by the screen printing method, a toner (a composite powder comprising an organic polymer, an inorganic pigment and a glass component, a binder resin, and a pigment for ceramics are contained on a transfer paper by using an electrophotographic method). For example, a method of forming an image for a pattern using a toner or the like, affixing a resin film holding the toner image to the surface of a ceramic product, and baking it is disclosed in, for example, JP-A-4-135798 and JP-A-7-199.
540, JP-A-7-2890, JP-A-7-228037, JP-A-7-300382, JP-A-8-104050, JP-A-8-114
No. 96, JP-A-8-119668 and the like. According to this method, a toner image for a picture can be easily formed, the process is dramatically simplified as compared with the screen printing method, and the method is excellent in immediacy and can easily produce a product of a small lot and many kinds. Can be made.

[0005]

However, when a toner image for a picture formed on transfer paper by electrophotography is pasted together with a resin film on a heat-resistant solid surface such as a ceramic product, and then baked, a heat-resistant solid is obtained. There is a problem in that the image printed on the surface has white spots and uneven printing which are not caused by the screen printing method.

Accordingly, an object of the present invention is to solve such a problem, and to provide a transfer having a toner image and a resin film without causing white spots or uneven printing on a pattern printed on a heat-resistant solid surface. An object of the present invention is to provide a sheet and a toner image printing method.

[0007]

According to the present invention, first, in a transfer sheet having a toner image comprising a thermoplastic resin on a support and being colored after firing and a resin film, A transfer sheet characterized in that the ashing temperature of the film is lower than the ashing temperature of the thermoplastic resin contained in the toner.

Second, in the transfer sheet according to the first aspect, a toner image and a resin film are sequentially laminated on a water-soluble layer of a support having a water-soluble layer. Is provided.

Third, in the transfer sheet according to the first aspect, a resin film and a toner image are sequentially laminated on the water-soluble layer of the support having the water-soluble layer. Is provided. Fourth, the toner image and the resin film of the transfer sheet according to any of the above first to third are peeled from the support, and the toner image and the resin film are heat-resistant by adhering the toner image side to the heat-resistant solid surface. Baking a heat-resistant solid having a toner image and a resin film thereon at a temperature higher than the ashing temperature of a thermoplastic resin contained in the toner. Is provided.

Hereinafter, the present invention will be described in more detail. When the pattern toner image formed on the transfer sheet by electrophotography is peeled off together with the resin film and attached to a heat-resistant solid surface such as a ceramic product, and baked,
Observation that a bumping phenomenon occurs partially at a baking temperature of about 200 ° C to 400 ° C, and white spots and uneven baking occur on the pattern printed on the heat-resistant solid surface, which did not occur when screen printing was used. Was done.

As a result of studying the cause, the thermoplastic resin and the resin film contained in the toner are changed from a solid to a liquid by increasing the temperature, become less viscous and then ash, but at this time, they adhere to the heat-resistant solid surface. In the layer structure of the applied toner image and the resin film, if the resin on the heat-resistant solid surface ashes earlier, bumping occurs, and the pattern printed on the heat-resistant solid surface has white spots and uneven printing. I found to do.

Further, in baking, heat supply to the toner image and the resin film attached to the heat-resistant solid surface is performed from the outer surface side as radiant heat because the heat source is provided on the wall surface of the furnace. Since the heat storage of the heat-resistant solid was large, heat was substantially supplied to the toner image and the resin film from the heat-resistant solid side, and it became clear that the bumping phenomenon described above easily occurred.

As a result of intensive studies based on such knowledge,
In a transfer sheet containing a thermoplastic resin and a toner image composed of a toner that is colored after firing and a resin film, the ash temperature of the resin film is determined by the ash temperature of the thermoplastic resin contained in the toner. The toner image and the resin film are peeled off from the transfer sheet, and the toner image side (the surface having the toner image of the resin film) is adhered to the heat-resistant solid surface and adhered. It has been found that bumping caused by the incineration process of the resin is suppressed, and a clear pattern free from white spots and uneven baking can be sintered on the heat-resistant solid surface.

A toner image comprising a toner which contains a thermoplastic resin on a support and is colored after firing, and a resin film, and the ash temperature of the resin film is the ash temperature of the thermoplastic resin contained in the toner. A lower transfer sheet of the present invention can be made, for example, as follows. That is, by a normal electrophotographic color copier or printer, etc., the electrostatic latent image formed on the electrophotographic photoreceptor contains a thermoplastic resin and is developed with a colored toner after firing,
Transfer the obtained toner image onto a support such as transfer paper,
After fixing by a fixing roller or the like, the transfer sheet of the present invention can be obtained by applying a resin solution on the toner image and drying the solution to form a resin film.

Further, the transfer sheet of the present invention can be obtained by a method in which a toner image is transferred onto a support such as transfer paper on which a resin film is formed in advance and fixed by a fixing roller or the like. In this case, if the toner image side is attached to the heat-resistant solid surface as described above, the pattern sintered on the heat-resistant solid surface becomes a mirror image. What is necessary is just to form it as an image.

As the thermoplastic resin contained in the toner, a thermoplastic resin having an ashing temperature of 280 ° C. to 530 ° C. is particularly preferable. In addition, the ashing temperature of the resin film is 2
10 ° C to 360 ° C is preferred. Examples of the resin for the resin film include a polystyrene resin, a polypropylene acrylate resin, and a polyvinyl butyrate resin. It is preferable that the ash temperature of the resin film be lower than the ash temperature of the thermoplastic resin contained in the toner by a combination of the above resins.

The measurement of the ashing temperature in the present invention can be performed by differential thermogravimetry. The measurement can be performed in a TG-DTA mode using a thermal analyzer (DSC3200, manufactured by Mac Science) or a suggestive thermogravimetric analyzer (TGD-3000, manufactured by Vacuum Riko).

As a transfer sheet for painting for sintering a toner image on a heat-resistant solid surface, particularly, a toner image and a resin are provided on a water-soluble layer of a support such as transfer paper having a water-soluble layer on the surface. A film on which a film is formed is preferred. The component forming the water-soluble layer may be any water-soluble substance, such as dextrin or polyvinyl alcohol.

Next, the toner containing a thermoplastic resin used in the present invention and colored after firing will be described in detail. The toner that is colored after firing is a toner that contains a colorant that does not incinerate when heated to 450 ° C. or higher. The toner containing a thermoplastic resin used in the present invention and colored after firing is, for example, a C 1 group of the periodic table.
u, Ag, Au, Group 2 Cd, Group 4 Ti, Group 5 V,
Sb, Group 6 Se, Cr, Mo, W, U, Group 7 Mn,
It contains a coloring agent, such as a pigment for ceramics, and a thermoplastic resin, which are used alone or in combination (mixed) with oxides of elements such as Fe, Co, Ni, Ir, and Pt of Group VIII.

Conventional ceramic pigments generally have a low absorption coefficient of the pigment itself. To form a full-color image having a high image density using a toner containing these ceramic pigments as a colorant, a large amount of toner adherence is required. It is necessary to. As a colorant in a toner containing a thermoplastic resin used in the present invention and colored after firing, a plurality of the above metals or oxides thereof are blended (mixed), and the mixture is heated to 1000 to 1200 ° C. and melted. An alloy pigment that has been subjected to an alloying treatment of a plurality of metals is preferable.

This alloy pigment has a high absorption coefficient, and a full-color image having a high image density can be formed with a small amount of toner by using a toner containing this alloy pigment as a colorant. The reason why the degree of coloring is increased by the alloying of multiple metals is that the d orbitals of the metal element that was heavy in the case of a single metal split due to the effect of the composite metal, increasing the number of orbitals that can make electron transition. ,
It is presumed that this is because the apparent oscillator strength increases.

As the thermoplastic resin, a binder resin component used in conventionally known toners can be used. Examples thereof include polyester, polystyrene, polyethylene, polyamide, epoxy, epoxy polyol, and terpene. And the like, and these can be used alone or as a mixture. Specifically, for example, epoxy resin, polyester resin, polystyrene,
Examples thereof include a styrene-methyl acrylate copolymer, a styrene-ethyl acrylate copolymer, and a styrene-n-butyl copolymer. As described above, as the thermoplastic resin, a thermoplastic resin having an ashing temperature of 280 ° C to 530 ° C is particularly preferable. Further, the content of the thermoplastic resin in the toner is preferably from 10 to 40% by weight.

Further, it is preferable to use a glaze frit together with a coloring agent and a thermoplastic resin for a toner containing a thermoplastic resin and colored after firing. As a method of including a glaze frit in the toner, for example, a method using a mixture of a colorant and a glaze frit, a mixture of a colorant and a glaze frit is heated and melted, then cooled, and then crushed to obtain a colorant. There are methods used. In particular, it is preferable to mix a predetermined amount of the alloy pigment and the glaze frit that have been subjected to the alloying treatment of a plurality of metals, heat and melt the mixture at, for example, 650 to 800 ° C., cool the mixture, pulverize it, and use it as a colorant.

By using a toner containing such a colorant, a clear full-color image having a high image density and a high image density can be formed on a transfer sheet with a small amount of toner adhered, and the toner image can be formed on a heat-resistant product such as a ceramic product. By transferring the image onto the solid surface and printing it, a sharp printed image having a high image density can be formed on the heat-resistant solid surface.

The content of the glaze frit in the toner is from 2/8 to the weight ratio of the colorant to the glaze frit.
6/4 is preferred, and 3/7 to 5/5 is particularly preferred. 2
Increasing the glaze frit component from / 8 lowers the degree of coloration of the toner, and reducing the glaze frit from 6/4 reduces the baked pattern from the heat-resistant solid surface when the toner image is printed on the heat-resistant solid surface. Desorption may occur. The glaze frit plays a role of sintering the colorant in the toner on the heat-resistant solid surface when printing the toner image transferred on the heat-resistant solid surface. When it is cooled, it solidifies completely and sinters the colorant on the heat-resistant solid surface.

As glaze frit, hydroxide of alkali metal or alkaline earth metal such as lithium hydroxide, carbonate of alkali metal or alkaline earth metal such as lithium carbonate,
Alkali metal or alkaline earth metal chloride, aluminum chloride, boric acid, alkali metal or alkaline earth metal chloride borate, alkali metal or alkaline earth metal chloride metaborate, alkali metal or alkali Earth metal phosphate, alkali metal or alkaline earth metal pyrophosphate, alkali metal or alkaline earth metal silicate, alkali metal or alkaline earth metal metasilicate, zirconium silicate, bone ash, shelf Sand, ammonium metavanadate, metal oxides such as tungsten oxide and vanadium pentoxide, tin oxide, zirconium oxide, cerium oxide, molybdenum oxide, metal fluorides such as calcium fluoride and aluminum fluoride, and glasslets as basic materials , Or a mixture thereof.

As a method of strengthening the binding of the glaze frit,
Feldspars such as lime feldspar, potassium feldspar, soda feldspar, betalite (lithium feldspar), kaolin, quartzite, alumina, silica, quartz, titanium oxide, lead oxide, chamotte, earth ash,
As a basic material, natural minerals such as limestone, magnesite, talc, and dolomite, and barium carbonate, zinc oxide, strontium carbonate, and the like may be mixed in advance, dissolved, and then contained in the toner.

Further, the toner containing the thermoplastic resin used in the present invention and colored after firing may contain a charge control agent, if necessary. As such a charge control agent, all conventionally known charge control agents can be used. For example, nigrosine dyes, quaternary ammonium salts, Cr-containing dyes,
Zn-containing dyes, Fe-containing dyes, molybdate chelate dyes, fluorine-modified quaternary ammonium salts and the like are appropriately selected and used according to the charging polarity.

The amount of the charge control agent used varies depending on the type of the thermoplastic resin, the presence or absence of additives used as necessary, and the toner production method including the method of dispersion in the toner. A suitable range is from 0.1 to 10 parts by weight, especially from 2 to 6 parts by weight per part by weight. If the amount is less than 0.1 parts by weight, the charge amount of the toner becomes insufficient,
Problems such as toner scattering and background contamination occur. When the amount exceeds 10 parts by weight, the electrostatic adhesion to the carrier becomes strong, which causes problems such as a decrease in the fluidity of the developer and a decrease in the amount of development. In addition, conventionally known additives such as hydrophobic silica, zinc stearate, aluminum stearate, and titanium oxide may be added as needed to improve the fluidity of the toner.

A toner which contains a thermoplastic resin and is colored after firing can be used as a so-called one-component developer for developing an electrostatic latent image as a developer of the toner alone,
Further, it can be used as a two-component developer obtained by mixing a toner and a carrier. Examples of the carrier when used as a two-component developer include iron powder, ferrite, and conventionally known carriers such as glass beads.Carriers include polyfluorocarbon, polyvinyl chloride, polyvinylidene chloride, a phenol resin, polyvinyl acetal, and silicon. It may be coated with a resin or the like. The mixing ratio of the toner and the carrier is as follows.
About 30 parts by weight is appropriate, and preferably 8 to 16 parts by weight.

In order to paint a heat-resistant solid surface such as a ceramic product using the transfer sheet of the present invention, for example, a toner image and a resin film are sequentially formed on a water-soluble layer of a support having a water-soluble layer. The water-soluble layer of the transfer sheet is dissolved by immersing the laminated transfer sheet in water, the resin film holding the toner image is peeled off from the transfer sheet, and the toner image is brought into close contact with the heat-resistant solid surface to form a toner image. Is applied to the surface of the heat-resistant solid, and the toner image and the heat-resistant solid having the resin film are heated to a temperature higher than the ashing temperature of the thermoplastic resin contained in the toner. Can be baked.

The method of baking on the surface of the heat-resistant solid is appropriately selected depending on whether baking is performed in the vicinity of the surface of the heat-resistant solid or deeper from the surface. In any case, the method is performed using an electric furnace or a gas furnace. Can be. When baking is performed near the surface of the heat-resistant solid surface, the temperature is gradually increased, for example, from room temperature to 200 ° C. for about 1 hour, and the temperature is maintained at 750 ° C. to 850 ° C. for about 30 minutes to 1 hour. After that, the temperature is lowered to room temperature and removed from the electric furnace or gas furnace, whereby the colorant in the toner is sintered on the heat-resistant solid surface with glaze frit and painted on a heat-resistant solid such as a ceramic product. The product is obtained.

When it is desired to perform baking deep inside the surface of the heat-resistant solid, the temperature is gradually increased from room temperature to about 200 ° C. for about 1 hour, and the temperature is raised from 1100 ° C. to 1300 ° C. for 3 hours.
A method in which the temperature is maintained for 0 minute to 1 hour, and then the temperature is lowered to room temperature is adopted. At this time, the temperature at which the temperature is raised is not limited to room temperature, but if a rapid temperature change is applied during the temperature rise and during the cooling, a slight difference may occur depending on the thickness and the material of the heat resistant solid depending on the heat resistant solid. However, since there are cases where cracks and shape changes may occur, the temperature change during baking is preferably 50 ° C./1 hour to 500 ° C./1 hour.

If the temperature change at the time of temperature rise or cooling is made slower than 50 ° C./1 hour, the baking time becomes longer and the efficiency becomes worse. If the temperature change at the time of temperature rise or cooling is made faster than 500 ° C./1 hour, uneven baking or a change in shape of the heat-resistant solid may occur. The condition of the temperature change at the time of heating or cooling is 100 ° C./1 hour to 300 ° C.
C / 1 hour is particularly preferred.

[0035]

The present invention will be described in more detail with reference to the following examples. Example 1 First, using a glaze frit manufactured as described below,
Produce each colorant, using each colorant,
A developer containing a toner that was colored after firing was manufactured as described below. <Manufacture of glaze frit> Al ₂ O ₃ (80 g), SiO ₂
(370 g), Na ₂ O (50 g) and PbO (500 g)
g) was blended and pulverized with a stamp mill, mixed with a Henschel mixer, fired at 1200 ° C, and pulverized to produce a glaze frit.

<Production of Black Colorant> Cr ₂ O ₃ (11
0g), MnO (270 g), Fe ₂ O ₃ (112 g) and Co ₂ O ₃ (508 g) were mixed and pulverized with a stamp mill, and then mixed with a Henschel mixer.
It was baked at 0 ° C. and pulverized. After mixing 300 g thereof and 500 g of the above glaze frit with a Henschel mixer, 75 g
It was baked at 0 ° C. and pulverized to produce a black colorant containing an alloy pigment.

<Production of Yellow Colorant> CuO (10
g), ZnO (190 g) and Sb ₂ O ₃ (800 g) were blended and pulverized by a stamp mill, then mixed by a Henschel mixer, and fired at 1100 ° C. to be pulverized. After mixing 300 g of the glaze frit and 500 g of the glaze frit with a Henschel mixer, the mixture was fired at 750 ° C. and pulverized to produce a yellow colorant containing an alloy pigment.

<Production of Magenta Colorant> Fe ₂ O ₃ (16
0g), NiO (40g), CuO (40g) and A
After mixing with u ₂ O (760 g) and pulverizing with a stamp mill, the mixture was mixed with a Henschel mixer, which was fired at 1100 ° C. and pulverized. 300 g of the glaze frit 5
After mixing 00 g with a Henschel mixer, the mixture was fired at 750 ° C. and pulverized to produce a magenta colorant containing an alloy pigment.

<Production of Cyan Colorant> Cr ₂ O ₃ (170
g), Fe ₂ O ₃ (10 g), Co ₂ O ₃ (690 g) and ZnO (130 g) were blended, pulverized by a stamp mill, and then mixed by a Henschel mixer.
And crushed. After mixing 300 g thereof and 500 g of the above glaze frit with a Henschel mixer, the mixture was mixed at 750 ° C.
And crushed to produce a cyan colorant containing an alloy pigment.

Using the above-mentioned coloring agent, a developer containing a toner containing a thermoplastic resin and colored after firing was produced as follows. <Production of Black Developer Containing Thermoplastic Resin and Colored Black Toner After Firing> Epoxy Resin (Tg
= 60 ° C), 4 parts by weight of a zinc salicylate derivative (Bontron E84, manufactured by Orient Chemical Co., Ltd.) and 230 parts by weight of the black colorant were mixed by a mixer, and then melt-kneaded with two rolls. The kneaded product was rolled and cooled, and then pulverized and classified to produce a black toner having a volume average particle diameter of 9.3 μm. Further, 0.5 wt% of hydrophobic silica (R972, manufactured by Nippon Aerogel Co., Ltd.) was added to the black toner, and the mixture was stirred with a mixer to obtain a black toner (bk).

On the other hand, 100 parts by weight of a silicone resin solution (KR50, manufactured by Shin-Etsu Chemical Co., Ltd.) and carbon black (BP20
00, manufactured by Cabot Corporation) 3 parts by weight and toluene 100
Parts by weight were dispersed with a homomixer for 30 minutes to prepare a coating layer forming liquid, and the coating layer forming liquid and an average particle diameter of 70 μm
Using a fluidized bed type coating apparatus, a carrier having a coating layer formed on the surface of the spherical ferrite carrier was manufactured using 1000 parts by weight of the spherical ferrite carrier. Next, 90 g of the black toner (bk) and 910 g of the carrier were placed in a ball mill and stirred for 30 minutes to produce a black developer.

<Production of a Yellow Developer Containing a Thermoplastic Resin and a Yellow Toner that is Colored After Firing> The yellow colorant was used in place of the black colorant in the production of the above black developer to obtain a volume average particle diameter of 9%. 0.3 μm
Was produced in the same manner as in the production of the black developer, except that the yellow toner was manufactured.

<Production of magenta developer containing magenta toner containing a thermoplastic resin and being colored after firing> The above magenta colorant was used in place of the black colorant in the production of the above black developer to obtain a volume average particle diameter of 9%. .1 μm
Magenta toner was manufactured, and a magenta developer was manufactured in the same manner as in the manufacture of the black developer, except that the magenta toner was used.

<Production of Cyan Developer Containing Thermoplastic Resin and Colored Cyan Toner After Firing> A volume average particle diameter using the cyan colorant instead of the black colorant in the above black developer production. A cyan developer was manufactured in the same manner as in the manufacture of the black developer, except that a cyan toner of 9.0 μm was manufactured and the cyan toner was used.

Next, 450 g of each of the black developer, yellow developer, magenta developer and cyan developer produced as described above was mounted on an electrophotographic color copying machine (Pretail 650, manufactured by Ricoh Company). A full-color image was formed on a transfer sheet (SN100, transfer paper for ceramics manufactured by Nitto Paper Industries: OK series) under the copying conditions described above to obtain a transfer sheet having a toner image. The temperature of the fixing roller at this time was set to 180 ° C.

[Copying conditions] Process speed: 180 mm / sec Charging potential: -650 V Exposure potential: -100 to -500 V Developing bias: -500 V Belt transfer bias: 1400 to 1700 V Transfer sheet transfer bias: 900 to 1500 V

A polystyrene resin solution was applied to the toner image surface of the transfer sheet obtained as described above, and dried to form a resin film. Thus, a transfer sheet having a toner image and a resin film was prepared. Indicate the ashing temperature of the epoxy resin used for the production of each color toner and the polystyrene resin used for forming the resin film. Measure 1.0 mg in TG-DTA mode using a thermogravimetric analyzer (TGD-3000, manufactured by Vacuum Riko Co., Ltd.). As a result, the ashing temperature of the epoxy resin was 480 ° C., and the ashing temperature of the polystyrene resin was 350 ° C.

The transfer sheet was placed in a water tank, the toner image held on the polystyrene resin film was peeled off from the transfer sheet, and the tile was adhered to a tile (RS252 / 1001, manufactured by INAX) so that the toner image side adhered to the tile.
After raising the temperature to 800 ° C. at a heating rate of
It was kept at 0 ° C. for 30 minutes, allowed to cool naturally, and the pattern was sintered on the tile. The sintered image on the obtained tile was a good image without any white spots.

Example 2 A transfer sheet (SN100, SN100, polystyrene resin solution used in Example 1) was used in advance in Example 1.
It was applied to Nitto Paper Industries transfer paper for ceramics: OK series) and dried to form a resin film. A toner image was formed on this resin film in the same manner as in Example 1, and the toner image and the resin film were formed. Was prepared. This transfer sheet is placed in a water tank, the toner image held on the polystyrene resin film is peeled off from the transfer sheet, and the toner image is adhered to the tile so that the toner image side is in close contact with the tile. Thereafter, a pattern is sintered on the tile in the same manner as in Example 1. I let it. The sintered image on the obtained tile was a good image without any white spots.

Example 3 Example 1 was repeated except that a polyester resin was used in place of the epoxy resin used in the production of the toner.
Each color toner was produced in the same manner as in Example 1, and each color developer was produced in the same manner as in Example 1 except that each color toner was used. A transfer sheet having a toner image and a resin film was prepared in the same manner as in Example 1 except that these color developers were used. The ash temperature of the polyester resin was 470 ° C. as measured in the same manner as in Example 1. Using this transfer sheet, a pattern was sintered on the tile in the same manner as in Example 1. The sintered image on the obtained tile was a good image without any white spots.

Example 4 A transfer sheet having a toner image and a resin film was prepared in the same manner as in Example 2 except that the color developers used in Example 3 were changed to the respective color developers. Using this transfer sheet, a pattern was sintered on the tile in the same manner as in Example 2. The sintered image on the obtained tile was a good image without any white spots.

Comparative Example 1 A toner image and a resin film were obtained in the same manner as in Example 1 except that a butyral resin having an ashing temperature of 500 ° C. was used instead of the polystyrene resin used for forming the resin film. A transfer sheet was prepared. Using this transfer sheet, a pattern was sintered on the tile in the same manner as in Example 1.
Fine white spots of about 1 mm were generated in the sintered image on the obtained tile.

Comparative Example 2 A toner image and a resin film were prepared in the same manner as in Example 1 except that a polyvinylidene chloride resin having an ashing temperature of 510 ° C. was used instead of the polystyrene resin used for forming the resin film. Was prepared. Using this transfer sheet, a pattern was sintered on the tile in the same manner as in Example 1. White spots of about 3 mm or more were generated in the sintered image on the obtained tile.

Comparative Example 3 A toner image and a resin film were formed in the same manner as in Example 1 except that a polyacrylonitrile resin having an ashing temperature of 530 ° C. was used instead of the polystyrene resin used for forming the resin film. A transfer sheet was prepared. Using this transfer sheet, a pattern was sintered on the tile in the same manner as in Example 1. The sintered image on the obtained tile was a mat-like image in which white spots of about 3 mm or more were continuously present.

Example 5 In Example 1, a dish, marble, enamel, and glass were used in place of the tile, and the temperature was raised at a rate of 100 degrees / hour, 200 hours.
Degree / 1 hour, 300 degree / 1 hour, 400 degree / 1 hour, 5
The pattern was sintered in the same manner as in Example 1 except that the temperature was changed to 00 degrees / 1 hour. As a result, in each case, a good sintered image having no white spots on the plate, marble, enamel, and glass could be obtained.

[0056]

According to the present invention, a toner image on a transfer sheet is transferred to a heat-resistant solid surface such as ceramics, glass, enamel, tile, stone and the like and baked, so that clear images without white spots and uneven printing are obtained. A simple pattern can be sintered on the heat-resistant solid surface.

Claims (4)

[Claims] 1. A transfer sheet comprising a resin image and a toner image comprising a color toner after baking and containing a thermoplastic resin on a support, wherein the ashing temperature of the resin film is contained in the toner. A transfer sheet having a temperature lower than the ashing temperature of the transfer sheet. 2. The transfer sheet according to claim 1, wherein a toner image and a resin film are sequentially laminated on the water-soluble layer of the support having the water-soluble layer. 3. The transfer sheet according to claim 1, wherein a resin film and a toner image are sequentially laminated on the water-soluble layer of the support having the water-soluble layer. 4. The toner image and the resin film of the transfer sheet according to claim 1, 2 or 3 are peeled off from a support, and the toner image and the resin film are adhered to a heat-resistant solid surface by heat-sealing the toner image and the resin film. A method for printing a toner image on a surface of a heat-resistant solid, which comprises applying the toner image and a heat-resistant solid having a resin film to a surface of the thermoplastic resin contained in the toner, the temperature being higher than the ashing temperature of the thermoplastic resin.