JP2002293021A - Transfer sheet and method for manufacturing decorated pottery using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer sheet capable of forming an image having excellent hue reproducibility and image clarity, and a method for manufacturing decorated pottery capable of forming a clear image without secondary color superposition even when a multi-color image is formed in a low cost. SOLUTION: The transfer sheet is used for a method for forming the image comprising the steps of imparting a latent image forming liquid in an image-like state to the surface of a transfer layer of the transfer sheet having the transfer layer made of a thermal transfer material on a support to form a latent image, and transferring to form the image corresponding to the latent image on an image receiver. The transfer sheet contains a latent image forming liquid absorber for absorbing the latent image forming liquid. The method for manufacturing the decorated pottery uses the transfer sheet.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer sheet containing an inorganic pigment and a method for producing a painted ceramic body using the transfer sheet.

[0002]

2. Description of the Related Art A painted ceramic body having a black-and-white or color image formed on a porcelain material such as a porcelain plate is used not only for building materials such as art tiles used for bathrooms and entrance walls, but also for ceramic photographs such as portraits and remains. It is expected to be applied to various uses such as accessories such as pendants and brooches. In order to form a clear image with excellent resolution and good storability on a ceramic, it is necessary to first form a clear image with excellent resolution using an inorganic pigment and then sinter it. The present inventors have proposed a method for manufacturing a painted ceramic body by a transfer method as the image forming method. Although this method is not known, the transfer layer of a transfer sheet having a transfer layer made of a thermal transfer material on a support,
One of the image receiving layers of the image receiving body having an image receiving layer capable of transferring the transfer layer (thermal transfer material) on a support contains a transferability promoting material or a tacky material capable of lowering the transfer temperature of the thermal transfer material. After the liquid (latent image forming liquid) is applied imagewise to form a latent image, the surface of the transfer layer of the transfer sheet and the surface of the image receiving layer of the image receiving body are brought into close contact with each other and heated to form a transfer layer corresponding to the latent image. This is an image forming method for transferring images onto an image receiving layer of an image receiving body.

In this method, when the latent image forming liquid is applied to the image receiving layer, after the first (first color) inorganic pigment image formation,
The latent image forming liquid itself or its solvent in the image receiving layer is dried to form a second (second color) inorganic pigment image. If the first drying is not sufficiently performed, the latent image formation is not performed. Even though the liquid itself or its solvent remains and the second color is a part where there is essentially no image, the part becomes a latent image and the inorganic pigment image is transferred, so-called secondary color coverage occurs Sometimes. When the latent image forming liquid is applied to the transfer layer side, the latent image forming liquid itself or its solvent diffuses in the layer in the horizontal direction, and in some cases, the liquid is not sufficiently absorbed by the layer and the liquid is formed on the layer surface. In some cases, they may remain as droplets. For this reason, there is a problem in that the latent image forming liquid also exists in a portion of the image receiving layer that should not be colored, and the transfer material is placed on that portion, causing color bleeding and a reduction in resolution. Therefore, the application amount of the latent image forming liquid is reduced,
In order to solve the problems of secondary color fogging and bleeding by sufficiently performing drying after applying the latent image forming liquid, in this case, the transferability of the thermal transfer material is reduced, and sufficient image density and uniformity are obtained. In some cases, an image could not be obtained.

[0004] On the other hand, a method is also conceivable in which a transfer sheet of each color is transferred to each image receiving body and then sequentially transferred to one image receiving body, thereby suppressing secondary color fogging. A large number of image receivers are required, resulting in high cost.

[0005]

SUMMARY OF THE INVENTION Accordingly, the present invention provides a transfer sheet capable of forming an image excellent in hue reproducibility and image sharpness, and a secondary color image forming apparatus capable of forming a multicolor image at low cost. An object of the present invention is to provide a method for manufacturing a painted ceramic body that can form a vivid image without fogging, and to achieve the object.

[0006]

Means for achieving the above object are as follows. <1> A latent image forming liquid is applied imagewise to the transfer layer surface of a transfer sheet having a transfer layer made of a thermal transfer material on a support to form a latent image, and an image is received corresponding to the latent image. A transfer sheet for use in an image forming method for transfer formation on a body, wherein the transfer sheet contains a latent image forming liquid absorbent for absorbing the latent image forming liquid.

<2> The latent image forming liquid absorbing layer containing a latent image forming liquid absorbing agent for absorbing the latent image forming liquid is provided on the surface of the transfer layer on the side where the latent image is not formed. Is a transfer sheet. <3> The transfer sheet according to <2>, wherein the latent image forming liquid absorbing layer has a minimum absorption amount of the latent image forming liquid of at least 1 ml / m ² or more. <4> The transfer layer contains a latent image forming liquid absorbent <
1>. <5> The latent image forming liquid absorption amount of the transfer layer containing the latent image forming liquid absorbent is at least 1 ml / m ² or more. <4>
<2. <6> The transfer sheet according to any one of <1> to <5>, wherein the latent image forming liquid absorbent mainly comprises a superabsorbent polymer.

<7> A latent image forming liquid containing a transfer promoting material or a tacky material capable of lowering the transfer temperature of a thermal transfer material on the transfer layer surface of the transfer sheet according to any one of <1> to <6>. A latent image forming step of forming a latent image by imagewise applying, at least contacting the transfer layer surface with the image receiving layer surface of an image receiving body having an image receiving layer capable of transferring the transfer layer on a support. Heating, transferring the transfer layer to the surface of the image receiving layer corresponding to the latent image, forming an inorganic pigment image of a thermal transfer material on the surface of the image receiving layer; An arranging step of arranging the inorganic pigment image on the surface of the porcelain, and an arranging step of arranging the inorganic pigment image on the surface of the porcelain, A method for producing a painted ceramic body, comprising:

<8> The method according to <7>, wherein the image receiving body has a water-soluble polymer-containing layer and an image receiving layer on the surface of the water-permeable support. <9> In the disposing step, the water-soluble polymer is partially dissolved, the water-permeable support of the image receiving member is peeled off, and the inorganic pigment image is placed on the porcelain material so that the peeled surface after peeling is in contact with the surface of the porcelain material. <8> is a method for manufacturing a painted ceramic body according to <8>, wherein <10> In the disposing step, before or after the water-soluble polymer is partially dissolved and the water-permeable support of the image receiving member is separated, the inorganic pigment image of the image receiving member is formed via a liquid in which a paste is dissolved or dispersed. The method according to <8>, wherein the inorganic pigment image is arranged on the surface of the porcelain so that the surface contacts the surface of the porcelain.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS <Transfer Sheet> The transfer sheet of the present invention comprises a transfer sheet having a transfer layer made of a thermal transfer material on a support. An image forming method for forming an image and transferring and forming an image on an image receiving member corresponding to the latent image, wherein the transfer sheet is a latent image forming liquid absorbing the latent image forming liquid. It contains an absorbent.

In the transfer sheet according to the first embodiment of the present invention, a latent image forming liquid absorbing layer containing a latent image forming liquid absorbent and a transfer layer made of a thermal transfer material containing an inorganic pigment are sequentially laminated on a support. It becomes. That is, the transfer sheet according to the first embodiment of the present invention has the latent image forming liquid absorbing layer containing the latent image forming liquid absorbing agent on the surface of the transfer layer on the side where the latent image is not formed. Note that another layer such as a cushion layer and a release layer may be provided between the support and the latent image forming liquid absorbing layer.

(Latent Image Forming Liquid Absorbing Layer) The latent image forming liquid absorbing layer contains at least a latent image forming liquid absorbing agent, and the absorption amount of the latent image forming liquid (the layer that the layer can absorb) is at least 1 ml / m 2.
² or more, preferably 2 ml / m ² or more, more preferably 4 ml / m ² or more.
ml / m ² or more, and preferably 30 ml / m ² or less. That is, the amount of latent image forming liquid absorbed by the latent image forming liquid absorbing layer (the amount that the layer can absorb) is preferably 1 ml / m ² to 1 ml / m ² .
30 ml / m ^2, more preferably 2 ml / m ² -30 mL
/ M ^2, more preferably at ^{4ml / m 2 ~30ml / m 2} . Note that a latent image forming liquid absorbent is contained so as to satisfy the above absorption amount. As the latent image forming liquid absorbent, an amphiphilic substance, a superabsorbent polymer, an oil absorbing substance, a porous substance, or the like can be appropriately used.

Examples of the amphiphilic substance include polyethylene oxide (PEO) and its modified products, polypropylene oxide (PPO) and its modified products, ethylene oxide-propylene oxide copolymer, poly N-vinylacetamide and the like. Can be Examples of the superabsorbent polymer include a water-soluble or water-swellable polymer. For example, a water-soluble polymer and a monomer having a carboxyl group (for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, and the like) described below are used. A water-soluble polymer containing at least 20 mol%, preferably at least 20 mol%, may be mentioned. Examples of the oil-absorbing substance include metal soaps (for example, aluminum soap), benzylidene sorbitol, a block copolymer composed of a styrene block polymer and a 1,3-butadiene block polymer, a norbornene polymer, 1,2-hydroxystearic acid, and an amino acid. System oil gelling agent (GP-1: manufactured by Ajinomoto Co., Inc.), Oleosoap (trade name of Nippon Shokubai Co., Ltd.) and the like.
Examples of the porous substance include clay (talc, hectorite, synthetic stephensite, montmorillonite, bentonite, kaolinite, sepiolite, etc.), amorphous silica (gel type, sedimentation type, fumed silica type, etc.) and the like. Can be In addition, these can be mixed and used appropriately.

Of these, the latent image forming liquid absorbent is preferably one containing a superabsorbent polymer as a main component. Here, the main component means that the superabsorbent polymer is 50% by mass or more, preferably 80% by mass in the latent image forming liquid absorbent.
It says above. The thickness of the latent image forming liquid absorbing layer is 0.5
μm to 10 μm, preferably 0.75 μm to 7.5 μm
Is more preferable, and 1 μm to 5 μm is further preferable. The latent image forming liquid absorbing layer can be formed by applying a liquid in which at least the latent image forming liquid absorbing agent is dissolved or dispersed in an appropriate solvent onto a support by a known coating method.

(Transfer Layer) The transfer layer is made of a thermal transfer material containing an inorganic pigment, preferably containing a binder together with the inorganic pigment, and optionally containing other components such as a flux, a plasticizer and a wax component. May be. The thickness of the transfer layer is 0.2 to 6.0 μm, preferably 0.5 to 6.0 μm.
3.0 μm.

As the inorganic pigment, there can be used upper paints and lower paints usually used for pottery. For example, the crystal structure of copper oxide, cobalt oxide or the like has a spinel, sphene, pichloa, rutile, priderite or the like. ,
Metal oxides such as phosphite, phenasite, perryclays, olivine, baddelite, borate, corundum, and zircon; sulfides such as cadmium yellow; and cadmium selenide compounds such as selenium red. Further, an inorganic pigment which is a fluorescent pigment or a phosphorescent pigment may be used.

It is also preferable to use a flux together with the inorganic pigment from the viewpoint of improving the fusibility when the inorganic pigment image is sintered on the porcelain. Examples of the flux include lithium carbonate, sodium carbonate, potassium carbonate, lead oxide, bismuth oxide, barium carbonate, strontium carbonate, calcium carbonate, magnesium carbonate, zinc oxide, aluminum oxide, aluminum hydroxide, silicon oxide, boric acid, Zirconium oxide, titanium oxide and the like can be mentioned. Further, composite components such as borax, feldspar, kaolin and the like can also be used. The flux may be dissolved alone or in combination of two or more, and may be used as a so-called frit.

The content of the inorganic pigment in the transfer layer is preferably from 10 to 80 vol%, preferably from 20 to 70 vol%.
ol% is more preferred. When the flux is used in combination with an inorganic pigment, the preferred amount of the flux varies depending on the inorganic pigment. However, as a mixture of the flux and the inorganic pigment, the content of the mixture in the transfer layer is 15 to 70 mass%. %, More preferably 30 to 80% by mass.

The binder may be either a homopolymer or a copolymer, and the polymer may be composed of one kind of monomer or two or more kinds of monomers. Above all, the transfer layer formed of the transfer material is transferred, and in relation to the image receiving layer of the image receiving body, the polymer used for the transfer layer and the polymer used for the image receiving layer have the same functional group as their constituent units. (Hereinafter, referred to as a “polymer having the same functional group”) containing at least 30 mol% of a monomer having the following formula: At least one of the monomers constituting the polymer in both layers may have the same functional group, and may have different functional groups. Here, as the same functional group, for example,
Butyral group, vinyl alcohol group, amino group, amide group, imino group, imide group, styrene group, alkoxy group,
Examples include a methacrylic group and its ester group, acrylic acid and its ester group, maleic acid and its ester group, a vinyl ether group, and a vinyl acetate group, with a butyral group being preferred.

The monomer having the “same functional group” is preferably contained in the polymer in the transfer layer and the polymer in the image-receiving layer described later as a large amount as a constitutional unit, respectively. 30 mol%
It is desirable that the content be not less than 50 mol%, more preferably 50 mol% or more, and particularly preferably 80 mol% or more. When the content of the monomer having the “same functional group” as the constituent unit in the polymer is less than 30 mol%, the properties of the polymer in the transfer layer and the properties of the polymer in the image receiving layer described later are significantly different, Image unevenness may easily occur.

Specifically, an amorphous organic high molecular polymer having a softening point of 40 to 150 ° C. is preferable. As the amorphous organic high-molecular polymer, for example, butyral resin, polyamide resin, polyethyleneimine resin, sulfonamide resin, polyester polyol resin, petroleum resin, styrene, vinyltoluene, α-methylstyrene, 2-methylstyrene, Chlorostyrene, vinylbenzoic acid, styrene such as amino styrene and derivatives thereof, homopolymers and copolymers of substituted methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate and methacrylic acid, methyl Acrylates such as acrylate, ethyl acrylate, butyl acrylate, α-ethylhexyl acrylate and acrylic acid, butadiene, diene such as isoprene, acrylonitrile, vinyl ether, Maleic acid and maleic esters, maleic anhydride, cinnamic acid, vinyl monomers such as vinyl acetate, etc.
Or a copolymer with another monomer or the like. Two or more of these binders may be used in combination.

The content of the binder is 10 to 300 vol based on the amount of the inorganic pigment and the flux (the amount of the inorganic component).
% Is preferable, and 20 to 200 vol% is more preferable.
If the content is less than 10 vol%, the layer may become brittle and the scratch resistance may decrease. If the content exceeds 300 vol%, the transfer layer may become thick and the resolution and gradation may decrease.

When forming a multicolor image on the image receiving layer,
From the viewpoint of improving the adhesion between images, the transfer material preferably contains a plasticizer. Examples of the plasticizer include phthalate esters such as dibutyl phthalate, di-n-octyl phthalate, di (2-ethylhexyl phthalate, dinonyl phthalate, dilauryl phthalate, butyllauryl phthalate, and butylbenzyl phthalate) Kind,
Aliphatic dibasic acid esters such as di (2-ethylhexyl) adipate and di (2-ethylhexyl) sebacate;
Examples include phosphate triesters such as tricresyl phosphate and tri (2-ethylhexyl) phosphate, polyol polyesters such as polyethylene glycol ester, and epoxy compounds such as epoxy fatty acid ester. Further, in addition to the plasticizer, polyethylene glycol dimethacrylate, 1,2,4-butanetriol trimethacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol-
Acrylic esters such as polyacrylate can also be suitably used depending on the kind of binder used. Incidentally, two or more plasticizers may be used in combination. Further, a surfactant, a thickener and the like may be further added as necessary.

The content of the plasticizer in the transfer layer includes the total mass (S) of the inorganic pigment and the binder and the mass of the plasticizer.
As a ratio (S: s) to (s), generally 100: 1 to 10
0: 5 is preferred, and 100: 1.5 to 100: 3 is more preferred.

The transfer layer preferably contains a wax component from the viewpoint of improving the resolution of the transferred image (dots) and the resolution of the film. As the wax component,
For example, paraffin wax, microcrystalline wax, carnauba wax, candelilla wax, rice wax, Fischer-Tropsch wax, beeswax, wood wax, spermaceti, Ibota wax, wool wax, shellac wax, betrolactam, polyester wax, lanolin, low molecular weight polyethylene wax, Amide wax,
Ester wax, oxidized polyethylene wax, rosin, rosin methylolated amide, ester gum, higher fatty acid, higher fatty acid ester, higher alcohol and the like.

Further, the transfer layer is compared to improve the adhesiveness of an image receiving body and a transfer sheet, which will be described later, and to improve the glue of the transfer layer (material) from the second time onward when a multicolor image is formed. Low melting point thermoplastic resin, for example, low molecular weight petroleum resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, styrene-acrylate copolymer, styrene-maleic acid -It is also preferable to add an acrylate copolymer, a terpene phenol resin or the like.

The transfer layer is prepared by dissolving or dispersing the components of the transfer material, such as the inorganic pigment and the binder, in an appropriate solvent, and coating the solution on a support (an undercoat layer described later on the support). When it has, it can be applied on the undercoat layer) and dried. As the solvent, an aqueous solvent is preferable from the viewpoint of environmental safety, but n-propyl alcohol, methyl ethyl ketone, propylene glycol monomethyl ether (MFG), methanol, or a mixed solvent thereof with water can also be used. Coating and drying
It can be carried out by using generally known coating and drying methods.

(Support) The support constituting the transfer sheet is not particularly limited and can be appropriately selected from various known materials according to the purpose and the like. For example, synthetic resin materials such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polycarbonate, polyethylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and styrene-acrylonitrile copolymer are preferably exemplified. Biaxially oriented polyethylene terephthalate is particularly preferred in terms of dimensional stability to heat and cost.

The support is preferably subjected to a surface roughening treatment and / or the provision of one or more undercoat layers for the purpose of adjusting the adhesion to the transfer layer provided on the surface. Examples of the roughening treatment include a glow discharge treatment and a corona discharge treatment. As a material for the undercoat layer, a material that exhibits appropriate adhesiveness to both surfaces of the support and the transfer layer, has low thermal conductivity, and is excellent in heat resistance is preferable. From this viewpoint, for example, styrene, styrene-butadiene copolymer, gelatin and the like are preferred. The thickness of the entire undercoat layer is usually 0.01 to 2 μm. Further, on the surface of the transfer sheet opposite to the side where the transfer layer is provided, various functional layers such as a release layer may be provided or surface treatment may be performed as necessary.

The transfer sheet according to the second embodiment of the present invention has a transfer layer made of a thermal transfer material containing an inorganic pigment on a support, and the transfer layer contains a latent image forming liquid absorbent. You. The transfer sheet has a latent image forming liquid absorbing layer,
Other layers such as a cushion layer and a release layer may be provided.

The amount of latent image forming liquid absorbed by the transfer layer of the transfer sheet according to the second embodiment of the present invention (the amount that the layer can absorb).
Is at least 1 ml / m ² or more, preferably ² ml / m ²
m ² or more, more preferably 4 ml / m ² or more;
It is preferably 1 / m ² or less. That is, the absorption amount of the latent image forming liquid in the transfer layer (the amount that the layer can absorb) is preferably 1 ml / m ^{2 to} 30 ml / m ² , more preferably 2 ml / m ² .
m ² ~30ml / m ^2, more preferably 4 ml / m ² to 3
0 ml / m ² . Note that a latent image forming liquid absorbent is contained so as to satisfy the above absorption amount. The thickness of the transfer layer is 0.5 to 6 μm, preferably 1 to 4 μm. As the latent image forming liquid absorbent, the same one as in the first embodiment can be used, and the preferred embodiment is also the same.

<Manufacturing Method of Painted Porcelain> A method of manufacturing a painted ceramic body using the transfer sheet of the present invention will be described below. The method for producing a painted ceramic body of the present invention is a latent image forming step of forming a latent image by applying a latent image forming liquid imagewise to the transfer layer surface of the transfer sheet of the present invention, and the transfer layer surface, An image forming step of transferring at least the image receiving layer surface of an image receiving body having an image receiving layer capable of transferring the transfer layer onto a support and heating the image receiving layer to transfer and form an inorganic pigment image made of a thermal transfer material on the image receiving layer surface; An arranging step of arranging the inorganic pigment image on the surface of the porcelain; and a firing step of heating the porcelain on which the inorganic pigment image is arranged and sintering the machine pigment image on the surface of the porcelain.

As described above, the method for manufacturing a painted ceramic body according to one embodiment of the present invention includes a latent image forming step, an image forming step,
It comprises at least an arrangement step and a firing step, but may have other steps as necessary. First, a method for manufacturing a painted ceramic body according to an embodiment of the present invention will be described with reference to FIG.
This will be described with reference to FIG. Here, FIG. 1 is a schematic process diagram for explaining a basic mode of the method for manufacturing a painted ceramic body of the present invention.

First, as shown in FIG.
A transfer sheet 4 having a latent image forming liquid absorbing layer 2 containing a latent image forming liquid absorbing agent for absorbing the latent image forming liquid and a transfer layer 3 made of a thermal transfer material on the surface of the transfer sheet 4 is prepared. Figure 1
As shown in (b), on the surface of the transfer layer 3 of the transfer sheet 4, a latent image forming liquid containing a transferability promoting material or an adhesive material capable of lowering the transfer temperature of the thermal transfer material is applied, for example, by an ink jet recording apparatus. A latent image i is formed by applying an image (not shown) in an image-like manner (latent image forming step).

At this time, the (excess) part of the applied latent image forming liquid is absorbed by the latent image forming liquid absorbent of the latent image forming liquid absorbing layer, and the latent image forming liquid diffuses in the horizontal direction. Can be suppressed, so that only the portion that is originally colored in the image forming step described later can be colored, bleeding is suppressed, and the resolution is excellent.

Subsequently, as shown in FIG. 1C, the image receiving layer 6 capable of transferring the transfer layer 3 (thermal transfer material) to the surface of the support.
Is prepared, and the surface of the transfer layer 3 on which the latent image i is formed and the surface of the image receiving layer 6 of the image receiver 7 are overlapped so as to be in contact with each other. Laminate by heating while applying pressure or the like according to. At the time of lamination, it is preferable to apply heat and pressure at the same time, and for example, a method of passing through a pair of heating nip rollers incorporating a heating means such as a heater is suitable. The heating temperature during heating is preferably from 60 to 200 ° C.

When the transfer sheet 4 is peeled off after the lamination, the transfer layer 3 is transferred only to the area of the latent image i, and the inorganic pigment image 6a (image formed of a transfer material) is formed on the image receiving layer 6.
(FIG. 1- (d)) is transferred and formed (image forming step). Subsequently, the inorganic pigment image 6 a is arranged on the porcelain material 8. At any stage before and after the arrangement, the support 5 of the image receiving body 7 is peeled off at the boundary with the image receiving layer 6.

For example, when the support 5 of the image receiving member 7 is composed of a water-permeable support and a water-soluble polymer layer and an image receiving layer are sequentially laminated on the support 5, a part of the image receiving member 7 is formed. Is brought into contact with or immersed in a liquid such as water, so that moisture penetrates through the support 5 to dissolve a part of the water-soluble polymer, and the support 5 is easily peeled off. (At this time, the surface on the side where the support 5 has been peeled and is partially dissolved is referred to as a “peel surface”.) After the support 5 is peeled, the inorganic pigment image 6 a is placed on the surface of the desired porcelain 8. As shown in FIG. 1- (e), the water-soluble polymer in the image receiving layer 8 is partially dissolved, and is disposed on a desired surface of the porcelain 8 so as to be in contact with the release surface.

On the other hand, the liquid in which the paste is dissolved or dispersed is applied so that the surface opposite to the release surface, that is, the surface of the image receiving layer 6 on which the inorganic pigment image 6a is formed (the surface on which the inorganic pigment image is formed) is in contact. In this case, the support 5 of the image receiving body 7 can be peeled after the inorganic pigment image 6a is arranged (arrangement step). In the former (the present embodiment), a normal image is formed on the porcelain 8 as viewed from the inorganic pigment image 6a formed on the image receiving body 7, and in the latter,
A mirror-inverted image is formed on the porcelain 8 as viewed from the inorganic pigment image 6 a formed on the image receiving body 7. The porcelain 8 can be arranged on the surface by thermocompression as needed.

When the support 5 of the image receiving member 7 is a plastic film support, the plastic film support is preliminarily subjected to a surface treatment for imparting releasability, so that the plastic film support is not immersed in water or the like. The film support can be easily peeled off. In this case, the paste can be disposed on the surface of the porcelain 8 via a liquid in which the paste is dissolved or dispersed.

The liquid in which the sizing agent is dissolved or dispersed is, for example, a solvent such as water, and the sizing agent is, for example, the above-mentioned water-soluble polymer, a thermoplastic resin having a glass transition point of 25 ° C. or lower, preferably 5 ° C. or lower. Alternatively, a dispersed liquid or the like may be used.

After the inorganic pigment image 6a is arranged on the surface of the porcelain 8 as described above, the porcelain 8 (FIG. 1- (e)) is heated and fired to obtain the porcelain 8 (FIG. 1- (f)). ),
The organic image receiving layer 6 and the like are burned off, and the inorganic pigment image 6a is sintered on the surface of the porcelain 8, forming an inorganic image 6b (firing step).

The heating in the firing step is preferably performed using, for example, an electric kiln from the viewpoints of temperature control, color development and the like. The heating conditions can be appropriately set according to the selected material, the volume of the porcelain, the size of the image, and the like. The heating is performed by gradually raising the temperature to the firing temperature, or 300 to 500
After heating at a constant temperature for a certain period of time at a temperature of ° C., it is preferable to gradually raise the temperature to the firing temperature. In the case of using a paint as the inorganic pigment, the firing temperature is usually set at 650 to 900.
° C, preferably 750-850 ° C, and the firing time is 10
It is preferable to set the time from minutes to 2 hours. When using an undercolor as an inorganic pigment, the firing temperature is set to 1000 to 1300.
° C, preferably 1100 to 1250 ° C, and the firing time is preferably 10 minutes to 8 hours.

<Latent Image Forming Solution> The latent image forming solution contains a transfer promoting material or a tacky material which can lower the transfer temperature of the thermal transfer material.

(Transfer-Promoting Material) The transfer-promoting material is a material capable of lowering the transfer temperature of the transfer material contained in the transfer layer. The transferability-promoting material is preferably a liquid composition, and preferably has a configuration that does not include a solid material or the like that is likely to precipitate over time. Examples of the transferability promoting material include water, organic solvents (preferably, organic solvents that are freely miscible with water at normal temperature), and surfactants (preferably, water-miscible surfactants). Or a mixture thereof. Further, the transferability-promoting material itself is preferably a colorless or light-colored one, does not chemically act on the inorganic pigment contained in the transfer material, and does not cause a coloring reaction or the like by heat energy optionally provided in a later step. Preferably, it is a material.

Examples of the organic solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
sec-butyl alcohol, isobutyl alcohol, ethylene glycol, diethylene glycol, thiodiethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, hexylene glycol, polypropylene glycol, glycerin, etc. Polyhydric or polyhydric alcohols: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monobutyl ether Ethers such as triethylene glycol monoethyl ether, triethylene glycol monobutyl ether and tripropylene glycol monomethyl ether; keto alcohols such as diacetone alcohol; nitrogen-containing solvents such as N-methyl-2-pyrrolidone and 2-pyrrolidone; And the like.

As the surfactants, any of anionic, cationic, nonionic and amphoteric surfactants can be used, and can be arbitrarily selected according to the characteristics of the transfer material used in combination. When used by dissolving in water, it can be used at a concentration within a range that can be dissolved in water. Specifically, for example, fatty acid salts, alkyl sulfate salts, polyoxyethylene alkyl ether sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, alkyl phosphates Salt, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, alkyl alkanolamine, alkylamine salt, alkyl betaine, mono- or dihydroxyacetylene compound And the like.

The transfer promoting material may be used singly or as a mixture of two or more. Among them, from the viewpoint of the effect, a transferability promoting material obtained by mixing the organic solvent and / or the surfactant and water is preferable. The transferability-promoting material includes a surface tension adjuster, an antifungal agent, a viscosity adjuster, a pH adjuster, for the purpose of adjusting ejection suitability when ejected as droplets, preventing the spread of droplets, and improving storage stability. An adjusting agent, an antifoaming agent, and the like can be contained in a range that does not impair the effects of the present invention.

The transferability promoting material preferably has good permeability to the transfer layer, and has a surface tension of 25 to 60 mN.
/ M, viscosity 50 mPa. It preferably has physical properties of s or less. Further, a material that does not solubilize the transfer material itself is preferable. When the transferability-promoting material dissolves the transfer material, penetration of the transferability-promoting material and dissolution of the transfer material (transfer layer) occur at the interface between the image portion and the non-image portion, and the sharpness of the image interface decreases. Sometimes. When using a solubilizing transfer material as the transferability promoting material,
It is preferable to reduce the discharge amount of the transferability promoting material.

The degree of decrease (reference) in which the transfer temperature of the transfer material is lowered by the action of the transferability-promoting material is as follows as compared with the transfer temperature of the transfer material when no transferability-promoting material is used. Is preferably 3 ° C. or higher. The transfer temperature is, for example, a pair of heating nip rollers, at least one of which is a variable temperature heating roller, a transfer sheet and an image receiving body are sandwiched by a thermocouple, and the laminate is passed between the heating nip rollers. Can be measured. The temperature is measured by a thermocouple while changing the heating temperature of the heating roller, and the transfer temperature can be determined as the lowest temperature at which transfer occurs.

Among the above-mentioned transferability promoting materials, a nonionic surfactant and water are used because they have a great effect of lowering the transfer temperature, improve the transferability of fine points, and can form a high-resolution transfer image. Those containing are particularly preferred. As the nonionic surfactant, a nonionic compound having an ethylene oxide group added as a hydrophilic group is particularly preferable. When a nonionic compound to which an ethylene oxide group is added is used, the effect of lowering the transfer temperature in the latent image forming portion is large, and high resolution can be achieved. Examples of the nonionic compound include compounds represented by any of the following general formulas 1 to 4.

[0052]

Embedded image

In the above general formula 1, R represents an alkyl group or an alkylene group, and n represents an integer of 2 to 30, preferably 2 to 20. In the general formula 2, R represents an alkyl group, and n represents an integer of 2 to 30, preferably 2 to 20. In the general formula 3, R represents an alkyl group, and n and l each independently represent an integer of 2 to 30, preferably 2 to 20. In the general formula 4, R
¹ and R ² each independently represent a hydrogen or an alkyl group, and m and n each independently represent an integer of 2 to 30, preferably 2 to 20. In addition, the general formula 1
In Examples 4 to 4, the addition number of ethylene oxide was 2
To 30 are preferable, and 2 to 20 are particularly preferable.

Specific examples of the compounds represented by any of the above formulas 1 to 4 include polyoxyethylene (4) lauryl ether, polyoxyethylene (7) cetyl ether,
Polyoxyethylene (13) stearyl ether, polyoxyethylene (5) oleyl ether, polyoxyethylene (10) nonylphenyl ether, ethylene oxide-propylene oxide copolymer (n = 10, l = 7), ethylene oxide addition of acetylene glycol Body (n + m
= 10). However, it is not limited to these.

The content of the nonionic surfactant in the transferability-promoting material containing the nonionic surfactant and water is preferably 0.1 to 20% by mass, and 0.1 to 1% by mass.
0 mass% is more preferable. The content is 0.1% by mass.
When the amount is less than the above, the transfer promoting effect may be difficult to be obtained. Further, a water-soluble organic solvent can be used in combination with the nonionic surfactant, and as the water-soluble organic solvent,
The above-mentioned "organic solvent freely miscible with water" is mentioned.
The content of the water-soluble organic solvent is suitably about 0 to 90% by mass in the transferability promoting material.

Further, as the transferability promoting material, a material having a boiling point of 100 ° C. or more at normal temperature and normal pressure and containing water and an organic solvent compatible with water is also preferable. The ejection stability of the solution is improved, ejection failure at the time of forming a latent image and restarting after standby can be prevented, and the transferability of fine dots is improved, so that a high-resolution transfer body can be obtained. Examples of the organic solvent having a boiling point of 100 ° C. or higher at normal temperature and normal pressure and compatible with water include, for example, ethylene glycol, diethylene glycol, thiodiethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol,
Monohydric or polyhydric alcohols such as polypropylene glycol and glycerin; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, propylene glycol monobutyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether,
Ethers such as tripropylene glycol monomethyl ether; keto alcohols such as diacetone alcohol;
Nitrogen-containing solvents such as N-methyl-2-pyrrolidone and 2-pyrrolidone; and the like.

The content of the “organic solvent having a boiling point of 100 ° C. or higher at normal temperature and normal pressure and compatible with water” in the transferability promoting material is preferably 1 to 90% by mass. If the content is less than 1% by mass, ejection stability and transferability of fine dots may not be improved. If the content exceeds 90% by mass, ejection stability at the time of latent image formation may be improved. On the other hand, the drying property of the transferred image may be reduced. Also in this case, in addition to the organic solvent, the above-mentioned "organic solvent freely miscible with water" and surfactants can be added.

(Tacky Material) The tacky material contains a substance having tackiness at normal temperature or when heated (tacky substance), and examples of the tacky substance include mainly organic polymers. Specifically, acrylic acid, methacrylic acid, acrylic acid esters, homopolymers and copolymers of acrylic monomers such as methacrylic acid esters, polyvinyl acetate, polystyrene, polyvinyl pyrrolidone,
Polyvinyl butyral, polyvinyl alcohol, homopolymers of vinyl monomers such as polyvinyl chloride and copolymers thereof such as ethylene-vinyl acetate, polyesters, condensation polymers such as polyamides, styrene-butadiene copolymer, Rubber-based polymers such as acrylonitrile-butadiene copolymer can be mentioned. Among these, a polymer having a glass transition point (Tg) lower than 90 ° C. is preferable. Further, these may be present as an emulsified dispersion in water, a so-called latex state.

Further, the adhesive material comprises the above-mentioned adhesive substance,
It may be a solution dissolved or dispersed (including solid dispersion and emulsified dispersion) in water or a solvent such as an organic solvent. The organic solvents referred to herein include, specifically, methyl alcohol,
Ethyl alcohol, n-propyl alcohol, alkyl alcohols of i-propyl alcohol, amides such as dimethylformamide, dimethylacetamide, etc., ethylene glycol, 1,2,6 hexanetriol, thiodiglycol, propylene glycol, diethylene glycol, triethylene Monohydric or polyhydric alcohols such as glycol, polyethylene glycol, polypropylene glycol and glycerin; ethers such as dioxane, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, triethylene glycol monobutyl ether and tripropylene glycol monomethyl ether Ketones such as acetone, methyl ethyl ketone, diacetone alcohol, etc. Mention may be made of a keto alcohol, and the like.

These water or organic solvents may be used alone or in combination of plural kinds of solvents to dissolve or disperse the adhesive material. In addition, the above solution is used in combination with a surface tension adjuster, an antifungal agent, a viscosity adjuster, a pH adjuster, a defoamer, a plasticizer, etc. in order to improve discharge suitability, storage stability of the liquid, and adhesive properties. can do.

When the latent image forming liquid contains the adhesive material in a dispersed form (solid dispersion or emulsified dispersion), it is preferable to add a compound represented by the following general formula (5). R
-(SP) _n ... General formula (5) By adding this compound, the tacky material in a dispersed form does not cause aggregation and the latent image forming liquid is stably held. The occurrence of clogging is also prevented. The compound represented by formula (5) is added in an amount of 3 to 20% by mass based on the solid content of the latent image forming solution.

In the general formula (5), R represents a hydrophobic group or a group consisting of a hydrophobic polymer, and P represents the following structural unit A:
Containing at least one of B and C and having a degree of polymerization of 10
It represents a polymer of 3500 or more. n represents 1 or 2.

[0063]

Embedded image

Here, R ¹ represents —H or an alkyl group having 1 to 6 carbon atoms, R ² represents —H or an alkyl group having 1 to 10 carbon atoms, and R ³ represents —H or —CH ₃ . And R ⁴
It is H, -CH _3, (including ammonium salt or metallic salt) -CH ₂ COOH or represents -CN, X is -H, -CO
OH (including ammonium salt or metal salt) or -CON
Represents H _2, Y (including ammonium salt or metallic salt) -COOH, - (including ammonium salt or metallic _{salt) SO 3 H, - OSO 3} H ( including ammonium salt or metallic salt), - CH ₂ SO ₃ (including ammonium salt or metallic _{salt) H, - CONHC (CH 3} ) ( including ammonium salt or metallic salt) ₂ CH ₂ SO ₃ H or -CONHCH ₂ CH ₂
Represents CH ₂ N ⁺ (CH ₃ ) ₃ Cl ⁻ .

In the general formula (5), R ¹ is preferably -H, and R ² is preferably -CH ₃ . Typical examples of the compound represented by the general formula (5) include a random or block copolymer of vinyl alcohol and a vinyl ester or a vinyl alcohol containing a third monomer component having an anionic group such as a carboxyl group. And random or block copolymers of vinyl and vinyl esters whose terminals are modified with an alkyl group or a hydrophobic polymer.

Examples of the hydrophobic group represented by R in the general formula (5) include an aliphatic group (eg, an alkyl group, an alkenyl group, an alkynyl group), an aromatic group (eg, a phenyl group and a naphthyl group) and There are alicyclic groups, including those substituted. Examples of the substituent include an aliphatic group, an aromatic group, an alicyclic group, a heterocyclic group, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an N-substituted sulfamoyl group, a carbamoyl group, an acylamino group, an alkylsulfonylamino group, and an aryl group. Examples include a sulfonylamino group, an alkoxy group, an aryloxy group, an aralkyl group, and an acyl group.

When the hydrophobic group is an alkyl group, it preferably has 3 to 70 carbon atoms, preferably 4 to 50 carbon atoms, particularly preferably 8 to 24 carbon atoms. A specific example when R is a hydrophobic group is disclosed in
No. 95942, paragraphs [0034] to [00]
42], the groups from (S-1) to (S-50) are preferred.

When R in the general formula (5) is a hydrophobic polymer, polystyrene and its derivatives, polymethacrylate (eg, polymethyl methacrylate) and its derivatives, polyarylic acid and its derivatives,
Water-insoluble vinyl polymers and vinyl copolymers represented by polybutene, polyvinyl acetate, polyvinyl versatate, etc., water-insoluble polyoxyalkylenes such as polyoxypropylene and polyoxytetramethylene, and furthermore Water-insoluble polymers such as polyamide and polyester are exemplified. In particular, polystyrene and its derivatives, polymethacrylate and its derivatives, polyacrylate and its derivatives, and polyvinyl chloride are preferably used. The degree of polymerization of the hydrophobic polymer is 2 or more and 50 or more.
It is 0 or less, preferably 2 or more and 200 or less, and more preferably 2 or more and 100 or less.

The polymer P in the compound represented by the general formula (5) is a polymer containing at least one of the above structural units A, B and C. As Specifically structural units A constituting the polymer A, vinyl alcohol, alpha-
Methyl vinyl alcohol, α-propyl vinyl alcohol and the like can be mentioned. Examples of the structural unit B constituting the polymer P include vinyl acetate, vinyl formate, vinyl propionate, and their α-substituted products. Further, as the structural unit C constituting the polymer P, acrylic acid, methacrylic acid or crotonic acid (each including an ammonium salt or a metal salt such as Na or K), maleic acid or itaconic acid (a monoalkyl ester or an ammonium salt, respectively) Or Na, K
Etc.), vinylphosphonic acid, vinylsulfuric acid,
Acrylic sulfonic acid, methacrylsulfonic acid, 2-acrylamido-3-methylpropanesulfonic acid or 2-methacrylamido-3-methylpropanesulfonic acid (including an ammonium salt or a metal salt such as Na or K, respectively), acrylamidopropyltrimethyl Monomer units that ion dissociate in water, such as ammonium chloride or methacrylamidopropyltrimethylammonium chloride. Particularly, itaconic acid and maleic acid are preferred.

Among them, the structural unit A includes a vinyl alcohol unit, the structural unit B includes a vinyl acetate unit, and the structural unit C includes a carboxylic acid (ammonium salt or a metal salt such as Na or K). ) Containing vinyl monomer units or sulfonic acids (ammonium salts, or Na,
(Including metal salts such as K) is a more preferred unit.

The content of the structural units A, B, and C constituting the polymer P is not particularly limited. However, when the contents of A, B, and C are x, y, and z mol%, respectively, x + y + z
= 100, 0 ≦ x ≦ 100, 0 ≦ y ≦ 75, 0 ≦ z ≦ 1
00 is preferable, x + y + z = 100, 0 ≦ x ≦ 10
0, 0 ≦ y ≦ 50 and 0 ≦ z ≦ 50 are particularly preferred. When the content of the structural unit C is 1 mol% or less, the polymer P
Is preferably water-soluble or water-dispersible, the content of the structural unit A is preferably from 50 mol% to 100 mol%.

The compounds represented by the general formula (5) include those in a wide range from water-soluble to water-dispersible. As long as the compound represented by the general formula (5) of the present invention is water-soluble or water-dispersible, the polymer P may contain structural units other than the structural units A, B and C at all. as these structural units, such as ethylene, propylene, Isoputen, acrylonitrile, acrylamide, methacrylamide, N- vinylpyrrolidone, vinyl chloride or vinyl fluoride units. The degree of polymerization of the polymer P is 10
It is 3500, preferably 10-2000, more preferably 10-1000, and particularly preferably 10-500.

R in the structural units A and B of the polymer P
^As the alkyl group for ¹ and R ^2, a methyl group is particularly preferred. Further, the alkyl group is a hydroxyl group, an amide group, a carboxyl group, a sulfonic acid group, a sulfinic acid group,
It may be substituted by a sulfonamide group or the like.

The compound represented by the general formula (5) has different optimum chemical compositions and molecular weights of P and R constituting the compound according to the purpose of the present invention.
Having a composition wherein the mass ratio of 0.001 ≦ R / P ≦ 2, more preferably 0.01 ≦ R / P ≦ 1, is particularly excellent.

<Receiver> The receiver may be any one as long as it can form an inorganic pigment image comprising a transfer layer via a latent image, and may have a single image-receiving layer on the surface of the support. A cushion layer, a release layer, an intermediate layer, and the like may be provided between the layers. In the present invention, those having at least one layer or two or more layers selected from a cushion layer, a release layer and an intermediate layer are preferable. In addition, a mode in which a back layer is provided on the side of the support opposite to the side having the image receiving layer for the purpose of improving transportability is also suitable.

The image receiving layer is not particularly limited as long as an inorganic pigment image can be transferred and formed, and may be a layer containing either a hydrophobic polymer or a water-soluble polymer as a binder. From the viewpoint of easy separation of the support in the disposing step and ease of disposition on the porcelain material, an image receptor (adhesive property) further comprising an image receiving layer on a water-soluble polymer layer provided on a water-permeable support. An image receiving layer is preferable, and an embodiment in which the above-mentioned “polymer containing the same functional group” (hydrophobic polymer) is contained in the image receiving layer as a binder (hereinafter, may be referred to as “hydrophobic polymer layer”). Is particularly preferred. In this case, the hydrophobic polymer layer plays a role as an image-receiving layer capable of forming an image, and the water-soluble polymer layer functions as a layer (release layer) for improving the peelability of the support and imparting adhesion to the porcelain. I do. By providing the hydrophobic polymer layer with the water-soluble polymer layer interposed, it is possible to eliminate image unevenness during multicolor transfer and improve transferability.

When the support is a paper support, when the image receiver is immersed in a liquid such as water, a part of the water-soluble polymer is dissolved and the paper support can be peeled off. At the same time, it is preferable that the inorganic pigment image after peeling can be bonded to the surface of the porcelain material on the peeling surface. Here, the adhesion by the water-soluble polymer layer is sufficient as long as it can be arranged on the surface of the porcelain material without displacement. In this respect, as the water-soluble polymer, for example, polymers used for painting ceramics, such as dextrin and gum arabic, polyvinyl alcohol, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, and gelatin are preferable.

As the hydrophobic polymer, for example, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, styrene-acrylate together with the above-mentioned “polymer having the same functional group” Copolymer, styrene-maleic acid-acrylate copolymer, polyamide, polystyrene, polyester, polyvinyl acetate resin, cellulose derivative,
Polystyrene methacrylic resin, polyvinyl ether resin, polyurethane resin, polycarbonate resin,
A thermoplastic resin such as a rosin resin can be used in combination. Further, a resin used as an overprint lacquer for overcoating a ceramic body such as a ceramic body is also suitable. For example, an acrylic resin, a urethane resin, or the like can be used in combination.

The layer thickness of the image-receiving layer capable of forming an image is as follows.
Generally, it is 0.3 to 20 μm, preferably 0.7 to 20 μm.
15 μm. The layer thickness of the “water-soluble polymer layer” in the case of the adhesive image receiving member is preferably from 0.2 to 20 μm. The water-soluble polymer layer preferably contains the water-soluble polymer in an amount of 30% by mass or more.
The content is more preferably at least 80% by mass, even more preferably at least 80% by mass.

Examples of the support for the image receiving member include ordinary sheet-like base materials such as a plastic sheet, a metal sheet, a glass sheet, and paper. Examples of the plastic sheet include polyethylene terephthalate sheet, polycarbonate sheet, polyethylene-2,6-naphthalate sheet, polyvinyl chloride sheet, polyvinylidene chloride sheet, polystyrene sheet, styrene-acrylonitrile sheet, polyester sheet and the like. Examples of the glass sheet include a glass epoxy sheet and the like, and examples of the paper support include printing paper and coated paper having good smoothness.

The thickness of the support of the image receiving sheet is as follows:
Usually, it is 10 to 400 μm, preferably 25 to 200 μm. Further, the surface of the support may be subjected to a corona discharge treatment, a glow discharge treatment or the like for the purpose of improving the adhesion to an image-receiving layer (or a cushion layer) capable of forming an image, or the adhesion to the transfer layer of the transfer sheet. Surface treatment may be applied.

<Porcelain> Examples of the porcelain include porcelain plates, porcelain, porcelain plates, porcelain, enameled products, and ceramic materials used for building materials such as tiles. The form such as the shape and thickness of the porcelain can be appropriately selected depending on the purpose and application.

[0083]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

(Example 1) <Preparation of transferability promoting material solution> The following components were mixed and stirred uniformly, and then filtered through a 0.45 μm microfilter to obtain a transferability promoting material solution. - n-propyl alcohol ... 45 parts by mass Emulgen 104P ... 5 parts by weight _{(C n H 2n + 1 -O-} (CH 2 CH 2 O) m -H system, manufactured by Kao Corporation) Distilled water ... 50 mass Department

<Preparation of Transfer Sheet> (1) Preparation of Yellow Transfer Sheet—Preparation of Inorganic Pigment Dispersion Y— The following components were dispersed in Micros MC-0 type (Nara Machinery Co., Ltd.) for 2 hours. Thus, an inorganic pigment dispersion Y was obtained.・ Yellow pigment (13651; manufactured by CELDEC) 100 parts by weight ・ Water 60 parts by weight

-Preparation of coating solution for yellow transfer layer-
Coating solution for layer (Coating solution Y ₁) Was prepared.

[0087] [Coating solution Y ₁ of Composition] The pigment dispersion Y ... 41 parts by mass of polyoxyethylene (n = 10) nonylphenol ether ... 0.5 parts by (20 wt% aqueous solution) Carnauba wax dispersion ( 20 parts by mass (K-332; manufactured by Chukyo Yushi Co., Ltd.)-Butyral resin dispersion (25 mass%) ... 60 parts by mass (Resem J667; manufactured by Chukyo Yushi Co., Ltd.)-Terpene phenol resin dispersed (35% by mass) 5 parts by mass (Resem J628; manufactured by Chukyo Yushi Co., Ltd.)

The components having the following composition were mixed and thoroughly stirred.
A coating solution for a latent image forming liquid absorbing layer was prepared.

[Composition of Coating Solution for Latent Image Forming Liquid Absorbing Layer] Block copolymer of acrylic acid and vinyl alcohol 4 parts by mass (acrylic acid / vinyl alcohol = 40/60 (molar ratio)) Water 100 Parts by mass

[0090] After coating the latent image forming liquid absorbent to a dry thickness of 4μm onto the surface of a polyester film having a thickness of 25 [mu] m, a latent image forming liquid absorbing layer was dried form, dry thickness 2μm coating solution Y ₁ and A yellow transfer layer was formed by coating and drying to form a yellow transfer sheet.

(2) Preparation of Magenta, Cyan, and Black Transfer Sheets In the preparation of the yellow transfer sheet, magenta pigments (77571; manufactured by Celdec), cyan pigments (121522; manufactured by Celdec) were used instead of the yellow pigments, respectively. A magenta transfer sheet, a cyan transfer sheet, and a black transfer sheet were produced in the same manner as in the case of the yellow transfer sheet, except that a black pigment (14209; manufactured by Celdec) was used. The absorption amount of the latent image forming liquid (the amount that the layer can absorb) in these transfer sheets is 2
It was 0 ml / m ² .

<Preparation of Image Receiver> A coating solution for an image receiving layer having the following composition was prepared.

[Composition of coating solution for image receiving layer] Polyvinyl butyral resin 16 parts by mass (Denka butyral # 2000-L; manufactured by Denki Kagaku Kogyo KK) N, N-dimethylacrylamide-butyl acrylate copolymer 4 parts by mass ・ Perfluoroalkyl group-containing oligomer: 0.5 parts by mass (MegaFac F-177; manufactured by Dainippon Ink and Chemicals, Inc.) ・ n-propyl alcohol: 200 parts by mass

First, a 10% aqueous solution of gum arabic was applied to a smooth paper support having a basis weight of 100 g to a dry thickness of 1.5 μm and dried to form a water-soluble polymer layer. Next, the coating solution for an image receiving layer was applied on the water-soluble polymer layer and dried at 100 ° C. to form an image receiving layer having a dry film thickness of 10 μm, thereby obtaining an image receiving body.

<Production of Painted Porcelain> First, an ink-jet apparatus (PM670: manufactured by Seiko Epson Corporation) having an ink-jet head having a heating element therein is filled with the liquid transferability promoting material (latent image forming liquid). Then, based on the image information, electricity is supplied to the heating element at a predetermined position to generate heat, the solvent of the nearby transferability promoting material is boiled, the pressure in the head is increased, and the transferability promoting material is caused to fly as droplets. A latent image was formed on the surface of the transfer layer of the yellow transfer sheet (latent image forming step).

Subsequently, the surface of the transfer layer of the yellow transfer sheet on which the latent image was formed and the surface of the image receiving layer of the image receiving body obtained above were overlapped so as to be in contact with each other, and passed through a heat roll laminator (80 ° C.). After lamination and adhesion, the yellow transfer sheet was peeled off, and the yellow transfer layer was transferred only on the adhesive latent image to form a yellow image (image forming step). Similarly, the magenta, cyan, and black transfer sheets were used to repeat the latent image forming step and the image forming step, respectively, to form magenta, cyan, and black images on the image receiving member.

Subsequently, a part of the image receiving body on which the full-color image was formed was immersed in water, and the support was peeled off while dissolving a part of the water-soluble polymer layer. Thereafter, the support was peeled off, and the surface (release surface) of the water-soluble polymer layer, which was exposed and dissolved, was placed in contact with the surface of the ceramic plate (placement step). Next, the above porcelain plate was
C. for 1 hour and further at 850.degree. C. for 1 hour, and the inorganic pigment was sintered on the surface of the ceramic plate to obtain a ceramic plate with a full-color image (a firing step).

As described above, by producing a painted porcelain using the transfer sheet of the present invention, excellent hue reproducibility without secondary color coverage on the porcelain can be obtained without using a large number of image receiving bodies. An image was formed.

(Example 2) <Preparation of transfer sheet> (1) Preparation of yellow transfer sheet-Preparation of inorganic pigment dispersion Y-The following components were supplied to Micros MC-0 type (manufactured by Nara Machinery Co., Ltd.). To obtain an inorganic pigment dispersion Y.・ Yellow pigment (13651; manufactured by CELDEC) 100 parts by weight ・ Water 60 parts by weight

-Preparation of Coating Solution for Yellow Transfer Layer- The components of the following composition are mixed and sufficiently stirred, and a coating solution for a yellow transfer layer containing a latent image forming solution absorbent (coating solution Y ₂ ).
Was prepared.

[0102] [Coating solution Y ₂ of Composition] The pigment dispersion Y ... 41 parts by mass of polyoxyethylene (n = 10) nonylphenol ether ... 0.5 parts by (20 wt% aqueous solution) Carnauba wax dispersion ( 20 parts by mass (K-332; manufactured by Chukyo Yushi Co., Ltd.)-Butyral resin dispersion (25 mass%) ... 40 parts by mass (Rezem J667; manufactured by Chukyo Yushi Co., Ltd.)-Terpene phenol resin dispersed 10 parts by mass (Resem J628; manufactured by Chukyo Yushi Co., Ltd.) 4 parts by mass of a block copolymer of acrylic acid and vinyl alcohol (acrylic acid / vinyl alcohol = 40/60 (molar ratio)) % Aqueous solution… 90 parts by mass

[0102] applying to the coating solution Y ₂ on the surface of a polyester film having a thickness of 25μm to provide a dry film thickness of 3 [mu] m,
After drying, a yellow transfer layer was formed to prepare a yellow transfer sheet.

(2) Preparation of Magenta, Cyan and Black Transfer Sheets In the preparation of the yellow transfer sheet, magenta pigments (77571; manufactured by Celdec) and cyan pigments (121522; manufactured by Celdec) were used instead of the yellow pigment, respectively. A magenta transfer sheet, a cyan transfer sheet, and a black transfer sheet were produced in the same manner as in the case of the yellow transfer sheet, except that a black pigment (14209; manufactured by Celdec) was used. The absorption amount of the latent image forming liquid in these transfer sheets was 11 ml / m ² . Others were the same as in Example 1 to produce a painted ceramic body.

As described above, by producing a painted ceramic using the transfer sheet of the present invention,
An image excellent in hue reproducibility without secondary color coverage was formed on the porcelain without using a large number of image receiving bodies.

[0105]

As described above, according to the transfer sheet of the present invention, it is possible to prevent a decrease in resolution and a secondary color fog due to the latent image forming liquid. Further, according to the method for manufacturing a painted ceramic body of the present invention, at low cost, even when forming a multi-color image, it is possible to produce a painted ceramic body having a vivid image without secondary color coverage. it can.

[Brief description of the drawings]

FIG. 1 is a schematic process diagram for explaining a basic mode of a method for manufacturing a painted ceramic body of the present invention.

[Explanation of symbols]

 1, 5: Support 2: Latent image forming liquid absorbing layer 3: Transfer layer 4: Transfer sheet 6: Image receiving layer 6a: Inorganic pigment image 6b: Image 7. ..Receiver 8: Ceramic material i ... Latent image

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C04B 41/86 C04B 41/86 HG F term (Reference) 2H086 BA01 BA05 BA12 BA15 BA26 BA35 BA36 BA41 BA51 BA59

Claims (10)

[Claims] 1. A transfer sheet having a transfer layer made of a thermal transfer material on a support, a latent image forming liquid is applied imagewise to the transfer layer surface to form a latent image, and an image corresponding to the latent image is formed. A transfer sheet for use in an image forming method for transferring and forming a latent image forming liquid onto an image receiving body, wherein the transfer sheet contains a latent image forming liquid absorbent for absorbing the latent image forming liquid. 2. A latent image forming liquid absorbing layer containing a latent image forming liquid absorbent for absorbing the latent image forming liquid is provided on a surface of the transfer layer on which a latent image is not formed. Transfer sheet. 3. The transfer sheet according to claim 2, wherein the latent image forming liquid absorbing layer absorbs the latent image forming liquid in an amount of 1 ml / m ² or more. 4. The transfer sheet according to claim 1, wherein the transfer layer contains a latent image forming liquid absorbent. 5. The latent image forming liquid absorption amount of a transfer layer containing a latent image forming liquid absorbent is 1 ml / m ² or more.
4. The transfer sheet according to 1. 6. The transfer sheet according to claim 1, wherein the latent image forming liquid absorbent mainly comprises a superabsorbent polymer. 7. A latent image forming liquid containing a transfer promoting material or a tacky material capable of lowering the transfer temperature of a thermal transfer material on the transfer layer surface of the transfer sheet according to claim 1. A latent image forming step of forming a latent image by applying to the image forming apparatus, and heating at least the transfer layer surface and the image receiving layer surface of an image receiving body having an image receiving layer capable of transferring the transfer layer on a support. An image forming step of transferring the transfer layer to the surface of the image receiving layer corresponding to the latent image to form an inorganic pigment image made of a thermal transfer material on the surface of the image receiving layer; An arranging step of arranging the inorganic pigment image on the surface of the porcelain, and a arranging step of arranging the inorganic pigment image on the surface of the porcelain, Characteristic method of producing painted ceramics. 8. The method according to claim 7, wherein the image receiving body has a water-soluble polymer-containing layer and an image receiving layer on the surface of the water-permeable support in this order. 9. In the disposing step, the water-soluble polymer is partially dissolved to peel off the water-permeable support of the image receiving body, and the inorganic pigment image is formed so that the peeled surface after peeling comes into contact with the surface of the porcelain. The method for manufacturing a painted ceramic body according to claim 8, wherein the ceramic body is arranged on a surface of the ceramic material. 10. An inorganic pigment for an image receiving body via a liquid in which a paste is dissolved or dispersed before or after the water-soluble polymer is partially dissolved and the water-permeable support of the image receiving body is separated in the disposing step. So that the image forming surface contacts the surface of the porcelain
The method according to claim 8, wherein the inorganic pigment image is disposed on a surface of the porcelain.