JP2002293669A - Method of manufacturing decorated pottery body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing decorated pottery body which is capable of well sintering an image having good resolution and gradation characteristic on a pottery material while maintaining the coloring density as a high degree. SOLUTION: This method of manufacturing decorated pottery body has a process step for forming the image pottery body with a flux layer which molds the image pottery body 24 with the flux layer having the inorganic pigment image 11 consisting of a transfer material of >= 35 mass% in the inorganic pigment content in inorganic components and the flux layer 14 disposed on at least either the top or bottom of the inorganic pigment image 11 on the pottery material 16 and a firing state of heating and firing the image pottery body 24 with the flux layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a painted ceramic body, and more particularly to a method for producing a painted ceramic body that can be used as a building material such as an art tile or a ceramic photo.

[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. As a method for forming a good image on porcelain, for example, a method using a transfer method in which an image is formed by thermally transferring the transfer material of a transfer sheet having a transfer layer made of a transfer material containing an inorganic pigment is known. Have been.

In this transfer method, an inorganic pigment has a lower absorption coefficient (color density per unit weight) than an organic pigment, so that the amount of transfer required to obtain a desired color density is increased. That is, in order to obtain the desired color density, it is necessary to increase the thickness of the transfer layer (for example, about 3 to 5 μm). However, when an image is formed by the transfer method, if the thickness of the transfer layer is large, there is a problem that the resolution and gradation of the obtained image are deteriorated. Therefore, it is conceivable to increase the image density by increasing the content of the inorganic colorant in the transfer layer, but in this case, sintering becomes insufficient when the inorganic pigment image is sintered on the ceramic, As a result, there arises a problem that the inorganic pigment image is separated from the porcelain.

In the method of forming an image by a thermal transfer method (for example, a fusion type) using an ink ribbon, the ink ribbon must be slit in accordance with the type of the printer, and furthermore, the slitting process must be performed. Must be rolled up in a cassette. In particular, when the number of colors is large, the cost is high and the operation is complicated. In addition, different printers require different cassettes to be processed, and therefore have a problem in versatility. Further, since the size of the ink ribbon to be used is constant even if the image is small, there may be a lot of wasted portions, which further increases the cost.

[0005]

SUMMARY OF THE INVENTION Accordingly, the present invention is to provide a simple and low-cost porcelain with a picture which can sinter an image having high color density, excellent resolution and gradation on a porcelain. An object of the present invention is to provide a method for producing a body, and to achieve the object.

[0006]

Means for achieving the above object are as follows. <1> On the porcelain, the inorganic pigment content in the inorganic component is 3
An inorganic pigment image comprising a transfer material having a content of 5% by mass or more, and an image ceramic with a frit layer, which is provided with a frit layer provided on at least one of the upper and lower sides of the inorganic pigment image. A method for manufacturing a painted ceramic body, comprising: a forming step; and a firing step of heating and sintering the image ceramic body with a frit layer.

<2> The image according to <1>, wherein the inorganic pigment image is formed by one of a transfer method using a latent image forming liquid and an electrophotographic method using a transfer sheet. This is a method of manufacturing ceramics. <3> an image forming step of forming an inorganic pigment image on a surface of the image receiving layer of the image receiving body A having an image receiving layer capable of forming an image on a support, Transferring an image to a surface of the frit layer of the image receiving member B having a frit layer capable of transferring the inorganic pigment image on a support, and transferring the frit layer and the inorganic pigment image to the image receiving member B. The method according to <1> or <2>, further comprising: arranging a part or all of the porcelain on the surface of the porcelain. <4> the image forming step of forming an inorganic pigment image on the surface of the image receiving layer of the image receiving body A having an image receiving layer capable of forming an image on a support, An image transferring step of transferring an image onto a surface of the image receiving layer of the image receiving body C having an image receiving layer capable of transferring the inorganic pigment image on a support, and on the image receiving layer on which the inorganic pigment image is transferred. <1> or <1> or a frit layer setting step of providing a frit layer, and an arrangement step of disposing the frit layer and the inorganic pigment image on a surface of the porcelain together with a part or all of the image receiving member C. <2> A method for producing a painted ceramic body according to <2>.

<5> The image receiving body A having the image receiving layer capable of forming an image on a support in the step of forming the image ceramic body with a frit layer
An image forming step of forming an inorganic pigment image on the surface of the image receiving layer; and forming the inorganic pigment image on the surface of the image receiving layer of an image receiving member C having an image receiving layer capable of transferring the inorganic pigment image on a support. An image transfer step of transferring, and an arrangement step of arranging the inorganic pigment image on a surface of the frit layer of a porcelain material having a frit layer on the surface together with a part or all of the image receiving body C. <1> or <2>. <6> The porcelain has a frit layer on its surface, and the frit layer and the inorganic pigment image are arranged on the frit layer surface of the porcelain in the arranging step. <3> or <4>.<7> an image forming step of forming an inorganic pigment image on a surface of the image receiving layer of the image receiving body A having an image receiving layer capable of forming an image on a support, An image transfer step of transferring an image onto the surface of the frit layer of the image receiving member B having a frit layer capable of transferring the inorganic pigment image on a support, and on the frit layer on which the inorganic pigment image has been transferred; A frit layer setting step of further providing a frit layer,
An arrangement step of arranging the frit layer and the inorganic pigment image on a surface of the porcelain together with a part or the entirety of the image receiving member B. <1> or <2>. It is a manufacturing method.

<8> The image receiving body B is characterized in that it has a release layer and a frit layer containing a hydrophobic polymer capable of transferring an inorganic pigment image on a support in this order.
>, <6>, or <7>. <9> The image receiving member B has a release layer, a hydrophobic polymer layer, and a frit layer on which an inorganic pigment image can be transferred sequentially on a support, wherein <3>, <6>, or < 7
> Is a method for producing a painted ceramic body described in <1. <10> The image receiving body B has a release layer, a frit layer, and a hydrophobic polymer layer capable of transferring an inorganic pigment image sequentially on a support, wherein <3>, <6>, or <
7>. <11> The image receiving body C according to any one of <4> to <6>, wherein the image receiving body C has a release layer and a hydrophobic polymer layer capable of transferring an inorganic pigment image sequentially on a support. This is a method for producing painted ceramics.

<12> an image forming step of forming an inorganic pigment image on the surface of the frit layer of the image receiving member B having the frit layer capable of forming an image on a support, An arrangement step of arranging the frit layer and the inorganic pigment image on a surface of the porcelain together with a part or the entirety of the image receiving member B. <1> or <2>. It is a manufacturing method. <13> The image forming step of forming an inorganic pigment image on a surface of the image receiving layer of the image receiving body C having an image receiving layer capable of forming an image on a support, wherein the image forming step with the frit layer is performed; A frit layer setting step of providing a frit layer on the image receiving layer on which an image is formed, and an arranging step of arranging the frit layer and the inorganic pigment image on the surface of the porcelain together with part or all of the image receiving body C. <1> or <
2>.

<14> an image forming step of forming an inorganic pigment image on a surface of the image receiving layer of the image receiving body C having an image receiving layer capable of forming an image on a support, An arrangement step of arranging the inorganic pigment image on a surface of the frit layer of a porcelain material having a frit layer on the surface together with a part or all of the image receiving body C.
> Or <2>. <15> The porcelain material has a frit layer on its surface, and the frit layer and the inorganic pigment image are arranged on the frit layer surface of the porcelain material in the arranging step. <12> or <13>.<16> an image forming step of forming an inorganic pigment image on the surface of the frit layer of the image receiving body B having the frit layer capable of forming an image on a support, wherein the image ceramic forming step with a frit layer is performed;
A frit layer setting step of further providing a frit layer on the frit layer on which the inorganic pigment image is formed, and an arrangement in which the frit layer and the inorganic pigment image are arranged on the surface of the porcelain together with part or all of the image receiving member B And <2>. The method for producing a painted ceramic body according to <1> or <2>, comprising:

<17> The image receiving body B is placed on a support,
<12>, <1> characterized by sequentially having a release layer and a frit layer containing a hydrophobic polymer capable of forming an image.
5> or <16>. <18> The image receiving body B has a release layer, a hydrophobic polymer layer, and an image-forming frit layer on a support in that order. <12>, <15>, or <16>
The method for producing a painted ceramic body according to the above. <19> The image receiving body B has a release layer, a frit layer, and a hydrophobic polymer layer capable of forming an image on a support in this order. <12>, <15>, or <16>
The method for producing a painted ceramic body according to the above. <20> The painted ceramic body according to any one of <13> to <15>, wherein the image receptor C has a release layer and an image-forming hydrophobic polymer layer sequentially on a support. It is a manufacturing method of.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION
An image porcelain with frit layer molding step of molding an image porcelain with a frit layer provided with an inorganic pigment image and a frit layer on porcelain, and a firing step of sintering the image porcelain with frit layer I have.

The image ceramic with a frit layer has a frit layer on at least one of the top and bottom of the inorganic pigment image. That is, the image ceramic body with a frit layer is a form in which an inorganic pigment image and a frit layer are sequentially laminated on a ceramic material, a frit layer on a ceramic material,
A form in which an inorganic pigment image is sequentially laminated, or a form in which a frit layer, an inorganic pigment image, and a frit layer are sequentially laminated on a porcelain material can be considered. Note that a form having another layer is also conceivable.

In the present invention, the transfer material preferably contains 35% by mass or more, more preferably 40% by mass or more, of an inorganic pigment in the inorganic component constituting the transfer material. More preferably, it is contained in an amount of not less than mass%. If the amount is less than 35% by mass, a problem that the color density is lowered occurs, or if the thickness of the transfer layer is increased in order to increase the color density, the resolution,
This is because there is a problem that the gradation is deteriorated. The inorganic pigment content of the generally used transfer material is about 10 to 35% by mass of the inorganic component, and the inorganic pigment content of the transfer material used in the present invention is higher than that of the commonly used transfer material. Thin thickness (0.5-3μm
), A high color density can be maintained. In the case where an inorganic pigment image is formed by performing transfer a plurality of times, the present invention is included if at least one of the transfer materials is within the above range, but it is preferable that all the transfer materials be within the above range.

Hereinafter, various aspects of the image porcelain forming step with a frit layer will be described with reference to the drawings. -Image porcelain forming step with frit layer (1)-The image porcelain forming step with frit layer (1) includes an image forming step of forming an inorganic pigment image on the surface of the image receiving layer of the image receiving member A, and A transfer step of transferring to the frit layer of the image receiving body B,
Arranging the frit layer and the inorganic pigment image on the porcelain material. Hereinafter, description will be made with reference to FIG. Here, FIG. 1 is a schematic process diagram showing one embodiment of a forming process of an image ceramic with a frit layer in the method for manufacturing a painted ceramic according to the present invention.

(Image Forming Step) As shown in FIGS. 1A and 1B, in the image forming step, the surface of the image receiving layer 2 of the image receiving member A3 having the image receiving layer 2 capable of forming an image on the support 1. To form an inorganic pigment image 11.

<Receiver A> The receiver A has at least one image-receiving layer capable of forming an image on the surface of the support.
The mode can be appropriately selected according to the method, purpose, application, and the like of forming an inorganic pigment image, and a cushion layer, a release layer, an intermediate layer, and the like may be provided between the support and the image receiving layer. 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 on which an image can be formed is not particularly limited as long as an inorganic pigment image can be formed, and a binder resin in a transfer material described later can be used. The thickness of the image receiving layer is generally from 0.3 to 20 μm, and preferably from 0.7 to 15 μm.

Examples of the support include ordinary sheet-like substrates such as plastic sheets, metal sheets, glass sheets, and paper. Examples of the plastic sheet include a polyethylene terephthalate sheet, a polycarbonate sheet, a polyethylene-2,6-naphthalate sheet, a polyvinyl chloride sheet, a polyvinylidene chloride sheet, a polystyrene sheet, a styrene-acrylonitrile sheet, a polyester sheet, and the like. Examples of the glass sheet include a glass epoxy sheet and the like, and the paper support includes a printing paper having good smoothness,
Coated paper and the like can be mentioned.

The thickness of the support is usually from 10 to 400
μm, and preferably 25 to 200 μm. The surface of the support may be subjected to a surface treatment such as a corona discharge treatment or a glow discharge treatment for the purpose of improving the adhesion to an image-receiving layer (or a cushion layer or the like) on which an image can be formed.

In the image forming step, first, as shown in FIG. 1A, an image receiving member A3 having at least one image receiving layer 2 capable of forming an inorganic pigment image on the surface of a support 1 is prepared. As shown in FIG. 1B, a transfer material containing an inorganic pigment is imagewise applied to the image receiving layer A3 on the surface of the image receiving layer 2 by a desired image recording method, as shown in FIG. An image 11 (inorganic pigment image) is formed. When forming a multicolor image, by repeating the main image forming process,
Inorganic pigment images (plural) corresponding to each color are formed on each image receiving member A, and the respective inorganic pigment images are transferred onto one image receiving member in a subsequent image transfer step to form one image. You can also. Thereby, it is possible to suppress the secondary color cast.

Method for Forming Inorganic Pigment Image (Image Recording Method)
Can be appropriately selected from known methods for forming an image by transfer, and a transfer method using a latent image forming liquid or an electrophotographic method using a transfer sheet is preferable.
According to the transfer method using the latent image forming liquid, it is possible to form an image having more excellent resolution and gradation. Further, according to the electrophotographic method using the transfer sheet, it is possible to omit the production of the toner for each color, and it is not necessary to use a color printer even when forming a multicolor image, so that the cost can be reduced. Can be Hereinafter, a transfer method using a latent image forming liquid,
An electrophotographic method using a transfer sheet will be described.

-Transfer Method Using Latent Image Forming Solution- The method using a latent image forming solution is capable of transferring the transfer layer surface of a transfer sheet having a transfer layer made of a transfer material containing an inorganic pigment, and the transfer material. A latent image forming liquid containing a transferability promoting material or a tacky material capable of promoting the transfer of the transfer material to the image receiving layer surface is applied imagewise to at least one of the image receiving layer surfaces of the image receiving body having the excellent image receiving layer. To form a latent image,
At least the transfer layer surface and the image receiving layer surface are brought into contact with each other, and the transfer material is transferred to the image receiving layer surface corresponding to the latent image, and an image (inorganic pigment image) composed of the transfer material is formed on the image receiving layer surface It is a method of forming. An example (image forming step) when the present method is applied will be described below with reference to FIG. FIG. 2 is a schematic process diagram showing one embodiment of an image forming step in the method for manufacturing a painted ceramic body of the present invention.

As shown in FIG. 2A, a transfer sheet 4 and an image receiving body 5 are prepared. The transfer sheet 4 is configured to have at least a transfer layer 7 made of a transfer material containing an inorganic pigment on the surface of a support 6, and the image receiver 5 is formed on the surface of the support 8.
It has at least an image receiving layer 9 capable of transferring a transfer material.

Next, on the surface of the image receiving layer 9 of the image receiving member 5, a latent image forming liquid is applied imagewise according to image information using an ink jet recording device (not shown) to form a latent image. Thereafter, as shown in FIG. 2B, the surface of the image receiving layer 9 of the image receiving body 5 on which the latent image is formed and the surface of the transfer layer 7 of the transfer sheet 4 are overlapped so as to be in contact with each other. Laminate by heating while applying pressure, if necessary. After the lamination, as shown in FIG. 2C, when the transfer sheet 4 is peeled off, the transfer layer 7 is transferred only to the region (latent image portion) of the image receiving layer 9 to which the transferability promoting material is provided, and the image receiving layer is transferred. An image 10 made of a transfer material (see FIG. 2D) is transferred and formed as an inorganic pigment image on 9. At the time of lamination, it is preferable to supply heat and pressure together, and for example, a method of passing through a pair of heating nip rollers incorporating a heating means such as a heater is suitable.

<Latent Image Forming Liquid> The latent image forming liquid contains a transfer promoting material or a tacky material capable of lowering the transfer temperature of the thermal transfer material.

(Transferability promoting material) The transferability 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 alone 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 reduction (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 the transferability-promoting material is not 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 spots, 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.

[0035]

Embedded image

In the above 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 compound represented by any of the above general 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 a 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.

As the transferability promoting material, a material having a boiling point of 100 ° C. or higher 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 more 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 is obtained by converting the above-mentioned adhesive substance to:
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 as a mixture 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 preferably 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
This represents a polymer portion of 3500 or more and 3500 or less. n represents 1 or 2.

[0046]

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.

The hydrophobic group represented by R in the general formula (5) includes an aliphatic group (eg, an alkyl group, an alkenyl group, an alkynyl group, etc.), an aromatic group (eg, a phenyl group, a naphthyl group, etc.) 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 esters 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 site 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. Specific examples of the structural unit A constituting the polymer A include vinyl alcohol,
α-methyl vinyl alcohol, α-propyl vinyl alcohol and the like. Examples of the structural unit B constituting the polymer site P include vinyl acetate, vinyl formate, vinyl propionate and α-substituted products thereof. Further, as the structural unit C constituting the polymer site P, acrylic acid, methacrylic acid, or crotonic acid (including an ammonium salt or a metal salt such as Na or K), maleic acid, or itaconic acid (monoalkyl ester, ammonium, respectively) salt,
Or a metal salt such as Na or K), vinylphosphonic acid,
Vinylsulfuric acid, acrylic sulfonic acid, methacrylsulfonic acid, 2-acrylamido-3-methylpropanesulfonic acid or 2-methacrylamido-3-methylpropanesulfonic acid (each including an ammonium salt or a metal salt such as Na or K), Monomer units that dissociate ions in water, such as acrylamidopropyltrimethylammonium 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 structural unit A constituting the polymer site P,
The content of B and C is not particularly limited, but A, B,
Assuming that the content of C is x, y and z mol%, x + y
+ Z = 100, 0 ≦ x ≦ 100, 0 ≦ y ≦ 75, 0 ≦ z
≦ 100 is preferable, x + y + z = 100, 0 ≦ x ≦ 1
00, 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 unit P is water-soluble or water-dispersible, so that the structural unit A
Is preferably 50 mol% to 100 mol%.

The compound represented by the general formula (5) includes 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 site P may contain structural units other than the structural units A, B and C at all. Examples of these structural units include ethylene, propylene, isopten, acrylonitrile, acrylamide, methacrylamide, N-vinylpyrrolidone, vinyl chloride and vinyl fluoride units. The polymerization degree of the polymer site P is 10 to 3500, preferably 10 to 2000, more preferably 10 to 1000, and particularly preferably 10 to 500.
It is.

The alkyl group of R ¹ and R ² in the structural units A and B of the polymer site P is particularly preferably a methyl group. Further, the alkyl group may be substituted with a hydroxyl group, an amide group, a carboxyl group, a sulfonic acid group, a sulfinic acid group, a sulfonamide group, or the like.

The compound represented by the general formula (5) is different in the optimum chemical composition and molecular weight of P and R constituting the compound according to the object 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.

-Electrophotography using transfer sheet-In electrophotography using a transfer sheet, first, the surface of the image receiving layer of the image receiving body having an image receiving layer on the surface of a support using electrophotographic technology. Then, an adhesive latent image (adhesive latent image) formed of a colorless or light-colored adhesive composition is formed. That is, using an adhesive composition containing a binder resin, an electrostatic latent image formed by electrophotography is developed to form an adhesive latent image, and then the adhesive latent image is transferred to form an image receiving member. A latent image having an adhesive property is formed on the image receiving layer of A.
The adhesive composition is preferably colorless (or pale) after firing, but a colored toner can also be used. When a colored toner is used, it is preferable that the color is similar to the hue of the transfer layer of the transfer sheet used later. After forming a latent image using electrophotographic technology, an image is transferred and formed according to the latent image. That is, at least the image receiving layer surface of the image receiving body on which the adhesive latent image is formed and the transfer layer surface of a transfer sheet having a transfer layer made of a transfer material containing an inorganic pigment are brought into contact with each other and heated to correspond to the latent image. Then, the transfer layer is transferred to the surface of the image receiving layer of the image receiving member, and an inorganic pigment image made of a transfer material is formed on the surface of the image receiving layer of the image receiving member.

The above-mentioned heating may be performed under pressure or the like, if necessary. From the viewpoint of the adhesion between the two layers, it is preferable to perform both heating and pressurization. For example, it can be suitably performed by laminating by passing through a pair of heating nip rollers or the like incorporating a heating means such as a heater. The heating temperature during heating is preferably from 60 to 200 ° C.

It is necessary that the adhesive composition adheres to the transfer layer in the image forming step so that the transfer layer (transfer material) can be peeled off (transferable) from the transfer sheet. It comprises a resin (binder resin) and, if necessary, a flux or the like. The thermoplastic resin can be appropriately selected from known thermoplastic resins, and examples thereof include a binder resin described below.
Examples of the flux include those similar to those usable for a transfer layer of a transfer sheet described later.

The adhesive strength of the adhesive latent image formed by the adhesive composition is that the adhesive strength between the transfer layer of the transfer sheet and the latent image is larger than the adhesive strength between the transfer layer of the transfer sheet and the support. Is required. By ensuring that the adhesive composition has sufficient adhesive strength for the transfer of the transfer layer, transferability capable of forming an image with high resolution and high gradation can be obtained.

The adhesive composition may be a toner having an adhesive property including a binder resin and manufactured according to a toner manufacturing technique in the field of electrophotography. As the toner, a commercially available toner can also be used. However, those which do not contain a magnetic component such as iron or iron oxide are preferable in that a desired image hue can be obtained without being colored by firing.

In the present invention, the electrophotographic technique using the adhesive composition is described in, for example, JP-A-9-197719.
In this method, a colorless or light-colored toner not containing an inorganic coloring material, that is, at least a binder resin and optionally It can also be carried out by developing with a toner having an adhesive function containing a flux or the like, forming a colorless or light-colored latent image, and then transferring the latent image to the surface of the image receiving layer of the image receiving body.

Here, as the binder resin contained in the adhesive composition, for example, those described in paragraph [0012] of JP-A-9-197719 can be mentioned, and sufficient adhesiveness can be ensured. From the viewpoint, polyester resins, butyral resins, ethylene-vinyl acetate, acrylic resins, and the like are preferable.

The content of the thermoplastic resin (binder resin) is not particularly limited, and from the viewpoint of securing the adhesiveness (ie, transferability) of the transfer layer and forming a high-resolution image.
The content is preferably 50% by mass or more of the total amount (mass) of the adhesive composition (adhesive toner). When the adhesive composition (adhesive toner) contains a binder resin and a flux, the content of the binder resin is preferably 10% by mass or more of the total amount (mass) of the toner, more preferably 45% by mass or more, Particularly preferred is 55% by mass or more. The upper limit is usually about 60 to 85% by mass. When the content is 55% by mass or more, it is possible to secure required characteristics as an electrophotographic toner, such as charging characteristics and fixing characteristics.

Examples of the flux include those described in paragraphs [0006] to [0011] of the publication. The content of the flux is 10 to 5 with respect to the content of the thermoplastic resin (binder resin).
0% by mass is preferred.

An auxiliary component such as a charge control agent can be added to the adhesive toner. As the charge control agent, those described in JP-A-9-197719 are preferred.

<Transfer Sheet> Next, a transfer sheet used for forming an inorganic pigment image will be described. The transfer sheet has a transfer layer made of a colored transfer material containing an inorganic pigment on the surface of the support, and another layer such as a cushion layer and a release layer and a cover sheet may be provided. . The transfer material preferably contains at least an inorganic pigment, and preferably contains a binder together with the inorganic pigment, and may further contain other components such as a flux, a plasticizer, and a wax component, if necessary.

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.

In the firing step, it is preferable to use a flux together with the inorganic pigment from the viewpoint of improving the fusion property of the inorganic pigment to the surface of 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 is
One type may be used alone or two or more types may be used in combination to be dissolved and used as a so-called frit.

The binder may be 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.

It is preferable that the monomer having the “same functional group” is contained in the polymer in the transfer layer and the polymer in the image receiving layer described later in 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 binder content 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. The transfer layer has a thickness of 0.2 to 6 μm.
Is preferable, and 0.5 to 3 μm is more preferable.

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.

It is preferable that a wax component is contained in the transfer layer from the viewpoint of improving the resolution and resolution of a transferred image (dot). 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.

The transfer layer has a relatively low adhesion in order to improve the adhesion between the image receiving member and the transfer sheet and to improve the transfer layer (material) in the second and subsequent times when forming a multicolor image. Melting point thermoplastics, for example, low molecular weight petroleum resins,
It is also preferable to add a polyvinyl butyral resin, an ethylene-vinyl acetate copolymer, an ethylene-acrylate copolymer, a styrene-acrylate copolymer, a styrene-maleic acid-acrylate copolymer, or the like.

The transfer layer is prepared by dissolving or dispersing the respective components of the transfer material such as the inorganic pigment and the binder in a suitable 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. Although an organic solvent can be used as the solvent, an aqueous solvent is preferable from the viewpoint of environmental safety. It is also possible to use n-propyl alcohol, methyl ethyl ketone, propylene glycol monomethyl ether (MFG), methanol or the like, or a mixed solvent thereof with water. Coating and drying can be performed by using generally known coating and drying methods.

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, polyethylene terephthalate,
Preferable are synthetic resin materials such as polyethylene-2,6-naphthalate, polycarbonate, polyethylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and styrene-acrylonitrile copolymer. Among them, mechanical strength and dimensional stability to heat are preferable. In this respect, biaxially stretched polyethylene terephthalate is particularly preferred.

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 cover sheet may be made of the same or similar material as the support. However, silicone paper, polyolefin and the like are suitable because they need to be easily separable from the transfer layer. . The thickness of the covering sheet is preferably about 5 to 100 μm. Particularly preferred is a polyethylene or polypropylene film having a thickness of 10 to 30 μm. These coated sheets are peeled off before transfer.

(Image Transfer Step) As shown in FIG.
In the image transfer step, the inorganic pigment image 11 formed on the surface of the image receiving layer 2 is transferred to the frit layer 14 of the image receiving member B15 having a frit layer 14 capable of transferring the inorganic pigment image 11 onto a support 12.
Transfer to the surface.

<Receiver B> The receiver B has at least one frit layer capable of transferring an inorganic pigment image on the surface of a support, and a cushion layer and a release layer are provided between the support and the frit layer. , An intermediate layer or the like may be provided.

The frit layer is mainly composed of a glass component or a solvent for sintering an inorganic pigment image in a firing step described later. The frit content is 0.1 to 5 g / g. m ² is preferred, and 0.3 to 3 g / m ²
Is more preferred. If the content is less than 0.1 g / m ² , the effect of assisting sintering is insufficient, and if it exceeds 5 g / m ² , applicability, production suitability and brittleness of the layer may be deteriorated. Examples of the frit 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, aluminum oxide, silicon oxide, boric acid, and oxide. Zirconium, titanium oxide, borax, feldspar, kaolin and the like,
These are also used as flux. Examples of the binder resin required for forming the frit layer include thermoplastic resins and waxes used for the transfer sheet and the adhesive toner.

In the present invention, the image receiving member B has a form in which a release layer and a frit layer containing a hydrophobic polymer capable of transferring an inorganic pigment image are sequentially formed on a support.
Is a form in which a release layer, a hydrophobic polymer layer, and a frit layer capable of transferring an inorganic pigment image are sequentially formed on a support, and the image receiving body B has a release layer, a frit layer, and an inorganic pigment image formed on the support. Is one of the forms having a hydrophobic polymer layer capable of sequentially transferring (other layers may be provided between layers)
Is preferred. By adopting these forms, the support of the image receiving member B can be easily peeled off by the release layer when the support is peeled off from the porcelain in the subsequent placement step. A layer containing a hydrophobic polymer serves as a support, and an image can be stably arranged on the porcelain. The hydrophobic polymer layer refers to a layer containing 50% by mass or more, preferably 80% by mass or more, of the composition of the hydrophobic polymer layer. When a hydrophobic polymer is contained in the frit layer, the hydrophobic polymer is used as a binder. At this time, the content of the hydrophobic polymer is preferably 20% by mass to 80% by mass, and more preferably 30% by mass with respect to the layer composition.
~ 70 mass% is more preferable. The release layer is desirably one of a layer containing a water-soluble polymer (hereinafter, referred to as a water-soluble polymer layer) and a layer containing a release agent. The water-soluble polymer layer refers to a layer containing at least 30% by mass or more, preferably 50% by mass or more, more preferably 80% by mass or more of a water-soluble polymer.

When a water-soluble polymer layer is used as the release layer, the support is more preferably a water-permeable support. In the disposing step, a part of the water-soluble resin can be easily peeled off by using the liquid permeability of the support. As the water-soluble polymer, when the support is a paper support, when the image receiver is immersed in a liquid such as water,
Part of it dissolves and the paper support becomes peelable,
It is preferable that the inorganic pigment image after peeling can be adhered to the surface of the porcelain at 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. From this point, as the water-soluble polymer, for example, polymers used for painting ceramics, such as dextrin and gum arabic, polyvinyl alcohol, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, gelatin, and modified products thereof are preferable. Among these, polyvinyl alcohol (PVA) and its modified products are particularly preferred.
In the case of polyvinyl alcohol (PVA) and its modified product, it also functions as a release layer even in a dry film state.

The layer containing the release agent may be, for example, a silicone-modified polymer, a polyethylene (PE) resin,
This is a layer containing a release agent such as an olefin wax, and the content of the release agent varies depending on the type of the release agent. However, it is necessary to adjust the transfer layer of the transfer sheet so that the support and the image receiving layer are not separated from each other in the release layer. By providing this release layer, the inorganic pigment image can be easily arranged on the porcelain.

As shown in FIG. 1C, in the image transfer step, first, a water-soluble polymer layer 13 is formed on a support 12.
And an image receiving member B15 (adhesive image receiving member), which sequentially has a frit layer 14 to which an inorganic pigment image can be transferred. The surface of the frit layer 14 of the adhesive image receiving body and the surface of the image receiving layer 2 on which the inorganic pigment image 11 has been formed in the image forming step are placed so as to face each other and overlap each other so as to be in contact with each other. While heating. After the heating, the support 1 of the image receiving member A3 is peeled off, so that the inorganic pigment image 11 is transferred onto the frit layer 14 of the image receiving member B15 as shown in FIG.

In the heating step, heating may be performed while applying pressure. For example, both layers can be brought into close contact with each other by a device having a pair of heating nip rollers incorporating a heating means such as a heater (for example, a heat roll laminator). . The heating temperature at the time of heating is generally 50 to 200.
C is preferred.

(Arranging Step) As shown in FIG. 1E, in the arranging step, the frit layer 14 and the inorganic pigment image 11 are arranged on the surface of the porcelain 16 together with a part or the whole of the image receiving member B15. The attached image ceramic 24 is formed.

<Porcelain> Examples of the porcelain include a porcelain plate, a porcelain, a porcelain plate, a porcelain, a ceramic material, an enamel, and the like used for building materials such as tiles. Porcelain shape,
The form such as the thickness can be appropriately selected according to the purpose and use. As shown in FIG. 1E, in the arrangement step, first, the support 12 of the image receiving member B15, the frit layer 14, and the inorganic pigment image 11 are separated at the boundary (the water-soluble polymer layer 13). Specifically, the image receiving member B15
When the support 12 is made of a water-permeable support, a part of the image receiving member B15 is brought into contact with or immersed in a liquid such as water from the support 12 side to allow moisture to permeate through the support 12. Dissolve part of the water-soluble polymer,
The support 12 can be easily peeled off. (At this time, the surface on the side where the support 12 is peeled off and the water-soluble polymer layer 13 is partially dissolved is referred to as a “peeling surface”.)

After the support 12 was peeled off, the inorganic pigment image 11 was placed on the surface of the desired porcelain 16 together with the frit layer 14, but as shown in FIG. 1 (e), the water-soluble polymer was partially dissolved. Then, it is arranged on the surface of the desired porcelain 16 so as to be in contact with the separation surface. Before or after the support is peeled off, the surface opposite to the release surface, that is, the inorganic pigment image 11 is removed.
The desired porcelain 16 is passed through a liquid in which a glue is dissolved or dispersed so that the porcelain 16 is in contact with the surface of the frit layer 14 on which the
May be arranged on the surface. By drying, it is adhered to the porcelain material, and the image porcelain body 24 with a frit layer is formed. In the former (this embodiment), a normal image is formed when viewed from the inorganic pigment image 11 formed on the image receiving member B15, and in the latter, a mirror-reversed image is formed when viewed from the inorganic pigment image 11 formed on the image receiving member B15. You. The arrangement on the surface of the porcelain material 16 may be performed by thermocompression as needed. A porcelain having a frit layer on the surface may be used, and in that case, the frit layer is disposed on the porcelain so as to sandwich the inorganic pigment image (as in the latter).

On the other hand, when the support 12 of the image receiving member B15 is a plastic film support, the plastic film support is preliminarily subjected to a surface treatment for imparting releasability, so that the plastic 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 via a solution in which the paste is dissolved or dispersed, a pressure-sensitive adhesive, a hot melt adhesive, or the like.

The liquid in which the sizing agent is dissolved or dispersed is, for example, in a solvent such as water, and the sizing agent is, for example, the water-soluble polymer or the thermoplastic resin having a glass transition point of 25 ° C. or less, preferably 5 ° C. or less. Or a solution in which is dissolved or dispersed.

-Image porcelain forming step with frit layer (2)-The image porcelain forming step with frit layer (2) includes an image forming step of forming an inorganic pigment image on the surface of the image receiving layer of the image receiving body A; A transfer step of transferring the inorganic pigment image to the image receiving layer of the image receiving member C, a frit layer setting step of providing a frit layer on the image receiving layer to which the inorganic pigment image has been transferred, and disposing the frit layer and the inorganic pigment image on a porcelain material And an arranging step. Hereinafter, description will be made with reference to FIG. Here, FIG. 3 is a schematic process diagram showing one embodiment of a forming process of the image ceramic with a frit layer in the method for manufacturing a painted ceramic of the present invention.

(Image Forming Step) As shown in FIGS. 3A and 3B, in the image forming step, the surface of the image receiving layer A3 of the image receiving member A3 having the image receiving layer 2 capable of forming an image on the support 1. To form an inorganic pigment image 11. The method of forming the inorganic pigment image is the same as the method described in the above-mentioned “Image ceramic body forming step with frit layer (1)”.

(Image Transfer Step) As shown in FIGS. 3C and 3D, in the image transfer step, the inorganic pigment image 11 formed on the surface of the Is transferred to the surface of the image receiving layer 19 of the image receiving body C20 having the transferable image receiving layer 19.

<Receiver C> The receiver C has at least one image-receiving layer capable of transferring an inorganic pigment image on the surface of a support, and a cushion layer and a release layer are provided between the support and the image-receiving layer. , An intermediate layer or the like may be provided. 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.

As the image receiving layer to which the inorganic pigment image can be transferred,
There is no particular limitation as long as the inorganic pigment image can be transferred, and a binder resin in a transfer material described below can be used,
The layer thickness is generally 0.3 to 20 μm,
Preferably it is 0.7 to 15 μm.

In the present invention, the image receiving member C has a release layer and a hydrophobic polymer layer (image receiving layer) capable of transferring an inorganic pigment image on the support in this order (with another layer between the layers). May be preferable). The release layer and the hydrophobic polymer layer are the same as those of the image receiver B. From the viewpoint of easy separation of the support and disposition on the porcelain, an image receiver (adhesive image receiver) having an image receiving layer on a water-soluble polymer layer provided on a water-permeable support is preferable. In the embodiment, the water-soluble polymer layer is provided. However, the image-receiving layer may be provided directly on the support. The support,
The same applies to the water-soluble polymer layer of the image receiving body B.

In the image transfer step, first, the support 17
Is provided, an image receiving member C20 (adhesive image receiving member) having a water-soluble polymer layer 18 and an image receiving layer 19 to which the inorganic pigment image 11 can be transferred sequentially. As shown in FIG. 3C, the surface of the image receiving layer 19 of the image receiving member C20 and the surface of the image receiving layer 2 on which the inorganic pigment image 11 has been formed in the image forming step are superposed so as to be in contact with each other. Heating is performed while applying pressure, if necessary. After the heating, the inorganic pigment image 11 is transferred onto the image receiving layer 19 by separating the image receiving body A3.

In the heating step, heating may be performed while applying pressure. For example, both layers can be brought into close contact with each other by using a device (for example, a heat roll laminator) having a pair of heating nip rollers incorporating a heating means such as a heater. . The heating temperature at the time of heating is generally 50 to 200.
C is preferred.

(Frit layer setting step) FIG.
As shown in (f), in the frit layer setting step, the frit layer 22 is placed on the image receiving layer 19 on which the inorganic pigment image 11 has been transferred.
Is provided. Here, the method for installing the frit layer is not particularly limited, and examples thereof include a transfer method for transferring and forming the frit layer, and a coating method for applying the frit layer using a liquid. The frit-containing liquid can be prepared by dissolving or dispersing the frit and the binder in an appropriate solvent.

As shown in FIG. 3E, in the frit layer setting step, first, a frit sheet 23 having a frit layer 22 provided on the surface of a support 21 is prepared. The surface of the frit layer 22 of the frit sheet 23 and the surface of the image receiving layer 19 on which the inorganic pigment image 11 has been formed in the transfer step are disposed so as to face each other and overlap each other so as to be in contact with each other. Heat. After the heating, the support 21 of the frit sheet 23 is peeled off, so that the image receiving body C2
The frit layer 22 is transferred onto the zero image receiving layer 19.

In the heating step, heating may be performed while applying pressure. For example, the two layers can be brought into close contact with each other by a device (eg, a heat roll laminator) having a pair of heating nip rollers incorporating a heating means such as a heater. . The heating temperature at the time of heating is generally 50 to 200.
C is preferred. As the frit of the frit layer, the same frit as that used for the image receiving body B can be used.

(Arrangement Step) As shown in FIG. 3G, in the arrangement step, the frit layer 22 and the inorganic pigment image 11 are arranged on the surface of the porcelain 16 together with part or all of the image receiving member C20. The attached image ceramic 25 is formed. In the disposing step, first, the support 17 of the image receiving body C20 is peeled off with the water-soluble polymer layer 18. Specifically, when the support 17 of the image receiving body C20 is formed of a water-permeable support,
A part of the image receiving member C20 after the transfer of the inorganic pigment image 11 is
By contacting or immersing in water from the 7 side, moisture penetrates through the support 17 and a part of the water-soluble polymer is dissolved to peel off the support 17. (At this time, the surface on the side where the support 17 is peeled off and the water-soluble polymer layer 18 is partially dissolved is referred to as a “peeling surface”.)

After the support 17 was peeled off, the inorganic pigment image 11 transferred to the image receiving layer 19 was placed on the surface of the desired porcelain 12 together with the frit layer 22, but as shown in FIG. With the polymer partially dissolved, it is placed on the desired surface of the porcelain 16 so as to be in contact with the release surface. Also, before or after the support is peeled off, so as to be in contact with the surface opposite to the peeled surface, that is, the surface of the frit layer 22,
The paste may be disposed on a desired surface of the porcelain 16 via a liquid in which the paste is dissolved or dispersed. By drying, it is adhered to the porcelain material, and the image porcelain body 25 with a frit layer is formed. In the former (this embodiment), a normal image is formed as viewed from the inorganic pigment image 11 formed on the image receiving member C20, and in the latter, the image receiving member C2 is formed.
As seen from the inorganic pigment image 11 formed at 0, a mirror-reversed image is formed. The arrangement on the surface of the porcelain material 16 may be performed by thermocompression as needed. Further, a porcelain having a frit layer on the surface may be used. In this case, the frit layer is disposed on the porcelain so as to sandwich the inorganic pigment image (as in the former).

-Image porcelain molding step with frit layer (3)-The image porcelain molding step with frit layer (3) includes an image forming step of forming an inorganic pigment image on the surface of the image receiving layer of the image receiving body A; A transfer step of transferring the inorganic pigment image to the frit layer of the image receiving member B, a frit layer setting step of providing a frit layer on the frit layer to which the inorganic pigment image has been transferred, and disposing the frit layer and the inorganic pigment image on the porcelain material And an arranging step. Hereinafter, description will be made with reference to FIG. Here, FIG. 4 is a schematic process chart showing one embodiment of a forming process of the image ceramic body with the frit layer in the method for manufacturing a painted ceramic body of the present invention.

(Image Forming Step) As shown in FIGS. 4A and 4B, in the image forming step, the surface of the image receiving layer 2 of the image receiving member A3 having the image receiving layer 2 on which the image can be formed on the support 1. To form an inorganic pigment image 11. The method of forming the inorganic pigment image is the same as the method described in the above-mentioned “Image ceramic body forming step with frit layer (1)”.

(Image Transfer Step) As shown in FIG.
In the image transfer step, the inorganic pigment image 11 formed on the surface of the image receiving layer 2 is transferred to the frit layer 14 of the image receiving member B15 having a frit layer 14 capable of transferring the inorganic pigment image 11 onto a support 12.
Transfer to the surface. The method of transferring the inorganic pigment image is the same as the method described in the above-mentioned “Image ceramic body forming step with frit layer (1)”.

(Frit Layer Setting Step) As shown in FIG. 4D, in the frit layer setting step, the frit layer 22 is provided on the frit layer 14 onto which the inorganic pigment image 11 has been transferred. As a method for installing the frit layer, a transfer method, a coating method, and the like can be mentioned in the same manner as described in the above-mentioned image porcelain molding step with frit layer (2).

As the frit of the frit layer, the same frit as that used in the frit layer setting step of the above-mentioned (Method (2) for forming image frit with a frit layer) can be used. The total frit content of the provided frit layer and the frit layer provided in this step is preferably 0.2 to 6 g / m ² .
More preferably, it is 4 to ⁴ g / m ² . The content is
If it is less than 0.2 g / m ^2, there is the effect that aids in sintering becomes insufficient, and when it exceeds 6 g / m ^2, coating property,
Manufacturing suitability tends to deteriorate.

(Arrangement Step) As shown in FIG. 4 (f), in the arrangement step, the frit layers 14, 22 and the inorganic pigment image 11 are formed.
Is arranged on the surface of the porcelain 16 together with a part or the whole of the image receiving body B15 to form the image porcelain 26 with the frit layer. The arrangement method is the same as the method described in the above-mentioned “Method for Forming Image Porcelain with Frit Layer (1)”.

-Image porcelain forming step with frit layer (4)-The image porcelain forming step with frit layer (4) includes an image forming step of forming an inorganic pigment image on the surface of the frit layer of the image receiving body B;
Arranging the frit layer and the inorganic pigment image on the porcelain material.

(Image Forming Step) In the image forming step, an inorganic pigment image is formed on the surface of the image receiving layer of the image receiving body B having a frit layer capable of forming an image on a support.

The method of forming the inorganic pigment image is the same as the method described in the above-mentioned “Image ceramic body forming step with frit layer (1)”.

(Arranging Step) In the arranging step, the frit layer and the inorganic pigment image are arranged on the surface of the porcelain together with part or all of the image receiving body B to form an image porcelain with a frit layer. The arrangement method is the same as the method described in the above-mentioned “Method for Forming Image Porcelain with Frit Layer (1)”. In addition, a porcelain having a frit layer on the surface may be used, and in that case, the frit layer is disposed on the porcelain so as to sandwich the inorganic pigment image.

-Image porcelain forming step with frit layer (5)-The image porcelain forming step with frit layer (5) includes an image forming step of forming an inorganic pigment image on the surface of the image receiving layer of the image receiving body C; The method includes a frit layer setting step of providing a frit layer on the image receiving layer on which the pigment image is formed, and an arrangement step of arranging the frit layer and the inorganic pigment image on a porcelain material.

(Image Forming Step) In the image forming step, an inorganic pigment image is formed on the surface of the image receiving layer of the image receiving member C having an image receiving layer capable of forming an image on a support. The method of forming the inorganic pigment image is the same as the method described in the above-mentioned “Image ceramic body forming step with frit layer (1)”.

(Frit Layer Installation Step) In the frit layer installation step, a frit layer is provided on the image receiving layer on which the inorganic pigment image has been formed. As a method for installing the frit layer, a transfer method, a coating method, and the like can be mentioned in the same manner as described in the above-described image porcelain molding step with a frit layer (2), and the components of the frit layer are also the same. be able to.

(Arranging Step) In the arranging step, the frit layer and the inorganic pigment image are arranged on the surface of the porcelain together with a part or the whole of the image receiving body C to form an image porcelain with a frit layer. The arrangement method is the same as the method described in the above-mentioned “Method for Forming Image Porcelain with Frit Layer (1)”. In addition, a porcelain having a frit layer on the surface may be used, and in that case, the frit layer is disposed on the porcelain so as to sandwich the inorganic pigment image.

-Image porcelain forming step with frit layer (6)-The image porcelain forming step with frit layer (6) includes an image forming step of forming an inorganic pigment image on the surface of the frit layer of the image receiving body B;
The method includes a frit layer installation step of providing a frit layer on the frit layer to which the inorganic pigment image has been transferred, and an arrangement step of arranging the frit layer and the inorganic pigment image on a porcelain material.

(Image Forming Step) In the image forming step, an inorganic pigment image is formed on the surface of the image receiving layer of the image receiving member B having a frit layer capable of forming an image on a support. The method of forming the inorganic pigment image is the same as the method described in the above-mentioned “Image ceramic body forming step with frit layer (1)”.

(Frit Layer Setting Step) In the frit layer setting step, a frit layer is provided on the frit layer to which the inorganic pigment image has been transferred. The method of setting the frit layer, its components, the layer thickness, etc. are as described in the above-mentioned image porcelain molding step with frit layer (3)-
This is the same as shown in FIG.

(Arranging Step) In the arranging step, the frit layer and the inorganic pigment image are arranged on the surface of the porcelain together with a part or the entirety of the image receiving body B to form an image porcelain with a frit layer. The arrangement method is the same as the method described in the above-mentioned “Method for Forming Image Porcelain with Frit Layer (1)”.

-Firing Step- As shown in FIGS. 1 (f), 3 (h) and 4 (g), in the firing step, the image ceramics 24, 25 and 26 with frit layers are heated and sintered. To be painted ceramics 27, 28 and 29. By heating and firing the image ceramics 24, 25, and 26 with the frit layer, the water-soluble polymer layer and the like are burned off, the inorganic pigment image 11 is sintered on the surface of the ceramics 16, and the ceramics 27, 28,
29 are formed.

The heating of the image ceramics 24, 25, and 26 with a frit layer 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. It is preferable that the heating is performed by gradually increasing the temperature to the firing temperature, or by heating at a constant temperature of 300 to 500 ° C. for a certain period of time, and then gradually increasing the temperature to the firing temperature.
In the case of using a paint as the inorganic pigment, the baking temperature is usually 650 to 900 ° C, preferably 750 to 850.
C. and the firing time is preferably 10 minutes to 2 hours. When an undercolor is used as the inorganic pigment, the firing temperature is 1000 to 1300 ° C, preferably 1100 to 1300 ° C.
It is preferable that the temperature is 250 ° C. and the firing time is 10 minutes to 8 hours.

As described above, since the image ceramics 24, 25, and 26 with the frit layer before firing have the frit layers,
Even when the inorganic pigment content in the inorganic pigment image 11 formed in the above-described image forming step is high, the inorganic pigment image 11 is firmly sintered on the porcelain 16. In addition, this makes it possible to make the transfer layer (layer made of a transfer material) of the transfer sheet used for forming the inorganic pigment image 11 thin while maintaining the color density at a high level, and has good resolution and gradation. Images can be formed on porcelain. When a frit layer is provided on the inorganic pigment image 11, the surface glossiness can be particularly improved. In addition, when a frit layer is provided below the inorganic pigment image 11, the adhesion between the inorganic pigment image and the porcelain can be further improved.

In the present invention, an image is formed using a transfer system, and a transfer sheet to be used can be manufactured in an arbitrary size, and can be used after being cut to a required size at the time of transfer (printing). . That is, there is no need to store the transfer sheet in a cassette like the ink ribbon, and the transfer sheet can be used efficiently. Further, since the transfer layer of the transfer sheet can be prepared by hand coating using a rod coat or the like, it is extremely versatile.

Although the embodiment of the method for producing a painted ceramic according to the present invention has been described above, the present invention is not limited to this. For example, the above-described image-porcelain ceramic forming step with a frit layer (2) -And-Image porcelain molding step with frit layer (5)
In-, the method of producing a painted porcelain can be performed by omitting the frit layer setting step, arranging an inorganic pigment image on the surface of the frit layer of a porcelain material having a frit layer on the surface, and then firing. When a porcelain material having a frit layer on its surface is used, the adhesion between the inorganic pigment image and the porcelain material after firing becomes particularly good, and peeling or the like hardly occurs even in a natural environment.

[0132]

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

Example 1 Transfer Method Using Latent Image Forming Solution (Transferability Promoting Material) <Preparation of Transferability Promoting Material Solution> The following components were mixed and uniformly stirred, and then a 0.45 μm microfilter was prepared. 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— 48 g of ZnO, 200 g of Sb ₂ O ₃ , and CuO 2.5
g were blended and pulverized by a stamp mill, then mixed well with an Ishikawa-type raiker and fired at 750 ° C. Further, after pulverizing with a stamp mill, 150 ml of water was added to the whole amount, and the mixture was pulverized with a Micros MIC-ONZ (manufactured by Nara Machinery Co., Ltd.) to an average particle size of 1.1 μm. ) Was prepared.

-Preparation of Yellow Transfer Layer Coating Liquid- The components of the following composition were mixed and sufficiently stirred to prepare a yellow transfer layer coating liquid (coating liquid Y). The content of the inorganic pigment in the inorganic component of the coating solution for yellow transfer layer was 63% by mass.

[Composition of Coating Liquid Y] • Pigment Dispersion Y: 41 parts by mass • Polyoxythylene (n = 10) Nonylphenol Ether: 0.5 part by mass (20% by mass aqueous solution) • Carnauba wax dispersion (31 20% by mass (K-332; manufactured by Chukyo Yushi Co., Ltd.)-Butyral resin dispersion (25% by mass) ... 60 parts by mass (Resem J667; manufactured by Chukyo Yushi Co., Ltd.)-Terpene phenol resin dispersion (35% by mass) 5 parts by mass (Rezem J628; manufactured by Chukyo Yushi Co., Ltd.)

The coating liquid Y was applied to the surface of a polyester film having a thickness of 25 μm so as to have a dry film thickness of 1.8 μm, and dried to form a yellow transfer layer, thereby producing a yellow transfer sheet.

(2) Preparation of Magenta, Cyan and Black Transfer Sheets -Preparation of Inorganic Pigment Dispersion M- Fe ₂ O ₃ , NiO 10 g, CuO 10 g, Au ₂ O
After compounding 190 g and pulverizing with a stamp mill, they were mixed with an Ishikawa-type raiker and fired at 1100 ° C. Further, after crushing with a stamp mill, 100 g of this and 100 g of flux (19167: Isehisa) were mixed with an Ishikawa-type raiker, baked at 750 ° C., crushed with a stamp mill, and 150 ml of water was added to the entire amount. MIC-ONZ
To obtain a magenta pigment dispersion (inorganic pigment dispersion M).

[0139] - Preparation of Inorganic Pigment Dispersion _{C - Cr 2 O 3 85g,} Fe 2 O 3 5g, Co 2 O 3 340
g, 65 g of ZnO, pulverized with a stamp mill,
After mixing with an Ishikawa-type raiger, the mixture was baked at 1100 ° C and pulverized. To 100 g of this, 110 g of flux (19167: Isehisa) was added and mixed with an Ishikawa-type raiker, and the mixture was mixed with 75 g
After firing at 0 ° C., pulverized by a stamp mill,
The resulting mixture was added to the mixture, and the mixture was refined to an average particle size of 0.95 μm with Micros MIC-ONZ to prepare a cyan pigment dispersion (inorganic pigment dispersion C).

Preparation of Inorganic Pigment Dispersion BK 55 g of Cr ₂ O ₃ , 135 g of MnO, 55 g of Fe ₂ O ₃ 55
g, blended with Co ₂ O ₃ 250g, to prepare black pigment dispersion (inorganic pigment dispersion BK) analogously to the following yellow pigment dispersion. The average particle size was 1.0 μm.

In the preparation of the yellow transfer sheet,
In place of the yellow pigment dispersion, magenta pigment dispersion, cyan pigment dispersion, and black pigment dispersion, respectively, except that magenta transfer sheet, cyan transfer sheet, and black transfer sheet were used in the same manner as the yellow transfer sheet. Were prepared respectively. The content of the inorganic pigment in the inorganic component of the transfer material in the magenta transfer sheet was 50% by mass, the content of the inorganic pigment in the inorganic component of the transfer material in the cyan transfer sheet was 48% by mass, and the content of the pigment in the black transfer sheet was 48% by mass. The content of the inorganic pigment in the inorganic component of the transfer material was 63% by mass. The layer thickness of the transfer layer of the magenta transfer sheet was 2 μm, the layer thickness of the transfer layer of the cyan transfer sheet was 1.8 μm, and the layer thickness of the transfer layer of the black transfer sheet was 1.8 μm.

<Preparation of Image Receiver A> A coating solution for the first layer and a coating solution for the second layer having the following compositions were prepared. [Composition of coating solution for first layer (cushion layer)]-Vinyl chloride-vinyl acetate copolymer ... 160 parts by mass (Solvain CL2; manufactured by Nissin Chemical Co., Ltd.)-Ethylene-vinyl acetate copolymer ... 61 parts by mass Part (Elvaloy 742; manufactured by Mitsui Dupont Chemical Co., Ltd.)-Polyester sebacate ... 28 parts by mass (FN-G25; manufactured by Nippon Soda Co., Ltd.)-Perfluoroalkyl group-containing oligomer ... 4 parts by mass (MegaFac F-178K Dainippon Ink and Chemicals, Inc.)-Methyl ethyl ketone ... 630 parts by mass-Toluene ... 210 parts by mass-Dimethylformamide ... 30 parts by mass

[Composition of coating solution for second layer (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

The first layer coating solution was applied on the surface of a PET film support having a thickness of 130 μm and dried at 100 ° C. to form a first layer (cushion layer) having a dry film thickness of 20 μm. Next, the coating solution for the second layer was applied on the first layer and dried at 100 ° C. to form a second layer (image receiving layer) having a dry film thickness of 2 μm.

<Preparation of Image Receiver B>
A smooth paper support of 00 g was prepared, and a 10% aqueous solution of gum arabic was applied on the surface of the paper support to a dry layer thickness of 1.5 μm.
And dried (water-soluble polymer layer). On top of this, a coating solution having the following composition was further dried to a thickness of 5 μm.
m and dried. From the above, an image receiving member B having a water-soluble polymer layer and a frit layer sequentially on the paper support surface was obtained.

-Flux (19164; manufactured by Celdec) ... 13 parts by mass-Sumikaflex 752 (27% by mass aqueous solution) ... 100 parts by mass (manufactured by Sumitomo Chemical Co., Ltd.)-Polyoxyethylene (n = 10) nonylphenyl ether ... 5 Parts by mass (20% by mass aqueous solution)

<Image Forming Method> First, an ink-jet apparatus (PM670: manufactured by Seiko Epson Corporation) equipped with an ink-jet head having a heating element inside is filled with the above-mentioned transferability-enhancing material solution, and a predetermined position is determined based on image information. A heat was applied to the heating element to generate heat, a nearby transferability enhancing material solution was boiled, and the pressure in the head was increased to cause the transferability enhancing material solution to fly, thereby forming a latent image on the surface of the image receiving member A. .

Subsequently, the surface of the transfer layer of the yellow transfer sheet and the surface of the image receiving layer of the image receiving body A on which the latent image has been formed are overlapped so as to be in contact with each other, and laminated through a heat roll laminator (85 ° C.). After that, the yellow transfer sheet was peeled off, and the yellow transfer layer was transferred only on the latent image to form a yellow image (image forming step). Similarly, magenta, cyan, and black images were formed on the image receiving member A using the magenta, cyan, and black transfer sheets, and a full-color image was obtained.

Subsequently, the surface of the image receiving layer on which the full-color image has been formed and the surface of the frit layer of the image receiving body B obtained above are overlapped so as to be in contact with each other, and laminated through a heat roll laminator (120 ° C.). After the contact, the image receiving member A was peeled off, and the inorganic pigment image was transferred to the frit layer (transfer step).

Subsequently, a part of the image receiving member B on which the full-color image or the like was formed was immersed in water, and the support was peeled off while dissolving a part of the first layer. Thereafter, the support (peeled surface) of the first layer (water-soluble polymer layer) which was peeled off and was exposed and dissolved was in contact with the surface of the ceramic plate (placement step). At this time, a water-soluble polymer layer, a frit layer, and a full-color image are sequentially laminated on the surface of the ceramic plate to form a full-color image (normal image). Next, the ceramic plate on which the full-color inorganic pigment image is formed together with the frit layer and the like is fired at 400 ° C. for 1 hour and further at 850 ° C. for 1 hour, and the inorganic pigment is sintered on the surface of the ceramic plate to obtain a ceramic plate with a full-color image. Was obtained (firing step).

By producing a painted ceramic body as described above, even when the content of the inorganic pigment in the inorganic component of the inorganic pigment image is high (48 to 63% by mass) as in the present embodiment, the inorganic pigment image is made of ceramic. Sintered firmly to the material. In addition, the transfer layer of the transfer sheet used for forming the inorganic pigment image can be made thin while maintaining the color density at a high level (1.
8 to 2 μm), and an image having good resolution and gradation was formed on the porcelain. In addition, since the frit layer was provided below the inorganic pigment image, the adhesion between the inorganic pigment image and the porcelain material was particularly enhanced, and sintering was performed more firmly. Further, by forming an image by a transfer method using a latent image forming liquid, an image (porcelain with a picture) having more excellent resolution and gradation was obtained. Further, the used transfer sheet could be cut and used corresponding to the portion where the latent image was formed, and the transfer sheet could be used efficiently.

Example 2 Electrophotography Using Transfer Sheet First, transfer sheets of four colors (yellow, magenta, cyan and black) were produced in the same manner as in Example 1.

<Production of Adhesive Toner> Subsequently, an adhesive toner was prepared as an adhesive composition as follows. The components having the following composition were mixed by a mixer and then melt-kneaded by a two-roll mill. The kneaded product was milled after rolling and cooling. This powder was classified to obtain a toner having an average particle diameter of 7.5 μm. Furthermore, hydrophobic silica (R972: manufactured by Nippon Aerosil Co., Ltd.)
Was added and mixed with a mixer to obtain an adhesive toner.・ Polyester resin: 100 parts by mass (acid value: 3, hydroxyl value: 25, molecular weight: 40,000, glass transition point: 60 ° C.) ・ Flux (19164: manufactured by Celdec Co.): 60 parts by mass ・ Zinc salicylate derivative: 3 parts by mass (Bontron E84: manufactured by Orient Chemical Co., Ltd.)

<Preparation of Image Receiver C>
A smooth paper support of 00 g was prepared, and a 10% aqueous solution of gum arabic was applied on the surface of the paper support to a dry layer thickness of 1.5 μm.
And dried (water-soluble polymer layer). Further, the coating solution for the second layer of the image receiving body A was applied so as to have a dry layer thickness of 5 μm, and dried. From the above, an image receiving body C having a water-soluble polymer layer and an image receiving layer on the surface of the paper support in sequence was obtained.

<Preparation of Frit Sheet>
A 5 μm PET film was prepared, and a frit layer having the following composition was applied thereon so that the dry layer thickness was 4 μm. [Composition of frit layer]-Flux (19164; manufactured by Celdec) ... 13 parts by weight-Sumikaflex 752 (27% by weight aqueous solution) ... 100 parts by weight (manufactured by Sumitomo Chemical Co., Ltd.)-Polyoxyethylene (n = 10) nonylphenyl Ether: 5 parts by mass (20% by mass aqueous solution)

<Image formation> First, the adhesive toner obtained above was applied to a monochrome laser printer (LP-8600FX,
Seiko Epson Corporation), and a desired electrostatic latent image (an image corresponding to the yellow component) formed in the printer is developed with the adhesive toner. A latent image having an adhesive property (adhesive latent image) was formed on the layer. Subsequently, the surface of the image receiving layer on which the adhesive latent image was formed and the surface of the yellow transfer layer of the yellow transfer sheet obtained above were overlapped so as to be in contact with each other, and laminated through a heat roll laminator (120 ° C.). After that, 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. Similarly, magenta, cyan and black images were formed on the image receiving member C using the magenta, cyan and black transfer sheets.

Next, the surface of the image receiving layer on which the full-color image (mirror image reversal image) was formed and the frit layer of the frit sheet were overlapped with each other so as to be in contact with each other, and were laminated by passing through a heat roll laminator (120 ° C.). After that, the support of the frit sheet was peeled off, and the frit layer was transferred so as to cover the full-color image (frit layer setting step).

Subsequently, it was placed on a ceramic plate and fired in the same manner as in Example 1 to obtain a ceramic plate (painted ceramic) with a full-color image (arrangement and firing process).

By producing a painted ceramic body as described above, even when the content of the inorganic pigment in the inorganic component of the inorganic pigment image is high (48 to 63% by mass) as in the present embodiment, the inorganic pigment image can be used. Sintered firmly to the material. In addition, the transfer layer of the transfer sheet used for forming the inorganic pigment image can be made thin while maintaining the color density at a high level (1.
8 to 2 μm), and an image having good resolution and gradation was formed on the porcelain. Further, since the frit layer was provided on the inorganic pigment image, a painted ceramic body having particularly improved glossiness was obtained. Furthermore, by electrophotography using a transfer sheet, there is no need to manufacture toner of each color, and a full-color image can be formed using a single type of toner and a monochrome printer, thereby producing a ceramic body with painting at low cost. We were able to.

[0160]

As described above, according to the method for manufacturing a painted porcelain of the present invention, an image having high color density, high resolution, and excellent gradation can be obtained on a porcelain easily and at low cost. A ceramic body with a picture can be manufactured.

[Brief description of the drawings]

FIG. 1 is a schematic process diagram showing one embodiment of a forming process of an image ceramic body with a frit layer in a method for manufacturing a painted ceramic body of the present invention.

FIG. 2 is a schematic process chart showing one embodiment of an image forming step in the method for manufacturing a painted ceramic body of the present invention.

FIG. 3 is a schematic process diagram showing one embodiment of a forming process of an image ceramic body with a frit layer in the method for manufacturing a painted ceramic body of the present invention.

FIG. 4 is a schematic process diagram showing one embodiment of a forming process of an image ceramic body with a frit layer in the method for manufacturing a painted ceramic body of the present invention.

[Explanation of symbols]

 1, 6, 8, 12, 17, 21 ... Support 2, 9 ... Image receiving layer 3 ... Image receiving body A 4 ... Transfer sheet 5 ... Image receiving body 7 ... Transfer layer 10 , 11 ... inorganic pigment image 13, 18 ... water-soluble polymer layer 14, 22 ... frit layer 15 ... image receiving member B 16 ... porcelain material 19 ... image receiving layer 20 ... image receiving Body C 23: Frit sheet 24, 25, 26: Image ceramic body with frit layer 27, 28, 29: Painted ceramic body

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C04B 41/89 C04B 41/89 D G03G 9/08 391 G03G 9/08 391 F term (reference) 2H005 AA25 AA29 2H086 BA01 BA05 BA15 BA26 BA51 3B005 EA01 EB05 EC11 EC30 FA02 FA03 FA04 FB01 FB23 FB25 FB61 GA02 GB01 GB03 GC03 GC06 GC08 GD10

Claims (20)

[Claims] 1. An inorganic pigment image comprising a transfer material having an inorganic pigment content of 35% by mass or more in an inorganic component, and at least one of an upper and lower inorganic pigment image provided on a porcelain material. A picture porcelain characterized by comprising: a frit layer-attached image porcelain forming step of forming a frit layer-attached image porcelain; and a firing step of heating and sintering the frit layer-attached image porcelain. How to make the body. 2. The painted ceramic according to claim 1, wherein the inorganic pigment image is formed by one of a transfer method using a latent image forming liquid and an electrophotographic method using a transfer sheet. How to make the body. 3. An image forming step of forming an inorganic pigment image on a surface of the image receiving layer of an image receiving body A having an image receiving layer capable of forming an image on a support, wherein the image ceramic body forming step with a frit layer is performed; An image transfer step of transferring an inorganic pigment image onto the surface of the frit layer of the image receiving member B having a frit layer capable of transferring the inorganic pigment image on a support; and transferring the frit layer and the inorganic pigment image to the image receiving member. The method for producing a painted ceramic body according to claim 1 or 2, further comprising an arrangement step of disposing the part or all of B on the surface of the ceramic material. 4. An image forming step of forming an inorganic pigment image on a surface of the image receiving layer of an image receiving body A having an image receiving layer capable of forming an image on a support, wherein the image ceramic body forming step with a frit layer is performed; An image transfer step of transferring an inorganic pigment image to the surface of the image receiving layer of the image receiving member C having an image receiving layer capable of transferring the inorganic pigment image on a support, and an image receiving step in which the inorganic pigment image is transferred. A frit layer setting step of providing a frit layer thereon, and an arranging step of arranging the frit layer and the inorganic pigment image on a surface of the porcelain together with a part or all of the image receiving body C. 3. The method for producing a painted ceramic body according to 1 or 2. 5. An image forming step of forming an inorganic pigment image on a surface of the image receiving layer of the image receiving body A having an image receiving layer capable of forming an image on a support, wherein the image ceramic body forming step with a frit layer is performed; An image transfer step of transferring an inorganic pigment image onto a surface of the image receiving layer of an image receiving member C having an image receiving layer capable of transferring the inorganic pigment image on a support; With some or all,
Arranging a porcelain material having a frit layer on the surface of the frit layer.
Or the method for producing a painted ceramic body according to 2. 6. The porcelain material has a frit layer on its surface, and the frit layer and the inorganic pigment image are arranged on the frit layer surface of the porcelain material in the arranging step. Or the method for producing a painted ceramic body according to 4. 7. An image forming step of forming an inorganic pigment image on a surface of the image receiving layer of an image receiving body A having an image receiving layer capable of forming an image on a support, wherein the image ceramic body forming step with a frit layer is performed; An image transfer step of transferring an inorganic pigment image to the surface of the frit layer of the image receiving member B having a frit layer capable of transferring the inorganic pigment image on a support; and an image transfer step of transferring the inorganic pigment image to the frit layer. A frit layer setting step of further providing a frit layer thereon; and an arranging step of arranging the frit layer and the inorganic pigment image on a surface of the porcelain together with part or all of the image receiving body B. Item 3. The method for producing a painted ceramic body according to Item 1 or 2. 8. The method according to claim 1, wherein the image receiving member B comprises a support, a release layer,
And a frit layer containing a hydrophobic polymer capable of transferring an inorganic pigment image.
6. The method for producing a painted ceramic body according to 6 or 7. 9. The image receiving member B comprises a support, a release layer,
The method according to claim 3, 6, or 7, further comprising a hydrophobic polymer layer and a frit layer capable of transferring an inorganic pigment image. 10. The image receiving member B having a release layer, a frit layer, and a hydrophobic polymer layer capable of transferring an inorganic pigment image on a support in this order.
Or the method for producing a painted ceramic body according to 7. 11. The image receiving member C according to claim 4, wherein the image receiving member C has a release layer and a hydrophobic polymer layer capable of transferring an inorganic pigment image on a support in this order. Manufacturing method of painted ceramics. 12. An image forming step of forming an inorganic pigment image on a surface of the frit layer of the image receiving member B having a frit layer capable of forming an image on a support, wherein: The method for producing a painted ceramic body according to claim 1, further comprising: an arrangement step of arranging a frit layer and an inorganic pigment image on a surface of the ceramic material together with a part or the entirety of the image receiving body B. 4. 13. An image forming step of forming an inorganic pigment image on a surface of the image receiving layer of an image receiving body C having an image receiving layer capable of forming an image on a support, A frit layer setting step of providing a frit layer on the image receiving layer on which the inorganic pigment image is formed, and an arranging step of arranging the frit layer and the inorganic pigment image on the surface of the porcelain together with part or all of the image receiving member C. The method for producing a painted ceramic body according to claim 1 or 2, comprising: 14. An image forming step of forming an inorganic pigment image on a surface of the image receiving layer of the image receiving body C having an image receiving layer capable of forming an image on a support, wherein the image ceramic forming step with a frit layer is performed; An inorganic pigment image together with part or all of the image receiving body C,
Arranging a porcelain material having a frit layer on the surface of the frit layer.
Or the method for producing a painted ceramic body according to 2. 15. The porcelain material has a frit layer on its surface, and the frit layer and the inorganic pigment image are arranged on the frit layer surface of the porcelain material in the arranging step. Or the method for producing a painted ceramic body according to 13 above. 16. An image forming step of forming an inorganic pigment image on a surface of the frit layer of the image receiving body B having a frit layer capable of forming an image on a support, wherein: A frit layer installation step of further providing a frit layer on the frit layer on which the inorganic pigment image is formed; and an arrangement step of arranging the frit layer and the inorganic pigment image on a surface of the porcelain together with part or all of the image receiving member B. The method for producing a painted ceramic body according to claim 1 or 2, comprising: 17. The image receiving apparatus according to claim 12, wherein said image receiving member B has a release layer and a frit layer containing an image-forming hydrophobic polymer on a support in order.
Or the method for producing a painted ceramic body according to 16 above. 18. The image receiving apparatus according to claim 12, wherein the image receiving body B has a release layer, a hydrophobic polymer layer, and an image-forming frit layer on a support in this order.
7. The method for producing a painted ceramic body according to item 6. 19. The image receiver B according to claim 12, wherein a release layer, a frit layer, and an image-forming hydrophobic polymer layer are sequentially formed on a support.
7. The method for producing a painted ceramic body according to item 6. 20. The painted ceramic body according to claim 13, wherein the image receiver C has a release layer and an image-forming hydrophobic polymer layer on a support in order. Manufacturing method.