JP2006035480A - Method for manufacturing ceramic object with picture - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a ceramic object with a picture by which a high resolution ceramic image of variegated hues including special colors can be formed on the surface of the ceramic object easily and at a low cost with the help of a less expensive device. <P>SOLUTION: In this method, a tacky latent image composed of a tacky composition is formed on an image receiving material, then an inorganic pigment image is formed by dusting an inorganic pigment powder on the surface of the image receiving material on the side where the tacky latent image is formed and thereby, sticking an inorganic pigment to the tacky latent image portion, and the inorganic pigment image formed on the image receiving material is arranged on the surface of the ceramic object. After that, the ceramic object with at least the inorganic pigment image arranged is heated and the inorganic pigment image is sintered on the surface of the ceramic object as a sintering process. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a method for producing a ceramic body with a picture for forming an inorganic image, and more specifically, an inorganic sintered image as a semi-permanent image on a ceramic body as a building material such as an art ceramic board, a photographic ceramic board, a sign ceramic board, or a landscape material. The present invention relates to a method of manufacturing a ceramic body with a picture to be formed.

Ceramic body with black and white or color image formed on the surface of building materials such as art tiles and ceramic materials, etc., is used outdoors for building materials such as bathroom tiles, entrances, outdoors, etc. It is expected to be applied not only to guide plates and sign ceramic plates but also to various uses such as photographic ceramic plates such as portraits and images, accessories such as pendants and brooches.
Conventionally, methods for producing photographic ceramic plates, art ceramic plates, signature ceramic plates, etc. used in these applications are as follows. <1> Transfer paper coated with a water-soluble polymer on a paper support by screen printing or the like. Print a pigment image, <2> apply a cover coat layer thereon, <3> immerse the transfer paper in water, dissolve the water-soluble polymer, peel off the paper support, and <4> the pigment. The image was made by adhering it to a ceramic or ceramic plate, <5> and firing it (see Reference Patent 1). However, this method requires a printing plate. In particular, in the case of a full-color image, at least four sheets, usually nearly ten sheets, are required, and it takes time and effort, and is extremely expensive.
In view of this, a simple manufacturing method has been proposed without using a printing plate. For example, after forming an image on ordinary photographic paper, the paper portion of the photographic paper is removed and adhered to the surface of a ceramic, ceramic plate, etc., and the image portion surface is laminated with an ultraviolet curable resin to form an image portion. A protection method is known (see Reference Patent 2). However, the image formed by this method has insufficient light resistance and heat resistance of the image area. It is also known that a thermoplastic image-receiving layer is provided on the surface of a ceramic body, and a dye image made of a sublimation dye is thermally transferred to the image-receiving layer to form an image (see Reference Patent 3). However, this image also has insufficient light resistance and heat resistance.

The inventor previously proposed a ceramic image forming method using a thermal transfer method instead of forming an inorganic pigment image by the above printing method as a method for easily forming an image having excellent light resistance and heat resistance. (See Reference Patent 4). In this method, an image-donating sheet having an image-donating layer comprising an inorganic pigment and a heat-meltable binder on a thin layer film is superimposed on the image-receiving sheet (or transfer paper), and the thermal head of the thermal printer from the back layer side of the image-donating sheet. The image-donating layer is transferred imagewise by heating imagewise to form an inorganic pigment image. However, in order to form a full-color image by this method, it is necessary to apply an image-donating layer of four colors of cyan, magenta, yellow, and black in order on the same support in advance. There is a problem that it is extremely difficult to add the symbol according to the pattern.
As another method, there has been proposed a method using an electrophotographic method in which a colored toner colored with an inorganic material is applied imagewise to form an image (see Reference Patent 5). This method is a method in which a colored toner image is formed from a previously formed electrostatic latent image using an inorganic colored toner and transferred. However, in this method, when a color image, that is, a multicolor or full color image is to be formed, for example, a general color such as yellow (Y), magenta (M), cyan (C), or a special color such as gold For example, a toner corresponding to each color pigment must be prepared and prepared. Therefore, a toner design corresponding to individual pigment characteristics is also required. Moreover, when iron or its oxide is included in the colored toner, it is easily colored black at the time of firing, and an image having a desired hue is difficult to obtain. In addition, when forming a multicolor or full color image, it is indispensable to use a printer for forming a color image, which is generally expensive.
The present inventor has developed a method for easily transferring and forming an inorganic pigment image by an ink jet method (see Reference Patent 6). This method uses an inexpensive ink jet printer, and after imagewise printing a transfer accelerator on an image receiving material, an image donating sheet having an image donating layer comprising an inorganic pigment and a heat-meltable binder on a thin film In this method, an inorganic pigment image is transferred and formed corresponding to an image made of a transfer accelerator by superimposing and passing through a heat roller. This method does not require a printing plate and can easily form a full-color image, but it is necessary to apply an inorganic pigment to a thin film or the like together with a thermoplastic or heat-meltable binder in advance. Material costs, application costs, etc.

JP-A-5-85099 JP-A-5-318990 JP-A-8-34158 JP-A-9-236999 JP 2002-293677 A JP 2002-097088 A

In view of the above, the present invention solves the above-mentioned conventional problems, and does not use a colored toner corresponding to the image hue in advance, and also includes an image made of an inorganic pigment and a heat-meltable or thermoplastic binder in advance. There is no need to prepare an image-donating material that has a donor layer, and a high-resolution inorganic material with various colors including special colors on the surface of ceramic materials such as building materials such as art tiles and ceramic materials, using an inexpensive device. It aims at providing the ceramic body manufacturing method with a picture which can form an image (a multicolor or full color image is included) simply and at low cost, and makes it a subject to achieve this objective.

Means for solving the above-mentioned problems are as follows. That is,
<1> a latent image forming step of forming an adhesive latent image made of an adhesive composition on an image receiving material;
An image forming step of forming an inorganic pigment image by applying an inorganic pigment powder to the surface of the image receiving material on the side on which the adhesive latent image is formed and adhering the inorganic pigment to the adhesive latent image portion;
An arrangement step of arranging an inorganic pigment image formed on the image receiving material on the surface of the ceramic body;
A firing step of heating the ceramic body on which at least the inorganic pigment image is disposed, and sintering the inorganic pigment image on a surface of the ceramic body;
A method for producing a ceramic body with a picture, comprising:

<2> The method for producing a ceramic body with a picture according to <3>, wherein the adhesive composition is colorless or light-colored.

<3> A cover coat layer forming step for forming a water-insoluble cover coat layer on the image receiving material on which the inorganic pigment image has been formed in the image forming step before the arranging step, and the inorganic pigment image is formed in the arranging step. The method for producing a ceramic body with a picture according to <1> or <2>, wherein the ceramic body is disposed on a surface of the ceramic body together with the cover coat layer.

<4> The method for producing a ceramic body with a picture according to any one of <1> to <3>, wherein the image-receiving material has a layer containing a water-soluble polymer as an image-receiving layer on the surface of the water-permeable support.

<5> The image receiving material according to any one of <1> to <3>, wherein the image receiving material has a layer containing a water-soluble polymer and an image receiving layer containing a water-insoluble polymer on the surface of the water-permeable support. The ceramic body manufacturing method of the picture.

<6> In the arranging step, the water-soluble polymer is partially dissolved by immersing the support side of the image receiving material in water to peel off the water permeable support of the image receiving material, and the peeled surface after peeling is on the surface of the ceramic body The method for producing a ceramic body with a picture according to the above <4> or <5>, wherein the inorganic pigment image is disposed on the surface of the ceramic body together with the image receiving layer so as to come into contact.

<7> In the arranging step, before or after peeling the water-permeable support of the image receiving material by partially dissolving the water-soluble polymer, the image forming surface is made of a ceramic body via a solution in which the glue is dissolved or dispersed. The method for producing a ceramic body with a picture according to the above <4> or <5>, wherein an inorganic pigment image is disposed on the surface of the ceramic body together with the image receiving layer so as to contact the surface.

<8> The method for producing a ceramic body with a picture according to any one of <1> to <7>, wherein the cover coat layer contains a hydrophobic polymer, and the glass transition point of the hydrophobic polymer is not more than room temperature.

<9> The cover coat layer forming step comprises heating at least the surface of the image receiving material on which the inorganic pigment image is formed and the surface of the cover coat layer of the transfer body having the cover coat layer. The method for producing a ceramic body with a picture according to any one of claims 1 to 8, which is a step of transferring the cover coat layer.

<10> The cover coat layer forming step is any of the above <1> to <8>, wherein the cover coat layer forming step is a step of forming a cover coat layer coating solution on the surface of the image receiving material on which the inorganic pigment image is formed. The method for producing a ceramic body with a picture.

<11> With a picture according to any one of <1> to <8>, wherein the cover coat layer forming step is a step of forming a liquid containing a hydrophobic polymer by uniformly printing on a whole surface with an ink jet printer Ceramic body manufacturing method.

<12> A latent image forming step of forming a tacky latent image made of a tacky composition on an image receiving material is carried out by using an inkjet printer to disperse dispersed ink in which a tacky composition is dispersed in an ink solvent. The method for producing a ceramic body with a picture according to any one of the above <1> to <11>, wherein the method comprises printing on the surface.

<13> The method for producing a ceramic body with a picture according to <12>, wherein the adhesive composition is a composition containing a tackifier.

<14> The method for producing a ceramic body with a picture according to <12> and <13>, wherein the adhesive composition is a composition containing a resin and a plasticizer of the resin.

<15> With the picture according to <12> to <14>, wherein the adhesive composition contains a terminal hydrophobic water-soluble polymer in a dispersed ink in which the adhesive composition is dispersed in an ink solvent. Ceramic body manufacturing method.

<16> The method for producing a ceramic body with a picture according to <15>, wherein the terminal hydrophobic water-soluble polymer is represented by the following general formula (1).

〔但し、式（１）中、Ｒは疎水性基又は疎水性重合体を表し、ｎは整数を表す。〕

[In the formula (1), R represents a hydrophobic group or a hydrophobic polymer, and n represents an integer. ]

<17> The method for producing a ceramic body with a picture according to <15>, wherein the terminal hydrophobic water-soluble polymer is represented by the following general formula (2).
General formula (2): R ′ — (SP) _n [In the formula (2), R ′ represents a hydrophobic group or a hydrophobic polymer, and P represents at least one of the following structural units A, B and C: 1 represents a polymer having a degree of polymerization of 10 or more and 3500 or less. n represents 1 or 2.

〔ここで、Ｒ^１は−Ｈ又は炭素数１〜６のアルキル基を表わし、Ｒ^２は−Ｈ又は炭素数１〜１０のアルキル基を表わし、Ｒ^３は−Ｈ又は−ＣＨ_３を表わし、Ｒ^４はＨ、−ＣＨ_３、−ＣＨ_２ＣＯＯＨ（アンモニウム基又は金属塩を含む）又は−ＣＮを表わし、Ｘは−Ｈ、−ＣＯＯＨ（アンモニウム基又は金属塩を含む）又は−ＣＯＮＨ_２を表わし、Ｙは−ＣＯＯＨ（アンモニウム基又は金属塩を含む）、−ＳＯ_３Ｈ（アンモニウム基又は金属塩を含む）、−ＯＳＯ_３Ｈ（アンモニウム基又は金属塩を含む）、−ＣＨ_２ＳＯ_３Ｈ（アンモニウム基又は金属塩を含む）、−ＣＯＮＨＣ（ＣＨ_３）_２ＣＨ_２ＳＯ_３Ｈ（アンモニウム基又は金属塩を含む）又は−ＣＯＮＨＣＨ_２ＣＨ_２ＣＨ_２Ｎ^＋（ＣＨ_３）_３Ｃｌ⁻を表わす。〕

[Wherein 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, R ³ represents —H or —CH ₃ , R ⁴ represents H, —CH ₃ , —CH ₂ COOH (including an ammonium group or a metal salt) or —CN, and X represents —H, —COOH (including an ammonium group or a metal salt) or —CONH ₂ . , Y represents —COOH (including an ammonium group or a metal salt), —SO ₃ H (including an ammonium group or a metal salt), —OSO ₃ H (including an ammonium group or a metal salt), —CH ₂ SO ₃ H ( including an ammonium salt or a metal _{salt), - CONHC (CH 3)} 2 CH 2 SO 3 containing H (ammonium salt or a metal salt) or ^{_{-CONHCH 2 CH 2 CH 2 N +}} (CH 3) 3 Cl - represent ]

<18> A latent image forming step of forming an adhesive latent image composed of an adhesive composition on an image receiving material is an imagewise ink-jet ink containing a solvent capable of swelling the composition on the surface of the image receiving material. The method for producing a ceramic body with a picture according to any one of the above <1> to <11>, wherein the method comprises printing on the surface.

In the method for producing a picture ceramic body according to the present invention, it is not necessary to produce a lith film or the like at the time of image formation, and the picture ceramic body can be produced in a simple process and at low cost. In the present invention, since an image is formed through a latent image forming step of forming a latent image using an adhesive composition, an ink in which an inorganic pigment having a relatively large specific gravity is dispersed in an aqueous medium or the like is used. Therefore, an image can be stably formed without causing sedimentation of the inorganic pigment. Furthermore, since the inorganic pigment constituting the image is sintered on the surface of the ceramic body, the image has high storage stability.

The method for producing a picture-enclosed ceramic body of the present invention includes a latent image forming step in which a pressure-sensitive adhesive capable of bonding an inorganic pigment powder for image formation is applied imagewise on an image receiving material. Next, an inorganic pigment image is formed by applying an inorganic pigment powder to the surface of the image receiving material on which the adhesive latent image has been formed in the latent image forming step, and adhering the inorganic pigment to the adhesive latent image portion. A forming step. After passing through a step of forming a transparent glass layer forming layer and / or an overcoat layer forming step to form a transparent glass layer on the surface of the ceramic body on which the inorganic pigment image is formed, if necessary, the inorganic pigment image together with the image receiving layer An arrangement process and a sintering process are carried out on the surface of the ceramic body. By repeating the first latent image forming step and the inorganic pigment image forming step using the same pigment or a pigment having a different hue, a high-density or multicolor inorganic pigment image can be formed.
Hereinafter, various materials and processes that can be used in the method for producing a picture-coated ceramic body of the present invention will be described.

-Adhesive composition-
The pressure-sensitive adhesive composition that can be used in the latent image forming step is a composition that can adhere the inorganic pigment powder. Examples of the adhesive composition include (1) a liquid composition that imparts adhesiveness by swelling, softening, or plasticizing a substance constituting the image receiving layer, and (2) a liquid composition in which the adhesive substance is dissolved. (3) There is a liquid composition in which a hydrophobic composition having adhesiveness is dispersed in an aqueous liquid. The above (1), (2) and (3) will be described in order below.

(1) Liquid composition that imparts tackiness by swelling, softening, or plasticizing a substance constituting the image receiving layer This type of liquid composition can itself adhere inorganic powder, but the main function is In other words, the material constituting the image receiving layer is swollen, softened, or plasticized to impart adhesiveness. Examples of the liquid composition include water, organic solvents, surfactants, and mixtures thereof. Of these, water, organic solvents that are freely miscible with water at room temperature, surfactants miscible with water, and mixtures thereof are desirable. Further, the pressure-sensitive adhesive composition is preferably a material that does not chemically act on the inorganic pigment powder and does not cause a color development reaction or the like in the subsequent baking step, and is itself a colorless or light-colored material. preferable.

Specific examples of the water-miscible organic solvents include alcohols (eg, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol). , Hexanol, cyclohexanol, benzyl alcohol), polyhydric alcohols (eg ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexane Triol, thiodiglycol), glycol derivatives (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Lenglycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amine (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, Ethylene di Amine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N -Methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone) and the like. In addition, the said water miscible organic solvent may use 2 or more types together. Among these water-miscible organic solvents, those having a boiling point of 100 degrees Celsius or higher under normal temperature and normal pressure are preferable. Solution ejection stability is improved, non-ejection phenomenon during latent image formation and restart after standby can be prevented, and the reproducibility of inorganic powder adhesion can be improved because it is difficult to evaporate after printing. it can.

As the surfactants, any of anionic, cationic, nonionic and amphoteric surfactants can be used, but nonionic surfactants are preferred. When used by dissolving in water, it can be used at a concentration within the range that can be dissolved in water.
As the nonionic surfactant, a nonionic compound having an ethylene oxide group added as a hydrophilic group is particularly preferable. Use of a nonionic compound to which an ethylene oxide group has been added is preferred because it has a high affinity for the binder constituting the image receiving layer, and is easily swelled and plasticized, and therefore, the adhesiveness of the printed portion is likely to increase and a high resolution can be obtained. Examples of the nonionic compound include compounds represented by any one of the following general formulas (3) to (6).

In the general formula (3), 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 (4), R represents an alkyl group, and n represents an integer of 2 to 30, preferably 2 to 20. In the general formula (5), R represents an alkyl group, and n and l each represent an integer of 2 to 30, preferably 2 to 20. In the general formula (6), R ₁ and R ₂ represent hydrogen or an alkyl group, and m and n each represent an integer of 2 to 30, preferably 2 to 20. In the general formulas (3) to (6), the addition number of ethylene oxide is preferably 2 to 30, particularly preferably 2 to 20. Specific examples of the compounds represented by the general formulas (3) to (6) include polyoxyethylene (4) lauryl ether, polyoxyethylene (7) cetyl ether, polyoxyethylene (13) stearyl ether, polyoxy Examples include ethylene (5) oleyl ether, polyoxyethylene (10) nonyl phenyl ether, ethylene oxide-propylene oxide copolymer (n = 10, l = 7), ethylene oxide adduct of acetylene glycol (n + m = 10), and the like. It is not limited to these.

As the surfactant, fatty acid salt, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfosuccinate, alkyl diphenyl ether disulfonate, alkyl phosphate , Naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, alkylalkanolamine, alkylamine salt, alkylbetaine, mono- or dihydroxyacetylene compound, etc. Also mentioned.

(2) Liquid composition in which a sticky substance is dissolved This type of liquid composition is divided into two types, (2-1) aqueous composition and (2-2) solvent composition, depending on the solvent. .
(2-1) Examples of the aqueous composition include those obtained by dissolving a water-soluble polymer in water and further adding a water-miscible high boiling point organic solvent. The water-miscible high-boiling organic solvent works as an ink wetting agent to prevent clogging of the head when printing with an ink-jet printer, and at the same time, acts as a plasticizer for the water-soluble polymer, increasing the adhesiveness of the water-soluble polymer. However, the adhesion of the inorganic pigment to the image by the water-soluble polymer is increased.

Examples of the water-soluble polymer constituting the adhesive water-based composition include, for example, a polyvinyl alcohol resin (polyvinyl alcohol (PVA), acetoacetyl-modified polyvinyl alcohol, cation) which is a resin having a hydroxy group as a hydrophilic structural unit. Modified polyvinyl alcohol, anion modified polyvinyl alcohol, silanol modified polyvinyl alcohol, polyvinyl acetal, etc.], cellulose resin [methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC) ), Hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, etc.], chitins, chitosans, polysaccharides [starch, dextrin, Kisstran, pullulan, etc.], gum arabic, resin having ether bond [polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol (PEG), polyvinyl ether (PVE), etc.), resin having carbamoyl group [polyacrylamide ( PAAM), polyvinylpyrrolidone (PVP), polyacrylic hydrazide, etc.], vinyl alcohol-acrylic acid copolymer, isobutene-maleic anhydride copolymer, and the like.
In addition, polyacrylic acid salts having a carboxyl group as a dissociable group, maleic acid resin, alginate, gelatins (gelatin, acetylated gelatin, phthalated gelatin, oxidized gelatin, and the like) can also be exemplified.
In addition, compounds described in [0011] to [0014] of JP-A Nos. 2001-205919, 2002-264489, and JP-A No. 11-165461 are also exemplified.
These water-soluble resins may be used alone or in combination of two or more.
These water-soluble polymers are not tacky by themselves, but are tacky in the presence of water and / or the water-miscible high boiling organic solvent.

(2-2) Examples of the solvent-based composition include those obtained by dissolving an oil-soluble polymer in a solvent, and those obtained by adding a plasticizer or the like. Examples of the oil-soluble polymer include natural rubber, synthetic isobutylene rubber, acrylonitrile-butadiene copolymer, styrene butadiene copolymer, or a copolymer thereof, polyacrylate resin, polymethacrylate ester Resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, styrene-acrylic acid ester copolymer, styrene-maleic acid-acrylic acid ester copolymer, polyamide resin Polyester resin, polyvinyl acetate resin, cellulose derivative resin, polystyrene methacrylic resin, polyvinyl ether resin, polyurethane resin, polycarbonate resin, rosin resin, hydrocarbon resin, coumarone resin, coumarone-indene resin , Inden resin Polyterpene resins. Among these, those having a low Tg (glass transition point) are preferable. In particular, those having a Tg of 0 ° C. or less are preferred. As monomers constituting these low Tg polymers, ethyl acrylate, n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-octyl acrylate, n-decyl acrylate, iso-butyl acrylate, iso-pentyl acrylate, iso Particularly preferred are acrylics such as -octyl acrylate, 2-ethylhexyl acrylate, iso-decyl acrylate, and iso-octyl acrylate.

  In addition, it is preferable to use a tackifier alone or in combination with the oil-soluble polymer as the oil-soluble polymer. Examples of the tackifier include at least one selected from the group consisting of rosin derivative resins, terpene resins (for example, polymer β-pinene), coumarone-indene resins, and petroleum hydrocarbon resins. Specific examples of the petroleum hydrocarbon resins include aliphatic petroleum resins, aromatic petroleum resins, dicyclopentadiene petroleum resins, copolymer petroleum resins, hydrogenated petroleum resins, and alicyclic petroleum resins. Is mentioned. The aliphatic petroleum resin preferably has 5 carbon atoms, and the aromatic petroleum resin particularly preferably has 9 carbon atoms.

In order to increase the tackiness of the solvent-based composition, it is preferable to add a plasticizer or the like.
Examples of the plasticizer include esters, dimethylnaphthalene, diethylnaphthalene, diisopropylnaphthalene, dimethylbiphenyl, diisopropylbiphenyl, diisobutylbiphenyl, 1-methyl-1-dimethylphenyl-2-phenylmethane, 1-ethyl-1-dimethyl. Phenyl-1-phenylmethane, 1-propyl-1-dimethylphenyl-1-phenylmethane, triallylmethane (eg, tritoluylmethane, toluyldiphenylmethane), terphenyl compound (eg, terphenyl), alkyl compound, alkylation Examples include diphenyl ether (for example, propyl diphenyl ether), hydrogenated terphenyl (for example, hexahydroterphenyl), diphenyl ether, and the like.
Examples of the esters include phosphate esters such as triphenyl phosphate, tricresyl phosphate, butyl phosphate, octyl phosphate, cresyl phenyl phosphate; dibutyl phthalate, 2-ethylhexyl phthalate, ethyl phthalate, Phthalic acid esters such as octyl phthalate and butyl benzyl phthalate; Dioctyl tetrahydrophthalate; Benzoic acid esters such as ethyl benzoate, propyl benzoate, butyl benzoate, isopentyl benzoate and benzyl benzoate; Ethyl abietic acid, abietic acid Abietic acid esters such as benzyl; dioctyl adipate; isodecyl succinate; dioctyl azelate; oxalic acid esters such as dibutyl oxalate and dipentyl oxalate; diethyl malonate; dimethyl maleate, diethyl maleate, di maleate Maleic acid esters such as chill; Tributyl citrate; Sorbic acid esters such as methyl sorbate, ethyl sorbate, and butyl sorbate; Sebacic acid esters such as dibutyl sebacate and dioctyl sebacate; Formic acid monoesters and diesters, butyric acid monoesters And ethylene glycol esters such as diester, lauric acid monoester and diester, palmitic acid monoester and diester, stearic acid monoester and diester, oleic acid monoester and diester; triacetin; diethyl carbonate; diphenyl carbonate; ethylene carbonate; propylene carbonate And boric acid esters such as tributyl borate and tripentyl borate. In addition, it can be appropriately selected from the high boiling point oils described in JP-A-2-141279.

(3) Liquid composition in which an adhesive hydrophobic composition is dispersed in an aqueous liquid The adhesive hydrophobic composition dispersed in an aqueous liquid includes the solvent system of (2-2) above. Oil-soluble polymers, oil-soluble polymers and plasticizers used in the composition are used. The oil-soluble polymer dispersion can be synthesized by emulsion polymerization or the like. When the oil-soluble polymer is in a liquid state, it can be emulsified and dispersed in an aqueous liquid as it is. When the oil-soluble polymer is solid at normal temperature, it can be melted at high temperature to be emulsified and dispersed, or dissolved and dissolved in a low boiling point organic solvent. When emulsifying and dispersing, it is preferable to add and disperse the plasticizer in the organic phase in order to increase the adhesiveness of the oil-soluble polymer. Alternatively, the plasticizer can be infiltrated into the oil-soluble polymer by mixing and stirring the emulsified dispersion containing the plasticizer and the dispersion of the oil-soluble polymer. When dispersing an oil-soluble polymer or the like in an aqueous liquid, the oil-soluble polymer can be dispersed without a surfactant by adding a small amount of carboxyl group, sulfonic acid group, hydroxyl group, etc. It can also be dispersed using an agent. Furthermore, it is preferable to add a dispersion stabilizer at the time of dispersion or after dispersion so that the dispersion does not aggregate with time.

As the dispersion stabilizer, a terminal hydrophobic group-modified water-soluble polymer is preferable.
Here, the terminal hydrophobic water-soluble polymer is not particularly limited as long as it can stably exist without causing the adhesive composition or the like to aggregate in an aqueous liquid. A compound represented by the general formula (1) or a compound represented by the following general formula (2) is preferable.

〔但し、式（１）中、Ｒは疎水性基又は疎水性重合体を表し、ｎは整数を表す。〕

[In the formula (1), R represents a hydrophobic group or a hydrophobic polymer, and n represents an integer. ]

General formula (2): R ′-(SP) _n
[In the formula (2), R ′ represents a hydrophobic group or a hydrophobic polymer, P contains at least one of the following structural units A, B and C, and has a polymerization degree of 10 or more and 3500 or less. Represents. n represents 1 or 2.

ここで、Ｒ^１は−Ｈ又は炭素数１〜６のアルキル基を表わし、Ｒ^２は−Ｈ又は炭素数１〜１０のアルキル基を表わし、Ｒ^３は−Ｈ又は−ＣＨ_３を表わし、Ｒ^４はＨ、−ＣＨ_３、−ＣＨ_２ＣＯＯＨ（アンモニウム基又は金属塩を含む）又は−ＣＮを表わし、Ｘは−Ｈ、−ＣＯＯＨ（アンモニウム基又は金属塩を含む）又は−ＣＯＮＨ_２を表わし、Ｙは−ＣＯＯＨ（アンモニウム基又は金属塩を含む）、−ＳＯ_３Ｈ（アンモニウム基又は金属塩を含む）、−ＯＳＯ_３Ｈ（アンモニウム基又は金属塩を含む）、−ＣＨ_２ＳＯ_３Ｈ（アンモニウム基又は金属塩を含む）、−ＣＯＮＨＣ（ＣＨ_３）_２ＣＨ_２ＳＯ_３Ｈ（アンモニウム基又は金属塩を含む）又は−ＣＯＮＨＣＨ_２ＣＨ_２ＣＨ_２Ｎ^＋（ＣＨ_３）_３Ｃｌ⁻を表わす。〕

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, R ³ represents —H or —CH ₃ , R ⁴ represents H, —CH ₃ , —CH ₂ COOH (including an ammonium group or a metal salt) or —CN, X represents —H, —COOH (including an ammonium group or a metal salt) or —CONH ₂ ; Y is —COOH (including an ammonium group or a metal salt), —SO ₃ H (including an ammonium group or a metal salt), —OSO ₃ H (including an ammonium group or a metal salt), —CH ₂ SO ₃ H (ammonium containing group or a metal _{salt), - CONHC (CH 3)} 2 CH 2 SO 3 containing H (ammonium salt or a metal salt) or ^{_{-CONHCH 2 CH 2 CH 2 N +}} (CH 3) 3 Cl - represent. ]

In the general formula (1), R represents a hydrophobic group or a hydrophobic polymer, and n represents an integer. The n is preferably 2 to 30, and more preferably 4 to 20. Here, when n is 2 to 30, it is water-soluble and satisfies the effects of the present invention.

Examples of the hydrophobic group of R in the general formula (1) include aliphatic groups (for example, alkyl groups, alkenyl groups, alkynyl groups, etc.), aromatic groups (for example, phenyl groups, naphthyl groups, etc.) and alicyclic groups. Yes, and these include substituted ones. As the substituent, aliphatic group, aromatic group, alicyclic group, heterocyclic group, halogen atom, hydroxyl group, cyano group, nitro group, N-substituted sulfamoyl group, carbamoyl group, acylamino group, alkylsulfonylamino group, aryl Examples include a sulfonylamino group, an alkoxy group, an aryloxy group, an aralkyl group, and an acyl group. When the hydrophobic group of R in the general formula (1) is an alkyl group, it has 3 to 70 carbon atoms, preferably 4 to 50 carbon atoms, particularly 8 to 24 carbon atoms, and among them, 12 is preferable.

When R in the general formula (1) is a hydrophobic polymer, polystyrene and its derivatives, polymethacrylic acid ester (for example, polymethyl methacrylate) and its derivatives, polyacrylic acid ester and its derivatives, polybutene, poly Water-insoluble vinyl polymers and vinyl copolymers typified by vinyl acetate and vinyl versatate, water-insoluble polyoxyalkylenes such as polyoxypropylene and polyoxytetramethylene, and polyamides and polyesters And water-insoluble polymers such as In particular, polystyrene and derivatives thereof, polymethacrylic acid esters and derivatives thereof, polyacrylic acid esters and derivatives thereof, and polyvinyl chloride are preferably used. The degree of polymerization of the hydrophobic polymer is 2 or more and 500 or less, preferably 2 or more and 200 or less, and more preferably 2 or more and 100 or less.

Specific examples in the case where R in the general formula (1) is a hydrophobic group are given below, but the present invention is not limited thereto.

The amount of the compound of the general formula (1) used in the present invention varies depending on the various hydrophobic dispersions in the coating layer to be used and the amount thereof, but is usually about 0. 0 to various hydrophobic dispersions in the aqueous liquid. It is 1-40 mass%, Preferably it is 1-20 mass%.

The compound represented by the general formula (1) includes a wide range of compounds from water-soluble to water-dispersible. The compound represented by the general formula (1) can be synthesized, for example, by a method described in Japanese Patent Application Laid-Open No. 09-157384. As a specific example of the compound represented by the general formula (1), for example, ML-10 (terminal alkylpolyglycerin) is marketed by Daicel Corporation.

Although the action of stably presenting various hydrophobic dispersions of the compound represented by the general formula (1) in an aqueous liquid without aggregation is not clear, this compound has a hydrophobic group in the molecule, In addition, since it has polymer units (water-soluble parts), it adheres firmly to the fine particle surface at a single point due to the affinity between the surface of various hydrophobic fine particles and this hydrophobic group, and has an affinity for the dispersion medium on the dispersion medium side. It is considered that a high polymer unit exists and contributes to the dispersion stability of the fine particles.

Next, as a typical example of the compound represented by the general formula (2), a vinyl containing a random or block copolymer of vinyl alcohol and a vinyl ester, or a third monomer component having an anionic group such as a carboxyl group. Examples of the random or block copolymer of alcohol and vinyl ester are modified with an alkyl group or a hydrophobic polymer.

The polyvinyl alcohol (PVA) polymer is conventionally used in the photographic field as a protective colloid itself or blended with a water-soluble protein protective colloid such as gelatin to improve the strength of the film (for example, JP-A 63-20349) agglomerates various hydrophobic dispersions in an aqueous liquid by using the compound represented by the formula (2) in an aqueous dispersion of an adhesive composition according to the present invention. Therefore, the production stability can be greatly improved.

One feature of the compound represented by the general formula (2) of the present invention is that it has a relatively higher molecular weight than the surfactants conventionally used in the photographic field. In contrast to a nonionic alkylene oxide group such as ethylene oxide, an anionic group such as a carboxyl group, a sulfone group, and a phosphoric acid group, and a cationic group such as a quaternary ammonium group as a functional group, The hydrophilic group of the compound represented by the general formula (2) of the present invention is any one or more of a repeating structure of a monomer unit containing an OH group, a repeating structure of an anionic group, and a repeating structure of a cationic group. The repeating structure is considerably larger than that of the conventional surfactant. Thus, when a hydrophilic part is large and a polyanion or a polycation is present, a large electrostatic repulsive force is generated between the dispersed particles. Furthermore, the compound represented by the general formula (2) of the present invention is strongly adsorbed at one point on the surface of the fine particles and adsorbed between the particles due to the affinity between the surface of various hydrophobic fine particles and this hydrophobic group. Since there is no cross-linking, cross-linking and aggregation are difficult to occur. It is presumed that the remarkable effects of the present invention are brought out by these.

Examples of the hydrophobic group for R ′ in the general formula (2) include an aliphatic group (for example, alkyl group, alkenyl group, alkynyl group, etc.), an aromatic group (for example, phenyl group, naphthyl group, etc.) and an alicyclic group. And these include substituted ones. As the substituent, aliphatic group, aromatic group, alicyclic group, heterocyclic group, halogen atom, hydroxyl group, cyano group, nitro group, N-substituted sulfamoyl group, carbamoyl group, acylamino group, alkylsulfonylamino group, aryl Examples include a sulfonylamino group, an alkoxy group, an aryloxy group, an aralkyl group, and an acyl group.

When the hydrophobic group of R ′ in the general formula (2) is an alkyl group, it has 3 to 70 carbon atoms, preferably 4 to 50 carbon atoms, and particularly preferably 8 to 24 carbon atoms. Further, R 'is a substituted or unsubstituted alicyclic group, aromatic hydrocarbon group or hydrophobic polymer, and is highly compatible with various hydrophobic dispersions, etc., and has the effect of increasing dispersion stability. large.

When R ′ in the general formula (2) is a hydrophobic polymer, polystyrene and its derivatives, polymethacrylic acid ester (for example, polymethyl methacrylate) and its derivatives, polyacrylic acid ester and its derivatives, polybutene, poly Water-insoluble vinyl polymers and vinyl copolymers typified by vinyl acetate and vinyl versatate, water-insoluble polyoxyalkylenes such as polyoxypropylene and polyoxytetramethylene, and polyamides and polyesters And water-insoluble polymers such as In particular, polystyrene and derivatives thereof, polymethacrylic acid esters and derivatives thereof, polyacrylic acid esters and derivatives thereof, and polyvinyl chloride are preferably used. The degree of polymerization of the hydrophobic polymer is 2 or more and 500 or less, preferably 2 or more and 200 or less, and more preferably 2 or more and 100 or less.

Specific examples in the case where R ′ in the general formula (2) is a hydrophobic group include the same as the specific examples of R in the general formula (1), but are not limited thereto.

Regarding the compound represented by the general formula (2), the polymer P is a polymer including at least one of the 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 P include vinyl acetate, vinyl formate, vinyl propionate, and α-substituted products thereof. Further, as the structural unit C constituting the polymer P, acrylic acid, methacrylic acid or crotonic acid (including ammonium salts or metal salts such as Na and K, respectively), maleic acid or itaconic acid (monoalkyl esters and ammonium salts, respectively) Or a metal salt such as Na or K), vinyl phosphonic acid, vinyl sulfuric acid, acrylic sulfonic acid, methacryl sulfonic acid, 2-acrylamido-3-methylpropane sulfonic acid or 2-methacrylamide-3-methylpropane sulfonic acid Monomer units that ionically dissociate in water, such as ammonium salts (or metal salts such as Na and K, respectively), acrylamidopropyltrimethylammonium chloride, and methacrylamidopropyltrimethylammonium chloride.

Among these, the structural unit A is a vinyl alcohol unit, the structural unit B is a vinyl acetate unit, and the structural unit C is acrylic acid (including ammonium salts or metal salts such as Na and K) or maleic. Acid or itaconic acid (each containing an ammonium salt or a metal salt such as Na or K) is a more preferred unit.

The content of the structural units A, B and C constituting the polymer P is not particularly limited, but when the content of the structural unit C is 1 mol% or less, the polymer represented by the general formula (2) is water-soluble. In order to be water-soluble or water-dispersible, the content of the structural unit A is preferably 50 mol% to 100 mol%.

The compound represented by the general formula (2) includes a wide range of compounds from water-soluble to water-dispersible. As long as the compound represented by the general formula (2) is water-soluble or water-dispersible, the polymer P may contain structural units other than the structural units A, B, and C. Examples of the structural unit include ethylene, propylene, isopten, acrylonitrile, acrylamide, methacrylamide, N-vinyl pyrrolidone, vinyl chloride, and vinyl fluoride units. The degree of polymerization of the polymer P is 10 to 3500, preferably 10 to 2000, more preferably 10 to 1000, and particularly preferably 10 to 500.

Examples of the lower alkyl group of R ² in the structural units A and B of the polymer P include an alkyl group having 1 to 10 carbon atoms, and a methyl group is particularly preferable. 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 (2) of the present invention is different in the optimum chemical composition, molecular weight, etc. of P and R ′ constituting the compound depending on the purpose of the present invention. Those having a mass ratio of 0.001 ≦ R ′ / P ≦ 2, more preferably 0.01 ≦ R ′ / P ≦ 1, are particularly effective.

Specific examples of the compound represented by the general formula (2) in the present invention are listed as compounds P-1 to P-37 in Tables 1 to 4, but the present invention is not limited thereto. In Tables 1 to 4, R, P, A, B, C, and n are as described in the general formula (2).

The amount of the compound of the general formula (2) used in the present invention varies depending on the various hydrophobic dispersions in the coating layer to be used and the amount thereof, but with respect to the various hydrophobic dispersions in the aqueous liquid usually used. It is 0.1-40 mass%, Preferably it is 1-20 mass%.

The compound represented by the general formula (2) is described in, for example, JP-A-62-288643, JP-A-61-254237, JP-A-61-254238, JP-A-61-254239, and JP-A-61-254240. Can be synthesized by the methods described. In addition, when the polymer R ′ in the polymer of the general formula (2) is an alkyl group, it is also available as a commercial product (for example, MP-103, MP-203, MP102, etc .; manufactured by Kuraray Co., Ltd.) .

An adhesive composition may be used individually by 1 type, or 2 or more types may be mixed and used for it. For adhesive compositions, surface tension modifiers, antifungal agents, viscosity modifiers, pH adjusters, etc., for the purposes of adjusting ejection suitability when ejected as droplets, preventing droplet diffusion, and improving storage stability An agent, an antifoaming agent, etc. can be contained in the range which does not impair the effect of this invention.

-Image receiving sheet-
The image receiving layer is usually provided on a support and is used in the form of an image receiving sheet comprising the support and the image receiving layer. The image-receiving sheet may have a configuration in which at least one image-receiving layer is provided on a support, and one or more peeling layers are provided between the support and the image-receiving layer as desired.

Examples of the support for the image receiving sheet include ordinary sheet-like substrates such as a plastic sheet, a metal sheet, a glass sheet, and paper. Examples of the plastic sheet include a polyethylene terephthalate sheet, a polycarbonate sheet, a polyethylene sheet, a polyvinyl chloride sheet, a polyvinylidene chloride sheet, a polystyrene sheet, a styrene-acrylonitrile sheet, and a polyester sheet. Further, as the paper support, printing paper having good smoothness, coated paper or the like can be used. In the case where the inorganic pigment image is arranged together with the entire image receiving sheet in the arrangement step, the support needs to be evaporated and / or incinerated in the sintering step. It is preferred not to contain atoms or compounds that do not disappear or to contain atoms or compounds that react with the pigment and change color. It is preferable to provide a back layer for improving transportability on the surface of the support opposite to the image receiving layer.

The thickness of the support of the image receiving sheet is usually 10 to 400 μm, preferably 25 to 200 μm. Further, the surface of the support may be appropriately subjected to surface treatment such as corona discharge treatment or glow discharge treatment in order to adjust the adhesion with the image receiving layer.

The image receiving layer on the surface of the image receiving sheet is preferably a layer mainly composed of an organic polymer binder. The binder is preferably water or a solvent swellable polymer. Examples thereof include the water-soluble polymer described in (2-1) of the adhesive composition and the oil-soluble polymer described in (2-2).

The oil-soluble polymer layer is preferably crosslinked with a crosslinking agent. As the crosslinking agent, an isocyanate compound, an active ester compound, an aldehyde compound, an epoxy compound, or the like can be preferably used.
The said crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type.

The thickness of the image receiving layer is generally 0.1 to 20 μm, preferably 0.5 to 10 μm.

It is preferable that the image-receiving sheet can be adhered to the surface of the ceramic body because the operation is facilitated even when a ceramic body having a curved surface such as a dish or a bottle is used. Examples of the image receiving sheet include (a) a sheet having a layer made of the water-soluble polymer (hereinafter sometimes referred to as “water-soluble polymer layer”) on the water-permeable support as an image-receiving layer; A sheet having a structure in which the water-soluble polymer layer is formed on a water-soluble support and an image receiving layer (hereinafter sometimes referred to as “oil-soluble polymer layer”) is formed on the water-soluble polymer layer; Sheet having a structure in which a release layer and the oil-soluble polymer layer are sequentially formed on (4) a sheet having a structure in which the oil-soluble polymer layer is formed on a film support.

Examples of the support include paper support, polyethylene terephthalate, polyamide, polycarbonate, glassine paper, cellulose ester, fluoropolymer, polyether, polyacetal, polyolefin, polyimide, polyphenylene sulfide, polypropylene, polysulfone, cellophane, polyethylene terephthalate, and the like. It is done. Examples of the water permeable support include a paper support and a film support having a through hole. When the support is a plastic film, it is preferable that the surface (the surface on which the water-soluble polymer layer is formed) has a release layer containing silicone, higher fatty acid, fluorine compound, or the like, Moreover, you may be comprised only from this mold release layer.

In the case of a sheet having a water-soluble polymer layer as an image receiving layer on the support (a), after forming an inorganic pigment image on the image receiving sheet, an oil-soluble polymer layer is formed as an overcoat layer on the surface. It is preferably provided by coating, transferring or the like. The oil-soluble polymer used as the overcoat layer has a glass transition temperature of room temperature or lower, preferably 10 ° C. or lower, particularly preferably 0 ° C. or lower. Resins used as overprint lacquers for ceramics such as ceramics are preferably used, and examples thereof include acrylic resins and urethane resins.

In the case of the image-receiving sheet having the constitutions (a) and (b), when immersed in water, a part of the water-soluble polymer is dissolved and the oil-soluble polymer layer can be peeled from the paper support. At this time, in the case of (A), the inorganic pigment image formed on the water-soluble polymer layer adheres to and peels off from the oil-soluble polymer layer side provided by coating or transferring thereon. At this time, since the water-soluble polymer partially adheres to the oil-soluble polymer layer side, it can be adhered by arranging the peeled surface as it is toward the surface of the ceramic body such as a ceramic plate.
On the other hand, in the case of the image receiving sheet having the structure (b), an inorganic pigment image is formed on the surface of the oil-soluble polymer layer. In this case, the peeled surface can be bonded to the ceramic body as in the case of (A), but the inorganic pigment image-forming surface faces the ceramic body surface and the aqueous solution of the water-soluble polymer is used as a paste. It is preferable to bond via this. The image formed on the image receiving layer is preferably a mirror image (reversed image). In this case, since the hydrophobic polymer layer is not interposed between the image and the surface of the ceramic body, it is preferable because the sintering of the inorganic pigment and the ceramic body proceeds more stably in the subsequent sintering step.
When the image receiving sheet having the structure (c) is used, an oil-soluble polymer layer on which an image is formed without being immersed in water by performing a surface treatment for forming a release layer on the film in advance as described above. Can be peeled from the support. The peeled oil-soluble polymer layer is formed with an inorganic pigment image and can be adhered to the surface of a ceramic body such as a ceramic plate via a paste.

Further, the image receiving layer is coated on a support having low adhesion to the image receiving layer as described in (d) above, or the image receiving layer is coated on the release layer applied as described in (c) above. If provided, inorganic pigment images are formed on the surfaces of these image receiving layers, and then the image receiving paper (a) and the coated surface are overlapped with each other and passed through a heat roller or the like, and transferred together with the image receiving layer. After the image receiving paper of type (a) to which the image has been transferred is immersed in water as described above, the paper support may be peeled off and disposed with the oil-soluble polymer layer (image receiving layer) on the surface of the ceramic body. it can.
Further, the image receiving layer is coated on a support having low adhesion to the image receiving layer as described in (d) above, or the image receiving layer is formed on the release layer applied as described in (c) above. In the case of coating, after forming inorganic pigment images on the surface of these image receiving layers, they can be superposed on the surface of the ceramic body and passed through a heat roll or the like to be transferred together with the image receiving layer. At this time, if the adhesiveness to the ceramic body is insufficient, the adhesive can be bonded via an adhesive. As the adhesive, the water-soluble polymer and oil-soluble polymer having the above-mentioned tackiness are useful. The adhesive layer can also be provided by applying the pressure-sensitive adhesive composition, or can be transferred by applying pressure and / or heating while superposing the material on which the adhesive layer is applied and the ceramic body. It can also be provided.

-Latent image formation process-
In the latent image forming step, the pressure-sensitive adhesive composition may be imagewise applied to the surface of the image receiving layer. In order to apply the adhesive composition to the surface of the image receiving layer like an image, a known ink jet recording type image forming method can be used. For example, a liquid adhesive composition is filled in an inkjet head having a heating element inside, and electricity is supplied to the heating element at a predetermined position in accordance with image information to cause the heating element to generate heat. The solvent of water (water, organic solvent, etc.) is boiled, the pressure in the head is increased, and the adhesive composition at a desired position can be ejected as droplets and landed on any surface of the image receiving layer . In addition, the adhesive composition can be applied to the surface of the image receiving layer in an image-like manner by using various ink jet recording methods such as an ink jet recording method using a piezo element. A method using a piezo element is preferable for the image forming method of the present invention.

-Inorganic pigment image formation process-
The adhesive latent image formed by the latent image forming step is sprinkled with an image forming inorganic pigment powder, and further lightly rubbed with a brush or the like, or the image receiving material is vibrated, thereby causing the adhesive latent image portion to adhere to the adhesive latent image portion. The inorganic pigment adheres to form an inorganic pigment image.

As the inorganic pigment for image formation used in the present invention, a powder composition comprising a colorant and a glass component (frit) is used. The powder composition includes a method using a mixture of a colorant and a glass component, a method in which a mixture of a colorant and a glass component is once heated and melted, cooled and solidified, and pulverized. is there. Alternatively, only a colorant is used as an inorganic pigment for image formation, and applying the glass component onto the image after forming the pigment image, or by uniformly coating or transferring the glass component on the pigment image, improves resolution. Is preferable.

As the inorganic pigment (colorant), the crystal structure of copper oxide, cobalt oxide or the like has a spinel, sphene, picroir, rutile, pridelite, phosphate, phenacite, perryclays, olivine, badelite, borate, corundum, Metal oxides such as zircon; sulfides such as cadmium yellow; cadmium selenide compounds such as selenium red; gold colloids and silver colloids.
Usually, two or more of these colorants are mixed, heated and melted to form an alloy. In addition, an inorganic pigment that is a fluorescent pigment or a phosphorescent pigment can also be used.

When the glass component is used in combination, it is preferable in the sintering process because the adhesion of the inorganic pigment to the surface of the ceramic body can be improved. Examples of the glass component include alkali metal compounds such as lithium carbonate, sodium carbonate, potassium carbonate, lead oxide, and bismuth oxide; alkaline earth metal compounds such as barium carbonate, strontium carbonate, calcium carbonate, magnesium carbonate, and zinc oxide; aluminum oxide And neutral components such as aluminum hydroxide; acidic components such as silicon oxide, boric acid, zirconium oxide, and titanium oxide; Also, feldspar such as borax, lime feldspar, potash feldspar, soda feldspar, betalite (lithium feldspar), kaolin, quartzite, alumina, silica, quartz, titanium oxide, lead oxide, chamotte, earth ash, limestone, magnesite, Natural minerals such as talc and dolomite and composite components can also be used. The glass component can be used as a so-called frit by dissolving one kind alone or a mixture of two or more kinds.

As a content of the colorant and the glass component (including natural minerals in the previous period), the weight ratio of the colorant to the glass component is preferably 2/8 to 6/4, and particularly preferably 3/7 to 5/5. When the glass component is increased from 2/8, the color density of the image after firing is lowered, and when the glass component is decreased from 6/4, the sinterability of the inorganic pigment image after firing is lowered, and the inorganic pigment image is reduced. It becomes easy to peel from the ceramic body.

-Transparent glass layer formation process-
After the inorganic pigment image is formed on the image receiving paper, it is preferable to provide a transparent glass forming layer on the surface and form the transparent glass layer by firing after the arranging step. With this transparent glass layer, even when the inorganic pigment content in the inorganic pigment image formed in the above-described image forming step is high, the ceramic body is easily sintered strongly, the hue becomes brighter, and the gloss of the surface is improved. The weather resistance and scratch resistance of the image are further improved. The transparent glass forming layer is preferably formed, for example, by the following methods (a) to (c).

(A) After spraying the ink containing the adhesive composition uniformly on the entire surface of the image receiving paper on which the inorganic pigment image has been formed, the transparent glass layer forming substance powder is sprinkled and adhered, and transparent by firing. A transparent glass layer forming layer for forming a transparent glass layer is uniformly formed.

(B) A liquid containing a transparent glass layer forming material is sprayed on the entire surface of the image receiving paper on which the inorganic pigment image has been formed to uniformly form the transparent glass layer forming layer.

(C) A coated surface of a transfer sheet in which a transparent glass layer-forming layer containing a transparent glass layer-forming substance and a thermoplastic polymer is coated on the entire surface of an image receiving paper on which an inorganic pigment image is formed. Superimposing and peeling the support after thermocompression bonding, the transparent glass layer forming layer is uniformly transferred onto the surface of the image receiving paper.

As the transparent glass layer forming component (glass component), flux, for example, lithium carbonate, sodium carbonate, potassium carbonate, lead oxide, bismuth oxide, barium carbonate, strontium carbonate, calcium carbonate, magnesium carbonate, sodium oxide, potassium oxide, Examples thereof include calcium oxide, zinc oxide, aluminum oxide, aluminum hydroxide, silicon oxide, boric acid, zirconium oxide, and titanium oxide. In addition, limestone, potassium feldspar, soda feldspar, betalite (lithium feldspar) and other feldspars, kaolin, quartzite, alumina, silica, quartz, titanium oxide, chamotte, borax, etc. The flux mentioned above may be used singly or as a mixture of two or more, and may be used alone or in combination of two or more so as to be used as a so-called frit.

-Cover coat layer formation process-
In the cover coat layer forming step, a cover coat layer is formed on the image receiving paper on which the inorganic pigment image is formed or on the image receiving paper on which the transparent glass layer forming layer is further formed. The method for forming the cover coat layer may be either a method by coating or a method of transferring using a transfer material.

The cover coat layer includes at least a hydrophobic polymer. By mainly comprising a hydrophobic polymer, the inorganic pigment image is distorted on the surface of the cover coat layer when the support of the image receiving material is peeled off by immersion in a liquid such as water in the arrangement step described later. It functions as a support material that can be held without any trouble and does not interfere with the image. The hydrophobic polymer is preferably a polymer having a glass transition point of room temperature (use environment temperature) or lower from the viewpoint of enabling adhesion and transfer to an uneven surface or curved surface. Here, the operating environment temperature or lower means 25 ° C. or lower. Furthermore, as said glass transition point, -50-25 degreeC is preferable and -30-15 degreeC is more preferable. Specific examples of commercially available products include cover coat resin LO-210, LO-176S, LO-200H, LO-170H, and LO-170H manufactured by Kyoyo Chemical Industry Co., Ltd.

When the cover coat layer is formed by coating, a coating solution in which at least a hydrophobic polymer is dissolved or dispersed in an appropriate solvent is prepared, and the coating solution is prepared by a known method such as a rod coating method, a silk screen method, or a blade method. It can be formed by applying and drying on the surface of the image receiving layer on which the inorganic pigment image has been formed by a coating method.

When the cover coat layer is formed by transfer, a transfer material having at least a cover coat layer on a temporary support is used, and in the image forming step, the surface of the image receiving layer on which the inorganic pigment image is formed and the transfer having the cover coat layer The cover coat layer surface of the material is heated at least in contact with the cover coat layer, and the cover coat layer is transferred onto the image receiving layer. That is, the cover coat layer is overlaid so as to cover the inorganic pigment image, and in this state, the laminate is formed by being in close contact with heating. Thereafter, the temporary support of the transfer body is peeled and removed from the laminate, whereby the cover coat layer can be transferred and formed on a part or the entire surface of the image receiving layer.

In the process of heating to form a laminate, heating may be performed while applying pressure. For example, the two layers are laminated by laminating with a device (for example, a heat roll laminator) equipped with a pair of heating nip rollers incorporating heating means such as a heater. It can be adhered. In general, the heating temperature during heating is preferably 50 to 200 ° C.

The transfer material has at least a cover coat layer on the surface of the temporary support, and other layers such as a frit layer and a cover sheet may be provided as necessary. Here, there is no restriction | limiting in particular as said temporary support body and a coating sheet, The thing similar to the temporary support body and coating sheet which comprise the transfer sheet mentioned above can be used. It is also preferable to provide a release layer between the temporary support and the cover coat layer. Preferable examples of the release layer include a layer mainly composed of polyvinyl alcohol or a modified product thereof, a silicone resin, and the like.

The cover coat layer may contain the glass component (a heat-meltable inorganic substance, frit, flux). By including a glass component, even when the inorganic pigment content in the inorganic pigment image formed in the above-described image forming step is high, the ceramic body is easily strongly sintered, and the image stability after sintering, And surface glossiness can also be improved.

  As content of the said glass component, 1-100 mass% is preferable with respect to the hydrophobic polymer content (mass) in a covercoat layer.

The layer thickness of the cover coat layer is preferably 5 to 50 μm, and more preferably 10 to 30 μm. When the layer thickness is less than 5 μm, workability in the placement step may be deteriorated, and when it exceeds 50 μm, the quality may be deteriorated during firing.

As described above, the glass component layer is preferably not provided on the cover coat layer or provided on the surface of the cover coat layer on the side not in contact with the temporary support. The glass component layer includes at least a glass component (a heat-meltable inorganic substance) and a thermoplastic resin, and the layer thickness of the layer is preferably 1 to 20 μm. As content of the glass component in the said glass component layer, 5-100 mass% is preferable with respect to a thermoplastic resin content (mass). The thermoplastic resin can be appropriately selected from known ones such as an amorphous organic polymer having a softening point of 40 to 150 ° C.
Examples of the thermoplastic resin include those described in paragraph No. [0012] of JP-A-9-197719. From the viewpoint of ensuring sufficient adhesiveness, ethylene-vinyl acetate resin and butyral resin are exemplified. A terpene phenol resin, an acrylic resin or the like is preferably used.

-Placement process-
In the arranging step, the machine pigment image is arranged on the surface of the ceramic body together with the cover coat layer before or after peeling off the support of the image receiving material. The arrangement on the surface of the ceramic body can be performed by heat-pressing the inorganic pigment image together with at least the cover coat layer on the surface of the ceramic body as necessary. The arrangement method may be arranged by interposing a water-soluble polymer layer as an adhesive between the ceramic body and the inorganic pigment image depending on the mode of the image receiving material, or the inorganic pigment image of the cover coat layer or the image receiving layer. You may arrange | position the surface of the side which has this to oppose the ceramic body surface. In the former, a desired image (normal image) is formed on the ceramic body, and in the latter, a mirror-inverted image of the desired image is formed on the ceramic body.

When an image-receiving sheet having a water-soluble polymer-containing layer and an image-receiving layer on the surface of the water-permeable support is used, a part of the image-receiving material on the water-permeable support side after the image forming step and the cover coat layer forming step The substrate is contacted or immersed in a liquid such as water to dissolve a part of the water-soluble polymer, and the support is peeled and removed. And can be disposed on the surface of the ceramic body. Therefore, in this case, a liquid in which the paste is dissolved or dispersed is not necessary for placement. In addition, when the support is a plastic film support, the plastic film is immersed in a liquid such as water without being immersed in a liquid such as water by preliminarily performing a surface treatment for imparting releasability to the plastic film support as described later. The support can be easily peeled off. In this case, it can arrange | position to the ceramic body surface through the liquid which melt | dissolved or disperse the paste. When the plastic film itself has releasability from the inorganic pigment image and the cover coat resin, the surface treatment may not be performed. In this case, it can also arrange | position to a ceramic body surface through the liquid which melt | dissolved or disperse | distributed the adhesive agent, and can also arrange | position by thermocompression bonding via a hot-melt-adhesive. Here, the liquid such as water may be appropriately selected from those capable of dissolving the water-soluble polymer in the image receiving material, such as a mixed solution of not only water but also water and a solvent compatible with the water. .

In the above, as the solution in which the paste is dissolved or dispersed, for example, as a paste in water, for example, a water-soluble polymer (for example, gelatin, starch, dextrin, hydroxyethyl cellulose, etc.), latex or emulsion (for example, polyester resin, ethylene, etc.) , Vinyl acetate resin, acrylic resin, etc.) and the like.

Examples of the ceramic body include ceramic plates, ceramics, ceramic plates, ceramics, enamels, and other ceramic materials used for building materials such as tiles. The shape and thickness of the ceramic body can be appropriately selected depending on the purpose and application.

-Sintering process-
In the sintering step, the ceramic body on which the inorganic pigment image is arranged is heated to sinter the inorganic pigment on the surface of the ceramic body. The inorganic pigment is sintered on the surface of the ceramic body, and the components other than the inorganic pigment, that is, the components such as the image receiving layer disposed on the surface of the ceramic body together with the image are evaporated or incinerated. The heating of the ceramic body is preferably performed using, for example, an electric kiln from the viewpoint of temperature control, color developability, and the like. The heating conditions can be appropriately set according to the selected material, the volume of the ceramic body, the size of the image, and the like. It is preferable that heating is performed by gradually raising the temperature to the firing temperature, or after heating at a constant temperature from 300 ° C. to 500 ° C. for a certain time, and then gradually raising the temperature to the firing temperature. Firing is preferably performed at a firing temperature of usually 650 ° C. to 900 ° C., preferably 700 ° C. to 850 ° C., and a firing time of 1 to 8 hours when an upper paint is used as the inorganic pigment. When a lower paint is used as the inorganic pigment, the firing temperature is preferably 1000 ° C. to 1300 ° C., preferably 1100 ° C. to 1250 ° C., and the firing time is preferably 1 to 12 hours.

In the sintering step, components other than the inorganic pigment in the transfer material and components such as the image receiving layer disposed on the surface of the ceramic body together with the image are evaporated or incinerated. Therefore, the materials (components in the transfer layer and components in the image receiving layer) disposed on the surface of the ceramic body together with the inorganic pigment during the sintering process contain atoms or compounds that do not disappear by evaporation or combustion in the sintering process. It is preferable not to contain atoms or compounds that react with inorganic pigments and change color.

The ceramic body with a picture produced by the production method of the present invention can be used for, for example, ceramics photography (portrait, funeral picture, pet photo, permanent storage, etc.) by selecting various shapes and formed images of the ceramic body to be painted. (For commemorative photos, etc.), amusement and accessory applications (including mugs, liquor bottles, family crests, fish farming, etc.), building materials applications (bathrooms, entrances, living rooms, lobby, art tiles used for walls in rooms, guest rooms, etc.) , Guide boards, room accessories, interior products, etc.).

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Preparation of adhesive latent image forming substance solution 1>
3,5-dimethyl-1-hexyl-3-ol 5 parts by mass distilled water 50 parts by mass n-propyl alcohol 45 parts by mass After stirring the above components uniformly, the mixture was filtered through a 0.45 μm microfilter, Image forming substance solution 1 was prepared.

<Production of image receiving sheet>
First layer coating solution and second layer coating solution having the following composition were prepared.
(Composition of coating solution for first layer)
160 parts by mass of vinyl chloride-vinyl acetate copolymer (manufactured by Nissin Chemical Co., Ltd .; Solvein CL2)
61 parts by mass of ethylene-vinyl acetate copolymer (Mitsui DuPont Chemical Co., Ltd .; Elvalloy 742)
Sebacic acid polyester 28 parts by mass (Nippon Soda Co., Ltd .; FN-G25)
Perfluoroalkyl group-containing oligomer 4 parts by mass (Dainippon Ink & Chemicals, Inc .; Megafuck F-178K)
Methyl ethyl ketone 630 parts by mass Toluene 210 parts by mass Dimethylformamide 30 parts by mass

(Composition of coating solution for second layer)
16 parts by mass of polyvinyl butyral resin (manufactured by Denki Kagaku Kogyo Co., Ltd .; Denkabutyral # 2000-L)
N, N-dimethylacrylamide-butyl acrylate copolymer 4 parts by mass Perfluoroalkyl group-containing oligomer 0.5 part by mass (manufactured by Dainippon Ink & Chemicals, Inc .; MegaFuck F-177)
200 parts by mass of n-propyl alcohol

The first layer coating solution was applied on a PET film support having a thickness of 130 μm and dried at 100 ° C. to form a first layer having a thickness of 20 μm at the time of drying. Next, the coating solution for the second layer is applied onto the first layer and dried at 100 ° C. to form a second layer (image receiving layer) having a thickness of 2 μm at the time of drying, and an image receiving sheet A is produced. did.

<Manufacture of ceramic plates with pictures>
Fill the black ink cassette of the thick ink jet printer PCM (manufactured by Asuka) with the adhesive latent image forming substance solution 1 and print a mirror image (reverse image) on the image receiving sheet A based on the image information. A sex latent image was formed.
A black pigment (14209, manufactured by Celdic) was applied to the image-receiving sheet on which the adhesive latent image was formed, the black pigment was adhered to the latent image portion, and the black pigment of the unadhered portion was worn off with a brush. .

When the image-forming surface of the image-receiving sheet on which the image is formed overlaps with the surface of the porcelain plate and is heat-pressed with a heat roller, and the image-receiving sheet is peeled off, the image composed of the inorganic pigment and the second layer are received. It peeled off from the sheet | seat and adhere | attached on the ceramic board. An inverted pigment image was formed on the ceramic plate. Next, the temperature of the ceramic plate on which the inorganic pigment image is formed is increased at a rate of temperature increase of 100 ° C./hour in an electric kiln, then at 400 ° C. for 1 hour and further increased to 800 ° C. in the same manner. The ceramic plate 100 with a picture was produced by firing at 30 ° C. for 30 minutes.

<Preparation of adhesive latent image forming substance dispersion 2>
3 parts by weight of dibutyl phthalate is added to 10 parts by weight of poly n-hexyl acrylate (degree of polymerization: 500), and dissolved in 10 parts by weight of ethyl acetate to form an adhesive latent image forming substance. To 100 parts by mass of distilled water, 1 part by mass of polyoxyethylene (4) lauryl ether, 0.5 part by mass of sodium dodecylbenzenesulfonate and 2 parts by mass of ML-10 (manufactured by Daicel Corporation) were added and dissolved. The entire amount of the adhesive latent image forming substance was added and emulsified and dispersed with a homogenizer. 10 parts by weight of glycerin was further added to the dispersion and stirred uniformly, followed by filtration through a 0.8 μm microfilter to prepare an adhesive latent image forming substance dispersion 2.

<Preparation of image receiving sheet B>
An image receiving sheet B was prepared by coating 8 g / m ^{2 of} dextrin on a smooth paper support having a pot amount of 100 g.

<Manufacture of ceramic plates with pictures>
The adhesive latent image forming substance solution 2 is filled in a black ink cassette of an ink jet printer PM770C (manufactured by Epson), and a mirror image (reversed image) is printed on the image receiving sheet B based on image information. Formed.
A black pigment (14209, manufactured by Celdic) was sprinkled on the image-receiving sheet on which the adhesive latent image was formed, the black pigment was adhered to the latent image portion, and the black pigment in the unadhered portion was worn off with a brush.
An overcoat lacquer mainly composed of a methacrylic resin (plus size LD-170; manufactured by Kyoyo Chemical Industry Co., Ltd.) was applied on the image receiving sheet B on which the inorganic pigment image was formed to have a dry film thickness of 15 μm. Dried.
Next, the image-receiving sheet B coated with the overcoat lacquer is immersed in water to dissolve dextrin, the overcoat layer to which the image is adhered is isolated, placed on the ceramic body, and surplus with a rubber spatula. Moisture was removed and adhered to the ceramic plate. After drying sufficiently, raise the temperature at a heating rate of 100 ° C./hour in an electric kiln, raise it to 400 ° C. for 1 hour, further increase to 800 ° C. in the same way, and baked at 800 ° C. for 30 minutes. A ceramic plate 200 was produced.

In the same manner as in Example 2, an adhesive latent image forming substance dispersion 2 and an image receiving sheet B were prepared.
Further, using these, a painted ceramic body was produced as follows.
The black ink cassette of the ink jet printer PM770C (manufactured by Epson) is filled with the adhesive latent image forming substance solution 2 and a mirror image (reversed image) of the Y component is applied to the image receiving sheet B based on the color separation image information of YMCK. Printed to form an adhesive latent image.
A yellow pigment (manufactured by Celdec; 13651) was sprinkled on the image-receiving sheet on which the adhesive latent image was formed, the yellow pigment was adhered to the latent image portion, and the yellow pigment of the unadhered portion was worn off with a brush.
In the same manner, on the surface of the image receiving sheet on which the yellow pigment image was formed, a magenta pigment (manufactured by Celdex; 77571), a cyan pigment (manufactured by Celdex; 121522), and a black pigment (manufactured by Celdex; 14209). ) Were sequentially formed to form a full-color inorganic pigment image on the image-receiving sheet B.
Further, an overcoat lacquer mainly composed of a methacrylic resin (plus size LD-170; manufactured by Kyoyo Chemical Industry Co., Ltd.) and a coated surface of polyethylene terephthalate film (thickness: 50 μm) coated so as to have a dry film thickness of 15 μm; Then, the image receiving sheet B on which the inorganic pigment image was adhered was superimposed and passed through a heat roller (roller temperature 120 ° C.) to transfer the overcoat layer to the surface of the image receiving sheet B.

Next, the image-receiving sheet B to which the overcoat layer has been transferred is immersed in water to dissolve dextrin, the overcoat layer to which the image is attached is isolated, placed on the ceramic body, and excess with a rubber spatula. Moisture was removed and adhered to the ceramic plate. After drying sufficiently, raise the temperature at a heating rate of 100 ° C./hour in an electric kiln, raise it to 400 ° C. for 1 hour, then increase to 800 ° C. in the same way, and baked at 800 ° C. for 30 minutes. A ceramic plate 300 was produced.

The ceramic boards with pictures 100, 200, and 300 were both formed with high-resolution and high-resolution images, and had good water resistance and light resistance.

Claims (18)

A latent image forming step of forming an adhesive latent image comprising an adhesive composition on the image receiving material;
An image forming step of forming an inorganic pigment image by applying an inorganic pigment powder to the surface of the image receiving material on the side on which the adhesive latent image is formed and adhering the inorganic pigment to the adhesive latent image portion;
An arrangement step of arranging an inorganic pigment image formed on the image receiving material on the surface of the ceramic body;
A firing step of heating the ceramic body on which at least the inorganic pigment image is disposed, and sintering the inorganic pigment image on a surface of the ceramic body;
A method for producing a ceramic body with a picture, comprising: The method for producing a ceramic body with a picture according to claim 1, wherein the pressure-sensitive adhesive composition is colorless or light-colored. A cover coat layer forming step of forming a water-insoluble cover coat layer on the image receiving material on which the inorganic pigment image has been formed in the image forming step, and the cover coat layer is coated with the inorganic pigment image in the arranging step. The method for producing a ceramic body with a picture according to claim 1 or 2, wherein the ceramic body is disposed together with the layer on the surface of the ceramic body. The method for producing a ceramic body with a picture according to any one of claims 1 to 3, wherein the image-receiving material has a layer containing a water-soluble polymer as an image-receiving layer on the surface of the water-permeable support. The ceramic body with a picture according to any one of claims 1 to 3, wherein the image-receiving material has a layer containing a water-soluble polymer and an image-receiving layer containing a water-insoluble polymer in order on the surface of the water-permeable support. Method. In the arranging step, the support side of the image receiving material is immersed in water to partially dissolve the water-soluble polymer and peel off the water permeable support of the image receiving material, and the peeled surface after peeling contacts the surface of the ceramic body. The method for producing a ceramic body with a picture according to claim 4 or 5, wherein the inorganic pigment image is arranged on the surface of the ceramic body together with the image receiving layer. In the arranging step, the image-forming surface comes into contact with the surface of the ceramic body through a solution in which the glue is dissolved or dispersed before or after the water-permeable support of the image receiving material is partially dissolved by removing the water-soluble polymer. The method for producing a ceramic body with a picture according to claim 4 or 5, wherein the inorganic pigment image is arranged on the surface of the ceramic body together with the image receiving layer. The method for producing a ceramic body with a picture according to any one of claims 1 to 7, wherein the cover coat layer comprises a hydrophobic polymer, and the glass transition point of the hydrophobic polymer is not more than room temperature. In the cover coat layer forming step, at least the surface of the image receiving material on which the inorganic pigment image is formed and the cover coat layer surface of the transfer body having the cover coat layer are heated by contact, and the cover is formed on the image receiving material. The method for producing a ceramic body with a picture according to any one of claims 1 to 8, which is a step of transferring a coat layer. The ceramic body with a picture according to any one of claims 1 to 8, wherein the cover coat layer forming step is a step of forming a cover coat layer coating solution on the surface of the image receiving material on the side where the inorganic pigment image is formed. Production method. The method for producing a ceramic body with a picture according to any one of claims 1 to 8, wherein the cover coat layer forming step is a step of forming a liquid containing a hydrophobic polymer by uniformly printing on a whole surface with an ink jet printer. In the latent image forming step of forming an adhesive latent image made of an adhesive composition on the image receiving material, the dispersed ink in which the adhesive composition is dispersed in an ink solvent is printed imagewise by an inkjet printer. It consists of this, The ceramic body manufacturing method with a picture in any one of Claims 1-11 characterized by the above-mentioned. The method for producing a ceramic body with a picture according to claim 12, wherein the composition having adhesiveness is a composition containing a tackifier. The method for producing a ceramic body with a picture according to claim 12 or 13, wherein the adhesive composition is a composition containing a resin and a plasticizer for the resin. 15. The method for producing a ceramic body with a picture according to claim 12, wherein a terminal hydrophobic water-soluble polymer is contained in the dispersed ink in which the adhesive composition is dispersed in an ink solvent. The method for producing a ceramic body with a picture according to claim 15, wherein the terminal hydrophobic water-soluble polymer is represented by the following general formula (1).

[Wherein, R represents a hydrophobic group or a hydrophobic polymer, and n represents an integer. ] The method for producing a ceramic body with a picture according to claim 15, wherein the terminal hydrophobic water-soluble polymer is represented by the following general formula (2).
General formula (2): R ′ — (SP) _n [In the formula (2), R ′ represents a hydrophobic group or a hydrophobic polymer, and P represents at least one of the following structural units A, B and C: 1 represents a polymer having a degree of polymerization of 10 or more and 3500 or less. n represents 1 or 2.

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, R ³ represents —H or —CH ₃ , R ⁴ represents H, —CH ₃ , —CH ₂ COOH (including an ammonium group or a metal salt) or —CN, X represents —H, —COOH (including an ammonium group or a metal salt) or —CONH ₂ ; Y is —COOH (including an ammonium group or a metal salt), —SO ₃ H (including an ammonium group or a metal salt), —OSO ₃ H (including an ammonium group or a metal salt), —CH ₂ SO ₃ H (ammonium containing group or a metal _{salt), - CONHC (CH 3)} 2 CH 2 SO 3 containing H (ammonium salt or a metal salt) or ^{_{-CONHCH 2 CH 2 CH 2 N +}} (CH 3) 3 Cl - represent. ] In the latent image forming step of forming an adhesive latent image made of an adhesive composition on an image receiving material, an ink containing a solvent capable of swelling the composition on the surface of the image receiving material is printed imagewise by an ink jet printer. It consists of this, The ceramic body manufacturing method with a picture in any one of Claims 1-11 characterized by the above-mentioned.