JP2002097089A - Method for manufacturing ceramic body with picture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a ceramic body with picture, in which the ceramic body having good image-preservation property can be stably manufactured at a low cost with a simple process, and in which an image with a high coloring density and a good gradation property can be formed. SOLUTION: A transfer-sheet has a transfer-layer comprising a transfer- material containing transfer-inorganic pigment, and an image-receiving-sheet has an image-receiving-layer to which the transfer material can be transferred. On forming the same colored-image in a transfer process, the surface of the transfer-layer of the transfer sheet is brought into at least contact with the surface of the image-receiving-layer of the image-receiving-sheet-the contact is carried out as divided for two or more times by using two or more transfer- sheets-, so that the transfer material is transferred to the surface of the image- receiving-layer and the image comprising the transfer material is formed on the surface of the image-receiving-layer. This image is arranged on the surface of the ceramic body, and the ceramic body is heated so that the inorganic pigment contained in the transfer material is sintered on the surface of the body.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method of manufacturing a ceramic body with a picture, and more particularly, to a simple method of manufacturing a ceramic body with a picture which can be used as a building material such as an art tile, a ceramic photo and the like.

[0002]

2. Description of the Related Art A ceramic body with a picture, in which black and white and color images are formed on a ceramic body such as a ceramic plate, is used not only for building materials such as art tiles used for walls such as bathrooms and entrances, 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. Conventionally, as a method of forming an image on the surface of a ceramic plate or the like, after forming an image on a normal photographic paper, the paper portion of the photographic paper is removed and adhered to the ceramic surface, and the image portion surface is cured with an ultraviolet curable resin. There is known a method of protecting the image portion by laminating the image portion. However, when an image is formed by this method, the light resistance and heat resistance of the image portion are insufficient.
If the image is excellent in light resistance and heat resistance and the image can be stored semi-permanently, applications can be advantageously expanded.

For example, JP-A-2-252683 discloses a method in which a photosensitive film is adhered to the surface of ceramics,
A method has been proposed in which halftone exposure is performed through a color-separated lith film, the film is developed, and an inorganic pigment for painting is successively placed and fired in accordance with the appearing image. JP-A-62-246887 discloses that a photosensitive polymer is applied directly on a ceramic in place of the photosensitive film, exposed to halftone dots, developed, and treated in the same manner as described above. Methods of forming and firing have been proposed. The images (porcelain photographs) formed by these methods are extremely preservable and semi-permanent. However, when the above method is used, a plurality of squirrel films in which a color original is color-separated must be produced. Also, when attaching the pigment to the surface of the developed photosensitive film, it is necessary to finely adjust the amount of pigment, poor reproducibility,
In many cases, the production must be repeated. Further, the formation and firing of each pigment layer must be repeated. Therefore, the method has a problem that the operation is extremely complicated and the manufacturing cost is high.

[0004] A method has also been proposed in which printing is performed on transfer paper with an ink mainly composed of a painting pigment by screen printing or gravure printing, and the transfer paper is adhered to porcelain and fired. . The image formed by the above method is also excellent in durability and is semi-permanent in the same manner as described above, but a plurality of lithographic films and printing plates obtained by color separation of a color original have to be produced in the same manner as described above. Image formation and baking must be repeated. Therefore, as in the above-described method, there is a problem that the operation is extremely complicated and the manufacturing cost is high. Further, since the pigments for painting tend to cause clogging of the screen mesh, the screen mesh cannot be made sufficiently small. As a result, it is difficult to reproduce a clear photograph-like image having excellent resolution. There's a problem.

[0005]

In order to form an image having good storability on a ceramic body, it is necessary to sinter the image formed by the inorganic pigment on the ceramic body.
It is necessary to select an image forming method suitable for the properties of the inorganic pigment. The present inventor has previously proposed a method of manufacturing a painted ceramic body by a transfer method using a transfer sheet having a transfer layer formed of a thermoplastic resin layer containing an inorganic pigment. In this transfer method, since the inorganic pigment has a lower absorption coefficient (color density per unit weight) than the organic pigment, the amount of transfer required to obtain a desired color density is increased. As a result, the required thickness of the transfer layer is considerably thick, about 3 to 5 μm. However, when an image is formed by the transfer method,
When the thickness of the transfer layer is large, there is a problem that the gradation of an obtained image is deteriorated.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method of manufacturing a ceramic body with a picture which can form an image with good gradation on a ceramic body while maintaining a high color density.

The above object is achieved by the following invention. (1) At least the transfer layer surface of a transfer sheet having a transfer layer made of a transfer material containing an inorganic pigment and the image receiving layer surface of an image receiving sheet having an image receiving layer capable of transferring the transfer material are brought into contact with each other to form the transfer material. Transferred to the image receiving layer surface,
A transfer step of forming an image of the transfer material on the surface of the image receiving layer, an arrangement step of arranging an image of the transfer material on a surface of a ceramic body together with a part or all of the image receiving sheet, and Heating the ceramic body on which the image is arranged, and sintering an inorganic pigment contained in the transfer material on the surface of the ceramic body, and forming an image of the same color in the transfer step. 2. A method for producing a painted ceramic body, wherein the image is transferred in two or more times by using two or more transfer sheets. (2) At least the transfer layer surface of a transfer sheet having a transfer layer made of a transfer material containing an inorganic pigment and the surface of an image receiving layer capable of transferring the transfer material formed on a ceramic body are brought into contact with the transfer material, Is transferred to the surface of the image receiving layer, and a transfer / arrangement step of forming an image made of the transfer material on the surface of the image receiving layer, and heating the ceramic body on which the image made of the transfer material is arranged is included in the transfer material. And a sintering step of sintering the inorganic pigment to the surface of the ceramic body, when forming the same color image in the transfer step, divided into two or more times using two or more transfer sheets A method for producing a painted ceramic body, which comprises transferring. (3) The method for producing a painted ceramic body according to (1) or (2), wherein the thickness of the transfer layer of the transfer sheet is 2 μm or less. (4) The method according to (1) to (3), wherein a pigment image is formed on a transfer layer of the transfer sheet via a thermal transfer printer, and the pigment image is transferred to an image receiving layer surface of the image receiving sheet. The method for producing a ceramic body with a picture according to any one of the above. (5) A latent image forming a latent image by applying a transferability-enhancing material capable of accelerating the transfer of the transfer material to the image-receiving layer surface on at least one of the surface of the transfer layer and the surface of the image-receiving layer. 2. The image forming apparatus according to claim 1, further comprising a forming step, wherein the transferring step includes a step of transferring the transfer material to the surface of the image receiving layer corresponding to the latent image to form an image on the surface of the image receiving layer. Or the method of manufacturing a ceramic body with a picture according to claim 2. (6) The painted ceramic according to any one of (1) to (5), further including a second transfer step of transferring an image made of a transfer material to another image receiving sheet between the transfer step and the arrangement step. How to make the body. (7) The image receiving sheet is a sheet in which a layer containing a water-soluble polymer and an image receiving layer are sequentially laminated on a support,
In the arranging step, the water-soluble polymer is partially dissolved in water, the support is peeled off, and the peeled surface or the opposite side is adhered to the surface of the ceramic body. The method for producing a painted ceramic body according to any one of (1) to (6), which is disposed on a surface of the body.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be described in detail. When a single color image is formed by one transfer by increasing the thickness of the transfer layer to about 3 μm, the transfer diameter of the image transferred to the image receiving sheet varies as shown in FIG. That is, as a result of the change in the thickness of the transferred layer, particularly at the peripheral portion, as shown in FIG. 6B, the area (a) where the transfer diameter of the image fluctuates becomes an area where the gradation is disturbed. . In the case of forming an image on a ceramic body, if the inorganic pigment particles are small, the coloring density is low, so that the inorganic pigment particles are adjusted to be relatively large. It becomes difficult to display clearly.

FIGS. 7 (A) and 7 (B) show three times transfer in forming the same color image in FIG. 6 (A).
3 shows a case where a transfer image having the same thickness as that of the case (1) is formed. In this case, each transfer layer (t ₁ , t ₂ , t ₃ )
As shown in FIG. 7A, the transfer diameter of each image transferred to the image receiving sheet varies (that is, the thickness of the transferred layer, particularly, the thickness of the peripheral portion varies), as shown in FIG.
Is considerably smaller than when an image is formed by one transfer by increasing the thickness of the transfer layer to about 3 μm. Therefore, as shown in FIG. 7B, the area (a ₁ ) in which the transfer diameter of this image fluctuates and the gradation is disturbed is as shown in FIG.
The area is considerably smaller than that of FIG.

As is apparent from FIG. 7, when the same color image is formed, when the transfer layer is made thinner and the transfer is performed a plurality of times, the more the number of copies, the more in principle the gradation property. Will be narrowed. However, considering the working efficiency and the transfer layer forming means, etc.,
It is desirable that the transfer is performed four times, preferably two or three times. In the case of transferring a plurality of transfer layers, the thickness of each transfer layer is not necessarily required to be the same, but may be different. However, when the same color image is transferred in plurals, the total thickness of the multiple transfer layers is
It is preferable that the thickness is about the thickness when an image of the same color is formed on one transfer sheet. From such a viewpoint, the thickness of the transfer layer of one transfer sheet is 3 μm or less,
Preferably 0.3 to 2 μm or less, more preferably 0.5 to 2 μm.
１．５1.5 μm.

Forming an image of the same color includes a case of forming a "monochrome" image and a case of forming an image of "each color in the case of multi-colors". When forming an image of “each color in the case of multi-color”, it is desirable to transfer the image in two or more times when forming each color image of all the colors. In the case of (1), when forming at least one color image which is most susceptible to the influence, the transfer may be divided into two or more times.

In the present invention, the method of forming an image by the transfer method includes: 1) a method using a thermal transfer printer using a thermal head or the like; 2) promoting transfer of a transfer material contained in a transfer layer to an image receiving layer. A method using the obtained transferability promoting material is exemplified.

(Method using a thermal transfer printer) Black-and-white and color photographs, printed matter, paintings, etc. are read by a scanner and converted into electric signals, or images taken by an electronic still camera, video camera, etc., or images created by a computer (CG), etc. A known method of forming a pigment image on a transfer layer by a thermal transfer printer using a thermal head or the like and transferring the pigment image to an image receiving layer to form an image can be applied. In this transfer step, two or more transfer sheets for forming the same color image by a thermal head or the like are used, and transfer is performed in two or more steps. An arranging step of arranging the image formed of the transfer material on the surface of the ceramic body together with part or all of the image receiving sheet, and heating the ceramic body on which the image formed of the transfer material is arranged, and converting the inorganic pigment contained in the transfer material into the ceramic body The sintering step and the like for sintering the surface are described together with the following method using a transfer promoting material.

(Method Using Transfer Acceleration Material) In this method, at least one of the transfer layer and the image receiving layer is formed by a transfer accelerating material capable of promoting the transfer of the transfer material contained in the transfer layer to the image receiving layer. A latent image forming step of forming a latent image on either side. Next, a transfer step of transferring a transfer material contained in the transfer layer to the image receiving layer according to the latent image formed in the latent image forming step to form an image made of the transfer material is provided. In the embodiment in which the image receiving layer is formed on the surface of the ceramic body, after the transfer step, the ceramic body is heated, and the inorganic pigment contained in the transfer material is sintered on the surface of the ceramic body, and the surface of the ceramic body is A sintering step to form an image can be performed. On the other hand, when the latent image forming step and the transfer step are performed using an image receiving sheet including a support and an image receiving layer, after the transfer step, an image formed of a transfer material is disposed on the surface of the ceramic body together with the image receiving layer. After the arranging step, the sintering step is performed. Between the transfer step and the arrangement step, a second transfer step of transferring an image made of a transfer material to another image receiving sheet may be performed.

Next, an embodiment of the method for manufacturing a painted ceramic body of the present invention will be described with reference to FIG. This embodiment is an embodiment using an image receiving sheet having an image receiving layer containing a thermoplastic resin on a support. First, a transfer sheet 10 and an image receiving sheet 20 are prepared (FIG. 1A).
The transfer sheet 10 has a support 12 and a transfer layer 14 made of a transfer material containing at least an inorganic pigment thereon.
On the other hand, the image receiving sheet 20 comprises a support 22 and a transfer layer 1 thereon.
4 has an image receiving layer 24 capable of transferring and fixing the transfer material in the transfer material 4. Next, on the surface of the image receiving layer 24 of the image receiving sheet 20, a droplet containing a transferability promoting material is formed on a ceramic body in accordance with image information by an ink jet recording device (not shown). An image is provided so as to form an image (latent image forming step). Then, the transfer sheet 10
The surface of the transfer layer 14 of FIG. 1 and the surface of the image receiving layer 24 of the image receiving sheet 20 are opposed to each other, brought into contact with each other, and heated and pressed.
(B)). The transfer material contained in the transfer layer 14 is transferred to the surface of the image receiving layer 24 only in a region to which the transferability promoting material is provided, and an image i (mirror image) made of the transfer material is transferred to the surface of the image receiving layer 24. (Transfer process; FIG. 1)
(C)).

Next, an image receiving layer 24 having an image i made of a transfer material is adhered to the surface of the ceramic plate 30, which is a ceramic body, by heating and pressing. At the same time, the support 22 is peeled off. The resulting image i (normal image) is arranged together with the image receiving layer 24 (FIG. 1D; arrangement step). The image i formed in this arrangement step is formed by two or more (for example, three) transfer steps when forming an image of the same color. Therefore, the image i is formed by the transfer image layer i-1, the transfer image layer i-2, and the transfer image layer i-3. Next, when the ceramic plate 30 is fired by an electric kiln, during firing, each component in the image receiving layer 24 and components other than the inorganic pigments contained in the transfer material constituting the image i (for example, as a binder) Polymer and the like are evaporated and / or incinerated, and at the same time, the inorganic pigment contained in the transfer material is sintered on the surface of the porcelain plate 30 and the painted porcelain plate 32
(FIG. 1 (e); sintering step).

Another embodiment of the present invention will be described with reference to FIG. This embodiment is an embodiment using an adhesive image receiving sheet in which a layer made of a water-soluble polymer and an image receiving layer are sequentially formed on a support. Note that the same members as those in FIG. 1 are denoted by the same reference numerals, and detailed description is omitted. First, a transfer sheet 10 including a support 12 and a transfer layer 14 and an image receiving sheet 20 'are prepared (FIG. 2A). The image receiving sheet 20 'has a support 22, a layer 26 made of a water-soluble polymer thereon, and an image receiving layer 24'. Image receiving layer 2
Reference numeral 4 ′ is configured so that the transfer material in the transfer layer 14 can be transferred and fixed. Next, the image receiving layer 24 'of the image receiving sheet 20'
On the surface of the ink jet recording device (not shown)
Droplets containing a transferability-promoting material are applied imagewise according to image information (latent image forming step). Then, transfer sheet 1
0 of the transfer layer 14 and the image receiving layer 2 of the image receiving sheet 20 '.
The surface 4 'is made to face and contact with the surface 4', and then thermocompression-bonded (FIG. 2B). The transfer material contained in the transfer layer 14 is
Image receiving layer 2 only in the area to which the transferability promoting material has been applied
The image i made of a transfer material is transferred to the surface of the image receiving layer 24 '.
(C)).

Next, the image receiving sheet 2 on which the image i is formed
0 'is partially immersed in water to dissolve the water-soluble polymer in the layer 26, and the layer 24' is peeled off from the support 22 together with the image i. When the layer 24 ′ is placed on the ceramic plate 30, the layer 24 ′ is adhered to the surface of the ceramic plate 30 because the water-soluble polymer in the layer 26 is partially dissolved. An image i made of a transfer material is arranged on the surface of the ceramic plate 30 together with the layer 24 '(FIG. 2D; image arrangement step). The image i formed in this arrangement step is formed by two or more (for example, three) transfer steps when forming an image of the same color. Therefore, the image i is composed of the transfer image layer i-1 and the transfer image layer i.
-2, formed by transfer image layer i-3. Next, the ceramic plate 30 on which the image i is arranged is fired by an electric kiln. During baking, each component in the layer 24 'and components other than the inorganic pigment (for example, a polymer as a binder) contained in the transfer material constituting the image i are evaporated and / or incinerated. The inorganic pigment contained in the transfer material is sintered on the surface of the porcelain
2 ′ is produced (FIG. 2E; sintering step).

Referring to FIG. 3, another embodiment of the present invention will be described. This embodiment is an embodiment using an adhesive image receiving sheet in which a layer made of a water-soluble polymer and an image receiving layer are sequentially formed on a support. Note that the same members as those in FIG. 1 are denoted by the same reference numerals, and detailed description is omitted. First, a transfer sheet 10 including a support 12 and a transfer layer 14 and an image receiving sheet 20 'are prepared (FIG. 3A). The image receiving sheet 20 'has a support 22, a layer 26 made of a water-soluble polymer thereon, and an image receiving layer 24'. Image receiving layer 2
Reference numeral 4 ′ is configured so that the transfer material in the transfer layer 14 can be transferred and fixed. Next, the image receiving layer 24 'of the image receiving sheet 20'
On the surface of the ink jet recording device (not shown)
Droplets containing the transferability-promoting material are applied in an image (mirror image) manner according to the image information (latent image forming step). After that, the surface of the transfer layer 14 of the transfer sheet 10 and the surface of the image receiving layer 24 'of the image receiving sheet 20' are opposed to each other, brought into contact with each other, and heated and pressed (FIG. 3B). The transfer material contained in the transfer layer 14 is transferred to the surface of the image receiving layer 24 ′ only in the area to which the transferability promoting material is provided, and an image i (mirror image) made of the transfer material is formed on the surface of the image receiving layer 24 ′. The image is transferred (transfer step; FIG. 3C).

Next, the image receiving sheet 2 on which the image i is formed
0 'is partially immersed in water to dissolve the water-soluble polymer in the layer 26, and the layer 24' is peeled off from the support 22 together with the image i. When the surface (image receiving layer surface) opposite to the peeling surface is arranged as shown in FIG. 3D via the liquid in which the paste is dissolved or dispersed, the layer 24 and the image i (normal image) adhere to the surface of the ceramic plate 30 (Image arrangement step). Next, the ceramic plate 30 on which the image i is arranged is fired by an electric kiln. Layer 2 during firing
The components other than the inorganic pigment (for example, a polymer as a binder) contained in the transfer material constituting the image i are evaporated and / or incinerated, and the components in the transfer material are contained in the transfer material. The inorganic pigment to be used is ceramic plate 30
(FIG. 3 (e); sintering step).

Referring to FIG. 4, another embodiment of the present invention will be described. This embodiment is an embodiment in which the image receiving layer is formed on the surface of a ceramic plate made of a ceramic body. In addition, FIG.
The same members as those in FIG. 3 are denoted by the same reference numerals, and detailed description will be omitted. First, a transfer sheet 10 comprising a support 12 and a transfer layer 14 and a ceramic plate 30 'having an image receiving layer 24''on its surface are prepared (FIG. 4A). Image receiving layer 24 ''
Is configured so that the transfer material in the transfer layer 14 can be transferred and fixed. Next, a droplet containing a transferability-enhancing material is imagewise applied to the surface of the image receiving layer 24 ″ in accordance with image information by an inkjet recording device (not shown) (latent image forming step). Thereafter, the surface of the transfer layer 14 of the transfer sheet 10 and the surface of the image receiving layer 24 '' are opposed to each other, brought into contact with each other, and heated and pressed (FIG. 4B). The transfer material contained in the transfer layer 14 is transferred to the surface of the image receiving layer 24 ″ only in the area where the transferability promoting material is provided, and the image i of the transfer material is transferred to the surface of the image receiving layer 24 ″. (Transfer step; FIG. 4C).

The image i formed in this transfer step is used twice or more (for example, when forming the same color image).
(3 times) transfer process. Therefore, the image i is formed by the transfer image layer i-1, the transfer image layer i-2, and the transfer image layer i-3. Next, the porcelain plate 30 '(FIG. 4D) having the image i formed on the surface is fired by an electric kiln. During baking, each component in the image receiving layer 24 ″ and components other than the inorganic pigment (for example, binder) contained in the transfer material constituting the image i are evaporated and / or incinerated. The inorganic pigment contained in the transfer material is sintered on the surface of the porcelain plate 30 'to produce a painted porcelain plate 32''(FIG. 4 (e); sintering step).

FIG. 5 shows an image forming apparatus for carrying out the method for producing a picture-coated ceramic body according to the present invention. This image forming apparatus 40 promotes transferability on the surface of the second layer (image receiving layer) of the image receiving sheet 20. The image forming apparatus includes a discharge head 42 that applies a droplet of a material solution in an image-wise manner, a support drum 44 and a pinch roller 46 that transport the image receiving sheet 20 and the transfer sheet 10 while heating and pressing the same. Further, it includes a take-up roller 48 provided at the end of the transfer path of the transfer sheet 10, and a rectangular parallelepiped peel bar 50 disposed downstream of the support drum 44 in the transfer path of the transfer sheet 10. The transport path further includes a heater 52 for heating and drying the transferability-promoting material solution on the image receiving sheet 20 discharged imagewise and a heater 54 for heating and drying the transferred image transferred on the image receiving sheet 20. Have.

Hereinafter, various materials that can be used in the method for producing a painted ceramic body of the present invention will be described. The transferability promoting material that can be used in the latent image forming step is a material that can lower the transfer temperature of the transfer material contained in the transfer layer. The transferability-promoting material is preferably a liquid composition, and preferably does not contain a solid material or the like that precipitates over time. Examples of the transferability promoting material include water, organic solvents, surfactants, and mixtures thereof. Among them, organic solvents freely miscible with water at room temperature, surfactants miscible with water, and mixtures thereof are desirable. Further, the transferability promoting material does not chemically act on the inorganic pigment contained in the transfer material,
It is preferable that the material does not cause a coloring reaction or the like even by the heat energy given as desired in a subsequent transfer step or the like, and it is preferable that the material itself be colorless or light-colored.

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, Monohydric or polyhydric alcohols such as triethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, hexylene glycol, 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 Recall diethyl ether,
Ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, and tripropylene glycol monomethyl ether; keto alcohols such as diacetone alcohol; Nitrogen-containing solvents such as 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, 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, Formalin condensate of naphthalene sulfonic acid, polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, alkylalkanolamine, alkylamine salt, alkylbetaine, mono- or dihydroxyacetylene compound, etc. No.

The transfer promoting material may be used alone or as a mixture of two or more. Above all, it is desirable to use the organic solvent and / or the surfactant mixed with water from the viewpoint of the effect. The transferability-promoting material includes a surface tension adjuster, a fungicide, a viscosity adjuster, and a pH adjuster for the purpose of adjusting the discharge suitability when discharging as droplets, preventing the spread of droplets, and improving storage stability. An agent, an antifoaming agent and the like can be contained within 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 / or the image-receiving layer, and has a surface tension of 25 to 60 mN / m and a viscosity of 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 may decrease. is there. When a material that solubilizes the transfer material is used as the transfer promoting material, the discharge amount of the transfer promoting material may be reduced.

As a guide for lowering the transfer temperature of the transfer material by the action of the transferability promoting material, the transfer temperature should be lowered by 3 ° C. or more with respect to the transfer temperature of the transfer material when no transferability promoting material is used. preferable. Note that 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 sheet 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.

When the transferability-promoting material contains a nonionic surfactant and water, the effect of lowering the transfer temperature is great, and the transferability of fine points is good, so that a transfer image with high resolution can be obtained. it can. As the nonionic surfactant, a nonionic compound having an ethylene oxide group added as a hydrophilic group is particularly preferable. It is preferable to use a nonionic compound to which an ethylene oxide group is added, since the effect of lowering the transfer temperature in the latent image forming portion is large and high resolution can be obtained. Examples of the nonionic compound include compounds represented by any of the following general formulas 1 to 4.

[0030]

Embedded image

In the above general formula 1, R represents an alkyl group or an alkylene group, and n represents 2 to 30, preferably 2 to 20.
Represents an integer of 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 represent an integer of 2 to 30, preferably 2 to 20. In the general formula 4, 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 above general formulas 1 to 4, the number of additions of ethylene oxide is preferably 2 to 30, particularly preferably 2 to 20.
It is. Specific examples of the compounds represented by the 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 adduct of acetylene glycol (n + m = 10), and the like. However, the present invention is not limited to this.

The nonionic surfactant is preferably contained in the transferability-enhancing material in an amount of 0.1 to 20% by mass.
More preferably, the content is 1 to 10% by mass. If the content exceeds 20% by mass, the resolution tends to decrease. On the other hand, when the amount is less than 0.1% by mass, it is difficult to obtain a transferability promoting effect. In addition, a water-soluble organic solvent can be used in combination with the nonionic surfactant for the transferability promoting material. As the water-soluble organic solvent, those mentioned above as the organic solvent freely miscible with water can be used. The content of the water-soluble organic solvent is from 0 to 90 in the transferability promoting material.
About mass% is appropriate.

Further, as the transferability-promoting material, those containing water and an organic solvent having a boiling point of 100 ° C. or higher at normal temperature and normal pressure and being compatible with water are also preferable. The ejection stability of the solution is improved, the non-ejection phenomenon 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. It is preferred. 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 monovalent solvents such as ethylene glycol, diethylene glycol, thiodiethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, and glycerin. 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; N-methyl-2-
Nitrogen-containing solvents such as pyrrolidone and 2-pyrrolidone; and the like.

The organic solvent in the transfer promoting material is 1
It is preferably contained in an amount of from 90% by mass. When the content exceeds 90% by mass, the ejection stability at the time of forming a latent image is increased.
The dryness of the transferred image tends to decrease. 1% by mass
If the amount is smaller, it becomes difficult to improve ejection stability and transferability of fine dots. Also, as a material for lowering the transfer temperature,
In addition to the above-mentioned organic solvents, the above-mentioned organic solvents that are freely miscible with water and the above-mentioned surfactants can also be added.

In the latent image forming step, the transferability promoting material may be applied imagewise to at least one of the transfer layer surface and the image receiving layer surface. In order to apply the transferability-promoting material imagewise to the surface of the transfer layer or the like, a known inkjet recording-type image forming method can be used. For example, an ink-jet head having a heating element therein is filled with the liquid transferability promoting material, and electricity is supplied to a heating element at a predetermined position according to image information to cause the heating element to generate heat. Boiling the solvent of the accelerating material (water, organic solvent, etc.), increasing the pressure inside the head,
The transferability-enhancing material at a desired position can be caused to fly as droplets and land on any surface of the transfer layer and the image receiving layer. In addition, the transferability promoting material can be applied imagewise to the surface of the transfer layer or the like by using various ink jet recording methods such as an ink jet recording method using a piezo element.

The latent image formed in the latent image forming step is developed in a transfer step. In the transfer step, the latent image formed by the transferability promoting material is developed by transfer using a transfer sheet. Examples of the transfer sheet include a sheet having a support and a transfer layer containing a transfer material provided thereon. The support of the transfer sheet is not particularly limited, and various support materials can be used according to the purpose. Preferred examples of the support material include synthetic resin materials such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polycarbonate, polyethylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and styrene-acrylonitrile copolymer. . Among them, biaxially stretched polyethylene terephthalate is preferable in consideration of mechanical strength and dimensional stability against heat.

The support of the transfer sheet may be subjected to a surface roughening treatment and / or the provision of one or more undercoat layers in order to adjust the adhesion to the transfer layer provided thereon. It is preferred to do so. Examples of the surface roughening treatment include a glow discharge treatment and a corona discharge treatment. It is preferable that the material of the undercoat layer has appropriate adhesiveness to both surfaces of the support and the transfer layer, has low thermal conductivity, and has excellent heat resistance. Examples of such a material for the undercoat layer include styrene, styrene-butadiene copolymer, and gelatin. The thickness of the entire undercoat layer is usually 0.01 to 2 μm. Also,
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 can be provided or surface treatment can be performed, if necessary.

The transfer layer is made of a transfer material. The transfer material contains at least an inorganic pigment, and further contains a binder for forming a layer and, if desired, other components. As the inorganic pigments, upper paints and lower paints usually used for pottery can be used, for example,
Metal oxides such as copper oxide, cobalt oxide, etc. having a crystal structure of spinel, spherine, pichlois, rutile, priderite, phosphite, phenasite, perryclays, olivine, buderite, borate, corundum, zircon, etc .; cadmium yellow, etc. And cadmium selenide compounds such as selenium red. Also,
An inorganic pigment which is a fluorescent pigment or a phosphorescent pigment may be used. The transfer layer may contain a glass component together with the inorganic pigment. It is preferable to use a glass component in combination, since the fusion property of the inorganic pigment to the surface of the ceramic body can be improved in the sintering step. 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, borax, feldspar,
Complex components such as kaolin 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 the binder of the transfer layer, an amorphous organic high molecular polymer having a softening point of 40 ° C. to 150 ° C. is preferable. In the case of the transfer layer used for the melt transfer method, a low polymerization degree is particularly preferable. Examples of the amorphous organic high-molecular polymer include butyral resin, polyamide resin, polyethylene imine resin, sulfonamide resin, polyester polyol resin, petroleum resin, styrene, vinyl toluene,
Styrene such as α-methylstyrene, 2-methylstyrene, chlorostyrene, vinylbenzoic acid, sodium vinylbenzenesulfonate, aminostyrene and derivatives thereof, homopolymers and copolymers of substituted products, methyl methacrylate, ethyl methacrylate, butyl Methacrylates, methacrylates such as hydroxyethyl methacrylate and methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, acrylates such as α-ethylhexyl acrylate and acrylic acid, butadiene, dienes such as isoprene, acrylonitrile, vinyl ethers, Use of vinyl monomers such as maleic acid and maleic esters, maleic anhydride, cinnamic acid, vinyl chloride, vinyl acetate, or copolymers with other monomers Can be. These resins can be used as a mixture of two or more kinds.

In the transfer layer, the content of the inorganic pigment is 10% by mass to 8%.
The content is preferably 0% by mass, more preferably 20% by mass to 70% by mass. When a glass component is used in combination, the preferred amount of the glass component used differs depending on the inorganic pigment used in combination. However, the mixture of the glass component and the inorganic pigment is contained in the transfer layer in an amount of 15% by mass to 70% by mass. Is preferably 30% by mass to 80% by mass.
More preferably, it is contained.

When a multicolor image is formed by repeatedly superimposing a number of image layers (transfer layers on which images have been formed) on the same image receiving layer, the transfer layer is formed of a plasticizer in order to enhance the adhesion between the images. It is preferable to include 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); Di (2-ethylhexyl) adipate, di (2-ethylhexyl) sebacate
And fatty acid diesters 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 general plasticizers described above, polyethylene glycol dimethacrylate,
Acrylic esters such as 1,2,4-butanetriol trimethacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol-polyacrylate are also suitable depending on the type of binder used. Used together. Incidentally, two or more plasticizers may be used in combination.

In the transfer layer, the ratio of the total mass of the inorganic pigment and the binder to the mass of the plasticizer is generally 100: 1 to 100: 3, preferably 100: 1.5. ~
Used to be 100: 2. If necessary, a surfactant, a thickener, and the like may be added to the transfer layer.

It is preferable that the transfer layer contains a wax component in order to improve the resolution and resolution of a transferred image (dot). It is preferable to include a wax component in both the method using a transfer promoting material and the method using a thermal transfer printer, but this is particularly important when an image is formed by the latter method.

The wax component includes, 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.

In the transfer layer, the adhesiveness to the image receiving sheet and the transfer sheet is improved, and in the case of printing a large number of times (monochrome and color images of two or more colors), the transfer layer (material A) a thermoplastic resin having a relatively low melting point to improve the glue, for example, a low molecular weight petroleum resin, a polyvinyl butyral resin, an ethylene-vinyl acetate copolymer, an ethylene-acrylate copolymer, a styrene-acrylic acid It is preferable to add an ester copolymer, a styrene-maleic acid-acrylate copolymer or the like.

For the transfer layer, a coating solution prepared by dissolving or dispersing the components of the transfer material such as the inorganic pigment and the binder is prepared, and the solution is coated on a support (if the support has the undercoat layer, the undercoat is used). On the layer) and dried. The solvent used for preparing the coating liquid is preferably an aqueous solvent from the viewpoint of environmental safety, but n-propyl alcohol, methyl ethyl ketone, propylene glycol monomethyl ether (MFG), methanol, and the like can also be used. Coating and drying can be performed by using ordinary coating and drying methods.

The image receiving layer is usually provided on a support and used in the form of an image receiving sheet comprising the support and the image receiving layer. Further, the image receiving layer may be formed on a ceramic body. When the transfer layer is applied in an aqueous system, the inorganic pigment, the wax component and the thermoplastic resin are dispersed in a solid medium or an organic solvent in an aqueous medium, or are melted and emulsified and dispersed at a high temperature to form a dispersion. Or, it is used as an emulsion.

The image receiving sheet has at least one image receiving layer on a support, and if necessary, any one or two of a cushion layer, a release layer, and an intermediate layer between the support and the image receiving layer. Although it is preferable to adopt a configuration having the above configuration,
If the affinity with the transfer layer is good, a resin sheet such as polyethylene terephthalate (PET), plain paper,
Coated paper, glass epoxy sheet, metal plate and the like can also be used. In the case of an image receiving sheet having an image receiving layer provided on a support, a back layer for improving transportability is preferably provided on the surface of the support opposite to the image receiving layer.

Examples of the support for the image receiving sheet 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 sheet, a polyvinyl chloride sheet, a polyvinylidene chloride sheet, a polystyrene sheet, a styrene-acrylonitrile sheet,
A polyester sheet can be used. Further, as the paper support, printing paper, coated paper or the like having good smoothness can be used. In the case where the image formed of the transfer material is arranged together with the entire image receiving sheet in the arrangement step,
Since the support needs to be evaporated and / or incinerated in the sintering process, the support may include atoms or compounds that do not disappear by evaporation or combustion in the sintering process, or may react with the pigment to change its color. It is preferably free of atoms or compounds.

It is preferable that the support of the image receiving sheet has minute voids (voids) because it functions as a cushion layer and can improve image quality. Such a support is, for example, a thermoplastic resin, a mixed melt obtained by mixing an inorganic pigment or a filler made of an incompatible polymer with the thermoplastic resin, a single-layer or multi-layer by a melt extruder. It can be produced by forming a film and stretching it uniaxially or biaxially. In this case, the porosity is determined by the selection of the resin and the filler, the mixing ratio, the stretching conditions, and the like.

The thickness of the support of the image receiving sheet is usually 1
It is 0 to 400 μm, preferably 25 to 200 μm. Further, the surface of the support is subjected to a surface treatment such as a corona discharge treatment or a glow discharge treatment in order to enhance the adhesion with the image receiving layer (or the cushion layer) or the adhesion with the image forming layer of the thermal transfer sheet. May be.

One or more image receiving layers are provided on the surface of the image receiving sheet for transferring a transfer material from a transfer layer and fixing the same. The image receiving layer is preferably a layer formed mainly of an organic polymer binder. The binder is preferably a thermoplastic resin, for example, acrylic acid, methacrylic acid, acrylate,
Homopolymers of acrylic monomers such as methacrylic acid esters and copolymers thereof, methylcellulose, ethylcellulose, cellulosic polymers such as cellulose acetate, polystyrene, polyvinylpyrrolidone, polyvinylbutyral, polyvinylalcohol, and vinyl such as polyvinylchloride Examples include homopolymers and copolymers of the system monomers, condensation polymers such as polyesters and polyamides, and rubber polymers such as butadiene-styrene copolymers. The binder of the image receiving layer is used in order to obtain an appropriate adhesive strength with the transfer material.
Preferably, the polymer has a glass transition temperature (Tg) lower than 90 ° C. For this purpose, it is also possible to add a plasticizer to the image receiving layer. Further, the binder preferably has a Tg of 30 ° C. or higher in order to prevent blocking between sheets. As the binder of the image receiving layer, the same as the binder contained in the transfer layer, in terms of improving the adhesion with the transfer layer during transfer recording, and improving the sensitivity and image strength,
Or it is particularly preferable to use a similar polymer.
The thickness of the image receiving layer is generally from 0.3 to 7 μm, preferably from 0.7 to 4 μm.

It is preferable that the image receiving sheet can be adhered to the surface of the ceramic body because the operation becomes easy even when a ceramic body having a curved surface such as a dish or a bottle is used. As the image receiving sheet, a layer composed of a water-soluble polymer (hereinafter, sometimes referred to as a “water-soluble polymer layer”) and an image receiving layer composed of a hydrophobic polymer (hereinafter, referred to as a “hydrophobic polymer layer”) are formed on a support. (Hereinafter, may be referred to as an “adhesive image-receiving sheet”). As the support, a paper support having excellent smoothness is preferably used.

When the support is a paper support, when the image-receiving sheet is immersed in water, a part of the water-soluble polymer is dissolved and the hydrophobic polymer layer can be peeled off from the paper support. At the same time, it is preferable that the peeled hydrophobic polymer layer can be bonded to the surface of a ceramic body such as a ceramic plate. As such a water-soluble polymer, for example, polymers used for painting ceramics, such as dextrin and gum arabic, polyvinyl alcohol, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, and gelatin are preferable. Examples of the hydrophobic polymer include polyvinyl butyral resin, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, styrene-acrylate copolymer, and styrene-maleic acid-acrylate copolymer. Thermoplastic resins such as polymers, polyamides, polystyrenes, polyesters, polyvinyl acetate resins, cellulose derivatives, polystyrene methacrylic resins, polyvinyl ether resins, polyurethane resins, polycarbonate resins, and rosin resins. Further, a resin used as an overprint lacquer for overcoating a ceramic body such as a ceramic body is preferably used, and examples thereof include an acrylic resin and a urethane resin.

As described above, the image receiving layer may be formed on the surface of the ceramic body. When the image receiving layer is formed on the surface of the ceramic body, the transferability promoting material is applied imagewise to at least one of the transfer layer surface of the transfer sheet and the image receiving layer surface of the ceramic body. The components in the image receiving layer when the image receiving layer is formed on the surface of the ceramic body are as described above.

In the latent image forming step, when a latent image is formed on the surface of the transfer layer or the surface of the image receiving layer by applying a transferability-promoting material imagewise, the transfer material among the transfer materials constituting the transfer layer is formed. Only the part of the latent image with the accelerating material attached,
The transferability-promoting material penetrates into the transfer layer, and the binding of the binder constituting the layer is loosened, and the binding force between the support and the transfer layer is reduced, and the transferability to the image receiving sheet is improved. It becomes possible to transfer at a temperature.

In the transfer step performed after the latent image forming step, the transfer material is transferred from the transfer layer to the image receiving layer in accordance with the formed latent image, and an image made of the transfer material is formed on the image receiving layer surface. . In the transfer step, at least the transfer layer and the image receiving layer are brought into contact with each other, and the transfer material in the transfer layer is transferred onto the image receiving layer only in a region to which the transferability promoting material is provided. At the time of transfer, it is preferable to apply pressure while applying heat. In the embodiment using the image receiving sheet, for example, the transfer step can be performed using a pair of heating nip rollers incorporating a heating unit such as a heater.

When the image receiving layer is not formed on the ceramic body, after the latent image forming step and the transferring step, the image formed of the transfer material formed on the image receiving sheet is arranged on the surface of the ceramic body. As the image receiving sheet,
When the image receiving layer uses a sheet containing a thermoplastic resin as a binder, the image receiving layer of the image receiving sheet is heated and pressed on the surface of the ceramic body, so that the image made of the transfer material is arranged on the surface of the ceramic body together with the image receiving sheet. can do. At the time of thermocompression bonding, the image made of the transfer material may be arranged so as to face the surface of the ceramic body, or the image receiving layer may be arranged so as to be sandwiched between the ceramic body and the image made of the transfer material. When the images made of the transfer material are arranged to face each other, a reverse image of the desired image is formed on the image receiving sheet.

When an adhesive image receiving sheet having a paper support is used, after the latent image forming step and the transferring step,
Part of the adhesive image-receiving sheet is immersed in water to partially dissolve the polymer of the water-soluble polymer layer, and peel off the hydrophobic polymer layer from the paper support, and place the peeled hydrophobic polymer layer on the surface of the ceramic body. The image formed of the transfer material and the transfer material can be attached to the surface of the ceramic body together with the image receiving layer.

When the image formed of the transfer material formed on the adhesive image-receiving sheet is disposed on the surface of the ceramic body, the image may be reversed. That is, after forming a reversal image on the image receiving layer in advance, the image portion may be arranged on the surface of the ceramic body by facing the surface of the ceramic body (reversing the image again). In this case, since the hydrophobic polymer layer is not interposed between the image and the surface of the ceramic body, the sintering of the inorganic pigment and the ceramic body proceeds more stably in the subsequent sintering step, which is preferable. Since the surface of the hydrophobic polymer layer (the surface on which the image formed of the transfer material is formed) does not have adhesiveness, when the ink image is arranged so that the image faces the ceramic body surface as described above, it is necessary to use the ceramic material. It is preferred to apply an adhesive water-soluble polymer to the body surface.

An image formed of a transfer material formed on an image receiving layer (a layer made of a thermoplastic resin or the like) of the image receiving sheet having no adhesiveness is transferred to an image receiving layer of the adhesive image receiving sheet. As described above, after partially immersing the adhesive image-receiving sheet (adhesive sheet having a paper support) in water, the paper support is peeled off, and an image formed of a transfer material together with a hydrophobic polymer layer on the surface of the ceramic body. Can also be arranged.

In the sintering step, the ceramic body on which the image of the transfer material is formed is heated, and the inorganic pigment contained in the transfer material is sintered on the surface of the ceramic body. The inorganic pigment is sintered on the surface of the ceramic body, and components other than the inorganic pigment in the transfer material and components such as an 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 development, 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. Heating may be performed by gradually increasing the temperature to the firing temperature, or after heating at a constant temperature of 300 ° C. to 500 ° C. for a certain time,
Preferably, the temperature is gradually increased to the firing temperature. In the case of using a paint as the inorganic pigment, the baking temperature is usually 650 ° C to 900 ° C, preferably 750 ° C to 850 ° C.
C., and the firing time at this temperature is preferably 1 to 8 hours. When an undercolor is used as the inorganic pigment, the baking temperature is set at 1000 ° C. to 1300 ° C., preferably 1 ° C.
It is preferable that the firing is performed at 100 ° C. to 1250 ° C. and the firing time is 1 to 8 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 (the components in the transfer layer and the components in the image receiving layer) disposed on the surface of the ceramic body together with the inorganic pigment during the sintering step contain atoms or compounds that are not lost by evaporation or combustion in the sintering step. It is preferable not to contain an atom or a compound which changes color by reacting with an inorganic pigment.

The ceramic body with a picture produced by the manufacturing method of the present invention can be used, for example, in a ceramic photo application (portrait, funeral photograph, pet photograph, etc.) by selecting various shapes and formed images of the ceramic body to be painted. , For commemorative photos you want to keep forever, amusement and accessories (mugs, liquor bottles,
Building crests, including fish crests, fish cultivation, etc., and building materials (art tiles used on walls of bathrooms, entrances, living rooms, lobbies, guest rooms, etc., signs, information boards, room accessories, interior goods, etc.)
And so on.

[0065]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. [Example 1] <Preparation of transferability promoting material solution 1> 3,5-dimethyl-1-hexyn-3-ol 5 parts by mass Distilled water 50 parts by mass n-propyl alcohol 45 parts by mass The above components were uniformly stirred. Thereafter, the solution was filtered through a 0.45 μm microfilter to obtain a transferability promoting material solution 1.

<Preparation of Transfer Sheet> (1) Preparation of Yellow Transfer Sheet (Preparation of Inorganic Pigment Dispersion Y) 100 parts by weight of yellow pigment (manufactured by Celdec; 13651) 4 parts by mass of dispersant (manufactured by Shin-Etsu Chemical Co., Ltd .; Surfy) Knol CT-324) Water 60 parts by mass The above components were dispersed in an automatic mortar for 3 hours to obtain an inorganic pigment dispersion Y.

(Preparation of Coating Solution) Pigment Dispersion Y 41 parts by mass Polyoxythylene (n = 10) nonylphenol ether 0.5 parts by mass (20% by mass aqueous solution) Carbana wax dispersion (31% by mass) 20 parts by mass ( Chukyo Yushi Co., Ltd .; K-332) Butyral resin dispersion (25% by mass) 60 parts by mass (Chukyo Yushi Co., Ltd .; Resem J667) Water 100 parts by mass The above components were sufficiently stirred to prepare a coating solution for a transfer layer. .

The transfer layer coating solution was applied to a 5 μm thick polyester film so as to have a dry film thickness of 1.2 μm to form a transfer layer, thereby producing a yellow transfer sheet.

(2) Preparation of Magenta, Cyan and Black Transfer Sheet In the preparation of the above yellow transfer sheet, a magenta pigment (manufactured by Celdec Co .;
1), a magenta transfer sheet, a cyan transfer sheet and a black transfer sheet were prepared in the same manner as the yellow transfer sheet, except that a cyan pigment (manufactured by Celdec; 121522) and a black pigment (manufactured by Celdec; 14209) were used. did.

(3) Preparation of Image Receiving Sheet 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 (Nissin Chemical Co., Ltd .; Solvain CL2) Ethylene-vinyl acetate copolymer 61 parts by mass (Mitsui DuPont) Chemical Co., Ltd .; Elvaloy 742) Sebacic acid polyester 28 parts by mass (Nippon Soda Co., Ltd .; FN-G25) Perfluoroalkyl group-containing oligomer 4 parts by mass (Dainippon Ink Chemical Industry Co., Ltd .; MegaFac F) -178K) Methyl ethyl ketone 630 parts by mass Toluene 210 parts by mass Dimethylformamide 30 parts by mass

[Composition of the coating solution for the second layer (image receiving layer)] Polyvinyl butyral resin 16 parts by mass (manufactured by Denki Kagaku Kogyo KK; Denka butyral # 2000-L) N, N-dimethylacrylamide-butyl acrylate copolymer Combined 4 parts by mass Perfluoroalkyl group-containing oligomer 0.5 part by mass (manufactured by Dainippon Ink and Chemicals, Inc .; Megafac 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 when dried. Next, the second layer coating solution is applied on the first layer,
After drying at 0 ° C., a second layer (image receiving layer) having a thickness of 2 μm upon drying was formed to obtain an image receiving sheet.

(4) Production of a Pictured Ceramic Plate A full-color image is formed on the image receiving sheet by using the image forming apparatus 40 shown in FIG. The image forming apparatus 40 includes:
A discharge head 42 for applying droplets of a transferability promoting material solution to the surface of the second layer (image receiving layer) of the image receiving sheet 20 in an image-wise manner, and a supporting drum for transporting the image receiving sheet 20 and the transfer sheet 10 while heating and pressing the same. 44 and a pinch roller 46. Further, it includes a take-up roller 48 provided at the end of the transfer path of the transfer sheet 10, and a rectangular parallelepiped peel bar 50 disposed downstream of the support drum 44 in the transfer path of the transfer sheet 10. The transport path further includes a heater 52 for heating and drying the transferability-promoting material solution on the image receiving sheet 20 discharged imagewise and a heater 54 for heating and drying the transferred image transferred on the image receiving sheet 20. Have.

The prepared image receiving sheet and yellow transfer sheet are set in the image forming apparatus 40 shown in FIG. 5, and the discharge head 42 is filled with the prepared transferability promoting material solution 1. An inverted image) was formed on the image receiving sheet. At this time, the temperature of the nip between the support drum 44 and the pinch roller 46 was set to 75 ° C. The same operation was repeated once for the yellow transfer sheet. The same operation was performed twice for magenta, cyan, and black transfer in the same manner as for yellow transfer, to form a full-color image (mirror image reversal image) on the image receiving sheet.

The image forming surface of the image receiving sheet on which the image is formed and the surface of the porcelain plate are overlapped so as to be in contact with each other, heated and pressed by a heat roller, and the image receiving sheet is peeled off. The layer was peeled off from the image receiving sheet and adhered to the ceramic plate. A pigment image (normal image) was formed on the ceramic plate. Next, the ceramic plate on which the inorganic pigment image was formed was fired at 400 ° C. for 1 hour, and further at 850 ° C. for 2 hours, and the inorganic pigment was sintered on the ceramic plate to produce a painted ceramic plate 100.

Example 2 <Preparation of Transfer Paper> Overcoat lacquer containing methacrylic resin as a main component on a smooth paper support having a basis weight of 100 g coated with 1.5 g / m ^{2 of} gum arabic. (Plus size LD-170; manufactured by Ryogo Chemical Industry Co., Ltd.)
The coating was dried to a thickness of μm to prepare a transfer paper.

<Preparation of a Painted Porcelain Plate> The image forming apparatus 4 shown in FIG.
Using 0, a full-color image (normal image) was formed on the image receiving sheet in the same manner as in Example 1. The image forming surface of the image receiving sheet was brought into contact with the coated surface of the prepared transfer paper, superposed, and heated and pressed by a heat roller to peel off the image receiving sheet. The image formed on the image receiving sheet and the second layer are transferred onto the transfer paper, and the image (mirror image) is transferred onto the transfer paper.
Was formed. Next, the transfer paper on which the image is formed is immersed in water, the paper support is peeled off, and the surface on which the image is formed is opposed to the ceramic plate side. The pieces were superimposed, excess water was removed with a rubber spatula, and the pieces were brought into close contact (adhesion) with a ceramic plate. After sufficiently drying, the resultant was baked in an electric kiln at 400 ° C. for 2 hours and further at 850 ° C. for 2 hours, thereby producing a painted ceramic plate 200.

Example 3 (1) Preparation of Yellow Image Sheet (Preparation of Pigment Dispersion) 100 parts by weight of yellow pigment (manufactured by Celdec; 13651) 4 parts by mass of dispersant (manufactured by Nissin Chemical Co., Ltd .; Surfynol CT) -324) Water 60 parts by mass The above components were dispersed in Micros MIC-ONZ (Nara Machinery Co., Ltd.) for 2 hours to obtain a yellow pigment dispersion.

(Preparation of Coating Solution) Pigment dispersion 41 parts by mass Polyoxythylene (n = 10) nonylphenol ether 0.5 part by mass (20% by mass aqueous solution) Carbana wax dispersion (31% by mass) 40 parts by mass (Chukyo Y-Fat Co .; K-332) Toho Chemical Co .; E5407B (54% by mass) 20 parts by mass Butyral resin dispersion (25% by mass) 20 parts by mass (Chukyo Yushi Co .; Resem V627) Water 60 parts by mass By sufficiently stirring, a coating solution for a transfer layer was prepared.

The transfer layer coating solution was applied to a 5 μm-thick polyester film so as to have a dry film thickness of 1.3 μm to form a transfer layer, thereby producing a yellow transfer sheet.

(2) Preparation of Magenta, Cyan and Black Transfer Sheet In the preparation of the above yellow transfer sheet, a magenta pigment (manufactured by Celdec Co .;
1), a magenta transfer sheet, a cyan transfer sheet and a black transfer sheet were prepared in the same manner as the yellow transfer sheet, except that a cyan pigment (manufactured by Celdec; 121522) and a black pigment (manufactured by Celdec; 14209) were used. did.

(3) Production of Image Receiving Sheet The image receiving sheet was produced in the same manner as in Example 1.

(4) Preparation of a painted ceramic plate (image transfer) First Pro manufactured by Fuji Photo Film Co., Ltd.
A full-color image is formed on the image receiving sheet by using a thermal printer for off. A part of the transfer sheet for First Proof is replaced with the yellow transfer sheet,
A yellow image was formed on the image receiving sheet by performing color separation into YMCK and successively transferring the yellow image twice. The magenta, cyan, and black images were successively transferred twice on the same image receiving sheet in the same manner as the yellow image to form a full-color image (mirror image) on the image receiving sheet. (Preparation of a painted ceramic plate) The coated surface of the transfer paper prepared in Example 2 and the image-formed surface of the image-receiving sheet on which the image was formed were brought into contact with each other, superposed, and heated and pressed by a heat roller to peel off the image-receiving sheet. The image formed on the image receiving sheet and the second layer were transferred onto the transfer paper, and an image (mirror image) was formed on the transfer paper. Next, the transfer paper on which the image is formed is immersed in water,
The paper support is peeled off, the surface on which the image is formed is opposed to the ceramic plate side, and a ceramic plate provided with a 2% aqueous solution of gum arabic is superimposed on the surface, and excess water is removed with a rubber spatula. Adhered (adhered). After being sufficiently dried, it was baked in an electric kiln at 400 ° C. for 2 hours and further at 850 ° C. for 2 hours to produce a painted ceramic plate 300.

Comparative Example 1 In Example 2, the coating film thickness of each of the yellow, magenta, cyan and black transfer sheets was doubled (2.4 μm), and the transfer of each color pigment image to the image receiving sheet was performed once. A painted ceramic plate 400 was produced in the same manner as in Example 2 except that the steps were performed one by one.

[Comparative Example 2] In Example 3, the coating film thickness of each of the yellow, magenta, cyan and black transfer sheets was doubled (2.6 μm), and the transfer of each color pigment image to the image receiving sheet was performed once. A porcelain plate with picture 500 was produced in the same manner as in Example 3 except that the steps were repeated.

[0086] The painted ceramic plate 100 thus produced
Samples 200 and 300 had higher resolution, better reproducibility of fine lines, and higher density and clearer images than the painted ceramic plates 400 and 500 (Comparative Example).

[0087]

According to the present invention, a ceramic body with a picture having good image storability can be stably manufactured at a low cost by a simple process and a high color density is maintained on the ceramic body. An image with good gradation can be formed.

[Brief description of the drawings]

FIG. 1 is a schematic process diagram for explaining one embodiment of a method for manufacturing a painted ceramic body according to the present invention.

FIG. 2 is a schematic process drawing for explaining another embodiment of the method for manufacturing a painted ceramic body according to the present invention.

FIG. 3 is a schematic process drawing for explaining still another embodiment of the method for manufacturing a painted ceramic body according to the present invention.

FIG. 4 is a schematic process drawing for explaining still another embodiment of the method for manufacturing a painted ceramic body according to the present invention.

FIG. 5 is a schematic diagram of an image forming apparatus used in the embodiment.

FIG. 6 is an explanatory diagram showing the gradation of an image by a conventional transfer method.

FIG. 7 is an explanatory diagram showing the gradation of an image by the transfer method of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 10 transfer sheet 12 support 14 transfer layer 20, 20 ′ image receiving sheet 22 support 24, 24 ′, 24 ″ image receiving layer 26 water-soluble polymer layer 30, 30 ′ ceramic plate 32, 32 ′, 32 ″, 32 ″ '' Painted ceramic plate i image formed of transfer material 40 image forming apparatus 42 discharge head 44 support drum 46 pinch roller 48 take-up roller 50 peeling bar 52, 54 heater

Claims (7)

[Claims] 1. The method according to claim 1, wherein at least a transfer layer surface of a transfer sheet having a transfer layer made of a transfer material containing an inorganic pigment and an image receiving layer surface of an image receiving sheet having an image receiving layer capable of transferring the transfer material are brought into contact with each other. Transferring a material to the surface of the image receiving layer and forming an image of the transfer material on the surface of the image receiving layer; and arranging the image of the transfer material on a surface of the ceramic body together with part or all of the image receiving sheet. And a sintering step of heating the ceramic body on which the image made of the transfer material is arranged, and sintering the inorganic pigment included in the transfer material on the surface of the ceramic body. A method of producing a picture-formed ceramic body, wherein the same color image is formed and transferred in two or more times using two or more transfer sheets. Law. 2. The method according to claim 1, wherein a transfer layer surface of a transfer sheet having a transfer layer made of a transfer material containing an inorganic pigment and at least an image receiving layer surface capable of transferring the transfer material formed on a ceramic body are brought into contact with each other. Transferring and arranging a transfer material onto the image receiving layer surface and forming an image made of the transfer material on the image receiving layer surface; heating a ceramic body on which the image made of the transfer material is arranged; And a sintering step of sintering the inorganic pigment included in the ceramic body on the surface of the ceramic body. In forming the same color image in the transfer step, the sintering step is performed twice or more using two or more transfer sheets. A method for producing a painted ceramic body, wherein the ceramic body is separately transferred. 3. The transfer layer of the transfer sheet has a thickness of 2 μm.
The method for producing a painted ceramic body according to claim 1 or 2, wherein: 4. The image forming apparatus according to claim 1, wherein a pigment image is formed on a transfer layer of the transfer sheet via a thermal transfer printer, and the pigment image is transferred to an image receiving layer surface of the image receiving sheet. The method for producing a ceramic body with a picture according to any one of the above. 5. A latent image is formed on at least one of the surface of the transfer layer and the surface of the image receiving layer by imagewise applying a transferability promoting material capable of promoting the transfer of the transfer material to the surface of the image receiving layer. A latent image forming step, wherein the transferring step comprises a step of transferring the transfer material to the surface of the image receiving layer corresponding to the latent image to form an image on the surface of the image receiving layer. The method for producing a painted ceramic body according to claim 1 or 2. 6. The painted ceramic according to claim 1, further comprising a second transfer step of transferring an image made of a transfer material to another image receiving sheet between the transfer step and the arranging step. How to make the body. 7. The image receiving sheet is a sheet in which a layer containing a water-soluble polymer and an image receiving layer are sequentially laminated on a support, and in the arranging step, the water-soluble polymer is partially dissolved in water to form a support. The image of a transfer material is arranged on the surface of the ceramic body together with the image receiving layer while the body is peeled off and the peeled surface or the opposite side is adhered to the surface of the ceramic body. The method for producing a ceramic body with a picture according to the above.