JP2002348496A - Coated inorganic pigment, transfer sheet, earthenware having image, earthenware having multicolor picture and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the title pigment suitable for disposing/sintering on the surface of an earthenware multicolor images that have high color development concentration and resolution and that retain hues intrinsic to inorganic pigments without discoloration, a transfer sheet that has a transfer layer containing the title pigment, an images-bearing earthenware that is provided on the surface of the ware with the images of the inorganic pigment containing the title pigment, a multicolor pictures-bearing earthenware that is provided on the surface of the ware with the images of the sintered inorganic pigment containing the title pigment, and a manufacturing method of the multicolor pictures-bearing earthenware. SOLUTION: There are provided the title pigment that is used for manufacturing the earthenware having pictures in which the images of the inorganic pigment is sintered on the surface of the ware and that is coated with an inorganic oxide having a melting point higher than the sintering temperature at the time of the manufacture; the transfer sheet having the transfer layer containing the title pigment; the earthenware having images provided on the surface of the ware with the images of the inorganic pigment containing the title pigment; the earthenware having the multicolor images provided on the surface of the ware with the images of the sintered inorganic pigment containing the title pigment; and the manufacturing method comprising the step of forming the earthenware having images and the step of sintering to obtain the earthenware having multicolor pictures by heating and sintering the earthenware having the images.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated inorganic pigment, a transfer sheet, an image porcelain, a multicolored porcelain, and a method for producing the same. Used as an image in the production of a painted ceramic body in which an inorganic pigment image is sintered, containing a coated inorganic pigment coated with an inorganic oxide, a transfer sheet containing the coated inorganic pigment in a transfer layer, and containing the coated inorganic pigment. The present invention relates to an image porcelain body provided with an inorganic pigment image on the surface of a porcelain material, a multi-colored porcelain body obtained by sintering the image porcelain body, and a method for producing the same.

[0002]

2. Description of the Related Art Porcelain having a black-and-white or color image formed on the surface of a building material such as an art tile or a ceramic material such as a ceramic material can be used only for a building material such as an art tile used for a bathroom or a wall such as an entrance. In addition, it is expected to be applied to various uses such as ceramic photos such as portraits and remains, accessories such as pendants and brooches. In recent years, there is a high demand for an image formed on the surface of a porcelain material, and the demand has been diversified individually.

Conventionally, as a method of forming an image having good storability on a porcelain material, there is a method of sintering an image formed with an inorganic pigment on a porcelain material. It is necessary to select an image forming method suitable for the characteristics. 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 order to form a full-color or other multi-color image on a porcelain material by this transfer method or the like, the inorganic pigment image arranged on the porcelain material is dried and then heated and sintered. There is a problem that the inorganic pigments of the colors react with each other and cause discoloration. Also, when the upper paint is used as the inorganic pigment, the discoloration is small, but when the lower paint is used,
Since the firing temperature is 1000 to 1300 ° C., which is a high temperature, there is a problem that discoloration easily occurs due to the reaction between the inorganic pigments.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. In other words, the present invention has a high color density, high resolution and excellent gradation, and retains the original hue of the inorganic pigment on the surface of a building material such as an art tile or a porcelain material such as a ceramic material. Coating inorganic pigment suitable for arranging and sintering a multicolor image, a transfer sheet containing the coating inorganic pigment in a transfer layer, and an inorganic pigment image made of a material containing the coating inorganic pigment provided on the surface of the porcelain It is an object of the present invention to provide an image porcelain body, a porcelain body with a multicolor picture, in which a sintered inorganic pigment image containing the coated inorganic pigment is provided on the surface of the porcelain material, and a method for producing the porcelain body with a multicolor picture.

[0006]

The specific means for solving the above problems are as follows. That is,

<1> A coated inorganic pigment used for producing a painted porcelain in which an inorganic pigment image is sintered on the surface of a porcelain material. A coated inorganic pigment which is coated with a colorless inorganic oxide.

<2> The melting point of the inorganic oxide is higher than the firing temperature at the time of manufacturing the painted ceramic body.
2. The coated inorganic pigment described in 1. above.

<3> The coated inorganic pigment according to <1> or <2>, wherein at least one of the inorganic oxides is silica, alumina, or zirconia.

<4> On the support, the above <1> to <3>
A transfer sheet comprising a transfer layer comprising a transfer material containing the coated inorganic pigment according to any one of <1> to <3>.

<5> An image porcelain characterized in that an inorganic pigment image made of a material containing the coated inorganic pigment according to any one of <1> to <3> is provided on the surface of porcelain. is there.

<6> A porcelain with a multicolor picture, wherein a sintered inorganic pigment image containing the coated inorganic pigment according to any one of <1> to <3> is provided on a surface of the porcelain. .

<7> An image porcelain molding step of molding the image porcelain according to <5>, and sintering the image porcelain with multicolor painting according to <6> by heating the image porcelain. And a firing step obtained by the method described above.

<8> An image in which the image porcelain molding step forms an inorganic pigment image made of a material containing the coated inorganic pigment according to any one of <1> to <3> on the surface of the image receiving body. The multicolor pictured porcelain according to <7>, comprising: a forming step; and an arranging step of arranging the inorganic pigment image on a surface of the porcelain together with part or all of the image receiving body. It is a manufacturing method.

<9> The production of the multicolor-painted porcelain according to <8>, wherein the image receptor is an adhesive image receptor having a water-soluble polymer-containing layer on the surface of a water-permeable support. Is the way.

<10> In the image forming step and the arranging step, after forming an inorganic pigment image on the layer containing the water-soluble polymer, a hydrophobic polymer layer is coated on the inorganic pigment image forming surface. Or, after laminating a hydrophobic polymer film, the water-permeable support side is immersed in water to dissolve a part of the water-soluble polymer, peeling the water-permeable support from the adhesive image-receiving body, the adhesive <9> The method for producing a ceramic body with a multicolor picture according to <9>, wherein the inorganic pigment image is arranged on the surface of the porcelain so that the peeled surface of the image receiving body contacts the surface of the porcelain.

<11> In the image forming step and the arranging step, the inorganic pigment is formed on the surface of the image receiving member, in which a layer containing a water-soluble polymer and a hydrophobic polymer layer are sequentially provided on the water permeable support. After forming an image, the water-permeable support side is immersed in water, a part of the water-soluble polymer is dissolved, and the water-permeable support is peeled from the adhesive image-receiving body,
The method for producing a ceramic body with a multicolor picture according to the item <9>, wherein the image forming surface of the adhesive image receiving body is arranged on the surface of the ceramic material by interposing a liquid or a hot melt adhesive in which a paste is dissolved or dispersed. is there.

<12> The inorganic pigment image is formed by any one of an electrophotographic method using a transfer sheet, a transfer method using a latent image forming liquid, a melt transfer method, and a solid ink jet method, and The transfer sheet used in the above method is the transfer sheet according to the above <4>, wherein the transfer sheet is from <8> to <1>.
1> The method for producing a ceramic body with a multicolor picture according to any one of <1> and <2>.

<13> The transfer in which the image forming step forms a transfer inorganic pigment image made of the material containing the coated inorganic pigment according to any one of <1> to <3> on the surface of the transfer image receiving body. An image forming step, and an image transferring step of transferring the transfer inorganic pigment image to the surface of the image receiving member to form the inorganic pigment image on the surface of the image receiving member, the image transferring step including:
11> The method for producing a ceramic body with a multicolor picture according to any one of the above items.

<14> An electrophotographic method using a transfer sheet, a transfer method using a latent image forming liquid,
The multicolor pictured porcelain according to <13>, wherein the transfer sheet formed by any one of a melt transfer method and a solid inkjet method and used in the method is the transfer sheet according to <4>. It is a manufacturing method of.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The coated inorganic pigment of the present invention is used for the production of a painted ceramic body in which an inorganic pigment image is sintered on the surface of a porcelain material. ,
And characterized by being coated with a colorless inorganic oxide after firing. And, the method for producing a multicolored porcelain of the present invention is an image porcelain molding step of molding an image porcelain obtained by providing an inorganic pigment image made of a material containing the coated inorganic pigment on the surface of the porcelain, And baking the image porcelain to obtain a multicolored porcelain body by sintering. Further, as the image ceramic forming step, an image forming step of forming an inorganic pigment image made of a material containing the coated inorganic pigment on the surface of the image receiving body, and forming the inorganic pigment image on a part of the image receiving body Or an arrangement step of arranging them together on the surface of the porcelain. Here, first, the method for producing the multicolor-painted ceramic body will be described, and among them, the coated inorganic pigment, the transfer sheet, the image ceramic body, and the multicolor-painted ceramic body of the present invention will also be described.

<< Method of Manufacturing Porcelain with Multicolor Pictures >> As described above, the method of manufacturing the ceramic bodies with multicolor pictures according to the present invention includes at least an image ceramic forming step and a firing step. Other steps may be provided accordingly. Preferably, the image porcelain molding step includes the image forming step and the arranging step. First, an example of a basic embodiment of the method for producing a multicolored ceramic body of the present invention will be described with reference to FIG. Here, FIG. 1 is a schematic process chart for explaining a basic aspect of the manufacturing method of the present invention.

First, as shown in FIG.
An image receiving body 5 having at least one image receiving layer 1 on which an image can be formed is prepared. As shown in FIG. 1- (b), a desired image recording method (electrophotographic method using a transfer sheet, using a latent image forming liquid) A desired image (inorganic pigment image) 11 is formed by applying a material containing the coated inorganic pigment imagewise by a transfer method or the like (image forming step in the image ceramic forming step).

Next, a transfer body 10 having the cover coat layer 6 on the surface of the temporary support 7 is prepared, and as shown in FIG. And the surface of the image receiving layer 1 on which the inorganic pigment image 11 has been formed in the image forming step is superposed so as to face each other,
Laminate by heating while applying pressure, if necessary.
After lamination, as shown in FIG.
The temporary support 7 is peeled off and the cover coat layer 6 is transferred onto the image receiving layer 1 (cover coat layer transfer step). At this time,
The cover coat layer is plasticized by heating, and the inorganic pigment image is in a state of sinking into the cover coat layer. Note that such a step is optional, and a coating liquid for a cover coat layer may be applied to the surface of the image receiving layer 1 on which the inorganic pigment image 11 has been formed to form a cover coat layer.
An image receiving member 5 provided with a cover coat layer in advance on the surface of the image receiving layer 1 was used.
1 may be formed. Although the cover coat layer 6 is not an essential component, it is preferable to provide the cover coat layer 6 from the viewpoint of workability. Further, the cover coat layer 6 is provided by the cover coat layer transfer step as described above. Is preferred.

Subsequently, the inorganic pigment image 11 is arranged on the porcelain material 12, and at any stage before and after this arrangement, the support 2 of the image receiving body 5 is peeled off at the boundary with the image receiving layer 1. For example, when the support 2 of the image receiving member 5 is formed of a water-permeable support and the image receiving layer 1 includes a water-soluble polymer,
When a part of the image receiving member 5 (see FIG. 1- (d)) provided with the inorganic pigment image 11 and the cover coat layer 6 is brought into contact with or immersed in water, water penetrates through the support 2 and becomes water-soluble. Part of the polymer is dissolved, and the support 2 can be easily peeled off (at this time, the support 2 is peeled off,
The surface of the image receiving layer that is in a partially dissolved state is referred to as a “peeling surface”. After peeling off the support 2, the inorganic pigment image 11 is arranged on the surface of the desired porcelain 12 together with the cover coat layer 6.
As shown in FIG. 1- (e), in a state where the water-soluble polymer in the image receiving layer 1 is partially dissolved, it is disposed on a desired surface of the porcelain 12 so as to be in contact with the peeled surface. In addition, it may be disposed on the surface of a desired porcelain material via a liquid in which a glue is dissolved or dispersed so as to be in contact with the surface opposite to the release surface, that is, the surface of the cover coat layer 6 (image ceramic). Arrangement step in the body formation step).

As described above, after the inorganic pigment image 11 is disposed on the surface of the porcelain 12 and the image porcelain is formed, the porcelain 12 (see FIG. 1- (e)) is heated and fired. As a result, as shown in FIG. 1- (f), the organic cover coat layer 6 and the image receiving layer 1 are burned off, the inorganic pigment image 11 is sintered on the surface of the porcelain material 12, and the inorganic image (sintered inorganic material) is formed. Pigment image) 1
1 'is formed (firing step).

Hereinafter, each step will be described in more detail. <Image forming step in image porcelain molding step> (Inorganic pigment image) In the image forming step in the image porcelain molding step, an inorganic pigment image made of a material containing the coated inorganic pigment of the present invention is formed on the surface of the image receiving body. Form. In the method for producing a multicolor-painted ceramic body of the present invention, in order to form a multicolor image, the inorganic pigment image corresponding to at least one hue may be formed of a material containing the coated inorganic pigment of the present invention. Further, the inorganic pigment images corresponding to all hues may be made of a material containing a coated inorganic pigment. Here, the inorganic pigment image is an image drawn using the material containing the coated inorganic pigment of the present invention, and the `` material containing the coated inorganic pigment '' is, in addition to the coated inorganic pigment of the present invention, A material that forms the above-mentioned inorganic pigment image, including other inorganic pigments, a binder component such as a binder resin, and a flux (a heat-fusible inorganic substance) as necessary. The coated inorganic pigment of the present invention, other inorganic pigments, a binder component, a flux, and the like, and details and preferred embodiments of the image receiving member will be described later.

-Coated Inorganic Pigment- As described above, the material for forming an inorganic pigment image in the present invention contains at least the coated inorganic pigment of the present invention. The coated inorganic pigment of the present invention is characterized by being coated with an inorganic oxide which does not inhibit the original coloration of the inorganic pigment during firing and is colorless after firing, and the inorganic oxide is a painted ceramic It is preferable that the inorganic oxide has a melting point higher than the sintering temperature at the time of the production of the above. Further, it is preferable that at least one of the inorganic oxides is silica, alumina, and zirconia. After forming the image porcelain by heating the image porcelain, the material for forming the inorganic pigment image, by using a material containing a coated inorganic pigment coated with the inorganic oxide as the inorganic pigment component, is used. When sintering,
Since the inorganic pigments having different hues do not react with each other to cause discoloration, it is possible to obtain a multicolor image without discoloration while maintaining the original hue of the inorganic pigment.

As the inorganic pigment used in the coated inorganic pigment of the present invention, there can be used an upper paint and a lower paint which are usually used for pottery. Metal oxides such as picrois, rutile, priderite, phophosphate, phenasite, perryclays, olivine, badderite, borate, corundum, zircon; sulfides such as cadmium yellow; cadmium selenide compounds such as selenium red Is mentioned. Further, an inorganic pigment which is a fluorescent pigment or a phosphorescent pigment may be used.

The above-mentioned inorganic pigment is coated with an inorganic oxide having a melting point higher than the sintering temperature at the time of producing the painted ceramic. The method for producing a painted ceramic body of the present invention comprises: an image ceramic body forming step of forming an image ceramic body having an inorganic pigment image formed of a material containing the coated inorganic pigment provided on a surface of the ceramic body; A sintering step of heating and sintering the body, in the sintering step, a porcelain (image porcelain) on which an inorganic pigment image is arranged
Is dried and then heated and sintered, but the firing temperature in the production of the painted ceramic, that is, the firing temperature in the firing step is usually 6 when using the upper paint as the coated inorganic pigment.
The temperature is from 50 ° C to 900 ° C, preferably from 750 ° C to 850 ° C, and the firing time is preferably from 10 to 180 minutes. On the other hand, when an undercolor is used as the coated inorganic pigment, the firing temperature is usually 1000 to 1300 ° C.,
The temperature is preferably from 00 to 1250 ° C.
It is preferably between minutes and 8 hours. Therefore, the inorganic pigment of the present invention is coated with an inorganic oxide having a melting point higher than the above-mentioned calcination temperature. Among such inorganic oxides, for example, silica (melting point: 1600 ° C. or more), alumina (melting point: 2000 ℃ or more), and zirconia (melting point: 270
0 ° C. or higher), and at least one of the inorganic oxides is preferably silica, alumina, or zirconia.

The melting point of the inorganic oxide is 1400 ° C. with respect to the firing temperature at the time of manufacturing the painted ceramic body.
Or higher, and more preferably 1600 ° C. or higher.

The coated inorganic pigment of the present invention is obtained by coating the above-mentioned inorganic pigment with the above-mentioned inorganic oxide. As a method of coating (coating) an inorganic pigment with an inorganic oxide,
A known method can be used, and the method is not limited. From the viewpoint of not affecting the properties of the inorganic pigment, the following liquid phase coating method is preferably used.

--Liquid phase coating method--In a liquid phase coating apparatus provided with a stirring tank and stirring blades, a liquid in which an inorganic pigment is suspended in water is put into a stirring tank, and 0.1 N of water is stirred. The pH of the suspension was adjusted to 10 using sodium hydroxide solution. afterwards,
The liquid was heated and heated up to 60 ° C. A predetermined amount of an aqueous solution of sodium silicate, an aqueous solution of sodium aluminate, and / or an aqueous solution of sodium zirconate was added thereto, followed by sufficient stirring. Thereafter, p of the suspension was added using 1N acetic acid aqueous solution.
H was adjusted to 7.5. As a result, the following reactions (1) and (2) occurred in the stirring tank, and silica, alumina, and / or zirconia precipitated on the surface of the inorganic pigment by the chemical reaction, and the surface of the inorganic pigment was coated with the inorganic oxide. In the obtained coated inorganic pigment, filtration,
After the washing, post-treatment such as heating at 100 to 300 ° C. was performed.
The inorganic pigment used here was finely pulverized so as to have an average particle size of 0.1 to 5.0 μm. The inorganic pigment has an average particle size of 0.2 to 3.
It is preferably 0 μm, and particularly preferably 0.3 to 1.5 μm.

The silica precipitation reaction _{Na 2 O · SiO 2 · 5H} 2 O + CH 3 COOH → SiO 2
+ 2CH ₃ COONa + 6H ₂ O Precipitation reaction of alumina NaAlO ₂ + CH ₃ COOH + nH ₂ O → (1/2) A
l ₂ O ₃ .nH ₂ O + CH ₃ COONa + (1/2) H ₂ O Precipitation reaction of zirconia Na ₂ ZrO ₃ + 2CH ₃ COOH + nH ₂ O → ZrO _2.
nH ₂ O + 2CH ₃ COONa + H ₂ O (precipitation reaction of zirconia)

In the liquid phase coating method, the inorganic pigment may be coated alone with one of silica, alumina and zirconia, and the inorganic pigment may be coated with two or more of silica, alumina and zirconia in combination. May be. That is, one of the sodium silicate aqueous solution, the sodium aluminate aqueous solution, and the sodium zirconate aqueous solution may be used alone, or two or more thereof may be used in combination.

The amount of the inorganic oxide coating the inorganic pigment is preferably from 0.05 to 2 parts by mass, more preferably from 0.1 to 1 part by mass, per 1 part by mass of the inorganic pigment. More preferred.

In the inorganic pigment image made of the material containing the coated inorganic pigment according to the present invention, an inorganic pigment which is a raw material of the coated inorganic pigment and which is not coated with the inorganic oxide is contained. However, in the same kind of inorganic pigment image, the content of the coated inorganic pigment is preferably 80% by mass or more, more preferably 90% by mass or more. When inorganic pigments that react with each other are used, both inorganic pigments may be coated, or only one of them may be coated.

(Image Forming Method) The method for forming the inorganic pigment image (image recording method) can be appropriately selected from known methods, for example, electrophotography, electrophotography using a transfer sheet. Method, a transfer method using a latent image forming liquid (hereinafter sometimes referred to as “LMIT method”), a melt transfer method, a solid ink jet method, and the like can be preferably used. Among them, in the present invention, the electrophotographic method using a transfer sheet, the transfer method using a latent image forming liquid (LMIT
Method) is preferred.

Electrophotography As the electrophotography, a method using a transfer sheet (hereinafter sometimes simply referred to as “electrophotography”) is preferable. In the electrophotographic method, first, using an electrophotographic technique, an adhesive latent image formed of an adhesive composition, preferably a colorless or pale color, is formed on the surface of the image receiving layer of the image receiving layer having an image receiving layer on the surface of a support. An image (adhesive latent image) is formed. That is, using an adhesive composition containing a binder resin, an electrostatic latent image formed by electrophotography is developed to form a colorless or light-colored adhesive latent image, and then the adhesive latent image is transferred. To form a latent image having adhesiveness on the image receiving layer of the image receiving body.

The adhesive composition must be capable of adhering to the transfer layer in the image forming step so as to form a state in which the transfer layer can be peeled off from the transfer sheet in an image-wise manner. Resin) and, if necessary, frit (a heat-meltable inorganic substance). The thermoplastic resin can be appropriately selected from known thermoplastic resins, and examples thereof include a binder resin described below. Examples of the frit (thermally fusible inorganic substance) include a flux that can be used for a transfer layer of a transfer sheet described below.

The adhesive force of the adhesive latent image formed by the adhesive composition is determined by the contact between the transfer layer of the transfer sheet and the latent image after heating while being brought into contact with the adhesive latent image in the image forming step. It is necessary that the adhesive strength is larger than the adhesive strength between the transfer layer of the transfer sheet and the temporary support. By securing a sufficient adhesive force for the transfer of the transfer layer, transferability capable of forming an image with high resolution and high gradation can be obtained.

The adhesive composition does not substantially contain a coloring material capable of forming a colored image, has an adhesive property including a binder resin, and is manufactured according to a toner manufacturing technique in the field of electrophotography. It may be toner. Commercially available toner can be used as the toner. However, from the viewpoint that a desired image hue is obtained without being colored black by baking, a material containing no magnetic component such as iron or iron oxide is preferable. That is, an image as a latent image is formed instead of a colored image finally formed on the porcelain material after firing.

As an electrophotographic technique using the colorless or light-colored adhesive composition, for example, JP-A-9-1977
No. 19, etc., in place of the colored toner, a colorless or light-colored toner containing no inorganic coloring material,
That is, a pre-formed electrostatic latent image is developed using a toner having an adhesive function (adhesive toner) containing at least a binder resin and, if necessary, a heat-fusible inorganic substance (frit) and the like. Alternatively, a method of transferring the adhesive latent image onto a desired porcelain material may be used. An adhesive latent image is formed by developing a previously formed electrostatic latent image using an adhesive toner to form a colorless or light-colored latent image, and then transferring the latent image to an image receiving layer surface of an image receiving body. Can be done by For details of the method, reference can be made to the description of JP-A-9-197719 (excluding the description of the inorganic coloring material).

Here, the adhesive toner contains at least a binder resin and, if necessary, a heat-fusible inorganic substance and the like. The layer is configured to be peelable for imaging. Examples of the binder resin include those described in paragraph [0012] of JP-A-9-197719, and the like.
From the viewpoint of ensuring sufficient adhesiveness, polyester resins, butyral resins, ethylene-vinyl acetate resins, acrylic resins, and the like are preferable.

The content of the above-mentioned thermoplastic resin (binder resin) is not particularly limited, and the adhesion (that is, transferability) of the transfer layer in the subsequent image forming step is ensured, and a high-resolution image is formed. From the viewpoint of forming, an adhesive composition (adhesive toner)
It is preferably at least 50% by mass of the total amount (mass). When the adhesive composition (adhesive toner) contains a binder resin and a heat-fusible inorganic substance, the content of the binder resin is preferably 10% by mass or more, more preferably 45% by mass or more based on the total amount (mass) of the toner. Is more preferable, and 55% by mass or more is particularly preferable. The upper limit is usually about 60 to 85% by mass. The content rate is 55
When the content is not less than% by mass, it is possible to secure necessary characteristics as an electrophotographic toner, such as charging characteristics and fixing characteristics.

The above-mentioned heat-fusible inorganic substance (frit) is described, for example, in paragraphs [0006] to [00] of the publication.
11]. The content of the heat-fusible inorganic substance is preferably from 10 to 50% by mass based on the content of the thermoplastic resin (binder resin).

The adhesive toner can be manufactured according to a toner manufacturing technique used in the electrophotographic art. In this case, an auxiliary component such as a charge control agent can be added to the adhesive toner. As the charge control agent, those described in JP-A-9-197719 are preferably used. In this method, for example, a kind of toner-like adhesive composition may be prepared, and it is not necessary to prepare a toner corresponding to each color or a special color toner, and a relatively inexpensive monochrome image forming printer is used. By using the electrophotographic technology and the transfer method, a high-resolution inorganic image (including multicolor or full color) of various hues can be formed simply and at low cost.

-LMIT Method- The LMIT method is used to transfer the transfer sheet of the present invention, that is, the transfer layer surface of a transfer sheet having a transfer layer comprising a transfer material containing a coated inorganic pigment on a support, and transferring the transfer material. On at least one of the image receiving layer surfaces of the image receiving sheet having a possible image receiving layer, a latent image forming liquid containing a transferability promoting material or a tacky material capable of promoting the transfer of the transfer material to the image receiving layer surface is imagewise. Forming a latent image by applying, at least bringing the transfer layer surface and the image receiving layer surface into contact with each other, transferring a transfer material to the image receiving layer surface corresponding to the latent image, and transferring the transfer material to the image receiving layer surface. This is a method of forming an image (inorganic pigment image) composed of After the formation of the inorganic pigment image, the image was placed on the surface of a porcelain material, such as a desired ceramic body, to obtain an image porcelain body. (Including other inorganic pigments) is fixed to the porcelain surface by sintering. Specifically, the present inventors have filed Japanese Patent Application No. 2000-1.
No. 43304 and Japanese Patent Application No. 11-281179 (method using a transfer promoting material). Example when LMIT method is applied (image forming step)
Will be described below with reference to FIGS. Figures 2 and 3
FIG. 3 is a schematic process diagram showing one embodiment of an image forming step in the manufacturing method of the present invention.

As shown in FIG. 2-((a) -2), a transfer sheet 15 of the present invention and an image receiving member 5 'are prepared. The transfer sheet 15 of the present invention includes, for example, at least a transfer layer 8 made of a transfer material containing a coated inorganic pigment on the surface of a temporary support 9. On the surface, a layer 1 containing a water-soluble polymer and an image receiving layer 3 are sequentially provided. As shown in FIG. 1A, a single-layer image receiving member 5 may be used as the image receiving member 5 '. Further, instead of the layer 1 containing a water-soluble polymer, a polymer layer having low adhesion such as a silicone resin or polyvinyl alcohol may be provided so as to have good releasability.

Next, on the surface of the image receiving layer 3 of the image receiving member 5 ′ or the surface of the transfer layer 8 of the transfer sheet 15, a transfer promoting material or Droplets containing an adhesive material are applied imagewise to form a latent image. Thereafter, as shown in FIG. 3 (b) -2), the surface of the image receiving layer 3 of the image receiving body 5 'on which the latent image is formed and the surface of the transfer layer 8 of the transfer sheet 15 are opposed to each other and contact each other. The layers are stacked as described above, and heated and laminated while applying pressure, if necessary. After laminating,
As shown in ((b) -3), when the transfer sheet 15 is peeled off, the transfer layer 8 is transferred only to the region (latent image portion) of the image receiving layer 3 to which the transferability promoting material or the tacky material has been applied, On the image receiving layer 3, an image 2 composed of a transfer material is formed as an inorganic pigment image.
1 (see FIG. 3-((b) -4)) is transferred and formed (image forming step). When the image receiving body 5 having a single layer (see FIG. 1A) is used, the image 21 is formed on the image receiving layer 1. At the time of lamination, it is preferable to apply pressure together with application of heat. For example, a pair of heating nip rollers incorporating a heating means such as a heater is suitable. In addition, as heating temperature at the time of heating, 60-150 degreeC is preferable.

Next, a transfer sheet, a transferability promoting material or a latent image forming liquid containing a tacky material used in the LMIT method will be described in detail. --Transfer Sheet-- The transfer sheet of the present invention is characterized by having a transfer layer made of a transfer material containing a coated inorganic pigment on a support.
The transfer material is colored, and other layers such as a cushion layer and a cover sheet may be provided in addition to the transfer layer. This transfer sheet can be suitably used in the below-described melt transfer method, the above-described electrophotographic method (an embodiment of an adhesive toner containing no inorganic pigment), and the electrophotographic method using a transfer sheet. In the method for producing a ceramic body with a multicolor picture according to the present invention, the transfer layer in the transfer sheet may include at least a coated inorganic pigment, and may further include other inorganic pigments and a binder component. Other components such as a meltable inorganic substance), a plasticizer, and a wax component may be included.

As the above-mentioned coated inorganic pigment, the coated inorganic pigment described above in the description of the inorganic pigment image can be used. it can. Examples of the other inorganic pigments include, for example, a crystal structure of copper oxide, cobalt oxide, or the like having a spinel, sphene, pichloa, rutile, priderite, phosphite, phenasite, perryclays, olivine, buderite, borate, corundum, Preferable examples include metal oxides such as zircon; sulfides such as cadmium yellow; and cadmium selenide compounds such as selenium red. Further, an inorganic pigment which is a fluorescent pigment or a phosphorescent pigment may be used.

In the firing step described later, it is preferable to use a glass component flux (heat-fusible inorganic substance) in view of improving the fusion property of the inorganic pigment image to the surface of the porcelain. Examples of the flux include lithium carbonate, sodium carbonate, potassium carbonate, lead oxide, bismuth oxide, barium carbonate, strontium carbonate, calcium carbonate, magnesium carbonate, zinc oxide, aluminum oxide, aluminum hydroxide, silicon oxide, boric acid, Zirconium oxide, titanium oxide, and the like can be given. Further, composite components such as borax, feldspar, kaolin and the like can also be used. The above flux can be dissolved alone or in combination of two or more, and used as a so-called frit.

The content (total) of the coated inorganic pigment and other inorganic pigments in the transfer layer of the transfer sheet is preferably from 10 to 80% by volume, more preferably from 20 to 70% by volume. When the above-mentioned flux (heat-fusible inorganic substance) is used in combination, the preferred amount of the flux varies depending on the type of the coated inorganic pigment. The content of the mixture is 15 to 70% by mass.
Is preferable, and 30 to 80% by mass is more preferable.

The binder component contained in the transfer layer of the transfer sheet of the present invention may be any one of a homopolymer and a copolymer. It may be configured. Above all, in relation to an image receiving layer of an image receiving member, to which a transfer layer made of a transfer material is transferred, the polymer and the polymer used in the image receiving layer are monomers having the same functional group as their constituent units. (Hereinafter, referred to as “polymer having the same functional group”). At least one of the monomers constituting the polymer in both layers may have the same functional group, and may have different functional groups.
Here, as the same functional group, for example, a butyral group, a vinyl alcohol group, an amino group, an amide group, an imino group, an imide group, a styrene group, an alkoxy group, a methacryl group and its ester group, an acrylic acid and its ester group , Maleic acid and its ester group, a vinyl ether group, a vinyl acetate group and the like, and among them, a butyral group is preferable.

The monomer having the same functional group is preferably contained in the polymer in the transfer layer and the polymer in the image-receiving layer described later in a large amount as a constitutional unit, respectively. % Or more is desirable, and 50 mol% or more is more preferable.
0 mol% or more is particularly preferred. When the content of the “monomer having the same functional group” as the constituent unit in the polymer is less than 30 mol%, the difference between the properties of the polymer in the transfer layer and the polymer in the image receiving layer described later is large. In the second and subsequent transfers in multicolor transfer, the absorptivity of the transfer promoting material (liquid) in the transfer portion and the untransferred region where transfer has already been completed, the swelling property of the image receiving layer by the transfer promoting material, the swollen image receiving layer Adhesion on the top becomes uneven, etc.
Image unevenness may easily occur.

Specifically, an amorphous organic high molecular polymer having a softening point of 40 to 150 ° C. is preferable. In the case of a transfer layer used in a melt transfer method, a polymer having a low degree of polymerization is particularly preferable. As the amorphous organic high-molecular polymer, for example, butyral resin, polyamide resin, polyethyleneimine resin, sulfonamide resin, polyester polyol resin, petroleum resin, styrene, vinyltoluene, α-methylstyrene,
Styrene such as 2-methylstyrene, chlorostyrene, vinylbenzoic acid, sodium vinylbenzenesulfonate, aminostyrene and derivatives thereof, homopolymers and copolymers of substituted products, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate Such as methacrylic acid esters and methacrylic acid,
Acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, α-ethylhexyl acrylate and acrylic acid, butadiene, dienes such as isoprene, acrylonitrile, vinyl ethers,
Examples include homopolymers of maleic acid and maleic esters, maleic anhydride, cinnamic acid, vinyl monomers such as vinyl chloride and vinyl acetate, and copolymers with other monomers. Two or more of these binders may be used in combination.

Further, as the binder component contained in the transfer layer, a terpene phenol resin is also preferably exemplified. By using a transfer layer containing a terpene phenol resin as a binder component in the transfer layer of the transfer sheet, the film forming property of the transfer layer is improved, the performance and handleability of the transfer sheet are improved, and the transfer property to the image receiving body is improved. Therefore, the resolution of the formed inorganic pigment image is increased, and an image having excellent gradation can be obtained. Further, when forming a multicolor image such as a full color image, color reproduction, transfer density, and image uniformity are improved.

Specific examples of the terpene which is a raw material of the terpene phenol resin include α-monoterpene.
Pinene, diterpene include camphorene, monoterpene alcohol includes borneol, diterpene alcohol includes hinokitol, and ketones include cedar. The terpenes may be used alone or in combination of two or more to produce a polymer with phenol. Specific examples of the phenols that are the raw materials of the terpene phenol resin include cresol, dioxynaphthalene, alkylphenol, halogenated phenol, allylphenol, polycresol, and the like. The phenols may be used alone or in combination of two or more to produce a polymer with the terpene.

The terpene phenol resin may be used alone or in combination of two or more. Moreover, you may use together with binder components other than a terpene phenol resin.

The content of the terpene phenol resin in the transfer layer is preferably 1 to 30% by mass,
-20 mass% is more preferable. If the content is less than 1% by mass, the effect may be insufficient, and 30% by mass.
If the length exceeds the limit, the image may be transferred to a place where there is no image originally.

Further, the total content of the binder component in the transfer layer is preferably from 10 to 70% by mass, more preferably from 20 to 50% by mass. The content is 1
If the amount is less than 0% by mass, the transfer layer becomes brittle, and the scratch resistance may decrease.

When a multicolor image is formed by repeatedly superposing a plurality of image layers (transfer layers on which images have been formed) on the same image receiving layer, a plasticizer is used from the viewpoint of enhancing the adhesion between the images. It is preferred to include. As the plasticizer, for example,
Phthalates such as dibutyl phthalate, di-n-octyl phthalate, di (2-ethylhexyl, dinonyl phthalate, dilauryl phthalate, butyl lauryl phthalate, butyl benzyl phthalate, etc .;
-Ethylhexyl), aliphatic dibasic acid esters such as di (2-ethylhexyl) sebacate, phosphoric acid triesters such as tricresyl phosphate, tri (2-ethylhexyl) phosphate, and polyol polyesters such as polyethylene glycol ester; Epoxy compounds such as epoxy fatty acid esters and the like can be mentioned. Further, in addition to the above plasticizer, polyethylene glycol dimethacrylate, 1,
Acrylic esters such as 2,4-butanetriol trimethacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol-polyacrylate can also be suitably used depending on the binder type used. Incidentally, two or more plasticizers may be used in combination.

The content of the plasticizer in the transfer layer is determined by the ratio (S: s) of the total mass (S) of the coated inorganic pigment (including the inorganic pigment) and the binder to the mass (s) of the plasticizer. In general, 100: 1 to 100: 5 is preferable, and 10
0: 1.5 to 100: 3 is more preferable. A surfactant, a thickener, and the like may be further added to the transfer layer as needed.

It is preferable that a wax component is contained in the transfer layer from the viewpoint of improving the resolution and resolution of a transferred image (dot). The content of the wax component is LM
It is preferable to any of the IT method (a method using a latent image forming liquid) and the below-described melt transfer method, but it is particularly important when an image is formed by the latter method.

Examples of the wax component include 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 adhesion to the image receiving member and the transfer sheet is improved, and in the case of multiple transfer (monochrome and two or more color images), the transfer layer (material A) a thermoplastic resin having a relatively low melting point for improving 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.

The transfer layer is prepared by dissolving or dispersing the components of the transfer material such as the above-mentioned coated inorganic pigment, other inorganic pigments and the binder component in an appropriate solvent, and preparing a coating solution. It can be provided by coating on a temporary support (on the undercoat layer when the support has the above-mentioned undercoat layer) and drying. In the present invention, the transfer layer in the transfer sheet is particularly preferably applied using an aqueous system as a solvent from the viewpoint of environmental safety, stability, and workability. However, as the solvent, n-propyl alcohol, methyl ethyl ketone Propylene glycol monomethyl ether (MFG), methanol, or a mixed solvent thereof with water can also be used. When used in an aqueous system, the above-mentioned hydrophobic compound is used as a dispersion (latex or emulsion). Coating and drying can be performed by using generally known coating and drying methods.

As the temporary support constituting the transfer sheet,
There is no particular limitation, and it can be appropriately selected from various known materials according to the purpose and the like. For example, synthetic resin materials such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polycarbonate, polyethylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and styrene-acrylonitrile copolymer are preferably exemplified. In terms of dimensional stability against heat and cost,
Biaxially oriented polyethylene terephthalate is particularly preferred.

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

The above-mentioned cover sheet is provided on the surface of the transfer layer with a weak adhesive force that can be temporarily held, and may be made of the same or similar material as the above-mentioned temporary support, but is easily separated from the cover coat layer. For example, silicone paper, polyolefin, polyethylene terephthalate film and the like are suitable because they need to be possible. The thickness of the covering sheet is preferably about 5 to 100 μm. Particularly preferred is a polyethylene terephthalate film having a thickness of 20 to 100 μm. These coated sheets are peeled off before transfer.

--Latent Image Forming Liquid--The latent image forming liquid contains a transfer promoting material or a tacky material capable of lowering the transfer temperature of the thermal transfer material. Hereinafter, the transferability promoting material will be described first.

The transfer promoting material 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 include a solid material or the like which is likely to precipitate over time. Examples of the transferability-promoting material include water, organic solvents (preferably, organic solvents that are freely miscible with water at room temperature), and surfactants (preferably, water-miscible surfactants). Water-soluble hot melt adhesive (such as a polymer having a low glass transition point), an emulsion or dispersion of ultrafine particles, or a mixture thereof.
Further, the transferability-promoting material itself is preferably colorless or light-colored, does not chemically act on the inorganic pigment contained in the transfer material, and does not cause a coloring reaction or the like due to heat energy optionally provided in a later step. Preferably, it is a material.

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

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

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

The above-mentioned transferability-promoting material preferably has good permeability into the transfer layer and / or the image-receiving layer of the image-receiving member described below, and has a surface tension of 25 to 60 mN / m and a viscosity of 50 mP.
a. It preferably has physical properties of s or less. Also,
What does not solubilize the transfer material itself is preferable. When the transferability-promoting material dissolves the transfer material, penetration of the transferability-promoting material and dissolution of the transfer material (transfer layer) occur at the interface between the image portion and the non-image portion, and the sharpness of the image interface decreases. Sometimes. When 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.

The degree of reduction (reference) in which the transfer temperature of the transfer material is lowered by the action of the transferability-promoting material is as follows. Is preferably 3 ° C. or higher. The transfer temperature is, for example, a pair of heating nip rollers, at least one of which is a variable temperature heating roller, a transfer sheet and an image receiving sheet sandwiched by a thermocouple, and the laminate is passed between the heating nip rollers. Can be measured. The temperature is measured by a thermocouple while changing the heating temperature of the heating roller, and the transfer temperature can be determined as the lowest temperature at which transfer occurs.

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

[0080]

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In the above general formula 1, R represents an alkyl group or an alkylene group, and n represents an integer of 2 to 30, preferably 2 to 20. In the general formula 2, R represents an alkyl group, and n represents an integer of 2 to 30, preferably 2 to 20. In the above general formula 3, R represents an alkyl group, and n and l each independently represent 2 to 30, preferably 2 to
Indicates any integer of 20. In the general formula 4, R ¹ and R ² each independently represent hydrogen or an alkyl group, and m and n each independently 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 2 to 30.
Is preferable, and 2 to 20 are particularly preferable.

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

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

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

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

The transferability-promoting material may be applied imagewise to at least one of the surface of the transfer layer of the transfer sheet and the surface of the image-receiving layer of the image-receiving body described later. As a method for imagewise applying the transferability-promoting material to the surface of the transfer layer or the like, a known inkjet method described below can be used. For example, an inkjet head with a heating element inside,
The liquid transferability promoting material is filled in place of ink, and electricity is supplied to a heating element at a predetermined position based on image information to generate heat, and a solvent (water, an organic solvent, or the like) of the nearby transferability promotion material is boiled. Then, the pressure in the head is increased to cause the transferability promoting material to fly as droplets, thereby forming a latent image on the surface of the transfer layer or the like.

Next, the adhesive material contained in the latent image forming liquid will be described. The adhesive material contains a substance having adhesiveness at normal temperature or when heated (adhesive substance),
As the tacky substance, an organic polymer can be mainly mentioned. Specifically, homopolymers and copolymers of acrylic monomers such as acrylic acid, methacrylic acid, acrylates, and methacrylates, polyvinyl acetate, polystyrene, polyvinylpyrrolidone, polyvinyl butyral, polyvinyl alcohol, and polyvinyl chloride Homopolymers of vinyl monomers such as vinyl and copolymers thereof such as ethylene-vinyl acetate, polyesters,
Examples include condensation polymers such as polyamides, and rubber polymers such as styrene-butadiene copolymers and acrylonitrile-butadiene copolymers. Among these, a polymer having a glass transition point (Tg) lower than 90 ° C. is preferable. Further, these may be an emulsion dispersion in water, that is, a so-called latex state.

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

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

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

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

[0092]

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

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

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

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

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

The polymer site P in the compound represented by the general formula (5) is a polymer containing at least one of the above structural units A, B and C. Specific examples of the structural unit A constituting the polymer A include vinyl alcohol,
α-methyl vinyl alcohol, α-propyl vinyl alcohol and the like. Examples of the structural unit B constituting the polymer site P include vinyl acetate, vinyl formate, vinyl propionate and α-substituted products thereof. Further, as the structural unit C constituting the polymer site P, acrylic acid, methacrylic acid, or crotonic acid (including an ammonium salt or a metal salt such as Na or K), maleic acid, or itaconic acid (monoalkyl ester, ammonium, respectively) salt,
Or a metal salt such as Na or K), vinylphosphonic acid,
Vinylsulfuric acid, acrylic sulfonic acid, methacrylsulfonic acid, 2-acrylamido-3-methylpropanesulfonic acid or 2-methacrylamido-3-methylpropanesulfonic acid (each including an ammonium salt or a metal salt such as Na or K), Monomer units that dissociate ions in water, such as acrylamidopropyltrimethylammonium chloride or methacrylamidopropyltrimethylammonium chloride. Particularly, itaconic acid and maleic acid are preferred.

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

The above structural units A constituting the polymer site P,
The content of B and C is not particularly limited, but A, B,
Assuming that the content of C is x, y and z mol%, x + y
+ Z = 100, 0 ≦ x ≦ 100, 0 ≦ y ≦ 75, 0 ≦ z
≦ 100 is preferable, x + y + z = 100, 0 ≦ x ≦ 1
00, 0 ≦ y ≦ 50 and 0 ≦ z ≦ 50 are particularly preferred. When the content of the structural unit C is 1 mol% or less, the polymer unit P is water-soluble or water-dispersible, so that the structural unit A
Is preferably 50 mol% to 100 mol%.

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

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

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

(Melting Transfer Method) As the above-mentioned melting transfer method,
For example, a known method using a thermal transfer printer provided with a heating element such as a thermal head for a transfer sheet having a transfer layer made of a transfer material containing the coated inorganic pigment of the present invention is preferably exemplified. Specifically, image data obtained by reading a black-and-white or color photograph, printed matter, painting, or the like with a scanner, or image data such as an image captured by an electronic still camera or a video camera or an image (CG) created by a computer is converted into an electric signal. Into a heating element such as a thermal head of a thermal transfer printer based on the signal,
In this method, an inorganic pigment image is formed by melting and transferring an image-transfer layer on an object to be transferred imagewise. The transfer sheet used in the melt transfer method contains a coated inorganic pigment,
It can be configured similarly to the transfer sheet in the IT method.

When the melt transfer method is applied, for example, FIG.
Using the transfer sheet 15 and the image receiving member 5 ′ configured in the same manner as ((a) -2), no latent image was formed with the transferability promoting material, and the transfer sheet 15 and the image receiving member 5 ′ were formed in the same manner as described above. By superimposing (see FIG. 3-((b) -2)), heat is applied imagewise directly from the surface of the support 9 of the transfer sheet 15 with a thermal head or the like and peeled off (see FIG. 3-((b) -2)). 3)), and an inorganic pigment image 11 can be formed on the surface of the image receiving layer 3 (see FIG. 3-((b) -4)).

(Solid Ink Jet Method) The solid ink jet method is described in JP-A-8-295836 and the like, and forms a latent image by discharging droplets having a certain degree of viscosity from an ejection nozzle. This is a method in which solid ink is transferred to an image to form an image. For example, by applying a pulse voltage to a piezoelectric element based on image information, a viscous droplet is ejected from a nozzle hole to form a latent image on an image receiving body, and the above-described transfer sheet or the like is formed on the surface of the latent image. By transferring the transferable material, an inorganic pigment image 11 as shown in FIG. 1- (b) can be formed. As the transfer sheet, those described above can be suitably used,
What is necessary is just to include a heat-resistant coloring material such as a coated inorganic pigment. Examples of the coated inorganic pigment are as described above.

<Image Receiver> In the present invention, the image forming step in the image ceramic forming step is a step of forming the above-mentioned inorganic pigment image made of a material containing a coated inorganic pigment on the surface of the image receiver as described above. It is. The image receiver preferably has at least one image-receiving layer capable of forming an image on the surface of the support, and the mode thereof depends on the above-mentioned “method for forming an inorganic pigment image”, the purpose, the use, and the like. Can be selected as appropriate,
A cushion layer, a release layer, an intermediate layer, and the like may be provided between the support and the image receiving layer. In the present invention, at least one selected from a cushion layer, a release layer and an intermediate layer
Those having at least two layers are preferred. Further, for the purpose of improving the transportability, an embodiment in which a back layer is provided on the side of the support opposite to the side having the image receiving layer, or an embodiment in which a cover coat layer is provided on the surface of the image receiving layer for the purpose of reinforcing strength. Is also good. Further, the cover coat layer is formed on the inorganic pigment image by, for example, forming an inorganic pigment image on the image receiving layer surface, transferring the image using a transfer body, or applying a coating liquid for the cover coat layer. May be. The method of transferring the cover coat layer using a transfer body (cover coat layer transfer step) will be described later.

The image-receiving layer capable of forming an image is not particularly limited as long as it can form an inorganic pigment image, and may be a layer containing either a hydrophobic polymer or a water-soluble polymer as a binder. A layer containing a water-soluble polymer (hereinafter, may be referred to as a “water-soluble polymer layer”) is preferable from the viewpoints of easy separation of the support and easy disposition on the porcelain material in the process. In this case, it is more preferable that the support is a water-permeable support, and it is more preferable that the cover coat layer is provided to reinforce the strength of the water-permeable support after peeling. In the image forming step, an inorganic pigment image is formed on the water-soluble resin layer by any of the aforementioned “methods for forming an inorganic pigment image”, and in the arranging step, the inorganic pigment image is formed using the water permeability of the support. Can be easily peeled off while dissolving a part of the conductive resin.

In the case where an inorganic pigment image is formed by a method using a transfer sheet, such as an electrophotographic method using the adhesive toner, an LMIT method, a melt transfer method or a solid ink jet method, a water-permeable support is used. An image receiving body (adhesive image receiving sheet) further comprising an image receiving layer on the provided water-soluble polymer layer is preferable. In the image receiving layer, the above-mentioned "polymer containing the same functional group" (hydrophobic polymer)
(Hereinafter sometimes referred to as “hydrophobic polymer layer”) is particularly preferable. In this case, the hydrophobic polymer layer serves as the above-mentioned "image-receiving layer capable of forming an image", and the water-soluble polymer layer functions as a layer (release layer) for improving the peelability of the support and imparting adhesion to the porcelain. I do. Since the hydrophobic polymer layer is provided with the water-soluble polymer layer interposed, unevenness such as liquid absorbency in a transferred portion and an untransferred portion during multicolor transfer, and adhesiveness when the layer swells, and the unevenness. Can be eliminated, and the transferability can be improved.

As the water-soluble polymer, when the support is a paper support, when the image receiver is immersed in water or the like,
Part of it dissolves and the paper support becomes peelable,
It is preferable that the inorganic pigment image after peeling can be adhered to the surface of the porcelain at the peeling surface. Adhesion in this case is
It suffices if it can be placed on the surface of the porcelain material without displacement. From this point, as the water-soluble polymer, for example, polymers used for painting ceramics, such as dextrin and gum arabic, polyvinyl alcohol, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, and gelatin are preferable. The content of the water-soluble polymer in the water-soluble polymer layer is 50
% By mass is preferable, 80% by mass is more preferable, and 90% by mass is particularly preferable.

The above-mentioned hydrophobic polymer is preferably the above-mentioned “polymer containing the same functional group”. Specifically, it is composed of atoms of carbon, oxygen, nitrogen and hydrogen and has a glass transition point (Tg Are preferred. Among them, those composed of carbon, oxygen, and hydrogen atoms are more preferable. Further, those having a glass transition point of 15 ° C or lower are more preferable, and those having a glass transition point of 5 ° C or lower are still more preferable. As the hydrophobic polymer, together with the "polymer containing the same functional group" described above, for example,
Polyvinyl butyral resin, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, styrene-acrylate copolymer, styrene-maleic acid-acrylate copolymer, polyamide, polystyrene, polyester, polyacetic acid Thermoplastic resins such as vinyl resin, cellulose derivative-based, polystyrene methacryl-based resin, polyvinyl ether-based resin, polyurethane-based resin, polycarbonate-based resin, and rosin-based resin can be used in combination. Further, a resin used as an overprint lacquer for overcoating a ceramic body such as a ceramic body is also suitable. For example, an acrylic resin, a urethane resin, or the like can be used in combination.

The thickness of the image-receiving layer capable of forming an image is as follows.
Generally, it is 0.3 to 20 μm, preferably 0.7 to 20 μm.
15 μm. The layer thickness of the “water-soluble polymer layer” in the case of the adhesive image-receiving sheet is 0.2 to 20 μm.
m is preferred.

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

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

(Transfer Image Forming Step / Image Transfer Step) In the production method of the present invention, an inorganic pigment image may be formed on the surface of the image receiving member by a transfer method. In this case, the image forming step includes a step of forming a transfer inorganic pigment image formed of a material containing a coated inorganic pigment on the surface of the transfer image receiver, and a step of forming the transfer inorganic pigment image on the surface of the image receiver. Transferring the image to form the inorganic pigment image on the surface of the image receiving member. When an inorganic pigment image is formed on the surface of an image receiving body by a transfer method, it is possible to prevent color mixing or the like when forming an image of two or more colors, and to obtain an image with high color purity. For example, a case where an inorganic pigment image is directly formed on a surface of a receiver by an LMIT method without using a transfer method will be described as an example. In some cases, a part of the transfer layer adheres to the toner, causing a so-called secondary color fog. On the other hand, if a transfer inorganic pigment image is formed on a transfer image receiving body for each color (transfer image forming step) and is transferred to the image receiving body to form an inorganic pigment image (image transferring step), substantially already, Since the transfer layer is not formed on the formed inorganic pigment image, secondary color fogging can be prevented.

The transfer image forming step is a step of forming a transfer inorganic pigment image made of a material containing a coating inorganic pigment on the surface of the transfer image receiving body. As the above-mentioned transfer image receiving member, the same one as the above-mentioned image receiving member can be suitably used, and the above-mentioned method can also be suitably used for forming an inorganic pigment image on the surface of the transfer image receiving member. The transfer inorganic pigment image is made of a material containing a coated inorganic pigment, and the material containing the coated inorganic pigment is the same as the material forming the coated inorganic pigment image described above. In addition, as a method of transferring the transfer inorganic pigment image to the surface of the image receiving member, a known transfer method can be used.

(Cover Coat Layer Transfer Step) In the present invention, when a cover coat layer is provided on the image receiving member on which the inorganic pigment image has been formed, it is cost and cost to provide the cover coat layer by the cover coat layer transfer step. It is preferable from the viewpoint of work efficiency. In the cover coat transferring step, at least the surface of the image receiving layer on which the inorganic pigment image is formed in the image forming step and the surface of the cover coat layer of the transfer body having the cover coat layer are contacted and heated to form the cover coat. The layer is transferred onto the image receiving layer. That is, a cover coat layer is overlaid so as to cover the inorganic pigment image, and is adhered while heating in this state to form a laminate. Thereafter, by removing the temporary support of the transfer body from the laminate,
The cover coat layer can be transferred and formed on a part or the whole of the image receiving layer.

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

The transfer member has at least a cover coat layer on the surface of the temporary support, and may be provided with another layer such as a frit layer or a cover sheet, if necessary. Here, the temporary support and the cover sheet are not particularly limited, and the same temporary support and cover sheet that constitute the transfer sheet described above can be used.

The above-mentioned cover coat layer comprises at least a hydrophobic polymer. Mainly composed of a hydrophobic polymer, the inorganic pigment image can be retained on the surface of the cover coat layer when the support of the image receiving member is peeled off by immersion in water or the like in an arrangement step described below, which hinders the image. I will not come. Examples of the hydrophobic polymer include the same binders as those usable for the transfer layer, and the above-mentioned “polymer containing the same functional group” is preferable. Above all, a polymer having a glass transition point of room temperature (operating environment temperature) or lower is preferable from the viewpoint of enabling adhesion and transfer to an uneven surface or a curved surface. Here, the use environment temperature or lower refers to 25 ° C. or lower. As the hydrophobic polymer, specifically, a hydrophobic polymer composed of atoms of carbon, oxygen, nitrogen, and hydrogen and having a glass transition point (Tg) of 25 ° C. or less is preferable. Among them, those composed of carbon, oxygen, and hydrogen atoms are more preferable. The glass transition point (T
g) is preferably -50 to 25 ° C, and -30 to 1
5 ° C. is more preferred. Specific examples of commercially available products of the hydrophobic polymer include cover coat resins LO-210, LO-176S, and LO-200 manufactured by Ryogo Chemical Industry Co., Ltd.
H, LO-170H and the like. The content of the hydrophobic polymer in the cover coat layer is preferably 50% by mass, more preferably 80% by mass, and 90% by mass.
Is particularly preferred.

The cover coat layer may contain a frit (a heat-meltable inorganic substance). By containing the frit, even if the content of the coated inorganic pigment in the inorganic pigment image formed in the image forming step described above is high, it is easy to be firmly sintered to the porcelain, and the image stability after sintering, And the surface glossiness can also be improved. Examples of the frit include the same fluxes as those usable for the transfer layer of the transfer sheet. As the content of the frit, the content (mass) of the hydrophobic polymer in the cover coat layer
Is preferably 1 to 100% by mass.

The thickness of the cover coat layer is preferably 5 to
50 μm is preferable, and 10 to 30 μm is more preferable.
If the layer thickness is less than 5 μm, the workability in the arranging step may deteriorate, and if it exceeds 50 μm, the quality may deteriorate during firing.

As described above, it is preferable that the cover coat layer contains no frit, or that the cover coat layer contains a frit and that a frit layer is provided on the surface of the cover coat layer not in contact with the temporary support. The frit layer includes at least a frit (a heat-fusible inorganic substance) and a thermoplastic resin, and the layer thickness of the layer is preferably 1 to 20 μm. Examples of the frit include the same frit that can be used for the transfer layer of the transfer sheet. The content of the frit is 20 to 100 with respect to the thermoplastic resin content (mass).
% By mass is preferred. Further, as the thermoplastic resin,
For example, the softening point of the transfer layer is 40 to 150.
It can be appropriately selected from known ones such as an amorphous organic high-molecular polymer at ℃.

<Arranging Step> The arranging step in the present invention is a step of arranging an inorganic pigment image composed of a material containing a coated inorganic pigment on the surface of the porcelain together with a part or all of the image receiving body. When the inorganic pigment image is disposed on the surface of the porcelain material by peeling the support from the image receiver, the image receiving layer of the image receiver and / or a layer containing a water-soluble polymer (water-soluble polymer layer) are not necessarily removed after the support is peeled. Need not be removed, and depending on the mode of the image receiving layer, an image receiving layer and / or a water-soluble polymer layer may be interposed between the porcelain and the inorganic pigment image, or a cover coat layer May be arranged so that the surface having no inorganic pigment image faces the porcelain surface.
At this time, the water-soluble polymer layer functions as an adhesive to the porcelain.

When an image receiving member having a layer containing a water-soluble polymer and an image receiving layer on the surface of the support in this order (hereinafter sometimes referred to as "adhesive image receiving member") is used, the support is made of a water-permeable support. In the case of a body, after the image forming step, a part of the image receiving body on the water-permeable support side is contacted or immersed in water, and a part of the water-soluble polymer is dissolved to remove and remove the support,
It can adhere to the porcelain surface on the peeled off surface. In this case, if the cover coat layer is provided in the cover coat layer transfer step, the inorganic pigment image can be arranged on the surface of the porcelain while the strength is supplemented by the cover coat layer. Therefore, in this case, a liquid in which the paste is dissolved or dispersed is unnecessary. Further, when the support is a plastic film support, the plastic film support is subjected to a surface treatment for imparting releasability in advance as described below, so that the plastic film support is not immersed in water or the like. It can be easily peeled off. When the plastic film itself has releasability from the inorganic pigment image, the cover coat resin, and the like, the surface treatment may not be performed. In this case, it can be arranged on the surface of the porcelain via a liquid in which the paste is dissolved or dispersed, and can be arranged on the surface of the porcelain by interposing a hot melt adhesive. Here, the liquid such as water may be appropriately selected from those which can dissolve the water-soluble polymer in the image receiving body, such as not only water but also a mixed solution of water and a solvent compatible with the water. Just fine.

When the inorganic pigment image on the image receiving layer is reversed on the surface of the porcelain material, an inverted image is formed on the image receiving layer in advance, and the side of the cover coat layer on which the inorganic pigment image is formed is formed. May be arranged on the surface of the porcelain at the surface of (the image is re-inverted), and a normal image can be formed. In this case, since the surface of the cover coat layer does not have adhesiveness, the surface of the porcelain material is interposed with a solution or a hot melt adhesive in which a paste is dissolved or dispersed on either of the surfaces of the porcelain material and the cover coat layer. Can be arranged.

In the above, the liquid in which the sizing agent is dissolved or dispersed is, for example, water, and the sizing agent is a water-soluble polymer (eg, gelatin, starch, dextrin, hydroxyethyl cellulose, etc.), latex or emulsion (eg, polyester resin, A liquid in which ethylene, vinyl acetate resin, acrylic resin, etc. are dissolved or dispersed.

Examples of the above porcelain include porcelain plates, porcelain, porcelain plates, porcelain, enamels, etc. used for building materials such as tiles.
Ceramic materials and the like can be mentioned. The color, shape,
The form such as the thickness can be appropriately selected according to the purpose and use.

<Firing Step> The firing step in the present invention means that the porcelain on which the inorganic pigment image made of the material containing the coated inorganic pigment is arranged, that is, the image porcelain is dried and then heated and sintered. It is a process. In the baking step, at least the porcelain (image porcelain) on which the inorganic pigment image is arranged is heated to sinter the inorganic pigment image on the surface of the porcelain. As a result, a sintered inorganic pigment image containing the coated inorganic pigment is provided on the surface of the porcelain material, and components other than the coated inorganic pigment (including other inorganic pigments), and an image-receiving layer disposed on the porcelain material surface together with the image Are evaporated or incinerated. Therefore,
Materials (such as components in the transfer layer and the image receiving layer) disposed on the surface of the porcelain along with the coated inorganic pigment contain atoms and compounds that do not disappear by evaporation or burning during the baking process, and include coated inorganic pigments and other inorganic pigments. It is preferable not to contain atoms, compounds, etc. which undergo discoloration upon reacting with.

The heating of the porcelain is preferably carried out 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 porcelain, the size of the image, and the like. It is preferable that the heating is performed by gradually increasing the temperature to the firing temperature, or by heating at a constant temperature of 300 to 500 ° C. for a certain period of time, and then gradually increasing the temperature to the firing temperature. When the upper paint is used as the coated inorganic pigment, the firing temperature is usually 650 ° C to 900 ° C, preferably 750 ° C to 850 ° C, and the firing time is preferably 10 to 180 minutes. On the other hand, when an undercolor is used as the coated inorganic pigment, the firing temperature is usually 10
The temperature is preferably from 00 to 1300 ° C, more preferably from 1100 to 1250 ° C, and the firing time is preferably from 10 minutes to 8 hours.

In the present invention, a material containing an inorganic pigment coated with an inorganic oxide having a melting point higher than the calcination temperature is used as the inorganic pigment component in the material for forming the inorganic pigment image. After the image porcelain is formed, in the firing step of heating and sintering the image porcelain, the inorganic pigments having different hues do not directly react with each other to cause discoloration, so that the original inorganic pigment has It is possible to obtain a multicolor image in which the hue is maintained without discoloration.

[0132]

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

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

<Preparation of Transfer Sheet> (1) Preparation of Transfer Sheet for Yellow -Preparation of Inorganic Pigment Dispersion- The following components were dispersed in Micros MC-0 type (manufactured by Nara Machinery Co., Ltd.) for 2 hours. Thus, an inorganic pigment dispersion W was obtained. -40 parts by mass of yellow pigment (13651; manufactured by Celdec)-60 parts by mass of water-Preparation of coated inorganic pigment-Using the above-mentioned yellow pigment (inorganic pigment dispersion W), coating with inorganic oxide by the following liquid phase coating method A yellow pigment was prepared. First, in a liquid phase coating apparatus provided with a stirring tank and stirring blades, 300 ml of water and 100 g of the inorganic pigment dispersion W were put into the stirring tank,
The pH of the suspension was adjusted to 10 by adding 0.1N sodium hydroxide solution with stirring. Thereafter, the liquid was heated to 60 ° C. 30 ml of a 30% by mass aqueous solution of sodium silicate was added thereto, followed by sufficient stirring. Thereafter, the pH of the suspension was gradually adjusted to 7.5 using a 1N acetic acid aqueous solution to prepare a coated yellow pigment dispersion. The coated yellow pigment dispersion was centrifuged, the supernatant was removed and dried at 200 ° C. to obtain a coated yellow pigment. 60 parts by mass of water was added to 40 parts by mass of the coated yellow pigment, and the mixture was dispersed by an ultrasonic disperser (manufactured by BRONSON) to prepare a coated inorganic pigment (silica coating) dispersion liquid Y.

-Preparation of Transfer Layer Coating Solution- The components of the following composition were mixed and sufficiently stirred to prepare a transfer layer coating solution. [Composition of transfer layer coating liquid]-40 parts by mass of the above-mentioned coated inorganic pigment dispersion Y-0.5 parts by mass of polyoxyethylene (n = 10) nonylphenol ether (20% by mass aqueous solution)-Carnauba wax dispersion (31 parts by mass) %) 20 parts by mass (K-332; manufactured by Chukyo Yushi Co., Ltd.)-Butyral resin dispersion (25% by mass) 60 parts by mass (Resem J667; manufactured by Chukyo Yushi Co., Ltd.)-Terpene phenol resin dispersion (35 mass%) %) 5 parts by mass (Resem J628; manufactured by Chukyo Yushi Co., Ltd.)

The transfer layer coating solution was applied to the surface of a polyester film having a thickness of 25 μm so as to have a dry film thickness of 2 μm, and dried to form a transfer layer, thereby producing a yellow transfer sheet.

(2) Preparation of Transfer Sheets for Magenta, Cyan, and Black In the preparation of the transfer sheet for yellow, the coated yellow pigment was coated with a coated magenta pigment (77571; manufactured by Celdec, coated with alumina) and cyan. Pigment (1
4209; manufactured by Celdec Corporation), black pigment (1420)
9; manufactured by Celdec Co., Ltd.), except that the transfer sheets for magenta, cyan, and black were prepared in the same manner as the transfer sheet for yellow, except for the respective changes.

<Preparation of Image Receiver> A 10% aqueous solution of gum arabic was applied to the surface of a smooth paper support weighing 100 g to a dry layer thickness of 5 μm, and dried to form a first layer (water-soluble polymer layer). Was formed. On this first layer, a cover coat resin (plus size LO-210, manufactured by Ryo Kagaku Kogyo Co., Ltd.) containing a methacrylic acid-based resin as a main component is further applied so as to have a dry layer thickness of 15 μm, and dried. The second layer (image receiving layer) was laminated to produce an image receiving body.

<Preparation of Transfer Body>
A 0 μm polyethylene terephthalate (PET) film is prepared, and a 10% by mass aqueous solution of polyvinyl alcohol (PVA-105, manufactured by Kuraray Co., Ltd.) is applied to the surface of the PET film so as to have a dry layer thickness of 0.2 μm. Dried (release layer). On top of this, a methacrylic acid-based resin is further coated with a main component cover coat resin (plus size LO-21).
0, manufactured by Ryogo Chemical Industry Co., Ltd.)
A flux (19164, manufactured by Celdec) was added in an amount of 5% by mass and dispersed by a three-roll mill. The resulting dispersion was applied to a dry layer thickness of 17 μm and dried to form a cover coat layer. did. From the above, a transfer member having a release layer and a flux-containing cover coat layer on the surface of the PET film sequentially was obtained.

<Image Formation by LMIT Method> Using an image forming apparatus 40 having a structure similar to that shown in FIG. 4, a transfer sheet of four colors obtained above is formed on the image receiving layer of the image receiver obtained above. Then, a full-color image (inorganic pigment image) composed of the transfer layer was formed (image forming step in the image porcelain molding step). Specifically, it is as follows.

The image forming apparatus 40 includes a support drum 44 and a pinch roller 46 which are opposed to each other so as to be able to convey the image receiving member 20 and the transfer sheet 10 while heating and pressing the same.
And a discharge head 42 which is located upstream of the support drum 44 in the transport path of No. 0 and is capable of imagewise applying a droplet of the transferability promoting material solution to the surface of the second layer (image receiving layer) of the image receiving body 20. Further, a take-up roller 48 disposed at the end point of the transfer path of the transfer sheet 10, and a rectangular parallelepiped disposed upstream of the take-up roller 48 of the transfer path of the transfer sheet 10 and downstream of the support drum 44. And a release bar 50 in a shape of a circle. Further, a heater 52 for heating and drying the transferability promoting material solution discharged imagewise and a heater for drying the transferred image transferred on the image receiving body 20 are provided in the transport path of the image receiving body 20. 54.

Image forming apparatus 40 constructed as shown in FIG.
Then, the image receiving body A and the yellow transfer sheet obtained above were set such that the image receiving layer surface and the yellow transfer layer surface face each other, and the ejection head 42 was filled with the transferability promoting material solution obtained above. When the image forming apparatus 40 is started, the support drum 44 and the pinch roller 46 rotate in the directions of the arrows, respectively, while the second layer (image receiving layer) of the image receiving body 20 is transferred from the ejection head 42 to the transferability enhancing material. The solution was discharged imagewise to form a latent image capable of forming a yellow image.

The latent image portion is further conveyed to the support drum 44 and the pressing portion of the pinch roller 46, where the latent image portion is heated (80 ° C.).
Under the conditions described above, the surface of the yellow transfer layer of the transfer sheet was in close contact with the surface of the image receiving layer of the image receiving body. When the sheet was further transported in the direction of the arrow in the contacted state, it was peeled off by the peeling bar 50, and a yellow image (mirror-reversed image) was formed on the image receiving layer after peeling. Thereafter, the same operation is repeated on the same image receiving body on which a yellow image is formed, using each of the magenta, cyan, and black transfer sheets obtained above,
A full-color image (mirror image reversal image) was formed on the image receiving layer surface of the same image receiving member.

Next, the surface of the image receiving layer on which the full-color image (mirror image reversal image) was formed and the surface of the cover coat layer of the transfer body obtained above were overlapped with each other so as to be in contact with each other, and were heated with a heat roll laminator (120 ° C.). Then, only the temporary support of the transfer body was peeled off, and the cover coat layer was transferred so as to cover the image. At this time, as shown in FIG. 1- (d), a full-color image (inorganic pigment image) and a cover coat layer were sequentially formed on the image receiving body.

Subsequently, a part of the image receiving member on which the full-color image was formed on the paper support side was immersed in water, and the paper support was peeled off while dissolving a part of the first layer. Then, the paper support was peeled off and exposed so that the surface (released surface) of the first layer (water-soluble polymer layer) in a dissolved state was placed in contact with the surface of the porcelain material (in the image porcelain molding step). Placement process). At this time, the first layer (water-soluble polymer layer), the second layer (image receiving layer), the inorganic pigment image, and the cover coat layer were sequentially laminated on the surface of the porcelain.

The image porcelain thus obtained, that is, the porcelain on which the inorganic pigment image was formed together with the cover coat layer, etc.
Baking at 50 ° C. for 1 hour, sintering the coated inorganic pigment on the surface of the porcelain material, and providing a sintered inorganic pigment image containing the coated inorganic pigment on the surface of the porcelain material. (Porcelain) was obtained (firing step).

As described above, by using the above-prepared transfer sheet of the present invention, a ceramic body with a multicolor picture with a full-color image could be manufactured in a simple process. In addition, there is no work of preparing a coating solution using a solvent, and workability and safety can be secured. Further, in the multicolored ceramics, the original hue of the inorganic pigment is retained, there is no discoloration, there is no color unevenness of the image, no unevenness of the density, and an image with high resolution and excellent gradation is formed. And both water resistance and light resistance were good.

[0148]

According to the present invention, the present invention provides a high color density, high resolution and excellent gradation property on the surface of a building material such as an art tile and a porcelain material such as a ceramic material. Coated inorganic pigment suitable for arranging and sintering a multicolor image that retains hue and does not change color, a transfer sheet containing the coated inorganic pigment in a transfer layer, an inorganic pigment made of a material containing the coated inorganic pigment Image porcelain provided with an image on the surface of porcelain, multicolored porcelain provided with a sintered inorganic pigment image containing the coated inorganic pigment on the surface of porcelain, and a method of manufacturing the multicolored porcelain. Can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic process diagram for explaining a basic embodiment of a production method of the present invention.

FIG. 2 is a schematic process diagram showing a part of an embodiment of an image forming step in an image porcelain molding step in the manufacturing method of the present invention.

FIG. 3 is a schematic process diagram showing a part of an embodiment of an image forming step in an image porcelain molding step in the manufacturing method of the present invention.

FIG. 4 is a schematic diagram of an image forming apparatus used in the embodiment.

[Explanation of symbols]

 Reference Signs List 1,3 image receiving layer (water-soluble polymer layer) 2 support 5 image receiver 6 cover coat layer 7,9 temporary support 8 transfer layer 10 transfer body 11,21 inorganic pigment image 12 ceramic Materials 15, 41: Transfer sheet

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C09J 7/02 C09J 7/02 BF Term (Reference) 3B005 EB01 EB05 EB09 EC30 FA03 FB03 FB25 FB33 FB40 FC20Z FE11 FF05 FF06 GA12 GA24 GC01 4G055 AA07 BA32 BA40 4J004 AA06 AA08 AA10 AA11 AA15 AA16 AA18 CA06 CC02 FA10 4J037 AA29 CA08 CA09 CA12 CA24 EE03 EE47 FF03

Claims (14)

[Claims] 1. A coated inorganic pigment used for producing a painted ceramic body in which an inorganic pigment image is sintered on the surface of a porcelain material. A coated inorganic pigment, which is coated with a colorless inorganic oxide. 2. The coated inorganic pigment according to claim 1, wherein a melting point of the inorganic oxide is higher than a firing temperature at the time of manufacturing the painted ceramic body. 3. The method according to claim 1, wherein at least one of the inorganic oxides is silica, alumina, or zirconia.
Or the coated inorganic pigment according to 2. 4. A transfer sheet comprising, on a support, a transfer layer comprising a transfer material containing the coated inorganic pigment according to claim 1. 5. An image porcelain body comprising an inorganic pigment image formed of the material containing the coated inorganic pigment according to claim 1 provided on a surface of the porcelain material. 6. A porcelain with a multicolor picture, wherein a sintered inorganic pigment image containing the coated inorganic pigment according to any one of claims 1 to 3 is provided on a surface of a porcelain material. 7. An image porcelain forming step of forming the image porcelain according to claim 5, and baking the multi-colored porcelain according to claim 6 by heating and sintering the image porcelain. And a method for producing a ceramic body with a multicolor picture. 8. An image forming step of forming an inorganic pigment image made of a material containing the coated inorganic pigment according to any one of claims 1 to 3 on the surface of an image receiving body, The method according to claim 7, further comprising: arranging the inorganic pigment image on a surface of the porcelain together with part or all of the image receiving body. 9. The method according to claim 8, wherein the image receiving body is an adhesive image receiving body having a water-soluble polymer-containing layer on the surface of a water-permeable support. 10. In the image forming step and the arranging step, after forming an inorganic pigment image on the layer containing the water-soluble polymer, a hydrophobic polymer layer is coated on the inorganic pigment image forming surface, or After laminating a hydrophobic polymer film, the water permeable support side is immersed in water, a part of the water soluble polymer is dissolved, the water permeable support is peeled from the adhesive image receiver, and the adhesive image receiver is removed. The method for producing a multicolored ceramic body according to claim 9, wherein the inorganic pigment image is arranged on the surface of the porcelain so that the peeling surface of the body contacts the surface of the porcelain. 11. In the image forming step and the arranging step, the inorganic pigment image is formed on the surface of the image receiving member on which a layer containing a water-soluble polymer and a hydrophobic polymer layer are sequentially provided on the water-permeable support. After forming, the water-permeable support side is immersed in water to dissolve a part of the water-soluble polymer,
The image-forming surface of the adhesive image receptor is disposed on a porcelain surface by peeling the water-permeable support from the adhesive image receptor, and interposing a hot melt adhesive or a solution in which a glue is dissolved or dispersed. Item 10. The method for producing a ceramic body with a multicolor picture according to Item 9. 12. The method according to claim 12, wherein the inorganic pigment image is formed by any one of an electrophotographic method using a transfer sheet, a transfer method using a latent image forming liquid, a melt transfer method, and a solid inkjet method. The method according to claim 8, wherein the transfer sheet used in the method is the transfer sheet according to claim 4. 13. The transfer image forming step of forming a transfer inorganic pigment image made of the material containing the coated inorganic pigment according to claim 1 on the surface of a transfer image receiving body. An image transfer step of transferring the transferred inorganic pigment image to the surface of the image receiving member to form the inorganic pigment image on the surface of the image receiving member. Method of manufacturing attached ceramic body. 14. The transfer inorganic pigment image is formed by any one of an electrophotographic method using a transfer sheet, a transfer method using a latent image forming liquid, a melt transfer method, and a solid ink jet method, and The method according to claim 13, wherein the transfer sheet used in the method is the transfer sheet according to claim 4.