JP2003246154A - Transfer sheet, method for forming image, and method for preparing ceramic material with image - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transfer sheet which is excellent in transfer responsiveness corresponding to an image signal and enables formation of an image free of dropout or noise and excellent in image quality. <P>SOLUTION: The transfer sheet has, on a substrate, a release layer containing a foaming agent which is decomposed by heat or light and produces gas and a coloring material layer sequentially from the substrate side. In the sheet, at least one layer selected from the release layer and layers provided in the direction of being apart from the substrate and from the release layer, contains a gas barrier substance. The gas barrier substance is preferably in a mode of an inorganic laminar compound and/or a polymer of which the glass transition point (Tg) is higher than a printing temperature and of which the oxygen permeability on the occasion when the polymer is made to have a film of a film thickness of 10 μm is 20×10<SP>-5</SP>ml/(m<SP>2</SP>Pa per 1 day) or below. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer sheet suitably used for thermal transfer, an image forming method for forming an image using a thermal transfer method using the transfer sheet, and a method for producing an image-bearing ceramic material.

[0002]

2. Description of the Related Art An image forming method using a thermal transfer method is widely used as a printer because it is a completely dry process that does not require a liquid developing step, does not require a complicated device, and is easy to maintain. . In recent years,
Images such as color proofs are being formed not only by printers but also by thermal transfer image recording methods. In the thermal transfer image forming method, usually, at the time of transfer, the image receiving sheet and the transfer sheet are overlapped, and the color material layer portion corresponding to the image portion of the transfer sheet is transferred to the image receiving sheet by thermocompression bonding, and then the image receiving sheet and When the transfer sheet is peeled off, an image is formed on the image receiving sheet.

At this time, it is important that the image material has a high responsiveness to the image signal, that is, there is no omission in the image area and the color material layer portion corresponding to the non-image area is not transferred. In other words, it is required that an image with a high S / N ratio can be formed. To that end, in the case where the image receiving sheet and the transfer sheet are superposed, the adhesive force (F ¹ ) between the color material layer and the support in the non-image portion (non-transfer portion) is It must be greater than the adhesive force (F ² ) between the image material (including the image area already formed) and the color material layer and the image receiving sheet (image area already formed) in the image area (transfer area). The adhesive force (F ² ) between the color material layer and the support must be larger than the adhesive force (F ³ ) between the color material layer and the support (that is, F ¹ > F ² > F ³ ). In addition to filling, there must be some separation between F ¹ , F ² and F ³ . However, this relationship can be said to be an antinomy relationship, and it has been difficult to produce an image receiving sheet and a transfer sheet that can satisfy the above relationship by adjusting only the composition of each layer.

[0004]

As described above, color loss can be prevented in the image portion and coloring due to transfer in the non-image portion can be prevented, and the image can be stably reproduced with good reproducibility with respect to the image signal. At present, the technology that can be formed is not yet established.

In view of the above situation, it is an object of the present invention to solve the above-mentioned conventional problems and achieve the following objects. That is, it is an object of the present invention to provide a transfer sheet which is excellent in transfer response corresponding to an image signal and which can form an image having a good image quality (S / N ratio). In addition, the present invention uses the above-mentioned transfer sheet of the present invention, can perform good transfer according to an image signal, and can form an image with high image quality (high S / N ratio). It is an object of the present invention to provide a method and a method for producing a ceramic material with an image.

[0006]

Based on the above situation, the inventor of the present invention has conducted research on a technique capable of forming an image with a high S / N ratio, and as a result, has found that between the support and the color material layer, It has been found that the responsiveness to image signals can be significantly improved by interposing a layer capable of reducing the adhesive force between the color material layer and the support by appropriately foaming if desired. On the other hand, it was also found that the foamed gas may be absorbed by an adjacent layer such as a color material layer before the foamed gas sufficiently acts to reduce the adhesive strength.

Based on the above findings, the means for achieving the above object are as follows. <1> A transfer sheet having, on a support, a release layer containing a foaming agent that decomposes by heat or light to generate a gas, and a color material layer in that order from the support side. And at least one layer selected from a layer having a direction away from the support from the release layer (that is, an upper layer of the release layer provided on the side not facing the support) contains a gas barrier substance. It is a transfer sheet. <2> The above, wherein the gas barrier substance is an inorganic layered compound
1> is a transfer sheet. <3> The gas barrier substance has a glass transition point (Tg) higher than the printing temperature and has an oxygen permeability of 20 × 10 ⁻⁵ ml / (m ² · Pa · 1 day) when the film has a thickness of 10 μm.
[20 ml / (m ² · atm · 1 day)] The transfer sheet according to the item <1>, which is a polymer having the following content. <4> The gas barrier substance is an inorganic layered compound, and has a glass transition point (Tg) higher than the printing temperature and a film thickness of 10 μm.
Oxygen permeability of 20 ml / (m ² · Pa
・ 1day) or less [20ml / (m ² · atm · 1day)]
The transfer sheet according to <1>, which is a polymer of

<5> A step of imagewise applying heat or light for decomposing the foaming agent to generate a gas, to at least the release layer of the transfer sheet according to any one of the above items <1> to <4>. An image comprising: a step of heating at least the color material layer or the color material layer and the release layer of the transfer sheet; and a step of transferring the color material layer onto an image receiving sheet to form an image. It is a forming method. <6> A step of image-wise applying heat to decompose the foaming agent and generate a gas to at least the release layer and the color material layer of the transfer sheet according to any one of the above items <1> to <4>, A step of transferring the color material layer onto an image receiving sheet to form an image, the image forming method.

<7> A step of applying imagewise heat or light for decomposing a foaming agent to generate a gas, on at least the release layer of the transfer sheet according to any one of the above items <1> to <4>. A step of heating at least the color material layer or the color material layer and the release layer of the transfer sheet; a step of transferring the color material layer onto an image receiving sheet to form an image; A method for producing a ceramic material with an image, comprising: a step of arranging the image above and a step of baking at least the image arranged. <8> A step of image-wise applying heat or light for decomposing a foaming agent to generate a gas to at least the release layer and the coloring material layer of the transfer sheet according to any one of the above items <1> to <4>. And a step of forming an image by transferring the color material layer onto an image receiving sheet, a step of disposing the formed image on a ceramic material, and a step of baking at least the arranged image. And a method for producing a ceramic material with an image.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. [Transfer Sheet] The transfer sheet of the present invention comprises, on a support, at least a release layer containing a foaming agent that decomposes by heat or light to generate a gas, and a coloring material layer in this order from the support side. The release layer, and a layer having a direction away from the support from the release layer, that is, a layer provided as an upper layer of the release layer on the side having no support as viewed from the release layer (hereinafter, simply referred to as “release Sometimes referred to as “upper layer of mold layer”) containing at least one gas barrier substance.

The gas generated in the release layer due to decomposition by heat or light then expands to foam the release layer and weaken the adhesive force between the color material layer and the support, but in the transfer sheet of the present invention. Since the gas barrier substance is contained in at least one layer selected from the following: a release layer, and a layer (including a coloring material layer) provided as an upper layer of the release layer, the generated gas is confined in the transfer sheet. Therefore, the adhesive force between the support of the transfer sheet and the color material layer can be more effectively reduced. As a result, the color material layer can be easily and satisfactorily transferred to the image receiving sheet. Therefore, in image formation using the transfer sheet of the present invention, it is possible to stably obtain a transferred image that corresponds well to an image signal and is free from omissions and noises.

The gas barrier substance is not particularly limited as long as it is a substance capable of sufficiently suppressing the passage of gas generated from the foaming agent, and examples thereof include an inorganic layered compound and a glass transition point (Tg) higher than the printing temperature. And the oxygen permeability is 20 × 10 ^-5 ml / (m ² · P when the film has a thickness of 10 μm.
a · 1day) [= 20 ml / (m ² · atm · 1day)]
The following polymers are preferred. Details will be described later.

The gas barrier substance is contained in at least one of the release layer and the layer provided in the direction away from the support from the release layer. The layer may be a release layer or a coloring material layer. It may be a layer provided for the purpose of gas barrier (hereinafter referred to as “gas barrier layer”) as an upper layer of the release layer, or a layer provided for other purposes (for example, a photothermal conversion layer). Etc.). still,
The gas barrier layer may be formed under the coloring material layer, for example, on the surface of the release layer (that is, between the releasing layer and the coloring material layer), or on the coloring material layer, for example, on the coloring material layer surface. You may form.

As a preferred mode of containing a gas barrier substance in the layer, for example, a mode of containing an inorganic stratiform compound in the layer (a) (preferably with a binder),
(B) “Oxygen permeability is 20 × 1 when the film has a glass transition point (Tg) higher than the printing temperature and a film thickness of 10 μm.
^{0 -5 ml / (m 2 ·} Pa · 1day) mode to be contained following polymers "as binder, when the (c) and" glass transition point than the printing temperature (Tg) high and having a thickness of 10μm film Oxygen permeability of 20 × 10 ^-5 ml / (m ² · P
a. 1 day) A mode in which an inorganic layered compound is further contained in the layer containing "a polymer below" as a binder. Among them, from the viewpoint of the gas barrier effect, the inorganic layered compound has a "oxygen permeability of 2 when the film has a glass transition point (Tg) higher than the printing temperature and a film thickness of 10 µm.
It is particularly preferable that the layer contains both “0 × 10 ⁻⁵ ml / (m ² · Pa · 1 day) or less polymer” (hereinafter, may be referred to as “high Tg low permeability polymer”) in the layer.

From the viewpoint of suppressing the increase in the number of layers,
A mode in which the release layer contains the gas barrier substance is preferable, and from the viewpoint of promoting foaming of the foaming agent, a mode in which the gas barrier substance is contained in a layer adjacent to the release layer is preferable. The gas barrier substance may be contained in multiple layers.

(Inorganic Layered Compound) The inorganic layered compound is preferably a swellable inorganic layered compound, and can be appropriately selected from known compounds. Among them, natural smectites, synthetic smectites, and swelling synthetic mica are particularly preferable in terms of excellent gas barrier properties.

The smectite is a tetrahedral sheet in which a Si-O tetrahedron containing Si atoms in the center spreads in a plane.
And an octahedral sheet having metal atoms such as Al and Mg in the center has a 2: 1 structure. Since the Si atoms are replaced by Al atoms in the tetrahedron or the Al atoms in the octahedron are replaced by Mg atoms, the crystal layer lacks positive charge and the surface charge becomes negative.

When the Si atoms in the tetrahedron are replaced by Al atoms, a tetrahedral substitution type (tetrahedral charged type)
Examples of smectites having such a structure include beidellite, nontronite, volkonskoite, saponite, and the like. Further, a case where Al atoms in the octahedron are replaced with Mg atoms is referred to as an octahedral substitution type (octahedral charged type), and smectites having such a structure include, for example, montmorillonite, hectorite, and steven. The site etc. are mentioned.

Among the above smectites, natural smectites include montmorillonite, saponite and hectorite. Further, as the synthetic smectite, saponite, hectorite, and stevensite are preferable.

Examples of the swelling synthetic mica include Na tetrasic mica NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ , Na or Li teniolite (NaLi) Mg ₂ Li (Si ₄ O).
₁₀ ) F ₂ , Na or Li hectorite (NaLi) _1/3
Suitable examples include Mg _2/3 Li _1/3 (Si ₄ O ₁₀ ) F ₂ and the like.

The above-mentioned inorganic layered compound has a laminated structure composed of unit crystal lattice layers having a thickness of 10 to 15 angstroms, and the substitution of metal atoms in the lattice is significantly larger than that of other clay minerals. As a result, the lattice layer is deficient in positive charge, and cations such as Na ⁺ , Ca ²⁺ and Mg ²⁺ are adsorbed between the layers to compensate for it. The cations existing between these layers are called exchangeable cations and can be exchanged with various cations. In particular, the cations between the layers are Li ⁺ , N
In the case of a ⁺ , since the ionic radius is small, the bond between the layered crystal lattices is weak, and it swells largely with water. When shear is applied in that state, it is easily cleaved to form a stable sol in water. The swelling synthetic mica has a strong tendency and is particularly preferably used.

Since the surface of the inorganic layered compound is hydrophilic, it swells easily in water and is easily dispersed by shearing. At this time, a water-miscible organic solvent,
For example, alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol and diethylene glycol; dimethyl sulfoxide, dimethylformamide, acetone and the like can be added.
Among them, ethanol, propanol, isopropanol and acetone are more preferable.

The surface of the inorganic layered compound is hydrophilic as described above, but it is negatively charged.
By using a quaternary salt compound and / or a quaternary salt compound, the surface can be hydrophobized, and the hydrophobized inorganic layered compound can be contained.

Specific examples of the tertiary salt compound and the quaternary salt compound include, for example, laurylamine hydrochloride (Pionine B-201), stearylamine hydrochloride (Pionine B-801), and oleylamine acetate (Pionine B-201).
709), stearylamine acetate (Pionine B-8)
09), stearylaminopropylamine acetate (Pionin B-104-DA) [In the parentheses, trade name (Pionin B series; manufactured by Takemoto Yushi Co., Ltd.) is shown. ] Amine salt compounds such as, laurylpyridinium chloride (Pionine B-251), myristylpyridinium chloride (Pionine B-451), cetylpyridinium chloride (Pionine B-651) [in brackets, trade name (Pionine B series; Takemoto Oils and fats Co., Ltd. are shown. ] Pyridinium salt compounds such as

Lauryl trimethyl ammonium chloride (Pionine B-211), cetyl trimethyl ammonium chloride (Pionine B-611), stearyl trimethyl ammonium chloride (Pionine B-)
811), dilauryldimethylammonium chloride (Pionine B-2211), distearyldimethylammonium chloride (Pionine B-8811), lauryldihydroxyethylmethylammonium chloride (Pionine B-221-B), oleylbispolyoxyethylene methylammonium chloride. (Pionine B-721-E), Stearyl hydroxyethyl dimethyl ammonium chloride (Pionine B-821-
A), lauryldimethylbenzylammonium chloride (Pionine B-231), lauroylaminopropyldimethylethylammonium ethosulfate (Pionine B-276), lauroylaminopropyldimethylhydroxyethylammonium perchlorate (Pionine B-277) [in brackets, Product name (Pionine B
Series: manufactured by Takemoto Yushi Co., Ltd. ], Etc. quaternary ammonium salt compounds and the like are preferable.

Further, the fourth having a polyoxyethylene group
Suitable examples thereof include secondary ammonium salt compounds. Examples of the polyoxyethylene group include a polyoxyethylene group, a trialkylammonium chloride polyoxyethylene group, a trialkylammonium bromide polyoxyethylene group, a dialkylammonium chloride polyoxyethylene group, a dialkylammonium acetate polyoxyethylene group, and benzyl.・ Dialkyl ammonium chloride polyoxyethylene group, benzyl dialkyl ammonium bromide di (polyoxyethylene) group,
Alkylammonium chloride di (polyoxyethylene) group, alkylammonium acetate di (polyoxyethylene) group, benzyl alkylammonium chloride di (polyoxyethylene) group, benzyl alkylammonium acetate di (polyoxyethylene) group,
Dialkylammonium chloride di (polyoxyethylene) group, dialkylammonium bromide tri (polyoxyethylene) group, alkylammonium chloride tri (polyoxyethylene) group, alkylammonium bromide tri (polyoxyethylene) group, alkylammonium acetate group, etc. Are preferred.

Further, a quaternary ammonium salt compound having a polypropylene group is also preferable. As the polypropylene group, for example, a polyoxypropylene group,
Trialkylammonium chloride polyoxypropylene group, trialkylammonium bromide di (polyoxypropylene) group, dialkylammonium chloride di (polyoxypropylene) group, dialkylammonium bromide tri (polyoxypropylene) group, alkylammonium chloride tri (polyoxy) Propylene) group,
Preferable examples include an alkylammonium bromide group.

Further, the cationic surfactants shown in Tables 1 to 4 below are also suitable as the tertiary salt compound or the quaternary salt compound used for making the inorganic layered compound hydrophobic.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

Of the above-mentioned tertiary salt compounds and quaternary salt compounds, those used for hydrophobizing the inorganic layered compound include:
N, N-dipolyoxyethylene-N-stearyl-N-
Methylammonium chloride, dodecyltrimethylammonium chloride, polyoxyisopropylenetriethylammonium chloride and the like are more preferable.

In order to make the inorganic layered compound hydrophobic by using the tertiary salt compound and / or the quaternary salt compound, one kind may be used alone, or two or more kinds may be used in combination.
Making the inorganic layered compound hydrophobic by using the tertiary salt compound and / or the quaternary salt compound means that the inorganic layered compound is subjected to cation exchange with these compounds. Specifically, it can be performed by the following method.
However, the present invention is not limited to this method.

First, in the first step, the inorganic layered compound is dispersed in water to obtain a suspension. The solid dispersion concentration in the suspension is preferably 1 to 15% by mass,
It can be freely set as long as the concentration of the inorganic layered compound is sufficiently dispersible. In this case, it is preferable to use an inorganic layered compound which has been previously freeze-dried. In the second step, a solution of the tertiary salt compound or the quaternary salt compound is added to the suspension of the inorganic layered compound, or the suspension of the inorganic layered compound is added to the solution, and the inorganic layered compound is suspended by cation exchange to form the inorganic layer The layered compound is hydrophobized. In the third step, the solid-liquid is separated and the hydrophobized inorganic layered compound is washed with water to sufficiently remove the by-product electrolyte. This is dried and, if necessary, pulverized to obtain the desired product.

The above reaction proceeds sufficiently at room temperature, but may be heated. The maximum temperature for heating is the tertiary salt compound used or 4
It is governed by the heat resistance of the graded salt compound, and can be arbitrarily set as long as it is below its decomposition point.

The amount of the tertiary salt compound and / or the quaternary salt compound added is preferably equivalent to the cation exchange capacity of the inorganic layered compound when converted into ions, but a smaller amount is also used for production. Is possible. Further, an excess amount may be added to the cation exchange capacity.
Specifically, the added amount is preferably 0.5 to 1.5 times (milliequivalent) of the cation exchange capacity of the inorganic layered compound, and more preferably 0.8 to 1.4 times.

Regarding the method for hydrophobizing the inorganic layered compound, JP-A-6-287014 and JP-A-9-175 are available.
It is described in detail in each publication of No. 817.

From the viewpoint of the barrier property of the coating film, the aspect ratio of the inorganic layered compound is preferably 20 or more, more preferably 30 or more, further preferably 100 or more, and particularly preferably 200 or more. When the inorganic layered compound is smectite, the aspect ratio is 30 to 100.
It is particularly preferable that the range is. The aspect ratio is a ratio of thickness to major axis of particles.

From the viewpoint of the barrier property and the smoothness of the coating film, the average particle diameter of the inorganic layered compound is preferably 0.3 to 20 μm, and 0.5 to 10 μm.
More preferably, it is 1 μm to 5 μm. The average thickness of the particles in the inorganic layered compound is preferably 0.1 μm or less, and 0.0
It is more preferably 5 μm or less, particularly preferably 0.01 μm or less. The inorganic layered compounds may be used alone or in combination of two or more.

When the inorganic layered compound is contained in the release layer, the content of the inorganic layered compound is preferably 0.1 to 50% by mass based on the total solid content (mass) of the release layer, 0.5 to 25 mass% is more preferable, and 1 to 15 mass% is particularly preferable. When the content is within the above range, sufficient gas barrier properties can be ensured without affecting the hue of the image formed, and a high-quality image with a high S / N ratio can be stably formed. You can

The inorganic layered compound can be used in combination with the high Tg / low permeability polymer described later. When a high Tg low permeability polymer is also used as a binder, the content ratio (i: ii) of the inorganic layered compound (i) and the high Tg low permeability polymer (i) is 0.005: 1 to 0. 0.3: 1 is preferable, and 0.01: 1 to 0.2: 1 is more preferable.

When an inorganic layered compound is contained in the upper layer of the release layer, for example, the gas barrier layer, the coloring material layer and the photothermal conversion layer described later, the content of the inorganic layered compound in each layer is the total solid content of each layer. 0.1-2 based on (mass)
0 mass% is preferable, 0.5-15 mass% is more preferable, 1-10 mass% is especially preferable. When a high Tg low permeability polymer is also used as a binder in the upper layer of the release layer, the content ratio (i: ii) of the inorganic layered compound (i) and the high Tg low permeability polymer (ii) is , 0.
005: 1 to 0.5: 1 is preferable, 0.01: 1 to
More preferably 0.25: 1.

The inorganic layered compound is preferably contained together with a binder. Examples of the binder include gelatin and its derivatives, and binder polymers such as hydrophilic colloids. For example, gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, dextran, dextrin, sodium alginate, starch derivatives. Various synthetic hydrophilic polymer substances such as sugar derivatives such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, etc. be able to.

As the gelatin, lime-processed gelatin, acid-processed gelatin, gelatin hydrolyzate, and gelatin enzyme dispersion may be used. Examples of the gelatin derivatives include various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, and epoxy compounds in gelatin. What is obtained by reacting is used.

(The glass transition point (Tg) is higher than the printing temperature, and the oxygen permeability is 2 when the film has a thickness of 10 μm.
0 × 10 ⁻⁵ ml / (m ² · Pa · 1 day) or less polymer) The above “glass transition point (Tg) is higher than the printing temperature,
And the oxygen permeability when the film is 10 μm thick is 20 ×
10 ^-5 ml / (m ² · Pa · 1 day) [= 20 ml / (m
² · atm · 1day)] or lower polymer ”(high Tg / low permeability polymer) also functions as a gas barrier substance. Therefore, as described above, as the binder polymer,
An embodiment containing a high Tg low permeability polymer is preferable, and it can be used in place of the binder polymer or together with the binder polymer as a binder.

As the high Tg low permeability polymer, among the above binder polymers, a polymer having a Tg of 100 ° C. or more, for example, an aqueous polymer such as gelatin, gelatin derivative, albumin, casein, dextran, polyimide, polycarbonate, polymethacrylic acid is used. Examples thereof include solvent-based polymers such as methyl, polyacrylonitrile, polyether ether ketone, polyhexamethylene terephthalamide, and polyether sulfone. Of these, gelatin is preferred for the water system, and polyimide and polycarbonate are preferred for the solvent system.

Here, the printing temperature means, when the gas is generated from the foaming agent by heat, the temperature by the heat applied in an imagewise manner (first or second foaming step described later) and the coloring material to be performed thereafter. Layer or color material layer and release layer is the temperature on the higher temperature side in the heating (heating step described below) .When gas is generated from the foaming agent by light, the color material layer or color material layer and release The temperature in heating the layer (heating step).

The temperature for applying heat imagewise is generally about 100 to 250 ° C., and 120 to 200 ° C. is preferable from the viewpoint of good image formation.

The heating temperature of the color material layer or the color material layer and the release layer is generally about 60 to 150 ° C., and 70 to 130 ° C. is preferable from the viewpoint of good image formation. Therefore, when the heating temperature of the color material layer or the color material layer and the release layer is higher than the temperature of heat applied in an imagewise manner, and when gas is generated from the foaming agent by light, the glass transition temperature is higher than the above temperature. A polymer having a high point is preferably used.

<Gas Barrier Layer> The gas barrier layer contains the above-mentioned inorganic layered compound, preferably contains a binder, and may contain other components as required. Examples of the binder include the binder polymer and the high Tg low permeability polymer. The layer thickness of the gas barrier layer is preferably 0.1 to 2 μm,
2 to 1.5 μm is more preferable. The layer thickness is 0.1 μm
If it is less than 2, the barrier properties may be insufficient, and 2
If it exceeds μm, the resolution may be degraded. When a high Tg low permeability polymer is used, it can be formed by appropriately selecting a method generally used for containing a binder in a layer and applying a coating solution, for example.

<Release Layer> The release layer contains at least a foaming agent which decomposes by heat or light to generate a gas, and may optionally contain other components such as a binder. . As the content of the foaming agent in the release layer,
Although it depends on the amount of gas generated by decomposition of the foaming agent, generally 0.001 to ² g / m ² is desirable, 0.01 to
More preferably 1.5 g / m ^2, about 0.02 to 1 g / m ² is particularly preferred.

The "foaming agent that decomposes upon heating to generate a gas" is preferably a chemical foaming agent, which can be appropriately selected from known chemical foaming agents, and among them, an organic foaming agent is particularly preferable. The chemical foaming agent generates nitrogen gas, carbon dioxide gas or the like by heating to the thermal decomposition temperature of the compound, and for example, a nitroso compound such as N, N′-dinitrosopentamethylenetetramine, 4,4 Azo compounds such as'-azodicarbonamide, barium azodicarboxylate, hydrazide compounds such as 4,4'-oxybis (benzenesulfonylhydrazide), p-toluenesulfonylhydrazide, hydrazodicarbonamide, semicarbazide compounds, azides Compounds, tetrazole compounds, and the like.

Further, a foaming accelerator may be used, and examples of the foaming accelerator include urea, salicylic acid, stearic acid, benzoic acid, diethylene glycol and the like. The thermal decomposition temperature of the chemical foaming agent is 60 to 300.
C is preferable, 70 to 250 C is more preferable, and 80 to
About 200 ° C. is particularly preferable.

The above-mentioned "foaming agent which decomposes by light to generate a gas" can be appropriately selected from known ones and is preferably a diazo compound or the like from the viewpoint of easy decomposition by ultraviolet light. Examples of the diazo compound include the following compounds. Ar-N ₂ ⁺ · X ^- wherein, Ar represents an aryl group, X ^- represents an acid anion. ]

Specific examples of the diazo compound include 4- (N
-(2- (2,4-di-tert-amylphenoxy)
Butyryl) piperazino) benzenediazonium, 4-dioctylaminobenzenediazonium, 4- (N- (2
-Ethylhexanoyl) piperazino) benzenediazonium, 4-dihexylamino-2-hexyloxybenzenediazonium, 4-N-ethyl-N-hexadecylamino-2-ethoxybenzodiazonium, 3-chloro-4-dioctylamino-2 -Octyloxyobenzenediazonium, 2,5-dibutoxy-4-morpholinobenzenediazonium, 2,5-octoxy-4-morpholinobenzenediazonium, 2,5-dibutoxy-4
-(N- (2-ethylhexanoyl) piperazino) benzenediazonium, 2,5-diethoxy-4- (N-
(2- (2,4-di-tert-amylphenoxy) butyryl) piperazino) benzenediazonium, 2,5-
Dibutoxy-4-tolylthiobenzenediazonium, 3
Examples thereof include acid anion salts such as-(2-octyloxyethoxy) -4-morpholinobenzenediazonium, and the following diazo compounds D-1 to D-5. Hexafluorophosphate salts, tetrafluoroborate salts, and 1,5-naphthalene sulfonate salts are also preferable.

[0057]

[Chemical 1]

In the present invention, a particularly preferable compound is a compound which can be photolyzed by light having a wavelength of 300 to 400 nm, for example, 4- (N- (2- (2,4-di-te.
rt-Amylphenoxy) butyryl) piperazino) benzenediazonium, 4-dioctylaminobenzenediazonium, 4- (N- (2-ethylhexanoyl) piperazino) benzenediazonium, 4-dihexylamino-2-hexyloxybenzenediazonium, 4- N-
Ethyl-N-hexadecylamino-2-ethoxybenzodiazonium, 2,5-dibutoxy-4- (N- (2-
Ethylhexanoyl) piperazino) benzenediazonium, 2,5-diethoxy-4- (N- (2- (2,4-
Di-tert-amylphenoxy) butyryl) piperazino) benzenediazonium and the diazo compound D-3
-D-5 are mentioned.

Here, the maximum absorption wavelength of the diazo compound means a spectrophotometer (Shimazu MPS-) obtained by coating each compound in a coating film of 0.1 g / m ² to 1.0 g / m ^2.
2000).

Regarding the usage form of the diazo compound,
There is no particular limitation, (1) a method of using by solid dispersion,
Examples include (2) a method of emulsifying and dispersing, (3) a method of dispersing a polymer, and (4) a method of dispersing and using a latex. In the case of the method (2) emulsified and dispersed, the diazo compound is dissolved in an organic solvent that is sparingly soluble or insoluble in water, added to an aqueous solution of a water-soluble polymer, and emulsified and dispersed using a homogenizer or the like. .

Examples of the organic solvent include low-boiling auxiliary solvents such as acetic acid ester, methylene chloride and cyclohexanone, and / or phosphoric acid ester, phthalic acid ester, acrylic acid ester, methacrylic acid ester and other carboxylic acid ester, Examples include fatty acid amides, alkylated biphenyls, alkylated terphenyls, alkylated naphthalenes, diarylethanes, chlorinated paraffins, alcohols, phenols, ethers, monoolefins, and epoxies.

Specific examples include tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, tricyclohexyl phosphate, dibutyl phthalate, dioctyl phthalate, dilaurate phthalate, dicyclohexyl phthalate, butyl oleate, diethylene glycol benzoate, sebacine. Acid dioctyl, dibutyl sebacate, dioctyl adipate, trioctyl trimellitate, acetyltriethyl citrate, octyl maleate, dibutyl maleate, isoamylbiphenyl, chlorinated paraffin, diisopropylnaphthalene, 1,1′-
High boiling point oils such as ditolylethane, 2,4-ditertiary-amylphenol, N, N-dibutyl-2-butoxy-5-tertiaryoctylaniline, hydroxybenzoic acid 2-ethylhexyl ester and polyethylene glycol can be mentioned. Of these, alcohol-based, phosphoric acid ester-based, carboxylic acid ester-based, alkylated biphenyl, alkylated terphenyl, alkylated naphthalene, and diarylethane are particularly preferable.

Further, a carbonization inhibitor such as hindered phenol or hindered amine may be added to the high boiling point oil. Further, as the high boiling point oil, one having an unsaturated fatty acid is particularly desirable, and examples thereof include α-methylstyrene dimer. For the α-methylstyrene dimer, for example, a trade name “MSD10” manufactured by Mitsui Toatsu Chemicals, Inc.
0 "etc.

As the water-soluble polymer, a water-soluble polymer such as polyvinyl alcohol is used, but an emulsion or latex of a hydrophobic polymer can be used together. Examples of the water-soluble polymer include polyvinyl alcohol, silanol-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amino-modified polyvinyl alcohol, itaconic acid-modified polyvinyl alcohol, styrene-maleic anhydride copolymer, butadiene-maleic anhydride copolymer. Coalescence, ethylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer,
Examples thereof include polyacrylamide, polystyrene sulfonic acid, polyvinylpyrrolidone, ethylene-acrylic acid copolymer, gelatin, and the like. Among them, carboxy-modified polyvinyl alcohol and gelatin are particularly preferable. Examples of the emulsion or latex of the hydrophobic polymer include styrene-butadiene copolymer, carboxy-modified styrene-butadiene copolymer, acrylonitrile-butadiene copolymer and the like. At this time, a conventionally known surfactant or the like may be added if necessary.

Although the content of the foaming agent depends on the amount of gas generated by decomposition of each foaming agent, it is generally preferably 1 to 70% by mass based on the total solid content of the release layer. Two
˜50% by mass is more preferable, and about 4 to 30% by mass is particularly preferable.

The release layer preferably contains a binder in addition to the foaming agent. As the binder here, a polymer having low breaking strength and small breaking elongation is preferable. In order to obtain a polymer having a low breaking strength and a small breaking elongation, it is preferable to add inorganic ultrafine particles or ultrafine particles of an organic polymer having a high glass transition point Tg to the release layer. The Tg here is 60 ° C. or higher, preferably 8
It is 0 ° C or higher, particularly preferably 100 ° C or higher. The content of the ultrafine particles, with respect to the total solid content of the release layer,
It is preferably 10% by volume or more, more preferably 20% by volume or more, particularly preferably 30% by volume or more, but preferably 80% by volume or less in order to prevent the film from becoming too brittle and peeling off.

The polymer used as the binder in the release layer may be either a homopolymer or a copolymer, and the polymer may be composed of either one kind of monomer or two or more kinds of monomers. . Specifically, an amorphous organic high molecular polymer having a softening point of 40 to 150 ° C. is preferable.

Examples of the amorphous organic polymer include butyral resin, polyamide resin, polyethyleneimine resin, polyimide resin, sulfonamide resin, polyester polyol resin, petroleum resin, styrene, vinyltoluene and α-methylstyrene. Styrene and its derivatives such as 2-methylstyrene, chlorostyrene, vinylbenzoic acid and aminostyrene, homopolymers and copolymers of substituted compounds, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate and other methacrylic acid esters. And methacrylic acid,
Acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate and α-ethylhexyl acrylate, and dienes such as acrylic acid, butadiene and isoprene, acrylonitrile and vinyl ethers,
Examples thereof include homopolymers of maleic acid and maleic acid esters, maleic anhydride, cinnamic acid, vinyl monomers such as vinyl acetate, and copolymers with other monomers. Two or more kinds of these binders may be used in combination.

The thickness of the release layer is preferably 0.03 to 3 μm from the viewpoint of the effect of the foaming agent and the resolution.
The thickness is more preferably 0.05 to 2 μm, and particularly preferably about 0.1 to 1 μm.

<Coloring Material Layer> The coloring material layer is a layer that can be transferred at the time of transfer to form an image, contains at least a coloring material, and preferably contains a binder together with the coloring material and, if necessary, a flux. , A plasticizer, a wax component, etc. may be contained.

Examples of the coloring material include various dyes and pigments. The dye or pigment can be appropriately selected from known dyes or pigments for heat-melt transfer sheets. Examples of the dye include D
isperse Red1, Disperse Yell
ow3, Disperse Yellow23, and D
Azo dyes such as isperse Yellow 60,
Disperse Violet 28, Dispers
e Blue14, Disperse Blue26,
Disperse Red4, Disperse Re
Anthraquinone dyes such as d60 and Disperse Yellow 13, and Disperse Ye
low 54, Disperse Yellow 61,
Disperse Yellow 82 and Disper
Examples include dyes such as se Blue 20.

The above-mentioned pigments are generally classified into organic pigments and inorganic pigments. The former is particularly excellent in transparency of the coating film, and the latter is generally excellent in hiding power. When the transfer sheet of the present invention is used for printing color proofing, an organic pigment that has a color tone similar to or close to that of yellow, magenta, cyan and black generally used for printing ink is preferably used. In addition, metal powder, fluorescent pigment, etc. may be used. Examples of suitable pigments include azo pigments, phthalocyanine pigments, antriquinone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, and nitro pigments.

Examples of typical pigments for each hue are shown below. 1) Yellow pigments: Hansa Yellow G, Hansa Yellow 5
G, Hansa Yellow 10G, Hansa Yellow A, Pigment Yellow L, Permanent Yellow NCG, Permanent Yellow FGL, Permanent Yellow HR. 2) Red pigment: Permanent Red 4R, Permanent Red F2R, Permanent Red FRL, Lake Red C, Lake Red D, Pigment Scarlet 3B,
Bordeaux 5B, Alizarin Rake, Rhodamine Rake B. 3) Blue pigments: phthalocyanine blue, Victoria blue lake, fast sky blue. 4) Black pigment: carbon black.

When an image is formed on a ceramic material, an inorganic pigment is used as the pigment. Usually, upper paint and lower paint used in pottery are used, but for example, the crystal structure of copper oxide, cobalt oxide, etc. is spinel,
Metal oxides such as sphene, pyrochlore, rutile, prideite, fufosfate, phenasite, periclace, olivine, badellite, borate, corundum and zircon; sulfides such as cadmium yellow; cadmium selenide compounds such as selenium red , And the like. Further, an inorganic pigment which is a fluorescent pigment or a phosphorescent pigment may be used.

Further, in the firing step of sintering the image arranged on the ceramic material, it is also preferable to use a flux together with the inorganic pigment from the viewpoint of improving the fusion property of the inorganic pigment to the surface of the ceramic material. 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, Examples thereof include zirconium oxide and titanium oxide. Further, it is also possible to use a composite component such as borax, feldspar and kaolin. The flux is 1
It is also possible to use one kind alone or a combination of two or more kinds to dissolve and use it as a so-called frit.

The binder contained together with the coloring material may be either a homopolymer or a copolymer, and the polymer may be composed of either one kind of monomer or two or more kinds of monomers. Among them, from the relationship with the image receiving layer of the image receiving material to which the color material layer is transferred upon image formation, that is, the relationship with the polymer containing the image receiving layer,
It is preferable that the constituent unit is a polymer containing 30 mol% or more of a monomer having the same functional group as the monomer constituting the image-receiving layer-containing polymer. That is, it suffices that at least one of the monomers constituting the polymers of both the color material layer and the image receiving layer have the same functional group.
Further, it may have functional groups different from each other.

Here, as the same functional group, for example,
Butyral group, vinyl alcohol group, amino group, amide group, imino group, imide group, styrene group, alkoxy group,
Examples thereof include a methacryl group and an ester group thereof, acrylic acid and an ester group thereof, maleic acid and an ester group thereof, a vinyl ether group, a vinyl acetate group, and the like, butyral group is preferable.

The monomer having the “same functional group” is preferably contained as a constitutional unit in a large amount in each of the polymer in the color material layer and the polymer in the image-receiving layer described later, and the content ratio is at least It is desired to be 30 mol% or more, more preferably 50 mol% or more, particularly preferably 80 mol% or more. When the content of the monomer having the "same functional group" as a structural unit in the polymer is less than 30 mol%, the properties of the polymer in the transfer layer and the polymer in the image receiving layer described later are greatly different, Image unevenness may easily occur.
As specific binders, those mentioned as examples of the binder polymer used in the release layer can be similarly mentioned.

<Support> The support is not particularly limited and may be appropriately selected depending on the purpose. As a preferred example of the support, a sheet formed from a synthetic resin material such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polycarbonate, polyethylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and styrene-acrylonitrile copolymer. Can be mentioned. Particularly, biaxially stretched polyethylene terephthalate is preferable in terms of mechanical strength and dimensional stability against heat. When the transfer sheet of the present invention is used for producing a color proof, since the support of the image receiving sheet is generally an opaque sheet material such as printing paper, the support of the transfer sheet is transparent so that laser light can pass therethrough. It is preferable to use a different synthetic resin material.

The thickness of the support is 3 to 100 μm.
m is preferable, 4 to 50 μm is more preferable, and 5 to 25
About μm is particularly preferable.

<Light-to-heat conversion layer> The transfer sheet of the present invention may further have a light-to-heat conversion layer. By providing the photothermal conversion layer, the light energy of the laser light is converted into heat to thermally decompose the foaming agent of the release layer, or the coloring material layer is melted or softened to adhere the surface of the coloring material layer ( Transferability).

The light-heat conversion layer contains at least a light-heat conversion substance and a binder. The light-heat converting substance can be appropriately selected from conventionally known light-heat converting substances. Generally, the photothermal conversion substance includes a dye (pigment or the like) capable of absorbing laser light, and the dye (pigment or the like) includes an organic dye or a black pigment such as carbon black. Above all, it is preferable to use the organic dye from the viewpoint of the film strength of the photothermal conversion layer.

Specific examples of the organic dye include pigments of macrocyclic compounds having absorption in the visible to near infrared region such as phthalocyanine and naphthalocyanine, and organic materials used as laser absorbing materials for high density laser recording such as optical disks. Dyes (cyanine dyes other than indolenine dyes, anthraquinone dyes, azulene dyes, phthalocyanine dyes),
And organic metal compound dyes such as dithiol nickel complex. Among them, the cyanine dye is preferable in terms of the photothermal conversion efficiency and the fact that the cyanine dye is not easily broken by the laser light. It is desired that the light-heat converting substance has a high light-heat converting ability, and a particularly preferable light-heat converting substance is an indolenine compound described as the general formula (I) in Japanese Patent Application No. 10-140924. Carbon is also preferable because it can absorb ultraviolet rays to infrared rays and convert it into heat.

As the binder constituting the light-heat conversion layer, for example, homopolymers or copolymers of acrylic monomers such as acrylic acid, cellulose polymers such as cellulose acetate, polystyrene, vinyl chloride / vinyl acetate copolymer, Examples include polyvinyl butyral, vinyl polymers such as polyvinyl alcohol, condensation polymers such as polyesters, polyamides and polyimides, rubber thermoplastic polymers such as butadiene / styrene copolymers, polyurethanes, epoxy resins, urea / melamine resins, etc. To be Of these, polymers such as polyvinyl alcohol, polyvinyl butyral, polyester and polyimide are preferably used. Further, as a particularly preferable binder, a polyimide resin described in Japanese Patent Application No. 10-140924 can be mentioned. In the case of a structure having a photothermal conversion layer,
It is preferable that the light-heat conversion layer also serves as a barrier layer.

Regarding the content of the photothermal conversion substance in the layer, the ratio (mass ratio) to the binder (solid content) is 1:
It is preferably in the range of 20 to 2: 1 (photothermal conversion substance: binder), and particularly preferably in the range of 1:10 to 2: 1. The layer thickness of the photothermal conversion layer is preferably 0.03 to 3 μm, and 0.05 to 1.5 μm.
m is more preferred. The photothermal conversion layer has a maximum absorption wavelength of 70.
It is preferably in the range of 0 to 1500 nm, and 750
More preferably, it is in the range of 1000 nm. The absorbance (optical density) in the wavelength range is preferably 0.1 or more, more preferably 0.3 or more. It is preferable that the photothermal conversion layer also serves as a release layer (foaming layer), and that this layer also has a function of a barrier layer. In this case, it is convenient to use fine carbon particles as the light-heat converting substance, because they can also serve as ultrafine particles that are usually used in the release layer.

[Image Forming Method] Next, the image forming method of the present invention will be described in detail. The image forming method of the first aspect of the present invention, the transfer sheet of the present invention described above is used,
A step of applying heat or light for decomposing a foaming agent to generate a gas imagewise to at least the release layer of the transfer sheet (hereinafter, sometimes referred to as “first foaming step”), and the transfer sheet of the transfer sheet. A step of heating at least the color material layer or the color material layer and the release layer (hereinafter, may be referred to as "heating step"), and a step of transferring the color material layer onto an image receiving sheet to form an image (hereinafter , "Transfer process").

In the image forming method of the second aspect of the present invention, the transfer sheet of the present invention described above is used, and the foaming agent is decomposed to generate gas in at least the release layer and the coloring material layer of the transfer sheet. It comprises a step of applying heat to be applied in an imagewise manner (hereinafter sometimes referred to as "second foaming step") and a transfer step. In each of the first and second aspects, other steps may be included if necessary.

In the first foaming step, heat or light is imagewise applied to at least the release layer to decompose the foaming agent, and gas is generated from the release layer. In the second foaming step, heat is applied imagewise to at least both of the release layer and the color material layer to decompose the foaming agent and generate gas from the release layer, and at the same time, the color material layer. On the other hand, the heating in the heating step of the first aspect is similarly performed (the heating step will be described later).

The application of heat (heating) in the first and second foaming steps can be performed by using a means capable of applying heat corresponding to an image signal. For example, a heating means such as a heating element such as a thermal head or a laser beam is used. It can be suitably performed by heating means or the like. When the foaming is not achieved by the heating by these means, the coloring material layer or the coloring material layer and the releasing layer can be foamed by heating in the heating step described later.

The light can be imparted by irradiating light having a wavelength that effectively decomposes the foaming agent in a desired image manner. For example, when the diazo compound is used, blue laser light is used as an image signal. Or by irradiating ultraviolet light through a negative silver image formed of a transmission type silver halide light-sensitive material (for example, lith film).

In the heating step, at least the coloring material layer, or the coloring material layer and the release layer of the transfer sheet are heated. By heating in this step, the surface of the coloring material layer can be melted or softened so that it can be transferred, and the gas generated by being decomposed by heat or light expands due to heat to foam the release layer, Due to the foaming, the adhesive force between the color material layer and the support is weakened, and the color material layer can be easily transferred to the image receiving sheet that is the transfer target. Further, when the foaming does not occur or the foaming is not sufficient in the foaming step, the foaming can be sufficiently performed in this step. Therefore, the foaming step is preferably provided at the same time as or before this step.

In the transfer step, the color material layer is transferred onto the image receiving sheet to form an image on the image receiving sheet.
Specifically, the transfer sheet and the image receiving sheet may be superposed on each other and pressure may be applied thereto, and then the transfer sheet and the image receiving sheet may be peeled off. It is preferable that the heating step and the main transfer step are performed at the same time, that is, the color material layer of the transfer sheet and the image receiving surface of the image receiving sheet are overlapped with each other to form a laminated body, and the laminated body is heated and pressurized. .

[Image-Receiving Sheet] The image-receiving sheet to be the transferred body will be described in detail below. As the image-receiving sheet, one having a support and at least one image-receiving layer containing a binder resin on the support is usually preferable, but it has an affinity with the color material layer of the transfer sheet. When the property is good, a resin sheet such as polyethylene terephthalate (PET), plain paper, coated paper, glass epoxy sheet, metal plate or the like may be used. Further, the image-receiving sheet has, if necessary, any one layer or two or more layers of a cushion layer, a peeling layer and an intermediate layer between the support and the image-receiving layer. In the case of an image-receiving sheet having an image-receiving layer on a support, it is preferable to have a back layer on the surface of the support opposite to the side having the image-receiving layer to improve the transportability.

Examples of the support include sheet-like base materials such as plastic sheets, metal sheets, glass sheets, and paper. Examples of the plastic sheet include polyethylene terephthalate sheet, polycarbonate sheet, polyethylene sheet, polyvinyl chloride sheet, polyvinylidene chloride sheet, polystyrene sheet, styrene-acrylonitrile sheet, polyester sheet and the like. Further, examples of the paper support include actual printing paper, coated paper, and the like. Further, in the method for producing a ceramic material with an image described later, when the image is finally arranged and formed on the ceramic material, a water-permeable support or a support having good releasability is used. preferable.

It is preferable that the support has minute voids (voids) because curling can be prevented, heat insulation and whiteness are excellent, and image quality can be improved. Such a support is, for example, a mixed melt obtained by mixing a thermoplastic resin and a filler composed of an inorganic pigment or a polymer incompatible with the thermoplastic resin into a single layer or a multi-layer by a melt extruder. It can be produced by forming a film and further stretching it uniaxially or biaxially. In this case, the porosity is determined by the selection of the resin and the filler, the mixing ratio, the stretching conditions and the like.

The thermoplastic resin is preferably a polyolefin resin such as polypropylene, or a polyethylene terephthalate resin, in terms of good crystallinity, good stretchability and easy formation of voids. Particularly, the polyolefin resin or polyethylene terephthalate resin is preferable. It is preferable to use as a main component and to appropriately use a small amount of another thermoplastic resin together. The inorganic pigment used as the filler preferably has an average particle size of 1 μm or more and 20 μm or less, and examples thereof include calcium carbonate, clay, diatomaceous earth, titanium oxide, aluminum hydroxide, and silica. Further, as the incompatible polymer used as the filler, when polypropylene is used as the thermoplastic resin, it is preferable to combine polyethylene terephthalate as the filler. The content of the filler such as the inorganic pigment in the support is generally about 2 to 30% by volume.

The thickness of the support of the image receiving sheet is usually 10 to 400 μm, preferably 25 to 200 μm. In addition, the surface of the support is subjected to surface treatment such as corona discharge treatment or glow discharge treatment in order to improve the adhesion with the image receiving layer (or cushion layer) or the adhesion with the image forming layer of the thermal transfer sheet. May be.

<Image Receiving Layer> It is preferable that at least one image receiving layer is provided on the surface of the support constituting the image receiving sheet so that the color material layer of the transfer sheet can be satisfactorily transferred and fixed. The image receiving layer is preferably a layer mainly composed of a binder resin made of an organic polymer.

The binder resin is preferably a thermoplastic resin, and examples thereof include homopolymers of acrylic monomers such as acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters, and copolymers thereof.
Methylcellulose, ethylcellulose, cellulosic polymers such as cellulose acetate, polystyrene,
Homopolymers and copolymers of vinyl monomers such as polyvinylpyrrolidone, polyvinyl butyral, polyvinyl alcohol, polyvinyl chloride, etc., polyesters,
Examples thereof include condensation type polymers such as polyamide and rubber type polymers such as butadiene-styrene copolymer.

The binder resin is preferably a polymer having a glass transition temperature Tg of lower than 90 ° C. in order to secure an appropriate adhesive force with the color material layer of the transfer sheet. For this reason, it is possible to add a plasticizer to the image receiving layer. The binder resin has a Tg of 30 ° C. in order to prevent blocking between the transfer sheet and the image receiving sheet.
The above is preferable. As the binder resin in the layer, a polymer which is the same as or similar to the binder resin contained in the color material layer of the transfer sheet in terms of improving the adhesion with the color material layer at the time of transfer and improving the sensitivity and the image strength. Is particularly preferable.

The image-receiving layer comprises a support, an organic solvent solution or an aqueous solution (aqueous solution, aqueous dispersion) containing a binder resin.
Can be formed, for example, by coating.
In addition, according to the image forming method of the present invention, an image may be once formed on the image receiving layer and then retransferred to a printing actual paper or the like.

The layer thickness of the image receiving layer is preferably 0.3 to 7 μm, and 0.7 to 7 μm, when retransferred to printing paper.
4 μm is more preferable. If the layer thickness is less than 0.3 μm, the function as an image receiving layer may not be achieved, image quality may be deteriorated, or film strength may be insufficient and the film may be easily torn when retransferred to a printing paper. If it exceeds 7 μm, for example, the gloss of the image after retransferred to the actual printing paper is increased, and the closeness to the printed matter may be reduced.

When the image-receiving sheet having the transferred image is used as it is, the thickness of the image-receiving layer is 0.3 to 30 μm.
Is preferred. If the layer thickness is less than 0.3 μm, for example, the function as an image receiving layer may not be achieved and the image quality may be deteriorated. If the layer thickness exceeds 30 μm, problems such as curling may occur or the cost may decrease. It may be up.

Further, in the case of the image receiving layer in the first method and the second method of the method for producing a ceramic material with an image described later,
The layer thickness is preferably 0.5 to 30 μm, more preferably 1 to 20 μm. If the layer thickness is less than 0.5 μm, for example, the function as an image receiving layer cannot be achieved, resulting in deterioration of image quality, or as an image supporting layer when disposed on the second image receiving paper or the ceramic body. The function of may not be fulfilled. If it exceeds 30 μm,
The incineration residue of the image receiving layer may occur, resulting in deterioration of image quality and color reproduction.

In the image forming method of the present invention, the step of applying heat or light imagewise to the release layer (first foaming step)
And a heating step of heating the color material layer or the color material layer and the release layer and a transfer step of imagewise transferring the color material layer to the image receiving sheet are particularly preferable. That is, by stacking so that the color material layer of the transfer sheet and the image receiving layer of the image receiving sheet are in contact with each other, a laminated body is formed, and the laminated body is heated imagewise by a thermal head or a laser beam while applying pressure. An image can be preferably formed.

For example, an image can be formed particularly preferably as follows. That is, a laminated body, in which the image receiving layer of the image receiving sheet and the color material layer of the transfer sheet are in contact with each other, is wound around the surface of the drum provided with suction holes for vacuum suction while applying a vacuum. The image can be heated from the outside of the sheet by applying heat with a thermal head or irradiating it with laser light to thermally decompose and foam the foaming agent in the release layer of the transfer sheet and transfer the surface of the color material layer. It is heated so as to be in such a state, and at the same time, the laminated body is conveyed while being pressed by the drum pressure by a pair of rollers including the drum. Then, the color material layer can be transferred in the image-wise manner on the image receiving layer of the image receiving sheet by peeling both sheets off from the laminate.

Further, according to the image forming method of the second aspect of the present invention, in the second foaming step, the foaming agent of the release layer is thermally decomposed and the coloring material layer is heated in the same step. Then, the image can be easily formed by transferring the color material layer to the image receiving sheet.

For example, an image can be formed particularly suitably as follows. That is, the image forming apparatus 40 configured as shown in FIG. 1 is prepared. Image forming apparatus 40
Comprises a pair of support rolls 44 and a pair of pinch rolls 46 that face each other and rotate in synchronization with each other at a constant speed in the direction of the arrow so that the transfer sheet 20 and the image receiving sheet 30 can be conveyed while being pressed under a desired pressure. It looks like this. At least one of the pair of rolls (in the figure, the pinch roll 4
A heating means capable of heating the laminate composed of the transfer sheet 20 and the image receiving sheet 30 is incorporated inside 6).
A heating means 60 such as a thermal head is arranged at a position where it can contact the transfer sheet 20 upstream of the support roll 44 or the like in the transfer path of the transfer sheet 20 or the like, and sandwiches the transfer sheet 20 or the like which is conveyed in the transfer path. A platen roller 42 is disposed on the opposite side so that it can contact the image receiving sheet 30. Further, a peeling bar 50 for peeling both sheets from the laminated body is arranged in the transport path located on the downstream side of the transport path and upstream of the winding section.

When the image forming apparatus 40 is started, the transfer sheet 20 having the color material layer and the image receiving sheet 30 having the image receiving layer are provided.
Are conveyed in the direction of the arrow and are laminated so that the color material layer and the image receiving layer are in contact with each other under pressure from the platen roller 42, and are not opposed to the image receiving sheet 30 of the transfer sheet 20 by the heating means 60 such as a thermal head. Side surface (hereinafter,
Also called the back side. ), Heat is applied at a temperature corresponding to the image signal. The heating is performed so that at least the temperature in the release layer is equal to or higher than the thermal decomposition temperature of the foaming agent. When it is further conveyed, it passes between the rolls 44 and 46 and is heated (heated to a temperature lower than the heating temperature by the thermal head) and pressed, and then both sheets are peeled by the peeling bar 50, and on the image receiving layer of the image receiving sheet 30. An image is formed on.

The image forming apparatus 40 configured as shown in FIG. 2 is used when the transfer sheet 20 provided with the photothermal conversion layer is used, and the laser irradiation means 70 is used in place of the heating means 60 in FIG. It is an example of an image forming apparatus provided. When the image forming apparatus 40 shown in FIG. 2 is activated, the transfer sheet 20 having the color material layer and the image receiving sheet 30 having the image receiving layer are conveyed in the arrow direction and the supporting roll 44 is provided.
Further, the color material layer and the image receiving layer are laminated so that the color material layer and the image receiving layer are contacted with each other by receiving pressure from a pair of rolls composed of the pinch rolls 46. On the upstream side of the support roll 44 and the like in the transfer path of the transfer sheet 20, the laser irradiation means 70 causes the laser light to image-wise in accordance with the image signal, or the back surface of the transfer sheet 20 on the side not facing the image receiving sheet 30 or the back surface. It is irradiated from the surface opposite to the surface. After the irradiation, when the rolls 44 and 46 are conveyed to a position where they face each other, they are laminated with the image receiving sheet 30 while being heated and pressed, and then both sheets are peeled by the peeling bar 50, and an image is formed on the image receiving layer of the image receiving sheet 30. Is formed.

Further, the step of irradiating the release layer with light, the step of heating the color material layer and / or the release layer, and the step of transferring the color material layer can be simultaneously performed.

[Preparation Method of Ceramic Material with Image] In the preparation method of the ceramic material with image of the first aspect of the present invention, the transfer sheet of the present invention described above is used, and the method for forming an image of the present invention is the same. The first foaming step, the heating step and the transfer step described above, a step of arranging the formed image on the ceramic material (hereinafter, sometimes referred to as “arrangement step”), and at least the arranged image is fired. And a process (hereinafter, may be referred to as a “firing process”).

In the method for producing the image-bearing ceramic material according to the second aspect of the present invention, the transfer sheet of the present invention described above is used,
The image forming method of the present invention includes the above-described second foaming step and transfer step, the arranging step, and the baking step. In each of the first and second aspects, other steps may be included if necessary.

As a method for producing a ceramic material with an image,
For example, the following method can be mentioned. (First Method) An image forming layer (including an inorganic pigment) formed on an image receiving sheet by the same steps as those of the image forming method of the present invention, which has a different image receiving layer from the image receiving sheet.
After retransferred to the image receiving sheet, at least the image is arranged on the ceramic material together with the image receiving layer of the second image receiving sheet (arrangement step), the arranged image is fired (firing step), and the inorganic pigment is applied on the ceramic material. It may be a method of forming an image.

In this case, as the second image receiving sheet,
It is preferable that the support is a water-permeable support such as paper and has a layer made of a water-soluble polymer between the image receiving layer and the support.
That is, by immersing the image-formed second image-receiving sheet in water, the water-soluble polymer is dissolved and the image-receiving layer can be easily peeled off from the paper support (the surface of the image-receiving layer after peeling is “peeled”). Surface "), and the inorganic pigment image can be formed on the ceramic material by arranging the image receiving layer on the ceramic material on the release surface, and drying and firing.
The water-soluble polymer layer serves as an adhesive between the ceramic material and the image receiving layer, and therefore does not necessarily need to be removed.

Instead of the water-soluble polymer layer, a peelable polymer layer such as silicone resin or olefin resin or a polymer layer having weak adhesion such as polyvinyl alcohol may be provided on the paper support or film. It is also possible to use a plastic film having good releasability or a plastic film subjected to a mold release treatment as the support. in this case,
The surface of the image receiving layer on which the image of the second image receiving sheet is formed and the ceramic material are overlapped so as to face each other, and the image is transferred onto the ceramic material together with the image receiving layer by passing through a heat roller or the like, and then the ceramic material is fired. To form an inorganic pigment image.

(Second Method) The image (including the inorganic pigment) formed on the image-receiving sheet by the same step as the image forming method of the present invention described above is directly arranged on the ceramic material (arrangement step), and then arranged. Alternatively, the image may be fired (firing step) to form an inorganic pigment image on the ceramic material. Also in this case, it is preferable to use the second image receiving sheet used in the first method as the image receiving sheet.

(Third Method) An image-receiving sheet having a layer containing a water-soluble polymer on a paper support is used, and an image (inorganic) is formed on the layer by the same steps as those of the image forming method of the present invention. (Including a pigment), a cover coat layer is formed on the formed image, and the water-soluble polymer is dissolved by immersing the cover coat layer in water to separate the image from the paper support together with the cover coat layer. Alternatively, a method of arranging on a ceramic material (arrangement step) and firing (firing step) to form an inorganic pigment image on the ceramic material may be used.

Examples of the ceramic material include ceramic plates, pottery, ceramic plates, ceramics, enamels, and ceramic materials used for building materials such as tiles. The shape and thickness of the ceramic material can be appropriately selected according to the purpose and application.

The image receiving layer of the second image receiving sheet in the first method, the image receiving layer in the second method, and the third image receiving layer.
In the method of (1), the cover coat layer has a function of holding the image (inorganic pigment image) so as not to be damaged when the support is peeled from the image receiving sheet when the image is arranged on the ceramic material. From the viewpoint of the function, these layers preferably include a hydrophobic polymer. As the hydrophobic polymer, the polymers mentioned as the binder polymer used for the color material layer of the transfer sheet described above can be similarly used. Further, the hydrophobic polymer used for these layers and the polymer used for the color material layer preferably include the same functional group as described above. Among them, a polymer having a glass transition point of room temperature (use environment temperature) or lower is preferable from the viewpoint of enabling close contact with and transfer to an uneven surface or a curved surface. here,
The operating environment temperature or lower means 25 ° C. or lower. The glass transition point is preferably −50 to 25 ° C., and −30 to
15 ° C is more preferable. Specifically, as a commercially available product, a cover coat resin LO-21 manufactured by Kyodo Chemical Co., Ltd.
0, same LO-176S, same LO-200H, same LO-1
70H etc. are mentioned.

The cover coat layer used in the third method may be formed by coating on the inorganic pigment image, or the cover coat layer previously formed on the temporary support may be transferred and formed by thermal transfer. Good. It is also preferable to provide a release layer between the temporary support and the cover coat layer. Further, the cover coat layer may contain the above-mentioned frit (flux). By including the frit, even when the content of the inorganic pigment in the inorganic pigment image is high, it can be easily strongly sintered to the ceramic material, and further, the image stability after sintering and the surface gloss can be improved. .

In the firing step, the ceramic material on which the inorganic pigment image (and the image receiving layer or the cover coat layer depending on the method) is arranged is dried and then heated to sinter the inorganic pigment image on the surface of the ceramic material. The inorganic pigment image is sintered on the surface of the ceramic material, and components other than the inorganic pigment and organic components such as an image receiving layer arranged on the ceramic material together with the inorganic pigment as an image are evaporated or incinerated. Therefore, the materials (components in the transfer layer or image receiving layer) that are finally placed on the ceramic material together with the inorganic pigment that forms the image include atoms that do not disappear due to evaporation or combustion during the firing process, compounds that cause coloring, etc. Is preferably not included,
It is preferable not to include an atom, a compound, or the like that reacts with the inorganic pigment and causes discoloration or the like.

From the viewpoint of temperature control, color developability and the like, it is preferable that the heating (firing) in the firing step is performed using, for example, an electric kiln. The heating conditions can be appropriately set according to the selected material, the volume of the ceramic material, the size of the image, and the like. It is preferable that the heating is performed by gradually raising the temperature to the firing temperature, or by performing constant temperature heating at 300 to 500 ° C. for a certain period of time and then gradually raising the temperature to the firing temperature. When using a paint as an inorganic pigment, the firing temperature is usually 650 to 900 ° C, preferably 750 to 850 ° C.
And the firing time is preferably 0.1 to 2 hours.
When an undercoat is used as the inorganic pigment, the firing temperature is 1000 to 1300 ° C, preferably 1100 to 125.
It is preferable that the temperature is 0 ° C. and the firing time is 0.1 to 2 hours.

[0124]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, "part" and "%" in an Example show "mass part" and "mass%", respectively. (Example 1) (1) Preparation of magenta transfer sheet 1) Formation of photothermal conversion layer / release layer-Preparation of hydrophobized inorganic layered compound-Swellable synthetic mica (ME-100, manufactured by Corp Chemical);
Inorganic layered compound) is dispersed in water to prepare a 2.5% suspension, while 5% quaternary ammonium salt having the following structure
An aqueous solution was prepared, and the suspension and the aqueous solution were mixed so that the swelling synthetic mica: quaternary ammonium salt had a mass ratio of 1: 1 and cation exchange (hydrophobicization of the swelling synthetic mica was performed for 2 hours. ), The solid-liquid was separated, and the solid was purified by water washing and dried to obtain a hydrophobized inorganic layered compound (hydrophobic swelling synthetic mica).

[0125]

[Chemical 2]

-Preparation of Coating Solution for Light-Heat Conversion Layer / Release Layer-Subsequently, among components shown in the following coating solution composition, and / or were mixed with stirring with a stirrer, and a paint shaker (manufactured by Toyo Seiki Co., Ltd.). After dispersing carbon for 1 hour by adding, and were added and dissolved to prepare a photothermal conversion layer / release layer coating solution.

[0127] [Composition of coating solution for light-heat conversion layer / release layer]   Photothermal conversion material 20 parts (Carbon, BLACK PEARLS 480, manufactured by CABOT)   Binder (Tg = 300 ° C) 60 parts   (Ricacoat SN-20, manufactured by Shin Nippon Rika Co., Ltd.)   N-methyl-2-pyrrolidone 600 parts   Surfactant 1 part     (Megafuck F-177, manufactured by Dainippon Ink and Chemicals, Inc.)   Pyrolysis foaming agent 3 parts   (Cellular D, manufactured by Eiwa Chemical Industry Co., Ltd.)   Degradation accelerator 3 parts   (Cell paste A, manufactured by Eiwa Chemical Industry Co., Ltd.)   10 parts of the hydrophobic swelling synthetic mica

As a support, a polyethylene terephthalate film (PET film) having a thickness of 75 μm was prepared, and one of the surfaces of the PET film was coated with the above-mentioned coating solution for light-heat converting layer and release layer to have a dry layer thickness of 1. After coating so as to have a thickness of 5 μm, it is dried in an oven at 100 ° C. for 2 minutes, and a photothermal conversion layer / release layer containing a gas barrier substance (synthetic mica content ratio to the binder is 16.7% by mass) on the support. Was formed. When the absorbance (optical density: OD) of the obtained photothermal conversion layer / release layer was measured by a Macbeth densitometer, it was OD = 1.81.

2) Formation of Coloring Material Layer (Magenta) Each component shown in the following composition was dispersed with a paint shaker (manufactured by Toyo Seiki Co., Ltd.) for 2 hours, glass beads were removed, and a magenta pigment dispersion mother liquor was obtained. Prepared. [Composition of magenta pigment dispersion mother liquor] -12.6 parts of 20% solution of polyvinyl butyral (Denka butyral # 2000-L, Vicat softening point 57 ° C, manufactured by Denki Kagaku Kogyo KK) -Coloring material (magenta pigment) 24 parts (Shimura Brilliant Carmine 6B-229, manufactured by Dainippon Ink and Chemicals, Inc.) ・ Dispersion aid (Solspers S-20000, manufactured by ICI Co., Ltd.) 0.8 part ・ n-propyl alcohol 110 parts ・ Glass beads 100 parts

The components shown in the following composition were mixed with stirring with a stirrer to prepare a magenta color material layer coating solution. [Composition of magenta color material layer coating liquid] 20 parts of the magenta pigment dispersion mother liquor, 60 parts of n-propyl alcohol, 0.05 parts of surfactant (Megafuck F-176PF, manufactured by Dainippon Ink and Chemicals, Inc.)

The magenta coloring material layer coating solution was applied to the surface of the release layer formed on the PET film by using a spin coater for 1 minute, and then dried in an oven at 100 ° C. for 2 minutes to release it. Magenta coloring material layer (pigment 64.2
%, Polyvinyl butyral 33.7%) was applied so that the dry film thickness was 0.5 μm. As described above, a magenta transfer sheet in which the light-heat conversion layer / release layer and the color material layer were provided in this order on the support was produced.

(2) Preparation of image-receiving sheet 1) Formation of cushion layer A cushion layer coating solution having the following composition was coated on the surface of a 100 μm polyethylene terephthalate support with a spin coater and dried at 120 ° C. for 5 minutes. Film thickness 20
A μm cushion layer was provided. [Composition of coating solution for cushion layer] -Vinyl chloride / vinyl acetate copolymer 12 parts (Solvain CL2, manufactured by Nissin Chemical Co., Ltd.)-Adipic acid polyester 8 parts (Paralex G25, manufactured by CP.HALL) -Fluorine-based interface Activator 0.02 parts (MegaFac F177, Dainippon Ink and Chemicals, Inc.)-Methyl ethyl ketone 80 parts

2) Formation of Image Receiving Layer Next, an image receiving layer coating solution having the following composition was prepared and applied onto the cushion layer with a spin coater to prepare 1
After drying at 20 ° C. for 5 minutes, an image receiving layer having a film thickness of 2 μm is laminated,
An image receiving sheet was obtained. [Composition of coating liquid for image receiving layer] -Polyvinyl butyral 5 parts (PVB2000L, manufactured by Denki Kagaku Kogyo Co., Ltd.)-Fluorosurfactant 0.05 part (Megafuck F177, manufactured by Dainippon Ink and Chemicals Co., Ltd.)-N-Propanol 95 copies

(3) Image Formation An image forming apparatus having the same structure as in FIG. 2 was prepared, and an image was formed on the image receiving sheet as follows. The details of the image forming apparatus are as described above. The magenta transfer sheet and the image receiving sheet obtained as described above were loaded into the image forming apparatus so that the color material layer and the image receiving layer face each other during transportation, and the image forming apparatus was started. At this time, the surface temperature of the pinch roll 46 paired with the support roll 44 is adjusted to 80 ° C. by the built-in heating means.

When the magenta transfer sheet 20 is conveyed by the start-up, before passing between the support roll 44 and the pinch roll 46, the laser irradiation means 70 causes the laser beam having the wavelength of 830 nm (intensity 300) from the back surface side of the transfer sheet.
mW) was irradiated corresponding to the image signal. Further, when the support roll 44 and the pinch roll 46 are conveyed to a position where they face each other, the image receiving sheet 3 is heated while being heated between these rolls.
After being pressure-bonded with 0, it was peeled off by a peeling bar 50 provided in the conveyance path. A magenta image was formed on the image receiving layer of the image receiving sheet after peeling.

(4) Retransfer to printing paper An image-receiving sheet having a magenta image obtained as described above is
Fine paper (Green Daio, Daio Paper Co., Ltd.) and thermal laminator (CA680T, Fuji Photo Film Co., Ltd.) so that they are in contact with each other on the image receiving layer provided with a magenta image.
The image forming layer was re-transferred onto the high quality paper together with the image receiving layer. As described above, it is possible to obtain an image having good reproducibility with respect to the image signal on the printing paper, without deterioration of image quality of the formed image due to omission in the image portion and coloring in the non-image portion.

(Example 2) (1) Preparation of transfer sheet-Preparation of yellow transfer sheet-1) Formation of release layer The composition of the following coating solution was mixed and roughly dispersed, and then dispersed using a sand mill to release it. A layer coating solution A was prepared. Then, a polyester film having a thickness of 25 μm was prepared as a support, and the release layer coating liquid A obtained on one surface of the film.
Was applied to a dry layer thickness of 0.8 μm and dried to form a release layer.

[0138] [Composition of Release Layer Coating Liquid A]   ・ Pyrolysis foaming agent: 3 parts     (Cellular D; manufactured by Eiwa Chemical Industry Co., Ltd.)   ・ Decomposition accelerator: 3 parts     (Cell paste A; manufactured by Eiwa Chemical Industry Co., Ltd.)   -Polymer dispersant (also binder) 10 mass% aqueous solution ... 60 parts     (MP-103; manufactured by Kuraray Co., Ltd.)   ・ Silica (AEROSIL50; manufactured by Nippon Silica Co., Ltd.) ... 3 parts

2) Formation of Undercoat Gas Barrier Layer The following composition of the undercoat gas barrier layer coating solution was mixed little by little while stirring with a stirring blade at a peripheral speed of 10 m / min in a constant temperature bath at 40 ° C. After mixing, the mixture was further stirred for 1 hour to prepare a gas barrier layer coating solution. Then, the coating liquid was applied on the surface of the release layer on the support so as to have a dry layer thickness of 0.4 μm, and dried at 50 ° C. to form an undercoat gas barrier layer.

[Composition of coating liquid for undercoat gas barrier layer] • Gelatin aqueous solution (8% by mass) ... 100 parts · ME-100 dispersion (4% by mass) ... 100 parts The ME-100 dispersion was Viscomil (manufactured by IMEX Co., Ltd.). ) Used for 3 cycles of dispersion treatment.

3) Formation of Coloring Material Layer (Yellow) The components having the following compositions were mixed and sufficiently stirred to prepare a yellow coloring material layer coating liquid. The obtained coating liquid was applied onto the undercoating gas barrier layer so that the dry film thickness was 2 μm, and dried to form a yellow coloring material layer, thereby preparing a yellow transfer sheet.

[0142] [Composition of coating liquid for yellow color material layer] ・ 41 parts of pigment dispersion (Yellow pigment (13651, manufactured by Celdec) 100 parts and water 60 parts microphone Ross MC-0 type (manufactured by Nara Machinery Co., Ltd.) for 2 hours ・ Polyoxyethylene (n = 10) nonylphenol ether 0.5 part   (20% aqueous solution) ・ Carnauba wax dispersion (31%) 20 parts   (K-332, manufactured by Chukyo Yushi Co., Ltd.) * Butyral resin dispersion (25%) 60 parts   (Resem J667, manufactured by Chukyo Yushi Co., Ltd.) ・ Terpene phenol resin dispersion (35%) 5 parts   (Resem J628, Chukyo Yushi Co., Ltd.)

-Preparation of magenta, cyan and black transfer sheet- In the preparation of the yellow transfer sheet, instead of the yellow pigment, magenta pigment (77571, manufactured by Celdec), cyan pigment (121522, manufactured by Celdec), black A magenta transfer sheet, a cyan transfer sheet, and a black transfer sheet were prepared in the same manner as in the case of the yellow transfer sheet except that a pigment (14209, manufactured by Celdec) was used.

(2) Preparation of image receiving sheet An image receiving sheet was produced in the same manner as in Example 1.

(3) Image Formation An image forming apparatus having the same structure as in FIG. 1 was prepared, and an image was formed on the image receiving sheet as follows. The details of the image forming apparatus are as described above. The yellow transfer sheet and the image receiving sheet obtained as described above were loaded into the image forming apparatus so that the color material layer and the image receiving layer faced each other during transportation, and the image forming apparatus was started. At this time, the surface temperature of the pinch roll 46 paired with the support roll 44 is adjusted to 80 ° C. by the built-in heating means.

When the yellow transfer sheet 20 is conveyed by the start-up, the image receiving sheet 30 is also conveyed in the arrow direction in synchronism with this, and the yellow transfer sheet 20 and the image receiving sheet 30 receive pressure from the platen roller 42 and are mutually moved. The color material layer and the image receiving layer were laminated so as to be in contact with each other. At this time, the thermal head 60 causes the temperature of the release layer of the yellow transfer sheet 20 to be equal to or higher than the decomposition temperature of the foaming agent from the back surface of the yellow transfer sheet 20 which does not face the image receiving sheet 30 in correspondence with the image signal. Yellow transfer sheet 20
Was thermally image-wise printed at 200 ° C. When further conveyed in a laminated state, the peeling bar 50 provided in the conveyance path passes between the support rolls 44 and 46 while being heated and pressurized.
Was peeled off. Then, a yellow image was formed on the image receiving layer of the image receiving sheet 30.

Thereafter, the same operation was repeated for each of the magenta, cyan and black transfer sheets with respect to the image receiving sheet on which the yellow image was formed, and a full color image was formed on the same image receiving sheet.

(4) Retransfer of Image 1) Preparation of Second Image Receiving Sheet A 10% aqueous solution of gum arabic (water-soluble polymer) was applied to the surface of a smooth paper support having a basis weight of 100 g so that the dry layer thickness would be 6 μm. Was applied and dried to form a water-soluble polymer layer. Further, a cover coat resin (plus size LO-210, manufactured by Kyouka Chemical Industry Co., Ltd.) containing methacrylic acid-based resin as a main component is applied onto the layer so as to have a dry layer thickness of 17 μm and dried to form an image receiving layer. (Cover coat layer) was formed to obtain a second image receiving sheet.

2) Retransfer of Image Subsequently, the surface of the image receiving layer on which the full-color image was formed and the surface of the cover coat layer of the second image receiving sheet were overlapped with each other, and a heat roll laminator (120 ° C.) was used. After laminating through Fuji Film Co., Ltd., both sheets were peeled off, and the full color image was retransferred onto the second image receiving sheet.

(5) Arrangement of Image Next, the paper support side of the second image receiving sheet on which the full-color image was transferred was immersed in water to remove the paper support while partially dissolving the water-soluble polymer layer. . Then, it was placed on the surface of the ceramic material (porcelain plate) such that the image surface was in contact with the surface of the ceramic material with a sizing agent (aqueous dextrin solution) interposed.

(6) Firing of Image Next, the ceramic material on which the full-color image was formed together with the cover coat layer and the like was fired at 400 ° C. for 1 hour and 875 ° C. for 30 minutes to sinter the inorganic pigment on the surface of the porcelain plate. A ceramic material with a full-color image was obtained. A good image was formed on the ceramic material without full-color color unevenness and density unevenness. As described above, it is possible to obtain an image having good reproducibility with respect to the image signal on the printing paper, without deterioration of image quality of the formed image due to omission in the image portion and coloring in the non-image portion.

(Example 3) (1) Preparation of Magenta Transfer Sheet In the preparation of the magenta transfer sheet of Example 1, the release layer coating solution B described below was used in place of the light-heat conversion layer / release layer for release. A magenta transfer sheet was produced in the same manner as in Example 1 except that the layers were formed. The dry layer thickness of the release layer is 1.5
μm.

-Preparation of Release Layer Coating Solution B- 2 parts of the diazo compound (1) represented by the following structural formula was added to 20 parts of ethyl acetate and 20 parts of diisopropylnaphthalene and heated to uniformly dissolve. . 60 parts of a 6% aqueous solution of gelatin, 2 parts of a 2% aqueous solution of sodium dodecylsulfonate, 2 parts of a swelling synthetic mica (ME-100, manufactured by Corp Chemical Co .; inorganic layered compound), 0.5 parts (synthetic mica for gelatin). Content of 5.5% by mass) and added, and then dispersed with a Filmix FM80-50 type (manufactured by Tokushu Kika Kogyo Co., Ltd.) at a peripheral speed of 50 m / min for 1 minute, and allowed to stand for 1 minute. Repeat the process for 10 cycles,
A release layer coating solution B was prepared.

[0154]

[Chemical 3]

(2) Image Formation Example 1 except that an image receiving sheet prepared in the same manner as in Example 1 was prepared and the wavelength of the laser beam was changed to 405 nm.
Similarly to the above, a magenta image was formed on the image receiving layer of the image receiving sheet. Subsequently, retransfer was performed in the same manner as in Example 1 to form an image on printing paper. The formed image did not deteriorate in image quality due to omission in the image area and coloring in the non-image area, and an image with good reproducibility for the image signal could be obtained on the printing paper.

(Example 4) (1) Preparation of transfer sheet In the preparation of the yellow transfer sheet and the magenta, cyan and black transfer sheet of Example 2, the release layer used in "1) Formation of release layer" Example 3 in place of the coating liquid A
Example 2 except that the release layer coating solution B prepared in
Similarly to, the yellow transfer sheet, magenta,
Cyan and black transfer sheets were prepared. The dry layer thickness of the release layer was 1.5 μm.

(2) Preparation of Image Receiving Sheet and Image Forming An image receiving sheet prepared in the same manner as in Example 1 was prepared, and a yellow transfer sheet was first prepared in the same manner as in “(2) Image formation” in Example 3. A yellow image is formed on the image-receiving layer of the image-receiving sheet using the same method, and then the same operation is repeated for each of the magenta, cyan and black transfer sheets for the image-receiving sheet on which the yellow image is formed,
A full color image was formed on the same image receiving sheet.

(3) Retransfer and Arrangement of Image Next, a second image-receiving sheet similar to that in Example 2 was prepared, and the second image-receiving sheet was used, and in the same manner as in Example 2, on the second image-receiving sheet. The full-color image was retransferred to, and further placed on a ceramic material and fired. A good image was formed on the ceramic material without full-color color unevenness and density unevenness. As described above, it is possible to obtain an image having good reproducibility with respect to the image signal on the printing paper, without deterioration of image quality of the formed image due to omission in the image portion and coloring in the non-image portion.

[0159]

According to the present invention, it is possible to provide a transfer sheet which is excellent in transfer response corresponding to an image signal and which can form an image having a good image quality (S / N ratio). And
According to the present invention, the transfer sheet of the present invention is used,
It is possible to provide an image forming method and a method for producing an image-bearing ceramic material, which can perform good transfer according to an image signal and can form an image with high image quality (high S / N ratio).

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of an image forming apparatus used in an image forming method of the present invention.

FIG. 2 is a schematic view showing an example of another image forming apparatus used in the image forming method of the present invention.

[Explanation of symbols]

20: Transfer sheet 30: Image receiving sheet 40: Image forming apparatus 44: Support roll 46: Pinch roll 50: Peeling bar 60: Heating means (thermal head) 70: Laser irradiation means

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B41M 5/26 AF term (reference) 2H111 AA06 AA14 AA26 AA50 BA07 BA09 BA32 BA53 BA55 BA61 BA71 BA76 CA28 4F100 AA01B AA01C AA37H AD00D AG00H AH03H AK23 AK42 AT00A BA03 BA04 BA07 BA10A BA10C BA10D BA26 CA01 CA13 CA18 DE04H EH46 EH462 EJ86 EJ862 GB41 HB00C JA05B JA05C JD02B JD02C JD03B JD03C JLYYCBL

Claims (8)

[Claims] 1. A transfer sheet comprising, on a support, a release layer containing a foaming agent that decomposes by heat or light to generate a gas, and a color material layer in that order from the support side. A transfer sheet, wherein at least one layer selected from a layer and a layer provided in a direction away from the support from the release layer contains a gas barrier substance. 2. The transfer sheet according to claim 1, wherein the gas barrier substance is an inorganic layered compound. 3. A gas barrier substance having a glass transition point (Tg) higher than the printing temperature and having a film thickness of 10 μm has an oxygen permeability of 20 × 10 ⁻⁵ ml / (m ² · Pa · 1d).
ay) The transfer sheet according to claim 1, which is the following polymer. 4. The oxygen barrier rate when the gas barrier substance is an inorganic layered compound and a film having a glass transition point (Tg) higher than the printing temperature and a film thickness of 10 μm is 20 × 10 ⁻⁵ m.
The transfer sheet according to claim 1, which is a polymer having a ratio of 1 / (m ² · Pa · 1 day) or less. 5. A step of image-wise applying heat or light for decomposing a foaming agent to generate a gas to at least a release layer of the transfer sheet according to claim 1, and the transfer sheet. 2. An image forming method comprising: a step of heating at least the color material layer or the color material layer and a release layer; and a step of transferring the color material layer onto an image receiving sheet to form an image. 6. A step of applying imagewise heat to at least a release layer and a color material layer of the transfer sheet according to claim 1 to decompose a foaming agent to generate a gas, And a step of forming an image by transferring the color material layer onto the image receiving sheet. 7. A step of image-wise applying heat or light for decomposing a foaming agent to generate a gas to at least a release layer of the transfer sheet according to claim 1, and the transfer sheet. Of at least the color material layer or the color material layer and the release layer, a step of transferring the color material layer onto an image receiving sheet to form an image, and arranging the formed image on the ceramic material. A method of manufacturing a ceramic material with an image, comprising: a step; and a step of firing at least an image that has been arranged. 8. A step of image-wise applying heat or light for decomposing a foaming agent to generate a gas to at least the release layer and the color material layer of the transfer sheet according to claim 1. And, a step of forming an image by transferring the color material layer onto an image receiving sheet, a step of disposing the formed image on a ceramic material, and a step of baking at least the arranged image. A method for producing a ceramic material with an image.