JPH08118831A - Image-receiving sheet material, transfer image-forming method, and laminate - Google Patents

Abstract

PURPOSE: To make a malti-gradation high quality color image free from a sticking phenomenon formable on an image receiving layer to which an ink layer is transferred, by a method wherein at least one layer out of the image-receiving layers on a substrate is transferred to a permanent substrate and polyvinyl butyral and a specific polymeric compound are contained in the image-receiving layer. CONSTITUTION: In an image-receiving sheet material to be used for formation of a transfer image to be retransferred on a permanent substrate after heat transfer of an ink layer onto an image-receiving sheet material from a transfer material, at least two layers of the image receiving layers are provided on the substrate. Then one layer out of the layers is transferred to the permanent substrate, the image receiving layer to which the ink layer is transferred is formed of a matter containing polyvinyl butyral resin and a polymeric compound of repeating unit of at least formula I and/or a formula II. In the formula, R1 indicates a hydrogen atom and methyl group, A indicates a substituting group possessing an amide bond and a nitrogen-containing hetero-cyclic compound, R4 indicates a hydrogen atom and methyl group, R6 -R8 indicate alkyl group, aralkyl group and aryl group and X indicates Cl or Br or I.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention transfers an image-receiving sheet material useful in a thermal transfer recording system and a thermal ink layer containing a coloring material onto the image-receiving sheet material by using a thermal head or by irradiating a laser beam. To form an image and then retransfer to form an image on a permanent support. The image obtained by the method of the present invention is particularly excellent in printed matter approximation and has high quality.

[0002]

2. Description of the Related Art With the progress of office automation in recent years, copying machines, printers and the like utilizing various recording systems such as an electrophotographic system, an inkjet system and a thermal transfer recording system have been used according to their respective applications. A coloring material is used for this image formation, and a recording medium such as a paper or a film sheet is usually used by an action such as melting, melting or evaporating or sublimating a coloring material-containing composition, adhesion, adsorption or dyeing. Etc. are getting the image over.

Of these, the thermal transfer recording system has advantages such as easy operation and maintenance, downsizing of the apparatus, and cost reduction. The following two types of thermal transfer recording methods are conventionally known.
That is, a heat-melting type in which a transfer sheet having a meltable ink layer on a support is heated imagewise (imagewise) by a laser or a thermal head to melt-transfer the meltable ink to a heat-sensitive transfer recording image-receiving sheet. Sublimation in which the thermal diffusible dye is diffuse-transferred to an image-receiving sheet for thermal transfer recording by using a transfer method and an ink sheet for thermal transfer recording having an ink layer containing a thermal diffusible dye (sublimable dye) on a support. There are two types of dye transfer method.

The sublimation type dye transfer system can control the gradation of an image by changing the transfer amount of the dye according to the change of thermal energy of the thermal head.
By performing magenta and yellow overprinting, there is an advantage that a color image having a continuous change in color shading can be obtained. However, this method has the following problems. It mainly reproduces the gradation of the image by using the density gradation, and is suitable for some purposes for consumer who prefer the gradation similar to the photograph, but for example, the gradation is reproduced only by the area gradation. It is not suitable for color proofing applications used in the printing field. Since the image formation uses dye sublimation, the edge sharpness of the finished image is not sufficient, and the solid density of the thin line is lower than that of the thick line. This is a big problem especially with respect to the quality of character images. The development of the image is limited to fields where the durability of the image is low and heat resistance and light resistance are required. Since the thermal recording sensitivity is lower than that of the heat-melt transfer method,
It is not suitable as a high-speed recording material using a high resolution thermal head, which is expected in the future. The sensitive material is more expensive than the heat-melt transfer material.

On the other hand, the heat-melt type transfer method has advantages such as high heat sensitivity, excellent light resistance of images, and low cost of materials, as compared with the sublimation type dye transfer method. It has the following drawbacks. Since gradation reproduction is not density gradation but binary recording, multi-gradation is poor. Usually, a low melting point crystalline wax is used as a binder for the ink layer, so the resolution decreases due to bleeding during thermal printing,
The strength of the transferred image is low. When crystalline waxes are used, it is difficult to obtain a transparent image due to light scattering of the crystalline phase.

In view of such a situation, the present inventors differ from the conventional sublimation dye transfer system and heat fusion transfer system,
As a new heat-sensitive recording material capable of obtaining a multi-gradation pigment color image only by area gradation of binary recording, a heat-adhesive thin film peeling method was previously proposed (Japanese Patent Application No. 5-263695). According to this method, a multi-tone high-quality color image or monochrome image, which has greatly improved the problems of the conventional thermal transfer recording method by the area-tone-only pigment transfer method, has been achieved. In addition, it is possible to develop into the card field, outdoor display field, meter display field, etc. by taking advantage of the light resistance of color proofs, block manuscripts, and pigments in the printing field.

On the other hand, various proposals have been made for materials to be transferred used in these various thermal transfer recording materials. When plain paper is used as an image receiving medium of the sublimation dye transfer system, dyeing is not likely to occur and the density of a recorded image is low, and a fading phenomenon occurs remarkably over time. Therefore, an image receiving paper in which an image receiving layer containing a thermoplastic resin as a main component is provided on plain paper has been proposed, and various improvements in recording sensitivity, resolution, sharpness, color density, etc. have been studied. In addition, it is possible in principle to use plain paper for the transfer material of the heat melting type transfer method, but defects such as uneven transfer and missing dots are likely to occur due to the smoothness of the transfer surface and ink acceptability. It is a difficult point. Therefore, various image receiving materials have been studied in order to improve surface smoothness, ink transfer acceptance, fixing ability, gradation, sharpness, and the like. Here, as a support for these various image receiving media, a dedicated transfer material such as plain paper, synthetic paper, a synthetic resin film or a white base filled with a white pigment is used. Therefore, in this method, the transferable material capable of forming an image is limited to a dedicated paper or a resin sheet provided with an image receiving layer, so that the quality is insufficient for proof use requiring a printed matter approximation. . Further, a method of transferring a recorded image to any desired transfer-receiving support is also known. Japanese Patent Application Laid-Open No. 52-27642 describes a method in which a transfer layer is heated and adhered to an intermediate receptor and then the adhered transfer material is transferred to an object to be transferred such as paper. However, nothing is said about improvement of image quality. Has not been done.

In Japanese Patent Laid-Open No. 63-82786, as a material constituting the coating film other than butyral contained in the coating layer material, other resins and waxes similar to the butyral resin contained in the thermal transfer layer are used. The technique for selecting is described, and examples of the resin include phenol resin, epoxy resin, urethane resin, rosin and polyamide resin, sulfonamide resin, etc., but when these are used, rosin and polyamide resin In this case, there was a problem that the shadow portion was significantly crushed, and when a polyamide resin was used, the influence of temperature and humidity on the reproduction gradation was great. Also,
If the addition amount is large, there are problems that the surface of the image receiving layer is remarkably sticky, and dust defects and unevenness increase.

As described above, various image-receiving sheet materials have been proposed so far as the material to be transferred of the heat-sensitive transfer recording material, but the recording sensitivity, the dot quality, and the gradation reproducibility are obtained by the thermal transfer method of only the area gradation. All were insufficient to obtain excellent images. In particular, when it is attempted to increase the thermal recording sensitivity, the thermal adhesion temperature of the image-receiving layer tends to be lowered and the tackiness tends to increase, causing a sticking phenomenon due to stickiness and a problem in the adhesion resistance during image storage after recording. For this reason, particularly when used as a multi-gradation high-quality color image, for example, when used as a color proof for color proofing, there is a big problem in the approximation of printed matter such as reproduction of texture of actual printing paper.

Further, a thermal transfer ink layer has also been studied. For example, in JP-A-5-254256, a toner obtained by adding a pigment to a polyamide resin (nylon) binder is used.
Although the layer prescription is described, such a toner layer has a problem that the dot cohesion is poor due to the high cohesive force of nylon, and further, gradation reproducibility and temperature / humidity change are weak.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a multi-gradation high quality color image which is excellent in recording sensitivity, dot quality, gradation reproducibility, and is free from stickiness and sticking phenomenon by a thermal transfer system using only area gradation. An object of the present invention is to provide an image-receiving sheet material for thermal transfer recording capable of achieving formation and a transfer image forming method using the same. Another object of the present invention is to provide a thermal transfer recording image-receiving sheet material and a transfer image forming method, which can be transferred onto a printing paper sheet and have excellent printed matter approximation such as reproduction of the printing paper sheet texture and image gloss.

[0012]

The objects of the present invention are as follows: 1) Transfer of an ink layer from a transfer material having a heat transferable ink layer onto an image-receiving sheet material, and then retransferred onto a permanent support. In the image-receiving sheet material used for forming, the image-receiving sheet material has at least 2 on the support.
Layer having an image receiving layer, at least one of the image receiving layers is transferred to a permanent support, and the image receiving layer to which at least the ink layer is transferred is a polyvinyl butyral resin and at least the following general formula (I) and / or general formula An image receiving sheet material containing a polymer compound having a repeating unit of (II),

[0013]

Embedded image

[In the formula, R ₁ is a hydrogen atom or a methyl group, A is a substituent having an amide bond or a nitrogen-containing heterocycle, R ₄ is a hydrogen atom or a methyl group, R ₆ , R ₇ and R ₈
Are alkyl groups having 1 to 25 carbon atoms, which may be the same or different, aralkyl groups having 7 to 25 carbon atoms, or 6 to 6 carbon atoms.
25 aryl groups (the alkyl group, aralkyl group, and aryl group may be substituted with a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, a halogen, a cyano group, or a combination of two or more of these, and an ether in the middle. Bond, -OCO
-, -COO- and a combination of two or more thereof may be used), and X represents Cl, Br or I. And 2) 30 to 70 parts by weight of a pigment, 25 provided on a support,
A thermal transferable ink layer comprising an amorphous organic high molecular polymer having a softening point of 40 to 150 ° C. of about 60 parts by weight and a film thickness of 0.2 μm to 1.0 μm. Transfer image formation, comprising closely contacting with the image receiving sheet material described above, forming an ink image on the image receiving sheet material by thermal transfer, and then transferring the ink image and at least one image receiving layer onto a permanent support. Method.
Hereinafter, the present invention will be described in detail.

As the support of the image-receiving sheet, a substance that is chemically and thermally stable and has flexibility is used. It may be actinic radiation transparent, if necessary. Specifically, biaxially oriented polyethylene terephthalate film, polyethylene, polypropylene and other polyolefins, polyvinyl chloride, polyvinylidene chloride and other polyvinyl halides, cellulose acetate, nitrocellulose, cellophane and other cellulose derivatives, polyamides,
It is also possible to use polystyrene, polycarbonate, polyimides, or paper laminated with polyethylene film in some cases. Of these, particularly preferred is a biaxially stretched polyethylene terephthalate film, which is excellent in dimensional stability and permeability, but is not limited thereto. Further, at least two layers are provided on the support, but it is preferable that the support preferably comprises a layer in contact with the support (hereinafter referred to as an image receiving layer) and a layer provided thereon (hereinafter referred to as an image receiving two layer).

In order to increase the adhesive strength between the support and the image receiving layer, a surface treatment such as corona discharge treatment or glow discharge treatment or an undercoat layer may be provided.
The undercoat layer is not particularly limited as long as it enhances the adhesive force between the support and the image receiving layer, but a silane coupling agent or the like is particularly preferable.

Next, the image receiving layer will be described. The elastic modulus of the image-receiving layer is preferably 200 kg · f / cm ² or less. The reason for this is that the use of a polymer having a small elastic modulus causes the image-receiving layer to have cushioning properties, whereby the recording sensitivity, dot quality, and gradation reproducibility can be improved. Further, even when foreign matter such as dust is present between the heat-sensitive recording material and the image-receiving sheet material during recording, there is an advantage that an image defect is less likely to occur because the image-receiving layer has more cushioning property. Further, after the image is transferred to the image receiving sheet material, when retransferred onto the actual printing paper such as paper by heat and pressure, the layer is embedded according to the unevenness of the paper, so that the adhesion with the paper is improved and the two image receiving layers are formed. An image having a surface gloss similar to that of a printed matter can be obtained without special treatment such as matting the surface after peeling.

Specific examples include polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or ethylene and acrylate, polyvinyl chloride, vinyl chloride copolymers such as vinyl chloride and vinyl acetate, and polychlorinated. At least one selected from vinylidene, vinylidene chloride copolymer, poly (meth) acrylic acid ester, copolymerized nylon, polyamide resin such as N-alkoxymethylated nylon, synthetic rubber, organic polymer substance such as chlorinated rubber. preferable. Among these, polyvinyl chloride having a degree of polymerization of 200 to 2000,
Particularly preferred are vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl alcohol copolymers, vinyl chloride-vinyl acetate-maleic acid copolymers, and the like. The reason is that polyvinyl chloride and vinyl chloride copolymer have (1) almost no tackiness at room temperature, (2) relatively low elastic modulus, and can easily follow irregularities of a transferred image during thermal transfer, (3) A plasticizer with good compatibility is abundant and it is easy to control the substantial elastic modulus, and (4) it is easy to control the interlayer adhesion force by the effect of the hydroxyl group or the carboxyl group in the copolymerization component, Etc. Of course, various polymers, adhesion improvers, surfactants, and release agents may be added to these organic polymers in order to adjust the adhesive strength with the image receiving sheet support and the image receiving bilayer. Further, for the purpose of lowering the elastic modulus, it is also very effective to use a part of the tacky polymer in combination as long as the tackiness does not occur at room temperature.

For example, a fluorine-based surfactant or the like can be used in each layer, and addition of the surfactant reduces the interlaminar adhesion and at the same time improves the wettability between the surface of the thermal transfer ink layer and the image receiving layer, thereby improving the dot shape. To do. However, if the amount of addition is too large, the adhesive force between the surface of the thermal transfer ink layer and the surface of the image receiving layer is reduced and the dot shape deteriorates. Therefore, the amount of release agent or surfactant added is preferably 0.0001 to 5 %, Particularly preferably 0.001 to 3%. In order to improve the coated surface state, it is preferable to add a small amount of a surfactant.

When a vinyl chloride resin is used, an organotin stabilizer such as butyltin stabilizer or octyltin stabilizer, which is generally known as a stabilizer for polyvinyl chloride and vinyl chloride copolymers, is used. It is also effective to add.

The thickness of the image receiving layer is preferably 1 μm to 50 μm, and particularly preferably 5 μm to 30 μm. 1 of this reason
The second reason is that when the image transferred on the image-receiving sheet material is transferred to the permanent support, it must be thicker than the irregularities on the surface of the permanent support. The second reason is that the relief of the portion where the four color image overlaps. This is because it is necessary to have a thickness that can sufficiently absorb the step. The third reason is to obtain sufficient cushioning property.

Next, the two image receiving layers provided thereon will be described. The purpose of the image-receiving two-layer is to peel off the image-receiving sheet material during retransfer to the permanent support to cause delamination between the image-receiving layer and the image-receiving two layers so that only a thin image-receiving two-layer is formed on the image on the permanent support. On the other hand, the unevenness of the permanent support is to obtain an image similar to the gloss of the actual printed matter without any special matting treatment. The second purpose is to improve the scratch resistance of the image.

Various materials can basically be used as the material for the image-receiving two-layer, but as the organic polymer material constituting the image-receiving two-layer, polyvinyl butyral resin and at least the above general formula (I) and / or the general formula are used. It is preferable to contain a polymer compound having the repeating unit (II).

The polymer compound having a repeating unit represented by the general formula (I) and / or the general formula (II) is represented by the following general formula (II)
Polymerization of a monomer represented by I) and / or (IV) in the presence of a polymerization initiator in a suitable solvent or without a solvent according to a conventional method,
Alternatively, it can be obtained by copolymerizing with another monomer.

[0025]

Embedded image

In the general formula (III), R ₁ represents a hydrogen atom or a methyl group, and A represents a substituent having an amide bond or a nitrogen-containing heterocycle. In the general formula (IV), R ₄ is a hydrogen atom or a methyl group, and R ₆ , R ₇ , and R ₈ are the same or different and are each an alkyl group having 1 to 25 carbon atoms, and 7 to 25 carbon atoms.
Or an aryl group having 6 to 25 carbon atoms (the alkyl group, aralkyl group, and aryl group are substituted with a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, a halogen, a cyano group, and a combination of two or more thereof. May be present, and an ether bond, —OCO—, —COO—, or a combination of two or more of these may be present in the middle), and X represents Cl, Br, or I.

When A in the general formula (III) is a substituent having an amide bond, for example, CONHR ₂ , CONR ₂
R ₃ may be mentioned. R ₂ and R ₃ are, for example, each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or 6 carbon atoms.
To 20 aryl groups (the alkyl group and aryl group may be substituted with one or more of a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, a halogen, a cyano group, and a combination of two or more thereof). , R ₂ and R ₃ are bonded to each other and have 1 to 2 carbon atoms.
0 alkylene, aralkylene (the alkylene and aralkylene may have a branch, an ether bond, -O
CO-, -COO-, and a combination of two or more thereof may be included. Further, when A is a nitrogen-containing heterocycle, imidazoles, pyrrolidones, pyridines, carbazoles and the like can be mentioned. An alkyl group having 1 to 5 carbon atoms,
It may be substituted with an aryl group having 6 to 10 carbon atoms, a halogen, a cyano group, or a combination of two or more thereof.

A more preferable range of A in the general formula (III) is CONHR ₂ , C in the case of a substituent having an amide bond.
ONR ₂ R ₃ ; R ₂ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms (the alkyl group or aryl group is a hydroxy group or an alkoxy group having 1 to 6 carbon atoms), A When is a nitrogen-containing heterocycle, examples thereof include imidazoles and triazoles, which have 1 to 5 carbon atoms.
May be substituted with an alkyl group or an aryl group having 6 to 10 carbon atoms.

Specific examples of the compound represented by the general formula (III) include (meth) acrylamide and N-alkyl (meth) acrylamide (the alkyl group includes, for example, methyl group, ethyl group, propyl group, butyl group). , T-butyl group, heptyl group, octyl group, ethylhexyl group,
Cyclohexyl group, hydroxyethyl group, benzyl group, etc.), N-aryl (meth) acrylamide (as the aryl group, for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group, hydroxyphenyl group, etc.), N, N-dialkyl (meth) acrylamide (as the alkyl group, for example, a methyl group, an ethyl group,
Butyl group, isobutyl group, ethylhexyl group, cyclohexyl group, etc.), N, N-diaryl (meth) acrylamide, (the aryl group includes, for example, phenyl group), N-methyl-N-phenyl (meth) Acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide, N-2-acetamidoethyl-N
-Acetyl (meth) acrylamide, N- (phenylsulfonyl) (meth) acrylamide, N- (p-methylphenylsulfonyl) (meth) acrylamide, 2 and 3 and 4-hydroxyphenylacrylamide,
(Meth) acryloylmorpholine, 1-vinylimidazole, 1-vinyl-2-methylimidazole, 1-vinyltriazole, 1-vinyl-3,5dimethylimidazole, vinylpyrrolidone, 4-vinylpyridine, vinylcarbazole, and the like. .

In the general formula (IV), R ₄ is a hydrogen atom or a methyl group, R ₆ , R ₇ and R ₈ are the same or different and are alkyl groups having 1 to 25 carbon atoms and aralkyl having 7 to 25 carbon atoms. A group or an aryl group having 6 to 25 carbon atoms (the alkyl group, aralkyl group and aryl group are substituted with a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, a halogen, a cyano group and a combination of two or more thereof. X may represent Cl, Br or I. It may be via an ether bond, —OCO—, —COO— or a combination of two or more thereof.

A more preferred range of general formula (IV) is R ₄
Is a hydrogen atom or a methyl group, and R ₆ , R ₇ , and R ₈ may be the same or different, and are an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, or an aryl group having 6 to 20 carbon atoms. The alkyl group, aralkyl group and aryl group are
It may be substituted with an alkoxy group having 1 to 6 carbon atoms, a halogen, a cyano group, or a combination of two or more kinds thereof, and an ether bond, —OCO—, —COO— and these 2
May be via a combination of two or more species), X is Cl, Br
Or represents I.

Specific examples of the compound represented by the general formula (IV) include N, N, N- (trialkyl) -N- (styrylmethyl) -ammonium chloride and N, N, N- (trialkyl). -N- (styrylmethyl) -ammonium bromide, N, N, N- (trialkyl) -N- (styrylmethyl) -ammonium iodide (as the alkyl group, for example, methyl group, ethyl group, propyl group , Butyl group, t-butyl group, heptyl group, hexyl group, octyl group, isooctyl group, dodecyl group, ethylhexyl group,
Such as cyclohexyl group), N, N- (dimethyl)
-N- (dodecyl) -N- (styrylmethyl) -ammonium chloride, N, N- (dimethyl) -N- (benzyl) -N- (styrylmethyl) -ammonium chloride,
N, N, N- (trimethoxyethyl) -N- (styrylmethyl) -ammonium chloride, N, N- (dimethyl)
-N- (phenyl) -N- (styrylmethyl) -ammonium chloride and the like can be mentioned.

Next, specific examples of the other monomer copolymerizable with the monomer represented by the general formula (III) and / or the general formula (IV) include (meth) acrylic acid esters and (meth) acrylic acid esters. ) A compound having a polymerizable unsaturated bond selected from acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters, and the like. Specifically, (meth) acrylic acid esters, for example, alkyl (meth) acrylate, or substituted (meth) alkyl acrylate, (for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) ) Acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, octyl (meth) acrylate, t-octyl (meth) acrylate, chloroethyl (meth) ) Acrylate, allyl (meth) acrylate,
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2,2-dimethyl-3-
Hydroxypropyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, benzyl (meth) acrylate, methoxybenzyl (meth) acrylate, chlorobenzyl (meth) ) Acrylate, furfuryl (meth)
Acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, etc., aryl (meth) acrylate (for example, phenyl (meth) acrylate, cresyl (meth) acrylate, naphthyl (meth) acrylate, etc., styrenes, for example Styrene, alkyl styrene (for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl) Styrene, acetoxymethylstyrene, etc.), alkoxystyrene (eg methoxystyrene,
4-methoxy-3-methylstyrene, dimethoxystyrene, etc., halogenostyrene (for example, chlorostyrene,
Dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene,
Trifluorostyrene, 2-bromo-4-trifluorostyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), hydroxystyrene, etc .; crotonic acid esters, for example, alkyl crotonic acid (eg, butyl crotonic acid, hexyl crotonic acid). , Glycerin monocrotonate, etc.), (meth) acrylic acid, crotonic acid, itaconic acid, and (meth) acrylonitrile.

Preferred specific examples of the polymer having the repeating unit represented by the general formula (I) and / or the general formula (II) are N, N-dimethylacrylamide / butyl (meth) acrylate copolymer. Polymer, N, N-dimethyl (meth) acrylamide / 2-ethylhexyl (meth) acrylate copolymer, N, N-dimethyl (meth)
Acrylamide / hexyl (meth) acrylate copolymer, N-butyl (meth) acrylamide / butyl (meth) acrylate copolymer, N-butyl (meth) acrylamide / 2-ethylhexyl (meth) acrylate copolymer Polymer, N-butyl (meth) acrylamide / hexyl (meth) acrylate copolymer, (meth) acryloylmorpholine / butyl (meth) acrylate copolymer,
(Meth) acryloylmorpholine / 2-ethylhexyl (meth) acrylate copolymer, (meth) acryloylmorpholine / hexyl (meth) acrylate copolymer,
1-Vinylimidazole / butyl (meth) acrylate copolymer, 1-vinylimidazole / 2-ethylhexyl (meth) acrylate copolymer, 1-vinylimidazole / hexyl (meth) acrylate -Tocopolymer, N, N
-Dimethylacrylamide / butyl (meth) acrylate-
/ N, N, N- (trihexyl) -N- (styrylmethyl) -ammonium chloride copolymer, N, N-dimethylacrylamide / butyl (meth) acrylate / N,
N, N- (trioctyl) -N- (styrylmethyl)-
Ammonium chloride copolymer, N, N-dimethylacrylamide / butyl (meth) acrylate / N, N, N-
(Tridodecyl) -N- (styrylmethyl) -ammonium chloride copolymer, N, N-dimethylacrylamide / butyl (meth) acrylate / N, N, N- (trihexyl) -N- (styrylmethyl)- Ammonium iodide copolymer, N, N-dimethyl (meth) acrylamide / hexyl (meth) acrylate / N, N, N- (trihexyl) -N- (styrylmethyl) -ammonium chloride copolymer, (Meth) acryloylmorpholine / 2
-Ethylhexyl (meth) acrylate / N, N- (dimethyl) -N- (benzyl) -N- (styrylmethyl)
-Ammonium chloride copolymer, N-butyl (meth) acrylamide / hexyl (meth) acrylate / N,
Examples include N, N- (trimethoxyethyl) -N- (styrylmethyl) -ammonium chloride copolymer, N, N, N- (trihexyl) -N- (styrylmethyl) -ammonium chloride polymer, and the like. . Further, the content of the unit of (I) and / or (II) is preferably 5 to 100 mol%, more preferably 10 to 100 mol%.
If the content of the units (I) and / or (II) is less than 5 mol%, the image quality will be poor. The weight average molecular weight range is preferably 1,000 to 200,000, more preferably 2,000 to 100,000. If the molecular weight is less than 1000, it is difficult to produce, and if it exceeds 200,000, the solubility in a solvent decreases.

There are various resins that can be used in combination with these resins, for example, polyolefins such as polyethylene and polypropylene, ethylene and vinyl acetate, ethylene and acrylates, ethylene copolymers such as ethylene and acrylic acid, polyvinyl chloride, Vinyl chloride copolymers such as vinyl chloride and vinyl acetate, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymers such as styrene and maleic acid ester, vinyl acetate copolymer, butyral resin, modified Polyvinyl alcohol, copolymerized nylon, polyamide resin such as N-alkoxymethylated nylon, synthetic rubber, chlorinated rubber, phenol resin, epoxy resin, urethane resin, urea resin, melamine resin, alkyd resin, maleic acid resin, hydroxystyrene Copolymers, sulfonamide resins, ester gums, cellulose resins, rosins and the like.

The amount of the polymer compound having the repeating unit represented by the general formula (I) and / or (II) added to these resins is preferably 5 to 50% by weight. The surface becomes sticky and causes trouble in handling. A particularly preferable range is 10 to 30% by weight.

It is a matter of course that other adhesion improvers, release agents, plasticizers, surfactants and the like can be added to these resins in order to satisfy the relationship of the adhesive strength at various interfaces.

The coating solvent used for the two image-receiving layers is such that the resin used for the image-receiving layer is not dissolved or swelled in order to prevent the image-receiving layer and the two image-receiving layers from being mixed with each other due to the penetration of the coating solvent into the lower layer during coating. It is necessary to use a coating solvent. For example, when a vinyl chloride resin, which is relatively soluble in various solvents, is used for the image receiving layer, it is preferable to use an alcohol or water-based coating solvent.

The thickness of the two image receiving layers is 0.1 μm to 1
It is preferably about 0 μm, and particularly preferably 0.5 μm to 5 μm. If the film thickness is too large, the unevenness of the surface of the permanent support is impaired, and the gloss becomes too high to deteriorate the print similarity.

In order to cause delamination by peeling of the image-receiving sheet material during transfer to the permanent support between the image-receiving one-layer organic polymer substance and the image-receiving two-layer organic polymer substance, the balance of the adhesive force between the respective layers is required. It is important to note that, in addition to selection of coating solvent to prevent mixing during multilayer coating used in the present invention in controlling interlayer adhesion, a combination of hydrophilic polymer and lipophilic polymer or polar polymer and non-polar polymer is used. Selection of materials, adhesion improvers such as silane coupling agents, various additives with fluorine or silicone release curing, surfactants. It is effective to add a plasticizer or the like to one image-receiving layer or two image-receiving layers.

On the two image-receiving layers, that is, the layer which receives the heat-transferable ink layer, various releasing agents and lubricants are used as an overcoat layer for the purpose of improving the slipperiness and scratch resistance of the image-receiving layer. Layers can be provided. Specifically, for example, higher fatty acids such as palmitic acid and stearic acid, fatty acid metal salts such as zinc stearate, fatty acid esters or partial saponification products thereof, fatty acid derivatives such as fatty acid amides, higher alcohols, polyhydric alcohols. Derivatives such as ether, waxes such as paraffin wax, carnauba wax, montan wax, beeswax, wooden wax, candelilla wax, and ammonium salts having a long-chain aliphatic group,
One or more selected from cationic surfactants such as pyridinium salts or the like, anions having long-chain aliphatic groups, nonionic surfactants, perfluorinated surfactants and the like can be selected and used.

An intermediate layer may be provided between the image receiving layer and the image receiving two layers for the purpose of adjusting transferability and the like.

Next, a transfer material having an ink layer capable of thermal transfer (hereinafter referred to as "thermal transfer sheet") useful in the present invention will be described.

As the support of the thermal transfer sheet, various supports known as conventional melt transfer and sublimation transfer supports are used. A polyester film subjected to a release treatment is particularly preferable.

As the pigment contained in the ink layer of the thermal transfer sheet, various known pigments can be used, for example, carbon black, azo type, phthalocyanine type, quinacridone type,
Examples thereof include thioindigo pigments, anthraquinone pigments, and isoindoline pigments. These can be used in combination of two or more, and a known dye may be added for adjusting the hue.

The amorphous organic polymer binder having a softening point of 50 ° C. to 150 ° C. contained in the ink layer of the thermal transfer sheet is, for example, butyral resin, polyamide resin, polyethyleneimine resin, sulfonamide resin, polyester polyol resin. , Petroleum resin, styrene, vinyltoluene,
Styrene and its derivatives such as α-methylstyrene, 2-methylstyrene, chlorostyrene, vinyl benzoic acid, sodium vinylbenzene sulfonate, and aminostyrene, substituted homopolymers and copolymers, methyl methacrylate, ethyl methacrylate and butyl. Methacrylate, methacrylic acid esters such as hydroxyethyl methacrylate and methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid esters such as α-ethylhexyl acrylate and acrylic acid, butadiene, dienes such as isoprene, acrylonitrile, vinyl ethers, Use of vinyl monomers such as maleic acid and maleic acid esters, maleic anhydride, cinnamic acid, vinyl chloride and vinyl acetate, or a copolymer with other monomers. You can Two or more kinds of these resins may be mixed and used.

Of these, a butyral resin and a styrene / maleic acid half ester resin are particularly preferable from the viewpoint of dispersibility which is a feature of the present invention described later. The softening point of these resins should be selected in the range of 50 ° C to 150 ° C. If the temperature exceeds 150 ° C, the thermal recording sensitivity will be low, while 50
If it is less than ℃, the ink layer has poor adhesion resistance.

From the viewpoint of improving the releasability of the ink layer from the support and the thermal sensitivity at the time of thermal printing, various releasing agents and softening agents are added to these ink layers from 1% by weight to the total amount of the ink layer. It is also possible to add in the range of 20% by weight. Specifically, for example, higher fatty acids such as palmitic acid and stearic acid, fatty acid metal salts such as zinc stearate, fatty acid esters or partial saponification products thereof, fatty acid derivatives such as fatty acid amides, higher alcohols, polyhydric alcohols. Derivatives such as ether, waxes such as paraffin wax, carnauba wax, montan wax, beeswax, wood wax, and candelilla wax, viscosity average molecular weight of about 1,
000 to about 10,000 low molecular weight polyethylene, polypropylene, polybutylene, and other polyolefins, or olefin, α-olefins and maleic anhydride, organic acids such as acrylic acid and methacrylic acid, and low molecular weight vinyl acetate. Polymer, low molecular weight oxidized polyolefin, halogenated polyolefins, lauryl methacrylate, stearyl methacrylate, etc. Methacrylic acid ester having long alkyl side chain, acrylic acid ester or acrylic acid ester having perfluoro group, methacrylic acid ester alone or styrene Copolymers with vinyl monomers such as polydimethylsiloxanes, low-molecular-weight silicone resins such as polydimethylsiloxane and polydiphenylsiloxane, and silicone-modified organic substances, and ammonium salts having long-chain aliphatic groups, Cationic surfactants such as Jiniumu salt, or anion having a similar long chain aliphatic group, a nonionic surfactant, perfluoro-containing surfactants, etc., from 1
It is possible to select and use one or more species.

For the optical density of these heat transferable ink layers, the reflection density must be 1.0 or more when thermally transferred onto a white support for the reasons described above. The film thickness is preferably in the range of 0.2 μm to 1.0 μm. 1.
In a thick ink layer having a thickness of more than 0 μm, the gradation reproducibility due to only the area gradation is apt to be crushed in the shadow portion and the highlight portion is easily skipped, resulting in poor gradation reproducibility. On the other hand, if the film thickness is less than 0.2 μm, it is difficult to obtain a predetermined concentration.

In order to obtain a predetermined concentration with these thin films, the pigment contains 30 to 70 parts by weight of pigment in the ink layer.
It is preferable that the amount of the amorphous organic polymer conjugate is 25 to 60 parts by weight, and the total amount of the releasing agent and the film softener added as necessary is 1 to 15 parts by weight. If the pigment ratio is less than this, it is difficult to obtain a predetermined density with the above-mentioned predetermined film thickness. Further, the particle size of the pigment needs to be 1.0 μm or less for 70% or more of the pigment. When the particle size is large, the transparency of the overlapping portion of each color at the time of color reproduction is impaired, and it becomes difficult to satisfy both the relationship between the film thickness and the density.

Regarding the dispersion of these pigments in the amorphous organic polymer binder, various dispersion methods used in the coating field including ball mills are applied by adding an appropriate solvent.

The heat transferable ink layer is mainly composed of a pigment and an amorphous organic polymer combination, and has a higher pigment ratio than the conventional wax-melting type. Since the viscosity does not become as low as 10 ² to 10 ³ cps and is at least higher than 10 ⁴ cps at a temperature of 150 ° C., the present invention is applicable to the thermal adhesion of a receiving sheet, or in the case of color image formation. It can be said that it is a thin film peeling development type image formation utilizing thermal adhesion between ink layers. This combined with the effect of thinning the ink layer, while maintaining high resolution, enables wide gradation reproduction from the shadow part to the highlight part, and makes the edge sharpness good, Furthermore, by making it possible to transfer an image of 100%, for example, a small character of 4 points and the uniformity of the density of the solid portion were realized. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[0053]

【Example】

Synthesis Example 1 <Synthesis of Polymer Compound (1)> 170 parts of propylene glycol monomethyl ether was heated and stirred under a nitrogen stream at 80 ° C. to obtain 2,2′-azobis (2,4-dimethylvaleronitrile). 07 parts was added and stirred for 30 minutes. Add to this 31.6 parts of butyl acrylate, 24.4 parts of N, N-dimethylacrylamide, 2,2'-azobis (2,4-
0.07 part of dimethylvaleronitrile) was added dropwise over 30 minutes. 30 minutes and 1 hour after the end of dropping,
0.15 parts of 2'-azobis (2,4-dimethylvaleronitrile) was added, respectively, and the mixture was further heated and stirred for 4 hours to obtain a 28% propylene glycol monomethyl ether solution of the polymer compound (1). The weight average molecular weight was 13,000 (in terms of polystyrene).

Synthesis Examples 2-5 Polymers (2) -using the monomers shown in Table 1
(5) was synthesized in the same manner as in Synthesis Example 1. Table 1: Polymer compounds (2) to (5) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Synthesis Example Monomer (mol ratio) Weight average molecular weight ───────────────────────────────────── 2 Hexyl acrylate / acryloyl Morpholine = (1/1) 31000 3 butyl methacrylate / vinyl imidazole = (1/1) 16000 4 butyl methacrylate / N, N-dimethylacrylamide / N, N, N- (trihexyl) -N- (styrylmethyl) -ammonium Chloride = (5/5/1) 3900 5 butyl methacrylate / N, N-dimethylacrylamide / N, N, N- (trioctyl) -N- (styrylmethyl) -ammonium chloride = (5/5/1) 400 6 N, N, N- (trihexyl) -N- (styrylmethyl) -ammonium chloride 3800 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━

Example 1 <Preparation of Image Receiving Sheet Material> Coating solutions for one image receiving layer and two image receiving layers having the following compositions were prepared. (Coating liquid for image receiving layer) ・ Binder: vinyl chloride / vinyl acetate copolymer 25 parts by weight (MPR-TSL, manufactured by Nisshin Chemical Co., Ltd.) ・ Plasticizer dibutyl octyl phthalate 12 parts by weight (DOP, Daihachi) Chemicals Co., Ltd. ・ Surfactant 4 parts by weight (Brand name Megafac F-177P, Dainippon Ink and Chemicals Co., Ltd.) ・ Solvent Methyl ethyl ketone 75 parts by weight (Coating liquid for image receiving two layers) ・ Binder polyvinyl Butyral 16 parts by weight (Denka Butyral # 2000-L, manufactured by Denki Kagaku Kogyo Co., Ltd.)-Polymer compound (1) 4 parts by weight-Surfactant 0.5 parts by weight (Brand name MegaFac F- 177P, manufactured by Dainippon Ink and Chemicals, Inc. ・ Solvent n-propyl alcohol 200 parts by weight

A polyethylene terephthalate (PET) film having a thickness of 100 μm was placed on a support and a coating solution for image-receiving layer was added at 300 rp by using a spin coater (foamer).
m, and dried in an oven at 100 ° C. for 2 minutes.
The film thickness of the obtained image receiving layer was 20 μm. The above image-receiving two-layer coating liquid was applied onto the above image-receiving layer at 200 rpm by using a spin coater (foamer), and the coating liquid at 100 ° C. was applied.
Dry in a bun for 2 minutes. The thickness of the obtained two image receiving layers is 2
μm.

<Preparation of Thermal Transfer Sheet> Next, the following three types of pigment dispersions for ink layers were prepared. Butyral resin 12 parts by weight (Denka Butyral # 2000-L, manufactured by Denki Kagaku Kogyo Co., Ltd.) Pigment A B C Cyan pigment (CI.P.B.15: 4) 12 parts by weight Magenta pigment (C.I.P.R. 57: 1) -12 parts by weight-Yellow-pigment (C.I.P.Y.14)-12 parts by weight Dispersion aid Solspers S-20,000 0.8 Parts by weight (ICI Japan Ltd.)-Solvent n-propyl alcohol 110 parts by weight

To 10 parts by weight of each of the above A, B, and C pigment dispersions, 0.24 parts by weight of stearic acid amide and 60 parts by weight of n-propyl alcohol were added to prepare a coating solution having a thickness of 5 μm.
m of the polyester film (manufactured by Teijin Ltd.) having a release treatment on its back surface, the dry film thickness A is 0.36 μm, and the film thickness B is 0.38
A thermal transfer sheet was prepared by coating so that C and C were 0.42 μm. First, a cyan thermal transfer sheet and an image receiving sheet material were overlaid, and printing was performed by a thermal head recording device (prototype experimental machine) by the sub-scanning division method. This principle is 75 μm
This is a method of performing multi-step modulation only for area gradation by turning on and off a head of X50 μm in a direction of 50 μm with a minute feed at a pitch of 3 μm. The cyan thermal transfer sheet was peeled off to form an image consisting of area gradation only on the image receiving sheet material. Next, the magenta heat transfer sheet is overlaid on the image receiving sheet material on which the cyan image is formed, aligned and printed in the same manner, and the heat transfer sheet is peeled off to form an image on the image receiving sheet material. A magenta image, a yellow image was formed in the same manner, and a color image consisting of area gradation alone was formed on the image receiving sheet material. Next, the image-receiving sheet material on which the color image was formed was overlaid on the art paper, and the temperature was 130 ° C., 4.5 Kg /
After passing through a heat roller of 4 m / sec at a pressure of cm, the polyester film of the image receiving sheet material is peeled off and the image receiving two layers having an ink image are transferred onto an art paper to form a color image. Let This color image is a chemical proof made from a squirrel manuscript (Fuji Photo Film Co., Ltd., trade name color
The closeness between the art) and the color image was very good.
The reflection densities of the individual colors at this time were as follows. The density of 4P characters was measured by a microdensitometer, and it was the same as the density of solid areas. The gradation reproducibility was 5% to 95%, the dot shape was good with no defects due to dust, and the surface following the irregularities of the paper was matted and the surface gloss was an image very similar to that of the printed matter. .

Example 2 An image receiving sheet was prepared in the same manner as in Example 1. (Coating liquid for image receiving layer) -Binder 20 parts by weight of ethylene / ethyl acrylate copolymer (Evaflex A-709, manufactured by Mitsui Petrochemical Co., Ltd.)-Solvent 100 parts by weight of toluene (Coating liquid for image receiving two layers) Binder Polyvinyl butyral 16 parts by weight (Denka Butyral # 2000-L, manufactured by Denki Kagaku Kogyo KK) Polymer compound (2) 4 parts by weight Surfactant 0.5 parts by weight (trade name) Megafac F-177P, manufactured by Dainippon Ink and Chemicals, Inc. ・ Solvent n-propyl alcohol 200 parts by weight

Using the obtained image-receiving sheet and the heat-sensitive transfer material prepared in the same manner as in Example 1, a color image was formed in the same manner as in Example 1 and the image was evaluated. Table 2 shows the evaluation results.

Examples 3 to 6 The same as Example 1 except that the image receiving layer of Example 1 was used and the polymer compounds (3) to (6) were used instead of the polymer compound (1) of the image receiving bilayer. Then, an image receiving sheet was prepared. Using this image-receiving sheet, a color image was formed in the same manner as in Example 1 and the image was evaluated. Table 2 shows the evaluation results.

Example 7 The same procedure as in Example 1 was carried out except that the image-receiving layer of Example 1 was used and 1 part by weight of polyethyleneimine (SP-200 manufactured by Nippon Shokubai Co., Ltd.) was added as an additive to the image-receiving two layers. An image receiving sheet was created. Using this image-receiving layer, a color image was formed in the same manner as in Example 1, but the image had a very good dot shape.

Example 8 An image receiving sheet was prepared in the same manner as in Example 1 except that the amount of the surfactant was 0.01 parts by weight instead of 4 parts by weight.
When the same evaluation was performed, the same good result was obtained.

Example 9 (1) Preparation of thermal transfer sheet (a) Preparation of photothermal conversion layer <Preparation of mother liquor for coating liquid> Carbon black (Mitsubishi Kasei Co., Ltd., Mitsubishi Carbon Black, MK) -100, CI Pigment Black 7) 20 parts by weight Dispersion aid (30% aqueous solution of John Cryl J-62 manufactured by Johnson Polymer Co., Ltd.) 6 parts by weight Deionized water 80 parts by weight Isopropyl alcohol 20 parts by weight Glass beads 100 parts by weight The above components were dispersed for 2 hours using a paint shaker (manufactured by Toyo Seiki Co., Ltd.) to prepare a mother liquor.

<Preparation of coating liquid> 100 parts by weight of the above mother liquor 3 parts by weight of polyvinyl alcohol (Kuraray Co., Ltd., Poval type 205) 3 parts by weight of isopropyl alcohol 100 parts by weight of ion-exchanged water 450 Parts by Weight The above components were mixed with stirring with a stirrer to prepare a coating solution for the photothermal conversion layer.

<Preparation of support> Coating thickness of photothermal conversion layer 7
A styrene-butadiene copolymer (thickness: 0.5 μm) was used as an undercoat layer on a polyethylene terephthalate film having a thickness of 5 μm.
m) and gelatin (thickness 0.1 μm) were provided in this order to prepare a support for a thermal transfer sheet. The above coating solution for light-heat conversion layer was applied onto this support for 1 minute by using a spin coater (foamer), and the coated product was coated with 100
It was dried in an oven at 0 ° C. for 2 minutes to prepare a photothermal conversion layer (film thickness by a stylus film thickness meter: 0.3 μm, light absorption rate 90% at a wavelength of 488 nm). When the cross section of the same sample was observed with a scanning electron microscope, the average film thickness was 0.3 μm.

(B) Lamination of thermal release layer <Preparation of coating liquid> 1 part by weight of nitrocellulose (Type RS1 / 2 manufactured by Daicel Corp.) 100 parts by weight of methyl ethyl ketone • Propylene glycol monomethyl ether acetate 20 Parts by weight The above components were mixed with a stirrer under stirring to prepare a coating solution for a heat release layer.

<Application of Thermal Release Layer and Measurement of Film Thickness> The coating solution for thermal release layer was applied to the surface of the photothermal conversion layer provided on the support for thermal transfer sheet by using a spin coater (foamer). Then 1
After coating for 1 minute, the coated product was dried in an oven at 100 ° C. for 2 minutes. Further, the above thermal release layer coating solution was used to coat and dry on a polyester film having a smooth surface under the same conditions. When the film thickness at that time was measured with a stylus type film thickness meter, it was 0.
It was 1 μm.

(C) Lamination of image forming layer (magenta) <Preparation of mother liquor for coating liquid> 20% by weight solution of polyvinyl butyral (Denka Butyral # 2000-L manufactured by Denki Kagaku Kogyo Co., Ltd.) Solvent: n-propyl alcohol) 63 parts by weight-Coloring material (magenta pigment, manufactured by Toyo Ink Co., Ltd., Lionol Red 6B4290G, CI Pigment Red 57: 1) 12 parts by weight-Dispersion aid (ICI Co., Solspa) -S S-20,000) 0.8 parts by weight-n-propyl alcohol 60 parts by weight-Glass beads 100 parts by weight The above components were used in a paint shaker (manufactured by Toyo Seiki Co., Ltd.). Dispersion treatment for 2 hours to prepare a mother liquor.

<Preparation of coating liquid> 10 parts by weight of the above mother liquor 60 parts by weight of n-propyl alcohol-Surfactant (Megafac F-176PF manufactured by Dainippon Ink and Chemicals, Inc.) 0.05 parts by weight The above components were mixed with a stirrer under stirring to prepare a magenta image forming layer coating solution.

<Application of Magenta Image Forming Layer Coating Solution and Measurement of Film Thickness> The image forming layer coating solution was applied onto the surface of the heat release layer provided on the thermal transfer sheet support by a spin coater ( (1) applied for 1 minute using an air conditioner), the coated material is dried in an oven at 100 ° C. for 2 minutes, and an image-forming layer having an optical density of 0.7 on a Macbeth densitometer is laminated and the thermal transfer coating is applied. -Created The coating solution for image forming layer was applied to a polyester film (100 μm thick) under the same conditions, dried, and the film thickness was measured to be 0.3 μm. When the film thickness of the magenta image forming layer of the thermal transfer sheet was measured by a scanning electron microscope by a cross-section observation method, the average was about 0.3 μm.
Met.

(2) Preparation of Image Receiving Sheet Material An image receiving sheet material was prepared in the same manner as in Example 1.

(3) Preparation of Laminated Body The thermal transfer sheet and the image receiving sheet material prepared as described above are passed through a heat roller having a surface temperature of 70 ° C. and a pressure of 4.5 kg / cm ^{2 at} a speed of 200 cm / min. A laminate was prepared so that the image receiving layer and the heat transferable ink layer were in substantially uniform contact with each other. Here, the pressure was measured through a roller at room temperature using a pressure-sensitive color-developing material for pressure measurement (press scale) manufactured by Fuji Photo Film Co., Ltd.

(4) The laminated body obtained as described above is provided with suction holes for vacuum suction so that the thermal transfer sheet support is in contact with the laser beam incident surface and the image receiving sheet material support is in contact with the rotating drum surface. It was wound around a rotating drum, evacuated and fixed. A semiconductor laser beam having a wavelength of 830 nm is condensed in a spot shape of 8 μm on the photothermal conversion layer, and is moved (sub-scanning) in a direction perpendicular to the rotating direction of the rotating drum (main scanning direction) according to a recorded image. Light was modulated and laser recording was performed under the following conditions. Laser power 100 mW Main scanning speed 8 m / sec Sub-scanning pitch (sub-scanning amount per rotation) 5 μm

(5) After recording, the laminate was removed from the drum, and the image receiving sheet material and the thermal transfer sheet were separated by hand, and it was found that the image forming layer of only the laser irradiation portion was transferred to the image receiving layer. Observed clearly. Furthermore, when the transferred image was observed with an optical microscope, it was 200 lines /
The halftone dots were reproduced in the range of 3 to 98%. The halftone dot shape was also good.

Example 10 An image was formed and evaluated in the same manner as in Example 9 except that the compound (1) was changed to the compound (4) as the compound to be added to the image receiving layer. Halftone dots were reproduced in the range of 4 to 96%. The halftone dot shape was also good.

Comparative Example 1 An image receiving sheet was prepared in the same manner as in Example 1 except that the polymer compound (1) was not used in the two image receiving layers. A color image was formed using this image receiving sheet in the same manner as in Example 1.
The dot shape was poor and the reproduction gradation was poor.

Comparative Example 2 Polymer compound (1) was not used in the two image-receiving layers, but instead a phenol resin (manufactured by Sumitomo Durres: trade name phenol formaldehyde polycondensate. PR-51600B, molecular weight about 450, melting point 55). An image receiving sheet was prepared in the same manner as in Example 1 except that (.degree. C.) was added. A color image was formed using this image-receiving sheet in the same manner as in Example 1, but the dot shape was poor, the reproduction gradation was poor, and the surface was sticky.

Comparative Example 3 The polymer compound (1) was not used in the two image-receiving layers, but rosin (manufactured by Arakawa Chemical Industry Co., Ltd .: trade name KR-610 hydrogenated rosin, softening point 85 ° C.) was added instead. An image-receiving sheet was prepared in the same manner as in Example 1. A color image was formed using this image-receiving sheet in the same manner as in Example 1, but the dot shape was poor and the reproduction gradation of the shadow portion was poor.

Comparative Example 4 The polymer compound (1) was not used in the two image-receiving layers, but instead of nylon (manufactured by Daicel Chemical Industries, Ltd., Daiamide X-187).
An image receiving sheet was prepared in the same manner as in Example 1 except that 4) was added. A color image was formed using this image-receiving sheet in the same manner as in Example 1. However, the surface of the image-receiving sheet was sticky, and there were many dust defects, resulting in poor image quality.

Comparative Example 5 In the preparation of a magenta transfer sheet, the addition amount of butyral resin was changed from 12 parts by weight to 36 parts by weight, and the film thickness was adjusted to 0.
When a color image was formed in the same manner as in Example 1 by using the same image receiving sheet as in Example 1 using the thermal transfer sheet changed from 38 μm to 1.14 μm, the toner layer was very sharp. Poor, the reproducibility of highlights and shadows was very poor, and the image had very poor dot quality.

Comparative Example 6 An image was prepared in the same manner as in Example 4 except that the material prepared in Comparative Example 1 was used as the image receiving sheet material. When the halftone dots were similarly observed, only 8 to 92% of the halftone dots were reproduced, and the shapes were irregular.

Table 2 summarizes the evaluation results. Table 2: Evaluation results ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Image receiving layer 2 layers Image receiving layer thickness Dot Floor Conditioning surface Staple dust Additive compound One layer Two layers Quality Positivity Kinking Defect ───────────────────────────────────── Example 1 Compound (1) 20 μm 2 μm OOOO 10 Example 2 Compound (2) 20 μm 2 μm OOOO 6 Example 3 Compound (3) 20 μm 2 μm OOOO 6 Example 4 Compound (4) 20 μm 2 μm ◎ O O O 6 Example 5 Compound (5) 20 μm 2 μm ◎ O O O 6 Example 6 Compound (6) 20 μm 2 μm ◎ O O O 9 Example 7 Compound (1) 20 μm 2 μm ◎ O O O 11 Polyethyleneimine Example 8 Compound (1) 20 μm 2 μm ◎ OO O 9 Surfactant 0.01 parts ──────────────── ──────────────────── Comparative Example 1-20 μm 2 μm △ △ OO 9 Comparative Example 2 Phenol resin 20 μm 2 μm × × × × 70 Comparative Example 3 Rosin 20 μm Comparative Example 4 Nylon 20 μm 2 μm 2 Δm Δ Δ Δ Δ 60 60 Comparative Example 5 Compound (1) 20 μm 2 μm 2 ×× O 2 O 10 (heat transfer layer thickness 1.14 μm) ─────────── ────────────────────────── Halftone dot shape Halftone dot reproduction% Example 9 Compound (1) 20 μm 2 μm Good 3-98 Example 10 Compound (4) 20 μm 2 μm Good 4-96 Comparative Example 6-20 μm 2 μm Bad 8-92 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━ * Dust defect (A4 size is counted)

[0084]

By the image-receiving sheet material, transfer image forming method and laminate of the present invention, recording sensitivity, dot quality (halftone dot shape), gradation reproducibility (halftone dot reproducibility) are good, and further, sticking and dust defects. It is possible to provide an image with less printed matter and good approximation to printed matter.

Claims (3)

[Claims] 1. An image receiving sheet material used for forming a transferred image, wherein an ink layer is thermally transferred from a transfer material having a heat transferable ink layer onto an image receiving sheet material, and then retransferred onto a permanent support, said image receiving sheet material. Has at least two image-receiving layers on a support, and at least one of the image-receiving layers
The layer is transferred to a permanent support, and at least the image-receiving layer to which the ink layer is transferred contains a polyvinyl butyral resin and a polymer compound having at least a repeating unit of the following general formula (I) and / or general formula (II). An image-receiving sheet material characterized in that Embedded image [In the formula, R ₁ is a hydrogen atom or a methyl group, A is a substituent having an amide bond or a nitrogen-containing heterocycle, R ₄ is a hydrogen atom or a methyl group, and R ₆ , R ₇ , and R ₈ are the same or different. Good alkyl group having 1 to 25 carbon atoms, 7 carbon atoms
To 25 aralkyl groups or C 6 to C 25 aryl groups (the alkyl group, aralkyl group and aryl group are a hydroxy group, a C 1 to C 6 alkoxy group, halogen,
It may be substituted with a cyano group and a combination of two or more kinds thereof, and may be intermediated via an ether bond, —OCO—, —COO— and a combination of two or more kinds thereof), X
Represents Cl, Br or I. ] 2. An amorphous organic high molecular polymer having a softening point of 40 to 150 ° C., which is 30 to 70 parts by weight of a pigment, provided on a support, and has a film thickness of 0.1. 2 μm-1.
A thermal transferable ink layer having a thickness of 0 μm is adhered to the image receiving sheet material according to claim 1, an ink image is formed on the image receiving sheet material by thermal transfer, and then the ink image and at least one layer of the image receiving layer are permanently supported. A transfer image forming method characterized by transferring onto a body. 3. An amorphous organic high-molecular polymer having a softening point of 40 to 150 ° C., which is 30 to 70 parts by weight of a pigment, provided on a support, and has a film thickness of 0. 2 μm-1.
A heat transferable ink layer having a thickness of 0 μm and the image receiving layer according to claim 1 are closely attached to each other.