JP2000280638A - Thermal transfer recording material and thermal transfer recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture an inexpensive thermal transfer recording material of superior sensitivity, image preservation properties and gloss provided with a hand close to a silver salt photograph not generating image defects and provide a thermal transfer recording method using the recording material. SOLUTION: A thermal transfer recording material is constituted of a substrate formed of a polyester film of 0.6-1.05 specific gravity laminated on a face on the side whereon an image is formed on a resin coated paper coating at least one face of a base, which is formed of a natural pulp as a main component, with a resin layer containing a resin having the film forming power, and the ratio of thickness of the resin coated paper and the polyester film on the substrate is 8:1-1:1. In a thermal transfer recording method in which an ink sheet having at least one in layer containing a heat diffusion dye on the substrate is so overlapped with an image receiving face of an image receiving sheet as to face each other and heated in the form of an image to transfer the heat diffusion dye on the image receiving layer and form an image thereon, the substrate of the image receiving sheet is formed of the substrate described above.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermal transfer recording material and a thermal transfer recording method for recording an image by thermal transfer.
More specifically, the present invention relates to a thermal transfer recording material and method having a texture similar to that of a silver halide photograph, having no image defects, and having excellent sensitivity, glossiness, and image storability.

[0002]

2. Description of the Related Art Conventionally, as a technique for forming a color or monochrome image, an ink sheet containing a heat-diffusible dye having a property of diffusing and transferring by heating is opposed to an image receiving layer of an image receiving sheet, and a thermal head or a laser is used. There is known a thermal transfer recording method in which an image is formed by transferring the thermal diffusible dye to the image receiving layer in an image-like manner by using a heating printing means such as described above.

Particularly, in recent years, with the progress of technology, even in the thermal transfer system, an image quality comparable to that of silver halide photography can be obtained, so that it is often used for the same purpose as conventional photography. It is also used in such a way that a portrait image taken in a studio and various backgrounds are combined on a computer to form a single photograph. As such uses have become widespread, there has been a demand for an image receiving sheet having an appearance similar to that of silver halide photography. In recent years, the sublimation thermal transfer method has been rapidly spreading even in ordinary households as an application for outputting images taken with a television or video camera, images taken with a digital camera, images outputted with a personal computer, and the like. In the future, it is essential that the price of the image receiving sheet be reduced.

[0004] Conventionally, the thermal transfer recording method has the greatest drawback to silver halide photography in that the preservation of the image is remarkably poor. One such technique is disclosed, and as one of them, an image is formed by reacting a dye precursor contained in an ink layer and a dye fixing body contained in an image receiving layer during thermal transfer to form a dye, An image forming method using a so-called reactive dye has been proposed. For example, JP-A-9-
Nos. 327976, U.S. Pat. Nos. 4,880,769 and 5,534,479 disclose deprotonated cationic dyes as dye precursors, organic polymer acids capable of protonating the cationic dyes as dye fixers, and the like. There has been proposed a method of forming an image by reprotonating a cationic dye by thermal transfer using an oligomeric acid or the like. And JP-A-59-78893 and JP-A-59-1093.
No. 94, No. 60-2398, and the like, use of a heat-diffusable compound capable of chelation (hereinafter also referred to as a post-chelating dye) as a dye precursor, and a metal ion-containing compound (hereinafter, referred to as a dye fixing body) by thermal transfer. , Also referred to as a metal source) to form an image.

[0005] A resin-coated paper whose base paper surface is coated with a resin capable of forming a film, which is mainly used as a support for silver halide photography, is a well-known technique. For example, Japanese Patent Publication No. 55-12584 discloses a technique of a photographic material support in which a base paper is coated with a resin capable of forming a film, preferably a polyolefin resin.
No. 1,298 discloses a technique of a photographic material support in which both sides of a base paper are coated with a polyolefin resin.
In recent years, many techniques using these as a support for a thermal transfer recording material have been disclosed, for example, US Pat.
The surface roughness of the resin coating of No. 74,224 is 7.5 μinc
There has been proposed a thermal transfer recording image receiving element having, as a support, a resin-coated paper having a h-AA or less, in particular, a polyethylene resin-coated paper in which the surface of a base paper is coated with a polyethylene resin.

However, when a resin-coated paper conventionally known as described above is used as a support for an image receiving sheet, a texture similar to that of a silver halide photograph can be obtained, but the unevenness of the surface of the base paper can be obtained. Image defects due to transfer omission (hereinafter, referred to as
The dye transferred to the coating resin via the image-receiving layer moves in the coating resin during storage, causing bleeding, and coating with high thermal conductivity such as polyethylene resin. In the case of using a resin, the sensitivity is lowered due to poor thermal efficiency in thermal transfer. Particularly, in the case of an image forming method using a reactive dye, there are various problems such as a decrease in thermal efficiency being a fatal problem. .

The present inventor has made various studies to improve this point. For example, when a resin-coated paper coated with a resin having lower thermal conductivity than polyethylene (such as polypropylene) is applied to an image receiving sheet, the above-described problem of blurring and sensitivity tends to be improved.
Even if the film thickness was adjusted, it could not be solved.
Further, a base paper having a high surface smoothness was also examined, but the image defect was in a tendency to be improved, but this did not reach the point where it could be completely eliminated. Furthermore, these improved means result in a resin-coated paper specified for a thermal transfer image-receiving sheet, which is disadvantageous in cost and is not preferred.

Accordingly, the present inventors have studied a configuration in which a thermoplastic resin film is laminated on a resin-coated paper. A thermoplastic resin film has been well known in recent years as a support for a thermal transfer image-receiving sheet, and generally a film containing cavities is often used. As a means for containing cavities, for example, a method of blending a thermoplastic resin with inorganic particles such as titanium dioxide or calcium carbonate, a crystalline resin incompatible with the thermoplastic resin, and stretching is known. I have. The reason for containing the cavities is to make the thermoplastic resin opaque and increase the whiteness by light scattering by the cavities,
The object is to improve the image quality and sensitivity by increasing the adhesion to the thermal head by lowering the specific gravity and imparting cushioning properties.

However, when the cavity-containing film is laminated on a resin-coated paper, if the cushioning property is insufficient,
Eventually, formation unevenness due to unevenness of the base paper surface or laminating surface occurs, and if there is foreign matter on the image receiving sheet or in the image receiving layer, the thermal head follows according to the shape of the foreign matter and only the area is In some cases, the image was not transferred and a foreign matter-like image defect was generated.

However, if the content of cavities is simply increased to lower the specific gravity of the film in order to satisfy the cushioning property, the size of the cavities becomes extremely large and the smoothness of the film surface is lost. There is a problem in that the wrinkles are easily formed, the image quality is remarkably deteriorated, the production stability is lowered, and stable production cannot be performed.

In particular, when it is desired to use a polyester-based void-containing film, the void content must be further increased because the rigidity is relatively high and the cushioning property is low with respect to other thermoplastic resins. In this case, it is difficult to reduce the specific gravity even if whiteness is obtained, and when a polyolefin resin or the like is added as an incompatible resin, the cushioning property is increased as compared with the addition of inorganic particles, but the free energy of the surface is reduced. Therefore, the adhesiveness and printability tend to be inferior, and it has been extremely difficult to improve the above-mentioned defect while satisfying the cushioning property with the current polyester-based film.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a thermal transfer recording material and method for recording an image by thermal transfer. An object of the present invention is to provide a thermal transfer recording material which is inexpensive, has excellent sensitivity, image storability and gloss, and has a texture close to that of a silver halide photograph free from image defects.

[0013]

The above object of the present invention is achieved by the following constitution.

(1) At least one surface of a base paper mainly composed of natural pulp is coated with a resin layer containing a resin capable of forming a film. A thermal transfer recording material having a structure in which a polyester film having a thickness of 0.6 to 1.05 is laminated, and a thickness ratio between the resin-coated paper and the polyester film is 8: 1 to 1: 1.

(2) The thermal transfer recording according to (1), wherein the polyester film has a composite structure of two or more layers having different specific gravities, and the specific gravity of the outermost surface layer on the side where an image is formed is higher than that of the adjacent layer. material.

(3) The resin-coated paper has a thickness of 100 to 2
(1) The thermal transfer recording material according to (1) or (2), wherein the polyester film has a thickness of 30 to 100 μm.

(4) The thermal transfer recording material according to (1), (2) or (3), wherein the resin capable of forming a film is a polyethylene resin.

(5) The resin layer is provided on the surface of the resin-coated paper on which the polyester film is not laminated, and the resin in the resin layer has a density of 0.935 g / c.
and m ³ or less of polyethylene resin, density 0.960 g / c
m ³ or more polyethylene resin, the composition ratio of which is 3
The thermal transfer recording material according to any one of (1) to (4), wherein the ratio is 5:65 to 100: 0.

(6) The ink layer surface of an ink sheet having at least one ink layer containing a heat diffusible dye on a support, and at least one image receiving layer of an image receiving sheet capable of receiving the dye on the support. In the thermal transfer recording method of forming an image by superimposing the image receiving layer surfaces of the image receiving sheet facing each other and transferring the heat diffusible dye to the image receiving layer by heating imagewise, the support of the image receiving sheet is A specific gravity of 0.6 to 1.05 is applied to a surface on which an image of a resin-coated paper in which at least one surface of a base paper mainly composed of natural pulp is coated with a resin layer containing a resin capable of forming a film is formed.
Wherein the ratio of the thickness of the resin-coated paper to the thickness of the polyester film is from 8: 1 to 1: 1.

(7) The thermal transfer recording according to (6), wherein the polyester film has a composite structure of two or more layers having different specific gravities, and the specific gravity of the outermost surface layer on the side where an image is formed is higher than that of the adjacent layer. Method.

(8) The resin-coated paper has a thickness of 100 to 2
(6) The thermal transfer recording method according to (6) or (7), wherein the polyester film has a thickness of 30 to 100 μm.

(9) The thermal transfer recording method according to (6), (7) or (8), wherein the resin capable of forming a film is a polyethylene resin.

(10) The resin layer is provided on a surface of the resin-coated paper on which the polyester film is not laminated, and the resin in the resin layer has a density of 0.935 g /
and cm ³ or less of polyethylene resin, density 0.960 g /
cm ³ or more of polyethylene resin having a composition ratio of 35:
Any one of (6) to (9) having 65 to 100: 0
The thermal transfer recording method described in the above item.

(11) The ink layer contains a dye precursor capable of forming a dye by reaction, and the image receiving layer contains a dye fixing body capable of forming a dye by reacting with the dye precursor. The thermal transfer recording method according to any one of (6) to (10).

(12) The thermal transfer recording method according to (11), wherein the dye precursor is a chelatable compound, and the dye fixing body is a metal ion-containing compound.

Hereinafter, the present invention will be described in detail.

The natural pulp used for the base paper of the resin-coated paper used in the present invention may be a normal bleaching treatment such as chlorine, hypochlorite, chlorine dioxide bleaching, or an alkali extraction or treatment, and if necessary. hydrogen peroxide,
Wood pulp of softwood pulp, hardwood pulp, softwood pulp mixed pulp which has been subjected to oxidative bleaching treatment with oxygen or the like, or a combination thereof is used. In addition, recycled pulp such as kraft pulp, sulfite pulp, soda pulp, etc. Various materials such as (used paper pulp) can be used. Also, in order to increase the internal bond strength of the base paper, a dry paper strength enhancer such as cationized starch, anionized starch, cationized or amphoteric polyacrylamide, or maploid gum, or polyaluminum hydroxide is added to the stock slurry. It may be added. In addition, a sizing agent (metal salt of fatty acid and / or fatty acid, Japanese Patent Publication No. 62-75)
No. 34, an alkyl ketene dimer emulsion, etc.), a wet strength agent (polyamine polyamide epichlorohydrin resin, etc.), a filler (clay, kaolin, calcium carbonate,
Titanium oxide, etc.), fixing agent (water-soluble aluminum, etc.), p
H adjusters (sodium hydroxide, sodium carbonate, etc.), coloring pigments, coloring dyes, fluorescent whitening agents, etc. described in JP-A-63-204251, JP-A-1-26637 and the like may be appropriately combined and contained. Good.

In the base paper, various water-soluble polymers,
A composition comprising a hydrophilic colloid, an emulsion, a latex, an antistatic agent, and various additives can be contained by a size press or a tab size press, a blade coating, an air knife coating, or the like. Examples of the water-soluble polymer include polymers described in JP-A-1-266538, and examples of the emulsion and latex include JP-A-55-4027 and JP-A-1-180.
Examples of antistatic agents such as those described in No. 538 include alkali metal salts such as sodium chloride, alkaline earth metal salts such as calcium chloride, colloidal metal oxides such as colloidal silica, and organic antistatic agents such as polystyrene sulfonate. Agents and the like can be used.

Further, in order to reduce the thickness unevenness in the papermaking direction of the base paper, for example, 30% by weight or more, preferably 50% by weight or more of hardwood sulphite pulp, which is made of short fibers and has good smoothness, is used. Refining is performed so that the long fiber content is as small as possible, for example, refining is performed so that the weighted average fiber length of the refining word is 0.4 to 0.75 mm. It is preferable to form a base paper by employing a paper making method so that a uniform formation can be obtained by a fourdrinier paper machine. After the papermaking, it is also preferable to perform a calendering treatment such as a machine calender, a super calender, and a heat calender.

The base paper surface of the present invention has a center plane average roughness SRa (the following formula) in the papermaking direction at a cutoff value of 0.8 mm measured using a stylus color three-dimensional surface roughness meter. 45 μm
The following are preferred, and the diameter is more preferably 1.35 μm or less, particularly preferably 1.25 μm or less.

[0031]

(Equation 1)

Here, Wx is the length of the sample surface area in the X-axis direction (papermaking direction), Wy is the length of the sample surface area in the Y-axis direction (direction perpendicular to the papermaking direction), and Sa is the sample surface area. Indicates the area of the area.

The base paper having an SRa value in the above range can be produced by appropriately combining the above-mentioned hardwood sulphite pulp content, calendering and the like.

The density of the base paper is 0.95 to 1.15 g.
/ Cm ³ is preferable, and a range of 1.0 to 1.1 g / cm ³ is particularly preferable. This density range can be achieved by optimizing the papermaking process and optimizing the calendering process. If the density of the base paper is less than 0.95 g / cm ³ , a resin-coated paper having good surface quality and excellent smoothness cannot be obtained, and 1.15 g / c.
If it is larger than m ^3, the stiffness of the resin-coated paper becomes weak.

At least one surface of the base paper in the present invention is covered with a resin layer containing a resin capable of forming a film. As the resin having a film forming ability, thermoplastic resins such as polyolefin resin, polycarbonate resin, polyester resin, polyamide resin and a mixture thereof are preferable, and among them, polyolefin resin is more preferable from the viewpoint of melt extrusion coating property, and polyethylene resin is preferable. Particularly preferred. Further, it may be covered with a resin layer composed of an electron beam-curable resin described in JP-B-60-17104.

In the present invention, a surface of the base paper on which the polyester film is not laminated (hereinafter also referred to as a BC surface).
Similarly, the side on which the polyester-based film is laminated is also referred to as an IM surface), and it is preferable to coat the film-forming resin, particularly the polyethylene-based resin described above. BC
As the polyethylene resin for the resin layer covering the surface,
The melt flow rate (MFR) specified in JIS K 6760 is 10 to 40 g / 10 min, and the density is 0.960.
g / cm ³ or more high-density polyethylene resin (HD
PE), the MFR is 0.2 to 3 g / 10 min, and the density is 0.1.
Low-density polyethylene resin (LDPE) or medium-density polyethylene resin (MDP) of 935 g / cm ³ or less
And E) is preferably a compound resin composition in which the composition is previously melted and mixed.

The mixing ratio of the above-mentioned HDPE and LDPE / MDPE can be appropriately selected.
Is 0 to 65 parts by weight, and LDPE / MDPE is 100 to 35 parts by weight.
It is preferably in parts by weight. This is a reverse action in which the plus curl (curl toward the IM surface) increases in comparison with the mixing ratio of the polyethylene resin on the BC surface side of the resin-coated paper conventionally used for silver halide photography. However, in the case of silver halide photography, gelatin is mainly used as a binder on the IM surface, and the binder shrinks significantly in a low humidity environment. In the case of the present invention, the IM side of the base paper is covered with a polyester film, and the binder used for the thermal transfer image receiving layer is smaller than that of a silver halide photograph. There is no need to do such a design because it is small, but rather B
Because only the C side is affected by humidity,
This is because it is preferable to design the lens to be slightly positive.

The HDPE used in the present invention may have various densities and MFs as long as the above-mentioned density range and MFR are satisfied.
R, molecular weight and distribution amount distribution can be used alone or as a mixture, and various types such as ordinary HDPE, copolymers of ethylene with α-olefins such as propylene and butylene, and mixtures thereof Can be used. If the MFR is lower than 10 g / 10 min, the curl physical properties and the cutting properties, the adhesion between the base paper and the resin layer, and the like tend to deteriorate, and the MFR is 40 g.
If it is longer than / 10 minutes, the mixing properties of the resin and the moldability will be poor. On the other hand, if the density is lower than 0.960 g / cm ^3, the elastic modulus of the resin layer becomes low, which affects the curl properties, stiffness and the like, which is not preferable.

As long as the LDPE / MDPE satisfies the above density range and MFR, various densities, MFR,
Those having a molecular weight and distribution amount distribution can be used alone or in combination. For example, a high pressure method LDPE (autoclave method LDP)
E, tubular LDPE), linear LDPE, MDP
Various materials such as E, a copolymer of ethylene and an α-olefin such as propylene and butylene, a carboxy-modified polyethylene resin, and a mixture thereof can be used. If the MFR is lower than 0.2 g / 10 min, the mixing property, the adhesiveness between the base paper and the resin layer, the high-speed processability deteriorate, and 3 g / min.
If it is longer than 10 minutes, the moldability and the like will be poor. On the other hand, when the density is higher than 0.935 g / cm ³ , the moldability of the resin composition, the adhesiveness between the base paper and the resin layer, and the like deteriorate.

As the polyethylene resin for the BC side resin layer, a compound resin prepared by melting and mixing in advance is preferable. As a method for preparing a compound resin by melting and mixing LDPE / MDPE and HDPE in advance, , A simple melt mixing method, a multi-stage melt mixing method, or the like. In the case where the resin is directly added to the melt extruder in the state of simple mixing as it is instead of the compound resin and coated, the adhesion between the base paper and the resin layer, the mixing property of the resin, and the moldability are deteriorated.

When a resin layer is also provided on the IM surface side, a polyethylene resin is preferable as described above, and LDPE,
Various materials such as MDPE, HDPE, linear LDPE, copolymers of ethylene with α-olefins such as propylene and butylene, carboxy-modified polyethylene resins, and mixtures thereof can be used. In addition, various densities,
MFR, molecular weight, and those having a molecular weight distribution can be used, and usually, a density in a range of 0.91 to 0.97 g / cm ³ ,
Those having a molecular weight of 1 to 30 g / 10 min and a molecular weight of 20,000 to 250,000 can be used alone or in combination.

The resin-coated paper of the present invention is formed by extruding a polyethylene resin composition for the resin layer on the BC side and, if provided, a resin composition for the resin layer on the IM side on a running base paper. Is produced by a so-called melt extrusion coating method in which a film is cast from the slit die and coated. Usually, on a running base paper, using a melt extruder, the molten resin composition is extruded from the slit die into a film, cast and coated, and pressed between a pressure roll and a cooling roll. , And is produced in a series of steps of being separated from the cooling roll. At that time, the temperature of the molten film is preferably 280 to 340 ° C. Before the coating, the base paper is preferably subjected to an activation treatment such as a corona discharge treatment or a flame treatment.

The thickness of the resin layer on the front and back sides of the resin-coated paper is not particularly limited. However, when the thickness of the resin layer on the IM surface side is provided, a range of 9 to 60 μm is useful. The BC side resin layer has a useful range of 5 to 60 μm, preferably 8 to 60 μm.
４０40 μm.

Various additives can be contained in the front and back resin layers of the resin-coated paper. For example, Japanese Patent Publication No. 60-34
No. 30, No. 63-11655, Tokiko 1-38291
Titanium oxide, zinc oxide, white pigments such as talc, fatty acid amides such as stearamide, zinc stearate, calcium stearate, zinc balmitate, etc.
Fatty acid metal salts such as zinc myristate;
No. 245, various antioxidants such as hindered phenols, hindered amines, phosphorus compounds and sulfur compounds; blue pigments and dyes such as cobalt blue and phthalocyanine blue; magenta pigments and dyes such as cobalt violet; Various additives such as a fluorescent whitening agent and an ultraviolet absorber described in JP-A-254440 can be appropriately combined and contained. These additives are preferably contained as a masterbatch or compound of the resin.

The resin layer on the IM side of the resin-coated paper may be subjected to an activation treatment such as a corona discharge treatment or a flame treatment.
After the BC surface side resin layer is subjected to an activation treatment such as a corona discharge treatment or a flame treatment, various back layers can be applied to prevent charge. The backing layer may contain an inorganic antistatic agent such as colloidal silica, colloidal alumina, hectorite clay colloid and a mixture thereof described in JP-A-5-107688, a binder, an organic antistatic agent, or both. JP-A-59-2148
No. 79, a water-soluble synthetic polymer compound having a carboxyl group or a sulfo group or a salt thereof, or a hydrophilic synthetic polymer colloid substance or a salt thereof,
No. 214849, polymer latex described in
Starch described in JP-A-14131, polyvinylpyrrolidone described in JP-A-58-45248, JP-A-62-22095
Polyvinyl alcohol described in No. 0, JP-A-63-189
Polymers such as chitosan described in No. 859, JP-B-58-5
A hardening agent described in No. 6859, a matting agent described in JP-A-59-21849, a surfactant and the like can be appropriately combined and contained.

Next, the polyester film laminated on the resin-coated paper will be described.

The polyester film used in the present invention is preferably biaxially stretched. A uniaxially stretched or unstretched film is unfavorable because of its low mechanical strength as a support for an image receiving sheet. Among the conventionally proposed thermoplastic resin films such as polyolefins such as polypropylene, polyvinyl chloride, polyesters such as polyethylene terephthalate, polystyrene, methacrylate, polycarbonate and the like, the reason for using polyester films is glossy. This is because they are easy to obtain properties, are relatively difficult to be plastically deformed, are excellent in flexibility, and have small heat shrinkage.

The polyester in the present invention includes dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid naphthalenedicarboxylic acid, adipic acid, sebacic acid and dimethyl esters thereof, and ethylene glycol, diethylene glycol and trimethylene glycol. And polymers obtained by polycondensing diols such as tetramethylene glycol, cyclohexane dimethanol, 1,4-butanediol and neopentyl glycol. A specific example of such a polyester is polyethylene terephthalate (PE
T), polybutylene terephthalate (PBT), polyethylene-p-oxybenzoate, poly-1,4-cyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalate (PEN) and the like. Among these, PET and PEN are particularly preferred. Further, various additives such as an antioxidant, an antistatic agent, organic fine particles, and inorganic fine particles may be added to the polyester as long as the effects of the present invention are not impaired.

The polyester film used in the present invention has a specific gravity of 0.6 to 1.05, preferably 0.6 to 1.05.
It must be in the range of 5-0.95. That is, the specific gravity is lower than that of a normal polyester film. Specific gravity is 1.0
If it is 5 or more, the cushioning property is inferior.
If it is less than 0.6, there is a problem that the mechanical strength is insufficient and, for example, creases easily occur.

Examples of the method for achieving a low specific gravity include a method of interposing a different polymer in the film layer, a method of forming a void around the containing polymer particles,
Examples thereof include a method using a composition of a polyester and a styrene polymer having a syndiotactic structure as described in JP-A-10-77355, a method of forming a composite film with a low specific gravity layer, and the like.

In the present invention, it is preferable to have a composite structure of two or more layers in which at least the image forming surface side is a layer having a high specific gravity, and it is preferable that the difference in specific gravity between the composite layers is 0.25 or more. . With such a configuration, it is possible to reduce the surface roughness of the surface while maintaining the cushioning property, and it is possible to increase the glossiness and the adhesion to the head.

Now, assuming that the low specific gravity layer is the layer A, it is preferable to provide a layer (layer B) having a higher specific gravity than the layer A on at least the surface of the layer A on which an image is formed. Similarly, a layer having a higher specific gravity than the A layer (C layer) is also provided on the surface opposite to the B layer.
Is also preferable to increase the adhesiveness when laminating. The thickness and composition of the B layer and the C layer may be the same or different.

In order to improve the film winding property, inorganic or organic particles may be added to the layer B and / or the layer C. As the inorganic particles, those usually added to polyester can be used, and examples thereof include calcium carbonate, titanium dioxide, barium sulfate, alumina, and silica. Further, as the organic particles, silicon resin particles, crosslinked acrylic particles, crosslinked polystyrene particles, and the like can be used. The preferred average particle size of the inorganic particles is 0.1 to 1
0 μm, preferably 0.5 to 5 μm.

The amount of addition of the inorganic particles is 0.0
It is preferably 1 to 30% by weight, more preferably 0.01 to 30% by weight.
20% by weight. If the addition amount is less than 0.01% by weight, the slipperiness of the film may be reduced and the handleability may be deteriorated. Conversely, if the content exceeds 30% by weight, the inorganic particles may be shaved during stretching, and the roll may be soiled. However, the addition of the inorganic particles to the B layer, although the above-mentioned effects can be obtained, the surface smoothness and gloss are reduced. Or it is preferable not to add.

The lamination ratio is preferably such that the thickness of the layer A is 80% or more, more preferably 90% or more. If the thickness constituting ratio is less than 80%, sufficient cushioning properties cannot be obtained. On the other hand, if it is close to 100%, the effect of the layer provided thereon cannot be obtained, so the upper limit is preferably about 95%. By adopting such a configuration, the layer A
Adhesiveness, image quality, and the like can be further improved to other layers while obtaining a more desired cushioning property.

An aqueous paint may be applied to at least one surface of the polyester film. Preferably, it is applied to the surface on which the image receiving layer is provided. The water-based paint is applied before all the stretching of the film is completed, for example, after stretching in the longitudinal direction, and before stretching in the width direction, and is stretched together with the base film after the application.

The water-based paint is not particularly limited, and specific examples thereof include polyester-based, acrylic-based, urethane-based, vinyl-based, chlorine-based, olefin-based, modified olefin-based, fluorine-based, silicon-based, phenol-based, and styrene-based paints. Water-soluble or water-dispersible resins alone, mixtures and grafts can be mentioned, and if necessary, melamine-based, isocyanate-based, isocyanurate-based, epoxy-based, oxazoline-based, urea-based crosslinking agents, etc. May be added.

The polyester film is laminated on the image forming side of the resin-coated paper. As a method of laminating, for example, lamination with a conventionally known adhesive, extrusion lamination,
Bonding by thermal bonding, etc., is not particularly limited, and is appropriately selected according to the materials of the composite film and the resin covering paper. Specific examples of the adhesive include an ethylene-vinyl acetate copolymer, an emulsion adhesive such as polyvinyl acetate,
A water-soluble adhesive such as a polyester containing a carboxyl group may be used, and an adhesive for laminating may be an organic solvent solution type adhesive such as a polyurethane-based or acrylic-based adhesive.

When laminating, it is preferable that both or any of the laminating surfaces has been subjected to an activation treatment such as a corona discharge treatment or a flame treatment.

The thickness of the resin-coated paper is 100 to 240 μm,
The thickness of the polyester film is preferably 30 to 100 μm. Further, the ratio of the thickness of the resin-coated paper to the polyester-based film is preferably from 8: 1 to 1: 1. If the polyester-based film is thicker, a texture close to that of a silver halide photograph cannot be obtained, and the texture of a plastic film is undesirably lumpy. If the ratio is 8: 1 or more, the thickness of the support as a whole becomes too thick, and there is a concern that the transportability of the printer may be impaired.

The image receiving layer is not particularly limited as long as it can receive a dye diffused by heating from the ink layer of the ink sheet, and is basically formed of a binder and various additives. As a method for forming the image receiving layer on the surface of the support, a coating solution for an image receiving layer is prepared by dispersing or dissolving the components for forming the image receiving layer in a solvent, and then coating and drying the coating solution on the surface of the support. Examples of the method include a coating method and a laminating method in which a mixture having a component for forming an image receiving layer is melted and extruded and laminated on the surface of a support. The thickness of the image receiving layer formed on the surface of the support is generally from 0.5 to
It is 50 μm, preferably about 1 to 20 μm.

As the binder for the image receiving layer, various binders such as a vinyl chloride resin, a polyester resin, a polycarbonate resin, an acrylic resin, a polyvinyl acetal resin and various heat resistant resins can be used. The type of binder may be selected arbitrarily, but polyvinyl acetal-based resin or vinyl chloride-based resin is preferable in terms of image storability.

Examples of the polyvinyl acetal resin include a polyvinyl acetoacetal resin, a polyvinyl butyral resin, and a polyvinyl formal resin.
Examples of the vinyl chloride resin include a polyvinyl chloride resin and a vinyl chloride copolymer. Examples of the vinyl chloride copolymer include a copolymer of vinyl chloride and another monomer containing vinyl chloride at a ratio of 50 mol% or more as a monomer unit.

In addition to the polyvinyl acetal resin and the vinyl chloride resin, a polyester resin can also be suitably used as the image receiving layer for thermal transfer. Examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, and compounds described in JP-A-58-188695 and JP-A-62-244696. Examples of the polycarbonate resin include, for example, JP-A-62-169694.
Various compounds described in the above item can be used. Examples of the acrylic resin include polyacrylester.

The heat-resistant resin is not a resin having good heat resistance and extremely low softening point or glass transition point (Tg).
Various known heat-resistant resins can be used as long as they are appropriately compatible with the vinyl chloride resin and are substantially colorless. The term "heat resistance" as used herein means that the resin itself does not cause coloring such as yellowing when stored under heat, and the physical strength does not extremely deteriorate. The heat-resistant resin preferably has a softening point of 30 to 200 ° C, particularly preferably a Tg of 50 to 150 ° C. If the softening point is less than 30 ° C., the transfer of the heat transferable dye is not preferred because the ink sheet and the image receiving layer may be fused. The softening point is 200 ° C
If the ratio exceeds, the sensitivity of the image receiving layer is undesirably reduced.

Examples of the heat-resistant resin satisfying the above conditions include a phenol resin, a melamine resin, a urea resin, and a ketone resin. Among them, a urea aldehyde resin and a ketone resin are preferable. Urea aldehyde resin is obtained by condensation of urea and aldehydes (mainly formaldehyde), and ketone resin is obtained by condensation reaction of ketone and formaldehyde.

It is also preferable to use an acrylic resin containing styrene and acrylonitrile as essential components for the purpose of improving glossiness as a binder for the image receiving layer. Acrylic resins containing styrene and acrylonitrile as essential components include acrylonitrile-styrene copolymers (AS
Resin), acrylonitrile-special acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin),
An acrylonitrile-butadiene rubber-styrene copolymer (ABS resin), an acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS resin) and the like are mentioned, and among them, the AS resin is preferable. The acryl resin containing styrene and acrylonitrile as essential components preferably has an acrylonitrile content ratio of 10 to 50%, more preferably 15 to 30%.

These resins can be easily obtained as general products. For example, as the AS resin, Tyryl-76 can be used.
7, 769, 789, 783, style racks 709, 7
27 (Asahi Kasei Corporation), Estyrene AS series (Nippon Steel Chemical Co., Ltd.), Sebian series (Daicel Chemical Industries, Ltd.), Lightac series (Mitsui Chemicals, Inc.), Sunrex SAN-C, SAN-H, Collimate S-325 , S
-320, S-315 (Mitsubishi Monsanto Kasei), AA
As S resin, Vitax series and Baifunen series (Hitachi Kasei Kogyo), and as AES resin, Unibright series (Sumitomo Nogatack), JSRAE
S series (Nippon Synthetic Rubber Co., Ltd.)
ACS resin NF series (Showa Denko KK) and the like.

The following resins can be further used as a binder for the image receiving layer.

Polyolefin resins such as polypropylene, other halogenated vinyl resins (eg, polyvinylidene chloride), other vinyl polymers (eg, polyvinyl acetate), polystyrene resins, polyamide resins, and olefins such as ethylene and propylene And other vinyl monomers, ionomers, cellulose resins such as cellulose diacetate, polyurethane resins, polyimide resins, epoxy resins and the like.

Combination use of a polycarbonate resin and an aromatic polyester resin described in JP-A-5-246152; a polyvinyl acetal resin containing a carboxyl group described in JP-A-5-246151, and a component constituting the carboxyl group. The above-mentioned polyvinyl acetal resin which is a carboxyl group-containing addition-polymerizable monomer, a resin in which the carboxyl group-containing monomer unit accounts for 0.5 to 20% by weight of the polyvinyl acetal resin;
No. 246150, a vinyl chloride copolymer resin containing an epoxy group; a random-co-polycarbonate resin described in JP-A-5-131758;
No. 978, a polyester resin containing at least one of a diol component and an acid component containing an alicyclic compound; a polyester resin wherein the alicyclic compound is tricyclodecanedimethanol, cyclohexanedicarboxylic acid, cyclohexanedimethanol or cyclohexanediol (The durability of the image, such as light resistance, fingerprint resistance, and plasticity, is improved by the resin); a polyamide resin having an isophorozinamine component described in JP-A-4-299187, and a resin having a molecular weight of 5,000. A resin having a softening point of 50 to 170 ° C .; an aqueous resin comprising a hydrophobic resin liquid described in JP-A-4-347690;
No. 99188, a polyamide resin having an amine value of 3 or less, a polyamide resin having a molecular weight of 5,000 to 20,000 and a softening point of 50 to 170 ° C., and an acid component of dimer acid, propionic acid, adipic acid or azelaic acid The above polyamide resin selected from acids;
No. 9184, a polyurethane resin and a polyester resin; JP-A-4-223194, a polymer substance having a film-forming ability or a film-forming ability, and a composition containing the polymer substance and a B1 and / or B2 component Cured resin; synthetic resin described in JP-A-4-131287;
Urethane-modified polyester resin described in No. 43082;
A vinyl chloride / vinyl acetate copolymer having an average degree of polymerization of 400 or less described in JP-A-4-135794;
No. 7485, an acid resin having an acid value of 2 or more, for example, the following acid-modified resins: (a) those having an ester bond, for example, a polyester resin, a polyacrylate resin, a polycarbonate resin, a polyvinyl acetate resin, Styrene acrylate resin, vinyl toluene acrylate resin, (b) those having urethane bonds, such as polyurethane resins, (c) those having amide bonds, such as polyamide resins (nylon), (d) those having urea bonds, such as urea (E) resins having a highly polar bond, such as polycaprolactone resin, polystyrene resin and polyacrylonitrile resin (especially preferred among these are polyester resins); The thermoplastic resin and the reactive functional group (melamine skeleton) An amino resin having a urea skeleton, a benzoguanamine skeleton or a glycoluril skeleton, and at least two or more compounds having an isocyanate compound (an amino resin having a melamine skeleton, a urea skeleton, a benzoguanamine skeleton or a glycoluril skeleton, and an isocyanate compound) ); JP-A-7-40670
The thermoplastic resin having a number average molecular weight of 15,000 or less described in (1) is excellent in quick drying property during production, and excellent in releasability from a thermal transfer sheet during image formation, color density, and sharpness), and as the thermoplastic resin, 5-100% by weight of a binder of the image receiving layer of a vinyl chloride-styrene copolymer (vinyl chloride-acrylstyrene copolymer, vinyl chloride-vinyl acetate-acryl-styrene copolymer, vinyl chloride-vinyl acetate-styrene copolymer) Copolymer, vinyl chloride-butyl acryl-styrene copolymer, vinyl chloride-butyl acryl copolymer, vinyl chloride-methacryl-styrene copolymer, vinyl chloride-vinyl acetate-methacryl-styrene copolymer, vinyl chloride-butyl acryl -Methacryl-styrene copolymer, vinyl chloride-vinyl acetate-butyl acryl-methacryl An aldehyde-modified vinyl alcohol resin and a polyester resin having a number average molecular weight of 10,000 or less as described in JP-A-5-270151 (effects: image density, light resistance, fingerprint resistance, thermoplasticity, etc.); Improvement of durability), the above-mentioned polyester resin in which the aldehyde-modified vinyl alcohol resin has an aldehyde modification ratio of 30 to 50%, the above-mentioned polyester resin in which the average degree of polymerization of the aldehyde-modified vinyl alcohol resin is 200 to 3000, and the polyol of the above-mentioned polyester resin. The polyester resin wherein at least one part of the component and / or the acid component is an alicyclic compound, the polyester resin wherein the aldehyde modification is formalin, acetaldehyde or butyraldehyde (particularly preferably acetaldehyde or butyraldehyde); 115272 Tensile strength 200 kg / cm ² or more resins (effects described: prevention of cracks in the image-receiving layer, for example, polyester resins, polyurethane resins, butyral resins, polyolefin resins such as polypropylene, polyvinyl chloride, vinyl chloride・
JP-A-6-799; vinyl acetate copolymer resin, ionomer, cellulose resin such as cellulose diacetate, polycarbonate, etc. (particularly preferred are polyester resin and vinyl chloride-vinyl acetate copolymer resin);
No. 74, polyvinyl alcohol and -100 to 2
A mixture of a synthetic resin having a glass transition temperature of 0 ° C. and having a polar group with an emulsion;
No. 4, a mixture of an aqueous dispersion of a polyester resin insoluble or hardly soluble in a solvent and an aqueous dispersion of a thermoplastic resin other than the polyester resin; a polyoxyalkylene polyol described in JP-A-6-15966; Reaction product with organic polyisocyanate; JP-A-58-215398
No. 61-199997, JP-A-2-17889
And reaction products of polyester resins and polyisocyanates described in JP-A-2-86494;
No. 681, No. 1-123794, No. 3-126587
The reaction product of a vinyl chloride-vinyl acetate copolymer having active hydrogen and a polyisocyanate described in JP-A No.
No. 8646, a hydroxyl group-containing thermoplastic resin such as a polyvinyl acetal resin, the polyvinyl acetal resin having a polyvinyl alcohol unit content of 5 to 50% by weight, a vinyl chloride-vinyl acetate copolymer, and a polyvinyl alcohol unit content The vinyl chloride-vinyl acetate copolymer resin having an amount of 1 to 30% by weight, polyester,
Partially saponified polyvinyl acetate, partially or completely saponified product of vinyl chloride-vinyl acetate copolymer, acrylic resin, polyurethane resin, etc., particularly preferred are polyvinyl acetal resin and vinyl chloride-vinyl acetate copolymer, preferred polyvinyl acetal resin Is a polyvinyl formal resin, a polyvinyl acetoacetal resin and a polyvinyl butyral resin (effect: a cross-linked product comprising the above resin and a cross-linking agent is excellent in releasability, and is excellent in color density, sharpness, various durability and non-embossing property. The content of polyvinyl alcohol units described in JP-A-5-294076 is 10% by weight.
Polyvinyl acetal resin having the above (or 10 to 50% by weight), the above-mentioned polyvinyl acetal resin having a degree of polymerization of 100 to 10,000, and the like.

In the formation of the image receiving layer, the above-mentioned various resins utilize their reactive active points (if no reactive active points are present, they are applied to the resin) to obtain radiation, heat, moisture, catalyst, and the like. Crosslinking or curing may be carried out. In that case, a radiation-active monomer such as epoxy or acrylic, or a cross-linking agent such as isocyanate can be used,
These monomers and crosslinking agents may be added as they are to the image receiving layer, or may be encapsulated in microcapsules.

When a reactive dye is used in the present invention, the image-receiving layer contains, in addition to the binder, a dye fixing body capable of reacting with the dye precursor contained in the ink sheet, as described above. In a preferred embodiment of the present invention, when a post-chelate dye described below is contained in the ink layer, a metal source capable of forming a metal chelate with the post-chelate dye is contained in the image receiving layer. When a metal source is contained in the image receiving layer and a post-chelate dye is used in the ink layer of the ink sheet, the formed dye image can exhibit high transfer density, high image storability, and particularly excellent effects of preventing bleeding.

Examples of the metal source include inorganic or organic salts and metal complexes of metal ions. Among them, salts and complexes of organic acids are preferable. As metals, I to I of the periodic table
Monovalent and polyvalent metals belonging to Group VIII include
Among them, Al, Co, Cr, Cu, Fe, Mg, Mn, M
o, Ni, Sn, Ti and Zn are preferred, especially Ni,
Cu, Cr, Co and Zn are preferred. Specific examples of the metal source include salts of Ni ²⁺ , Cu ²⁺ , Cr ²⁺ , Co ²⁺ and Zn ²⁺ with fatty acids such as acetic acid and stearic acid, or aromatic carboxylic acids such as benzoic acid and salicylic acid. And salts with acids.

The complex represented by the following general formula (MI) is particularly preferable because it is stable and can be added to the image receiving layer and is substantially colorless.

General formula (MI) [M (Q ₁ ) _x (Q ₂ ) _y (Q ₃ ) _z ] ^{p +} (L ⁻ ) p In the formula, M is a metal ion, preferably Ni ²⁺ , Cu ^{2 +} , C
represents r ²⁺ , Co ²⁺ or Zn ²⁺ . Q ₁ , Q ₂ and Q ₃ each represent a coordination compound capable of coordinating with the metal ion represented by M, and may be the same or different. These coordination compounds can be selected, for example, from the coordination compounds described in Chelate Science (5) (Nankodo). L ⁻ represents an organic anion group, and specific examples thereof include a tetraphenylboron anion and an alkylbenzenesulfonic acid anion. x represents 1, 2 or 3, y represents 1, 2 or 0, z represents 1 or 0,
These are determined by whether the complex represented by the general formula (MI) is tetradentate or hexadentate, or Q ₁ ,
It is determined by the number of ligands of Q ₂ and Q ₃ . p represents 1 or 2.

As a specific example of this kind of metal source,
Compounds exemplified in U.S. Pat. No. 4,987,049 or compound Nos. Exemplified in JP-A-9-39423.
1 to 99 and the like. Usually, the addition amount of the metal source is preferably from 5 to 80% by weight, more preferably from 10 to 70% by weight, based on the binder of the image receiving layer. If the amount of the metal source in the image receiving layer is too large, the tint of the metal source appears in the color tone of the white background of the image receiving sheet, which is not preferable.

A release agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a pigment and the like may be added to the image receiving layer. Further, a plasticizer, a heat solvent and the like may be added as a sensitizer.

The release agent can improve the releasability between the ink layer of the ink sheet and the image receiving layer of the image receiving sheet.
Examples of such a release agent include silicone oils (including those referred to as silicone resins); solid waxes such as polyethylene wax, polypropylene wax, amide wax, Teflon (registered trademark) powder, and microclostalin wax; Fluorine compounds, silicon compounds or composites thereof, fluorine-based or phosphate-based surfactants; coupling agents; long-chain alkyl compounds; polyoxyalkyl polyols, etc., among which silicone oil is preferred.

Silicone oils are classified into two types: those that are simply added (simple addition type) and those that are cured or reacted (curing reaction type). In the case of the simple addition type, it is preferable to use a modified silicone oil in order to improve the compatibility with the binder. Examples of the modified silicone oil include polyester-modified silicone resin (or silicone-modified polyester resin), acryl-modified silicone resin (or silicone-modified acrylic resin), urethane-modified silicone resin (or silicon-modified urethane resin), and cellulose-modified silicone resin (or silicone-modified silicone resin). Cellulose resin), alkyd-modified silicone resin (or silicon-modified alkyd resin), epoxy-modified silicone resin (or silicon-modified epoxy resin), and the like.

The curing reaction types include amino-modified silicon having an amino group, epoxy-modified silicon having an epoxy group, isocyanato-modified silicon having an isocyanate group, alcohol-modified silicon having a hydroxyl group, and carboxyl-modified silicon having a carboxyl group. And the like, and are appropriately combined and used depending on the reaction form in order to perform reaction curing. For example, modified silicon having an amino group or a hydroxyl group reacts with modified silicon having an epoxy group, an isocyanato group, or a carboxyl group, respectively. Further, a catalyst-curable type is also preferably used, for example, alcohol-modified silicon using a carboxylate such as titanate, zinc, iron, tin or the like as a catalyst; And those composed of vinyl-modified silicon having a metal as a catalyst and vinyl-modified silicon having a part of an organic group of -H.

The ultraviolet absorber may be any as long as it functions as an ultraviolet absorber for dye images and is capable of thermal transfer.
For example, JP-A-59-158287 and JP-A-63-7468.
No. 6, No. 63-145089, No. 59-196292
Nos. 62-229594 and 63-122596
No. 61-283595, JP-A-1-204788
And compounds known to improve image durability in photographs and other image recording materials. The weight ratio of the binder to the ultraviolet absorber is preferably from 1:10 to 10: 1, and more preferably from 2: 8 to 7: 3.

Examples of the antioxidant include JP-A-59-182.
No. 785, No. 60-130735, JP-A-1-127
The antioxidants described in No. 387 and the like, and known compounds for improving image durability in photographs and other image recording materials can be exemplified.

Examples of the filler include inorganic fine particles and organic resin particles. As the inorganic fine particles,
Silica gel, calcium carbonate, titanium oxide, acid clay,
Activated clay, alumina and the like can be mentioned, and organic fine particles include resin particles such as fluorine resin particles, guanamine resin particles, acrylic resin particles, and silicon resin particles. These inorganic / organic resin particles vary depending on the specific gravity, but are preferably added in an amount of 0.1 to 70% by weight. Representative examples of the pigment include titanium white, calcium carbonate, zinc oxide, barium sulfate, silica, talc, clay, kaolin, activated clay, and acid clay.

Examples of the plasticizer include phthalates (dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, didecyl phthalate, etc.) and trimellitates (octyl trimellitate, i-nonyl trimellitate, Pyromellitic esters such as octyl pyromellitate, adipates and the like. Since excessive addition of the plasticizer deteriorates the storability of the image, the amount of the plasticizer is usually in the range of 0.1 to 30% by weight based on the binder of the image receiving layer.

A slippery backside layer may be provided on the backside of the image receiving sheet.

When a smooth back layer is provided on the back surface of the image receiving sheet, the resin used is preferably one having low dye-dyeability. Specifically, as such a resin, an acrylic resin, a polystyrene resin, a polyolefin resin, a polyamide resin, polyvinyl butyral, polyvinyl alcohol,
A cellulose acetate resin is exemplified. Also, JP-A-7-
The amorphous polyolefin resin described in 186557 can also be used.

In addition, curable resins obtained by curing polyvinyl butyral, melamine, cellulose, acrylic resin and the like by means of chelate, isocyanate, irradiation with radiation and the like are also preferable. Commercially available products include, for example, BR85, BR80 and BR113 (Mitsubishi Rayon Co., Ltd.) for an acrylic resin and AP as an amorphous polyolefin resin.
L6509, 130A, 291S, 150R (Mitsui Petrochemical Industries, Ltd.), Zeonex 480, 250, 480S
(Zeon Corporation), polyvinyl butyral resin 30
00-1 (Denki Kagaku Kogyo Co., Ltd.), as polyvinyl alcohol resin, SMR-20H, SMR-20HH, C-2
0, C-10, MA-23, PA-20, PA-15
(Shin-Etsu Chemical Co., Ltd.), L as cellulose acetate resin
-30, LT-35 (above, Daicel Chemical Industries, Ltd.), and melamine resin such as Cymel 303 (Mitsui Said), but are not limited thereto.

In order to improve the suitability for automatic sheet feeding, at least one of the layers constituting the back surface of the image receiving sheet may contain an organic and / or inorganic filler. Specific examples include polyethylene wax, bisamide, nylon, acrylic resin, cross-linked polystyrene, silicone resin, silicone rubber, talc, calcium carbonate, titanium oxide and the like, but are not particularly limited and any can be used.

Among the above, nylon filler is particularly preferable from the viewpoint of suppressing abrasion of the paper feed rubber roller of the printer and fluctuation of frictional characteristics of the roller due to transfer. As a nylon filler, the molecular weight is 100,000 to 90.
It is preferable that the particles have an average particle diameter of 0.01 to 30 μm, and more preferably have a molecular weight of 100,000 to 500,000 and an average particle diameter of 0.01 to 10 μm.
As the type of nylon filler, nylon 12 filler is more preferable than nylon 6 or nylon 66 because it has excellent water resistance and does not change its properties due to water absorption.

The nylon filler has a high melting point, is thermally stable, and has good oil resistance, chemical resistance, and the like, and thus is hardly dyed with a dye. Further, it has a self-lubricating property, a low coefficient of friction, and a molecular weight of 100,000 to 900,000 hardly wears and does not damage a mating material. The preferred average particle size is 0.1 to 30 μm. If the particle diameter is too small, the filler will be hidden in the back-side constituent layer, and will not fulfill the function of sufficient slipperiness, and if the particle diameter is too large, the protrusion from the back-side constituent layer will increase, and as a result, the friction coefficient will be reduced. However, it is not preferable because the height of the filler is increased or the filler is missing. Incidentally, the amount of the filler to be added depends on the amount of the resin 10 in the layer to be added.
The range of 0.01 to 200 parts by weight relative to 0 parts by weight is preferable.

The center line average surface roughness SRa of the surface of the back layer is preferably 0.5 to 2.5 μm. The average number of projections per unit area is preferably 2000 to 4500 / mm ² . As a method of giving such a property,
For example, in addition to adjusting using the filler as described above, the surface shape of the cooling roll at the time of resin extrusion coating is set to the above-described property, and when the extruded resin is cooled, the shape is also transferred by transferring the shape. I can do it.

Between the lubricating back layer and the surface on which it is provided,
An intermediate layer may be provided for the purpose of increasing the adhesive strength. As a preferred embodiment of the intermediate layer, an intermediate layer having a reaction-curable resin is provided. As the reaction curable resin, JP-A-6-25
It is preferable to use a thermosetting resin and / or an ionizing radiation-curable resin as described in No. 5276.

The intermediate layer having the same structure may be provided between the image receiving layer and the surface on which the image receiving layer is provided.

As the heat diffusing dye to be contained in the ink layer used in the present invention, conventionally known dyes can be used, and there is no particular limitation, but from the viewpoint of obtaining good image storability, the reaction type dye described above is used. It is preferable to use a dye.

As described above, the reaction type dye is a dye capable of forming an image by reacting the dye precursor contained in the ink layer side with the dye fixing body contained in the image receiving layer side by thermal transfer. Show. Specifically, known reactive dyes including those described above can be used, but in the present invention, from the viewpoint of particularly excellent image storability, a combination of a post-chelating dye and a metal source is used. Is preferred.

The support for the ink sheet is not particularly limited as long as it has good dimensional stability and can withstand the heat at the time of recording with a thermal head, and any known support can be used.

Examples of the binder for the ink layer include cellulose resins such as cellulose adducts, cellulose esters and cellulose ethers; polyvinyl acetal resins such as polyvinyl alcohol, polyvinyl formal, polyvinyl acetoacetal and polyvinyl butyral; polyvinyl pyrrolidone, polyvinyl acetate; Vinyl resins such as polyacrylamide, styrene resin, poly (meth) acrylic acid ester, poly (meth) acrylic acid, (meth) acrylic acid copolymer; rubber resins, ionomer resins, olefin resins, polyester resins And the like. Among these resins, polyvinyl butyral, polyvinyl acetoacetal, or cellulosic resins having excellent storage stability are preferable.

As the binder of the ink layer, the following resins can be further used.

A reaction product of an isocyanate and a compound having active hydrogen selected from polyvinyl butyral, polyvinyl formal, polyester polyol and acrylic polyol described in JP-B-5-78437, isocyanate is a diisocyanate. The reaction product, which is an isocyanate or a triisocyanate, and the reaction product in an amount of 10 to 200 parts by weight based on 100 parts by weight of the compound having active hydrogen; natural and / or semi-synthetic water-soluble polymer Examples of the organic solvent-soluble polymer in which an intramolecular hydroxyl group is esterified and / or urethanized, and natural and / or semi-synthetic water-soluble polymers include α-glucose α-glucose.
Starch which is a polymer of 1,4-glucoside bond, water-soluble derivative of cellulose which is a polymer of β-1,4-glucoside bond, β-1,4-pyranose ring
Alginic acid and glucose, which are glucoside-linked polymers
It is a polymer containing D-glucopyranose as a unit, which is made from maltotriose, which is a dimer, pullulan, which is a water-soluble polysaccharide repeatedly linked by 1,6-bonds of α-D-1,6-glucose, and sucrose. Dextran, linear β- in which D-glucose is β-glucoside-linked by 1,3 bond
1,3-glucan curdlan, etc .;
No. 4393, cellulose acetate having a degree of acetylation of 2.4 or more and a total degree of substitution of 2.7 or more; polyvinyl alcohol (Tg = 85 ° C.), polyvinyl acetate (Tg = 32)
° C), vinyl chloride / vinyl acetate copolymer (Tg = 77
C), polyvinyl butyral (Tg = 8
4 ° C.), polyvinyl acetoacetal (Tg = 110)
C)), vinyl resins such as polyacrylamide (Tg = 165 ° C), polyester resins such as aliphatic polyester (Tg = 130 ° C);
JP-A-7-52564 describes a reaction product of an isocyanate and a polyvinyl butyral containing 15 to 40% by weight of a vinyl alcohol part, and the isocyanate is a diisocyanate or a triisocyanate. The above reaction products, specifically, para-phenylenediisocyanate, 1-chloro-2,4-phenylenediisocyanate, 2-chloro-1,4-phenylenediisocyanate, 2,4-toluene diisocyanate , 2,
6-toluene diisocyanate, hexamethylene diisocyanate, 4,4'-biphenylene diisocyanate, 4,4 ', 4 "-trimethyl-3,3', 2-triisocyanato-2,4,6- Triphenyl cyanurate and the like; phenyl isocyanato-modified polyvinyl acetal resin of the formula I described in JP-A-7-32742;
No. 155,935, one type of isocyanate-reactive cellulose or isocyanate-reactive acetal resin, isocyanate-reactive acetal resin, isocyanate-reactive vinyl resin, isocyanate-reactive acrylic resin, isocyanate-reactive phenoxy Cured product of a composition containing one resin selected from a resin and an isocyanate-reactive styrene resin and a polyisocyanate compound; a polyvinyl butyral resin (preferably having a molecular weight of 6
Acrylic-modified cellulose-based resin having a glass transition temperature of 60 ° C. or more, more preferably 70 ° C. to 110 ° C. or less, and having a vinyl alcohol portion of 10% to 40%, preferably 15% to 30% by weight in a polyvinyl butyral resin. As the resin and the cellulose-based resin, a cellulose-based resin (preferably ethylcellulose) such as ethylcellulose, hydroxyethylcellulose, ethylhydroxycellulose, hydroxypropylcellulose, methylcellulose, cellulose acetate, and cellulose butyrate, and the above-mentioned cellulose-based resin are modified with an acrylic resin. Examples of the organic solvent used at this time include ester solvents such as methyl formate, ethyl formate, ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone and the like. Ketone solvents, toluene, benzene, hydrocarbon solvents such as xylene, include ether solvents such as n- butyl ether, cellulose resin preferably used in a concentration of about 5 to 50 wt%.

One of the above various binders can be used alone, or two or more of them can be used in combination.

The post-chelating dye to be contained in the ink layer in the dye-containing region is not particularly limited as long as thermal transfer is possible, and various known compounds can be appropriately selected and used. Specifically, for example, Japanese Patent Application Laid-Open No. 59-78
Nos. 893 and 59-109349, JP-A-4-949.
No. 74, 4-97894, 4-89292, cyan dyes, magenta dyes, yellow dyes and the like can be used.

Among the above-mentioned dyes, it is preferable to use a methine dye which can form a bidentate chelate with a metal source because the object of the present invention is more effectively exhibited. Examples of such a dye include a dye represented by the following general formula (1).

[0104]

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In the formula, X represents an atomic group having at least a bidentate chelate-forming group or atom, Y represents an atomic group necessary for forming an aromatic carbocyclic or heterocyclic ring,
₁ , R ₂ and R ₃ each represent a hydrogen atom, a halogen atom or 1
Represents a valent substituent. n represents 0, 1 or 2. Y is preferably an atomic group forming a 5- to 6-membered aromatic carbocyclic or heterocyclic ring, and the ring may further have a substituent.

X is particularly preferably represented by the following general formula (2).

[0107]

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In the formula, Z represents an atom group necessary for forming an aromatic nitrogen-containing heterocyclic ring substituted with a group containing at least one chelatable nitrogen atom.

Specific examples of the ring include benzene, pyridine, pyrimidine, furan, thiophene, thiazole, imidazole, naphthalene and the like. These rings may form a conjugation ring with another carbon ring (such as a benzene ring) or a heterocyclic ring (such as a pyridine ring).

The substituent on the ring includes an alkyl group, an aryl group, an acyl group, an amino group, a nitro group, a cyano group,
Examples thereof include an acylamino group, an alkoxy group, a hydroxy group, an alkoxycarbonyl group, and a halogen atom, and these groups may be further substituted.

The halogen atom represented by R ₁ , R ₂ and R ₃ is a fluorine atom, a chlorine atom and the like, and the monovalent substituent is an alkyl group, an alkoxy group, a cyano group and an alkoxycarbonyl group. No.

As X =, those represented by the following general formulas (3) to (6) are particularly preferred.

[0113]

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In the formula, R ₄ and R ₅ each represent a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.) or a monovalent substituent (an alkyl group, an aryl group, an acyl group, an amino group, a nitro group). Group, cyano group, acylamino group, alkoxy group, hydroxyl group, alkoxycarbonyl group, etc.).

Specific examples of the compounds are shown below, but the present invention is not limited thereto.

[0116]

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[0117]

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[0118]

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[0119]

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The content of these post-chelating dyes cannot be unconditionally determined from the properties of the respective dyes, the solubility in the binder, the purpose of use, and the like, but is usually from 10 to 80% by weight based on the total weight of each dye-containing region. Used in

Various additives can be appropriately added to the ink layer in addition to the above components. Additives include the above-mentioned silicone resin, silicone oil (reaction curing type is also possible), silicone-modified resin, fluorine resin, surfactant, wax and other release compounds; metal fine powder, silica gel, metal oxide, Fillers such as carbon black and resin fine powder; curing agents capable of reacting with binder components (radiation-active compounds such as isocyanates, acrylics and epoxies)
And the like.

The ink sheet is not limited to the two-layer structure including the support and the ink layer, and may have other layers. For example, an overcoat layer may be provided on the surface of the ink layer for the purpose of preventing fusion with the image receiving layer and offset (blocking) of the dye.

The support of the ink sheet has a subbing layer for the purpose of improving the adhesiveness of the ink layer to the binder and preventing transfer and dyeing of the sublimable dye to the support. Is also good. Further, a sticking prevention layer may be provided on the back surface of the support (the side opposite to the ink layer) for the purpose of preventing the head from fusing to the support, sticking, and wrinkling of the ink sheet. The above overcoat layer,
The thicknesses of the undercoat layer and the anti-sticking layer are usually 0.1.
1 to 1 μm.

Examples of the binder resin used for the sticking layer include cellulose resins such as ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, and nitrified cotton, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, and the like. Vinyl resins such as polyvinyl acetal and polyvinylpyrrolidone, acrylic resins such as polymethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polyacrylamide, acrylonitrile / styrene copolymer, polyamide resins,
Examples thereof include vinyl toluene resin, coumarone indene resin, polyester resin, polyurethane resin, silicon-modified urethane resin, and fluorine-modified urethane resin.

These resins may be used as a mixture. In order to further improve heat resistance, of the above resins, use a resin having a reactive group such as a hydroxyl group,
A crosslinked resin layer may be formed by using a polyisocyanate or the like as a crosslinking agent. Further, in order to improve the slipperiness, a solid or liquid release agent or lubricant may be added to impart heat-resistant lubrication. Examples of the release agent or lubricant include various waxes such as polyethylene wax and paraffin wax, higher aliphatic alcohols, oreganopolysiloxane,
Anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, fluorine surfactants,
Organic carboxylic acids and derivatives thereof, fluorine-based resins, silicon-based resins, fine particles of inorganic compounds such as talc, silica and the like can be used. A preferable addition amount of the slipping agent or the release agent is 5 to 50% by weight, preferably 10 to 30% by weight based on the total solid content of the sticking layer.

The ink sheet is prepared by dispersing or dissolving the various components for forming the ink layer in a solvent to prepare an ink layer forming coating liquid, and applying the coating liquid to the surface of the ink sheet support, for example, by gravure printing. It can be manufactured by coating and drying in a system. The thickness of the ink layer to be formed is usually from 0.2 to 10 μm, preferably from 0.3 to 3 μm.

In the ink layer, a sensitizer of 50 to 150 is used.
It may contain a low molecular weight substance having a melting point of ° C. If the melting point is lower than 50 ° C., the sensitizer is likely to migrate to the surface of the ink layer, causing problems such as blocking, while the melting point is lower than 15 ° C.
If the temperature exceeds 0 ° C., the sensitizing effect is undesirably sharply reduced.

Further, the molecular weight of the sensitizer is preferably in the range of 100 to 1500. If the molecular weight is less than 100, the melting point is 50 ° C
Is difficult to maintain, while the molecular weight is 15
If it exceeds 00, the sharpening of the melting of the sensitizer at the time of thermal transfer is lost and the sensitizing effect becomes insufficient, which is not preferable.

The sensitizer is preferably used in an amount of 1 to 100 parts by weight per 100 parts by weight of the binder forming the ink layer. If the amount is less than 1 part by weight, it is difficult to obtain a satisfactory sensitizing effect.

The sensitizer as described above may be any known low molecular weight substance as long as it has a melting point of 50 to 150 ° C., but is preferably a thermoplastic resin oligomer such as a polyurethane oligomer, a polystyrene oligomer, a polyester oligomer, or a polyether. Acrylic oligomer, polyethylene oligomer, polyvinyl chloride oligomer, polyvinyl acetate oligomer, ethylene-vinyl acetate copolymer oligomer, ethylene-acryl copolymer oligomer, polyoxyethylene oligomer, polyoxypropylene oligomer, polyoxyethylene propylene oligomer, etc. Various oligomers, fatty acids such as myristic acid, palmitic acid, margaric acid, stearic acid, arachinic acid, montanic acid, caproic acid amide, caprylic acid amide, lauric acid amide, stearin Amide, oleic acid amide, fatty acid amide such as eicosenoic acid amide, methyl behenate, pentadecyl palmitate, hexacosyl stearate,
Carbamate [1,4-phenylenebis (methylene)]
Other fatty acid esters such as bisdimethyl ester, etc.
Examples include aromatic compounds such as 1,4-dicyclohexylbenzene, benzoic acid, aminobenzophenone, dimethyl terephthalate, fluoranthene, phenols, naphthalenes, and phenoxys, and various waxes.

In the present invention, the image receiving sheet and / or the ink sheet may have an antistatic function. In order to provide an antistatic function, a conventionally known technique can be used. That is, conductive substances such as metal, metal oxide, and carbon fine powder, and organic compounds called “antistatic agents” (cationic, anionic, amphoteric, nonionic surfactants, polysiloxanes, etc.) System), electron-conductive inorganic fine powder (fine powder such as titanium oxide, zinc oxide, tin oxide, indium oxide, etc.) mixed with impurities and baked to disturb the crystal lattice and enhance electron conductivity. A well-known conductive substance such as one subjected to doping treatment) can be used. The conductive substance as described above may be contained in at least one of the constituent layers of the image receiving sheet and / or the ink sheet, or at least one layer is formed as a conductive layer to which a paint containing the conductive substance is applied. You may. Of course, the combination is also preferable.

When the above-mentioned conductive substance is used as the conductive layer, the conductive coating can be prepared by a usual method. Preferably, the antistatic agent is used in the form of an alcohol solution or an aqueous solution, The inorganic fine powder is used as it is, and is prepared by dissolving or dispersing the former in an organic solvent solution of a resin to be a binder, and dispersing the latter in the latter.

The resin to be used as a binder for the conductive paint is a thermosetting resin such as a thermosetting polyacrylate resin or a polyurethane resin, or a resin such as a polyvinyl chloride resin, a polyvinyl butyral resin, or a polyester resin. It is preferable to use a suitable thermoplastic resin. In addition, it is preferable to determine the ratio of the binder to the conductive substance so that the surface resistivity of the conductive layer after coating and drying (after curing in some cases) is 1 × 10 ¹⁰ Ωcm or less.

The prepared conductive paint was prepared by a usual coating method,
For example, coating with a blade coater, a gravure coater, or the like, spray coating, or the like can be employed.

In the case where a conductive layer is provided on the core material to provide a charge treatment function, an aqueous solution of an antistatic agent is applied, or the above-mentioned electron conductive inorganic fine powder is mixed with a synthetic resin emulsion.
It is preferable to disperse or dissolve in a water-based paint such as an aqueous solution of a synthetic rubber latex or an aqueous solution resin to form a dry coating film. Examples of the synthetic resin emulsion include emulsions of a polyacrylate resin and a polyurethane resin, and the like. Examples of the synthetic rubber latex include a rubber latex such as methyl methacrylate-butadiene and styrene-butadiene. Aqueous solutions such as acrylamide resin and starch can be exemplified. Alternatively, an aqueous solution of an antistatic agent may be more easily spray-coated.

When an image is formed using a post-chelating dye and a metal source, it is preferable to provide a heating step after transferring the dye, and to perform a heat treatment on the resulting transferred image. As the method of the heat treatment, a known method, that is, a hot plate, a heat roller, a thermal head (which may be the same as or different from that at the time of dye transfer) or the like via a thin film material can be used, and there is no particular limitation.

[0137]

Next, the present invention will be described more specifically with reference to examples. In the following examples, “parts” means “parts by weight” and “%” means “% by weight” unless otherwise specified.

<Preparation of Polyester Film> (Film 1) PET and polytetramethylene glycol (hereinafter, PTMG, molecular weight 40
00) and 1% by weight of a PET-PTMG copolymer produced by adding PTMG at the time of polymerization of PET so as to have a weight ratio of 1: 1 with polyethylene terephthalate (hereinafter referred to as PE).
T) Using a mixture of 90% of resin and 9% of polystyrene (hereinafter, PS) resin (amorphous, Styron 666: manufactured by Asahi Kasei Kogyo Co., Ltd.), a vented twin-screw extruder heated to 270 to 300 ° C. It was supplied and formed into a sheet from an extruded T-die while being degassed and dried by a vacuum pump. Further, the sheet was cooled and solidified by a cooling drum having a surface temperature of 25 ° C., led to a group of rolls heated to 80 to 100 ° C., stretched three times in the machine axis direction, and cooled by a group of rolls of 25 ° C.
Subsequently, the longitudinally stretched film was guided to a tenter while holding both ends of the film with clips, and was horizontally stretched 3.6 times in a direction perpendicular to the machine axis direction in an atmosphere heated to 115 ° C. Thereafter, heat fixation is performed at 220 ° C. in a tenter, and then gradually cooled, then cooled to room temperature and wound up, and has a thickness of 95 μm and a specific gravity of 1.
2 was obtained.

(Film 2) In film 1, PS
Was replaced with polypropylene (hereinafter referred to as PP) to obtain a film 2 having a thickness of 95 μm and a specific gravity of 0.9 in the same manner.

(Film 3) In film 1, PS
Instead of syndiotactic polystyrene (hereinafter S
YN-PS) resin (Zarek A100: manufactured by Idemitsu Petrochemical Co., Ltd.) except that a thickness of 95 μm and a specific gravity of 0.
8 was obtained.

(Film 4) As a raw material of the A layer, P
The weight ratio of ET to PTMG (molecular weight 4000) is 1: 1
A mixture of 1% of PET-PTMG copolymer produced by adding PTMG at the time of polymerization of PET, 94% of PET resin and 5% of SYS-PS resin (Zarek A100: manufactured by Idemitsu Petrochemical Co., Ltd.) is used. , As a raw material of the B layer,
A mixed chip of 99% PET and 1% calcium carbonate (Softon 3200 manufactured by Shiroishi Calcium Co., Ltd.) was vacuum dried at 180 ° C. for 3 hours, and these raw materials were supplied to separate vented twin-screw extruders and kneaded. A layer is an inner layer,
The layer A and the layer B were laminated and extruded using a co-extrusion die so that the layer B had a three-layer structure of outer layers (B / A / B).
Further, the sheet was cooled and solidified by a cooling drum having a surface temperature of 25 ° C., led to a group of rolls heated to 80 to 100 ° C., stretched three times in the machine axis direction, and cooled by a group of rolls of 25 ° C. Subsequently, both ends of the longitudinally stretched film were guided to a tenter while holding both ends with clips, and were horizontally stretched 3.6 times in a direction perpendicular to the machine axis direction in an atmosphere heated to 115 ° C. Thereafter, the film was heat-set at 220 ° C. in a tenter, cooled slowly to room temperature after uniform cooling, and wound up to obtain a film 4 having a thickness of 95 μm and a specific gravity of 1.1. The thickness configuration is 5/90/5
Met.

(Film 5) In the film 4, the amounts of PET and SYS-PS as the raw materials of the layer A were adjusted to 90, respectively.
%, 9%, and wound up in the same manner as Film 4.
Film 5 having a thickness of 95 μm and a specific gravity of 0.8 was prepared. The thickness configuration was 5/90/5.

(Film 6) In the film 4, the amounts of PET and SYS-PS as the raw materials of the layer A were set to 89, respectively.
% And 10%, and wound up in the same manner as the film 4 to prepare a film 6 having a thickness of 95 μm and a specific gravity of 0.7. The thickness configuration was 5/90/5.

(Film 7) In the film 4, the amounts of PET and SYS-PS as raw materials for the layer A were adjusted to 88
%, 11%, and the amounts of PET and calcium carbonate in the layer B were changed to 95% and 5%, respectively.
m and a specific gravity of 0.6 were prepared. Thickness configuration is 4
/ 92/4.

(Film 8) In the film 7, the amounts of the PET and SYS-PS as the raw materials of the layer A were adjusted to 86
% And 13%, and wound up in the same manner as the film 7 to produce a film 8 having a thickness of 95 μm and a specific gravity of 0.5. The thickness configuration was 4/92/4.

(Film 9) The film 6 was wound in the same manner as in the film 6 except that the extrusion conditions were adjusted.
A film 9 having a specific gravity of 0.7 and a specific gravity of 0.7 was prepared.

(Film 10) The film 6 was wound in the same manner as in the film 6 except that the extrusion conditions were adjusted.
Film 10 having a thickness of 0 μm and a specific gravity of 0.7 was produced.

<Preparation of resin-coated paper> Hardwood bleached kraft pulp 80% and hardwood bleached sulfite pulp 20%
Is mixed with the fiber length of the pulp after beating (JA
PAN TAPPI paper pulp test method No. 52-89
After beaten so that the length-weighted average fiber length measured in accordance with the “paper and pulp fiber length test method” is 0.56 mm, 100 parts of pulp is treated with cationized starch 3
Part, anionized polyacrylamide 0.2 part, epoxidized higher fatty acid amide 0.2 part, alkyl ketene dimer emulsion (as ketene dimer) 0.4 part, polyamide epichlorohydrin resin 0.4 part and an appropriate amount of fluorescence enhancement A whitening agent, a blue dye, and a red dye were added to prepare a stock slurry. Thereafter, the stock slurry is placed on a fourdrinier paper machine running at 200 m / min to form a web while giving appropriate turbulence, and 15 to 100 kg in a wet part.
After performing a three-stage wet press in which the linear pressure was adjusted in the range of / cm, a treatment was performed with a smoothing roll, and in the subsequent drying part, a two-stage in which the linear pressure was adjusted in the range of 30 kg / cm to 70 kg / cm. After performing the pressing under a gentle pressure, it was dried.
Then, during the drying, 4 parts of carboxy-modified polyvinyl alcohol, 0.05 parts of a fluorescent whitening agent, and 0.002 of a blue dye
Parts, 4 parts of sodium chloride and 92 parts of water, and a size press liquid is subjected to 25 g / m ² size pressing, and the finally obtained base paper is dried so that the moisture content of the base paper becomes 8% by absolute dry moisture, and the linear pressure is 70 kg / m ^2. machine calendering in cm and thickness 13
Base paper A having a thickness of 0 μm, a density of 1.04 g / cm ³ , and a center-side average roughness SRa of 1.1 to 1.2 μm on the front side was manufactured.

A base paper B having a thickness of 95 μm and a base paper C having a thickness of 170 μm were produced in the same manner as described above except for the thickness.

Next, after the BC surface was subjected to corona discharge treatment, any of the following resin compositions R1 to R4 was applied to the BC surface at a resin temperature of 315 ° C. to a thickness of 20 μm and a running speed of the base paper of 200 m.
/ Min. At this time, the cooling roll used had a roughness such that the square value of the center plane average roughness SRa of the back layer surface after coating the following back layer was 0.75 μm ² . The cooling roll used was a cooling roll roughened by a liquid honing method and operated at a cooling water temperature of 12 ° C.

(Resin composition R1) HDPE resin (density 0.967 g / cm ³ , MFR = 15 g / 10 min) 80
Part, LDPE resin (density 0.926 g / cm ³ , MFR
= 0.6 g / 10 minutes) A compound resin composition prepared by melting and mixing 20 parts in advance using a melt extruder, and used as pellets thereof.

(Resin composition R2) HDPE resin and LDP
Same as R1 except that the amount of E resin was 60 parts and 40 parts, respectively.

(Resin composition R3) HDPE resin and LDP
Same as R1 except that the amount of E resin was 30 parts and 70 parts, respectively.

(Resin composition R4) HDPE resin and LDP
Same as R1 except that the amounts of E resin were 0 parts and 100 parts, respectively.

Subsequently, after the surface of the base paper was subjected to a corona discharge treatment, the surface was coated with LDPE resin (density 0.920 g / cm
³ , MFR = 8.5 g / 10 min) 47.5%, 50% anatase type titanium dioxide pigment surface-treated with hydrous aluminum hydroxide (0.75% as Al ₂ O ₃ relative to titanium dioxide) and stearic acid 20 parts of a titanium dioxide pigment master patch consisting of 2.5% zinc, LDPE resin (density 0.920 g / cm ³ , MFR = 4.5 g / 10 min)
65 parts and HDPE resin (density 0.970 g / cm ³ , M
(FR = 7.0 g / 10 min) 15 parts of the resin composition was melt-extruded and coated at a resin temperature of 315 ° C. to a thickness of 15 μm at a running speed of the base paper of 200 m / min. still,
The melt extrusion coating of the front and back polyethylene resins was performed by a so-called tandem method in which successive extrusion coating was performed.

Further, before the front and back resin layers are processed and wound up, the BC side resin layer surface of the resin-coated paper is subjected to a corona discharge treatment, and then, as a dry weight, colloidal silica: styrene-based latex = 1: 1. And a coating amount of 0.21 g / m ² as a latex content (calculated on a solid weight) of a coating solution for a back layer containing an appropriate amount of a coating aid in addition to 0.021 g / m ² of sodium polystyrene sulfonate. Was applied on-machine.

The polyester films 1 to 10 obtained as described above, the base papers A to C, and the BC side resin composition R1
To R4 were combined as shown in Table 1 to prepare support samples 1 to 15 for an image receiving sheet. The bonding between the polyester-based film and the resin-coated paper was performed by melting the polyethylene-based adhesive between the film and the resin-coated paper at 315 ° C., extruding, and then cooling through a cooling roll. Before lamination, the lamination surface of the resin-coated paper was subjected to corona discharge treatment. The thickness of the adhesive layer was adjusted to be 10 μm.

[0158]

[Table 1]

Example 1 <Preparation of Image-Receiving Sheet> As the support of the image-receiving sheet, the films 1 to 15 prepared above were used. An anchor layer having the following composition and an image-receiving layer were applied in this order on the polyester film surface. An anchor layer having a thickness of 0.2 μm and an image receiving layer having a thickness of 4 μm were formed, and image receiving sheets 1 to 15 were obtained.

(Anchor Layer) Polyvinyl Butyral (Sekisui Chemical Co., Ltd .: Eslec BL-1) 7.5 parts Isocyanate (Nippon Polyurethane Industry Co., Ltd .: Coronate HX) 2.5 parts Methyl ethyl ketone 80 parts Butyl acetate 10 parts (Image receiving) Layer) Polyvinyl butyral (Sekisui Chemical Co., Ltd .: Esrec BX-1) 6.5 parts Metal source (MS-1) 3.0 parts Polyester modified silicon (Shin-Etsu Chemical Co., Ltd .: X-24-8300) 0.5 parts Methyl ethyl ketone 80 parts butyl acetate 10 parts MS-1: Ni ²⁺ as _{(NH 2 COCH 2 NH 2)} 3 · 2B (C 6 H 5) 4 < Preparation of ink sheet 1> support, a thickness of 0.1μm on one side 6 μm-thick PET film provided with a heat-resistant lubricating layer (SP-712: manufactured by Dainichi Seika) (Lumirror 6CF531 manufactured by Toray Industries, Inc.) The back surface of the heat-resistant slip layer, having the following composition yellow, magenta, each ink layer and reheat treatment layer of cyan was coated by a gravure process (coating amount after drying 1.1 g / m ^3), yellow, magenta , The cyan ink layers and the heat treatment layer in the order shown in FIG.
An ink sheet formed in the following manner (referred to as "surface sequential") was obtained.

(Yellow Ink Layer) Exemplified Compound 26 3.0 parts Polyvinyl butyral (Denka Butyral KY-24, manufactured by Denki Kagaku Kogyo Co., Ltd.) 5.5 parts Epoxy-modified acrylic resin (Reseda GP-305, manufactured by Toa Gosei Chemical Co., Ltd.) 1.0 part Urethane-modified silicone oil (manufactured by Dainichi Seika: Dialomer SP-2105) 0.5 part Methyl ethyl ketone 80 parts Toluene 10 parts (magenta ink layer) Exemplary compound 25 3.0 parts Polyvinyl butyral (Denka butyral KY-24) : 5.5 parts) Epoxy-modified acrylic resin (Reseda GP-305: above) 1.0 part Urethane-modified silicone oil (Dialomer SP-2105: above) 0.5 parts Methyl ethyl ketone 80 parts Toluene 10 parts (cyan) Ink layer) Exemplified compound 28 3.0 parts Polyvinyl butyl Tylal (Denka butyral KY-24: supra) 5.5 parts Epoxy-modified acrylic resin (Reseda GP-305: supra) 1.0 part Urethane-modified silicone oil (Dialomer SP-2105: supra) 0.5 part Methyl ethyl ketone 80 parts Toluene 10 parts (reheating treatment layer) Metal source (MS-1) 0.1 part Polyvinyl acetal (denka butyral KY-24: supra) 5.9 parts Polymethyl methacrylate (Reseda GP-305: supra) 3.5 parts Urethane-modified silicone oil (Dialomer SP-2105: supra) 0.5 parts <Image formation> (Step pattern image formation) The image-receiving layer part of the thermal transfer image-receiving sheet and the ink sheet produced by the above procedure. The ink layers were overlapped, the resolution was 12 dots / mm, and the average resistance was 3
Pressure contact with 100Ω thermal head with platen roll,
The yellow, magenta, and cyan step patterns, which were sequentially increased in the applied energy range of 5 to 80 mJ / mm ^2, were heated from the back side of the ink layer at a feed speed of 10 msec / line to transfer the dye onto the image receiving layer. Then, the reheat-treated layer and the image-receiving sheet to which the dye has been transferred are pressed against each other with the same thermal head and a platen roll, and the applied energy is 50 mJ / mm ² and the feeding speed is 8.5 msec / lin.
Under the condition of e, the reheating treatment was performed by heating from the back side of the reheating treatment layer.

(Formation of Intermediate Gray Pattern Image) Each of the yellow, magenta, and cyan colors transmits an applied energy of 40 m.
The procedure was the same as that for forming the step pattern image, except that overprinting was performed over the entire print area under the conditions of J / mm ² and a feed speed of 10 msec / line.

<Evaluation> The obtained samples were measured and evaluated as follows.

<< Sensitivity >> Each of Y, M and C in the step pattern
Is the maximum density of the reflection densitometer (X-RITE: X-RI
TE310).

<< Curl >> The image-receiving sheets 1 to 15 before printing cut into A4 size were humidified in an atmosphere of 23 ° C. and 55% RH for one week, and the raised heights of the four corners when placed on a flat surface were raised. Measure the temperature, then 23 ℃ ・ 80% RH 、 23 ℃ ・
After standing for 7 days in an atmosphere of 20% RH, the heights of the four corners were measured in the same manner, and the curl was evaluated in four steps based on the larger difference (the direction of contraction toward the image receiving sheet was defined as +).
It is preferably at most 10 mm or less.

：: Almost no curl (±± 5 mm) Δ: Slightly curled but at a level that can withstand practical use (〜 ± 10 mm)
mm) ×: The curl is considerable and there is a problem in practical use (up to ± 30 mm) ××: The curl is so severe that it cannot withstand practical use (± 30 mm)
<< Image Defects >> In the sample on which the intermediate gray pattern was printed, the presence or absence of image omission was evaluated in four steps. If the cushioning property is poor, when foreign matter such as dust and dust is present on the surface of the image receiving layer, the surface of the ink layer or in the image receiving layer, the shape is not printed and color loss occurs in its shape.

：: None at all △: Slightly generated but at a level that can withstand practical use ×: Omission is large and there is a problem in practical use XX: Omission is severe and cannot be endured practically << Uneven formation >> In a low density region of a step pattern ,
The presence or absence of image unevenness was visually observed and evaluated in the following four grades. When the cushioning property is poor, unevenness, which is considered to be caused by unevenness of the resin-coated paper or the adhesive layer, that is, so-called formation unevenness is observed.

：: Not at all △: Slightly generated but at a level that can withstand practical use X: There is considerable unevenness and there is a problem in practical use XX: Severe unevenness and cannot withstand practical use << Breaking wrinkle resistance >> Image reception before printing The sheet is 5cm long and 1 width
The sample was cut into a strip having a diameter of 5 cm, wound around a glass rod having a diameter of 5 cm, squeezed, and then the sample was stretched again.

：: Not at all △: Slightly generated but at a level that can withstand practical use ×: Fold wrinkles are observed and cannot be used XX: Fold wrinkles are severe and cannot be put to practical use << Surface gloss >> manufactured by Nippon Denshoku Industries Co., Ltd. VGS-1001DP
Was used to measure the reflectance at a measurement angle of 60 degrees.

<< Image Preservation >> Y,
A portion near each concentration of 1.0 for M and C was measured with a xenon fade meter (Suga Test Instruments Co., Ltd .: WEL-6X-HC-).
The residual ratio of the concentration was determined from the concentration after exposure to Ec (light source illuminance: 75000 lux) for 14 days and before exposure. The residual ratio is preferably 70% or more.

<< Texture >> The texture when holding the image receiving sheet by hand was evaluated on a three-point scale as follows.

：: Texture equivalent to silver halide photograph Δ: Texture close to silver halide photograph ×: Texture of plastic and different texture from silver halide photograph The results obtained are also shown in Table 2.

[0173]

[Table 2]

As described above, when the film having the specific gravity range according to the present invention is used, there are no failures such as image defects and unevenness, and the sensitivity,
It can be seen that a silver salt photographic-like sample with high storage stability can be obtained, and a sample excellent in mechanical resistance and gloss can be obtained particularly when a composite structure is used.

Example 2 <Preparation of Ink Sheet 2> In Example 1, the composition of the ink layer was changed to the following composition, and the ink sheet 2 was prepared in the same manner as the ink sheet 1 except that the reheating region was not provided. I got

(Yellow ink layer) Dye Y-1 3 parts Polyvinyl butyral (Denka butyral KY-24: supra) 5.5 parts Epoxy-modified acrylic resin (Reseda GP-305: supra) 1 part Urethane-modified silicone oil ( Dialomer SP-2105: supra) 0.5 part Methyl ethyl ketone 80 parts Toluene 10 parts (magenta ink layer) Dye M-1 3 parts Polyvinyl butyral (Denka butyral KY-24: supra) 5.5 parts Epoxy-modified acrylic resin ( Reseda GP-305: supra) 1 part Urethane-modified silicone oil (Dialomer SP-2105: supra) 0.5 part Methyl ethyl ketone 80 parts Toluene 10 parts (cyan ink layer) Dye C-1 3 parts Polyvinyl butyral (Denka butyral KY) -24: supra) 5.5 parts epoxy Modified acrylic resin (Reseda GP-305: supra) 1 part Urethane modified silicone oil (Dialomer SP-2105: supra) 0.5 part Methyl ethyl ketone 80 parts Toluene 10 parts

[0177]

Embedded image

<Preparation of Image-Receiving Sheet>
In the same manner except that the image receiving layer was changed to the following composition,
Using No. 15, image receiving sheets 16 to 30 were produced.

(Image-Receiving Layer) Polyvinyl Butyral (Eslek BX-1: supra) 9.5 parts Polyester-modified silicon (X-24-8300: supra) 0.5 parts Methyl ethyl ketone 80 parts butyl acetate 10 parts <Image formation Evaluation and Evaluation> An image was prepared and evaluated in the same manner as in Example 1 except that the reheating treatment was not performed during image formation.

Table 3 shows the obtained results.

[0181]

[Table 3]

As described above, when no reactive dye was used, the same effect as that of Example 1 was obtained except that the storage stability was reduced as a whole.

[0183]

According to the present invention, there can be obtained a silver halide photographic-like image which is free from defects such as image defects and unevenness, and has high sensitivity and storability, and is excellent in mechanical resistance and gloss.

[Brief description of the drawings]

FIG. 1 is a plan view showing an example of an embodiment of an ink layer and a reheating treatment layer provided on an ink sheet used in the method of the present invention.

[Explanation of symbols]

 Reference Signs List 1 reheat treatment layer 2Y area containing yellow dye 2M area containing magenta dye 2C area containing cyan dye 3 ink sheet support

Claims (12)

[Claims] 1. A resin-coated paper in which at least one surface of a base paper mainly composed of natural pulp is coated with a resin layer containing a resin capable of forming a film, a specific gravity of 0. A thermal transfer recording material having a structure in which polyester films of 6 to 1.05 are laminated, and a thickness ratio of the resin-coated paper to the polyester film is from 8: 1 to 1: 1. 2. The method according to claim 1, wherein the polyester film has a composite structure of two or more layers having different specific gravities, and a specific gravity of an outermost surface layer on the side where an image is formed is higher than that of an adjacent layer. The thermal transfer recording material as described in the above. 3. The resin-coated paper has a thickness of 100 to 240.
μm and the thickness of the polyester film is 30
The thermal transfer recording material according to claim 1, wherein the thickness is from 100 μm to 100 μm. 4. The thermal transfer recording material according to claim 1, wherein the resin having a film forming ability is a polyethylene resin. 5. The resin-coated paper is provided with the resin layer on a surface on which the polyester film is not laminated, and the resin in the resin layer has a density of 0.935 g / cm ^3.
The following polyethylene resin and a density of 0.960 g / cm ³
Including the above polyethylene resin, the composition ratio of which is 35: 6
The thermal transfer recording material according to any one of claims 1 to 4, wherein the ratio is 5 to 100: 0. 6. An ink layer surface of an ink sheet having at least one ink layer containing a heat diffusible dye on a support, and at least one image receiving layer of an image receiving sheet capable of receiving the dye on the support. In a thermal transfer recording method of forming an image by superposing the image receiving layer surfaces of the image receiving sheets so as to face each other and transferring the heat diffusible dye to the image receiving layer by heating imagewise, the support of the image receiving sheet is made of natural material. At least one surface of a base paper mainly composed of pulp is coated with a resin layer containing a resin capable of forming a film. A polyester film is laminated, and the ratio of the thickness of the resin-coated paper to the polyester film is 8: 1.
To 1: 1. 7. The polyester film according to claim 6, wherein the polyester film has a composite structure of two or more layers having different specific gravities, and the specific gravity of the outermost surface layer on the side where an image is formed is higher than that of an adjacent layer. The thermal transfer recording method described in the above. 8. The resin-coated paper has a thickness of 100 to 240.
μm and the thickness of the polyester film is 30
The thermal transfer recording method according to claim 6, wherein the thermal transfer recording method is in a range of from 100 μm to 100 μm. 9. The thermal transfer recording method according to claim 6, wherein the resin capable of forming a film is a polyethylene resin. 10. The resin-coated paper is provided with the resin layer on a surface on which the polyester-based film is not laminated, and the resin in the resin layer has a density of 0.935 g / cm.
³ or less polyethylene resin and density 0.960g / cm ³
The composition ratio of the above polyethylene resin is 35:65 to 65:65.
The thermal transfer recording method according to any one of claims 6 to 9, wherein the ratio is 100: 0. 11. The ink layer contains a dye precursor capable of forming a dye by reaction, and the image receiving layer contains a dye fixing body capable of forming a dye by reacting with the dye precursor. The thermal transfer recording method according to any one of claims 6 to 10, wherein: 12. The thermal transfer recording method according to claim 11, wherein the dye precursor is a chelatable compound, and the dye fixing body is a metal ion-containing compound.