JP3056266B2 - Image receiving sheet for thermal transfer recording - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image-receiving sheet for thermal transfer recording, and more particularly, to an image-receiving sheet for thermal transfer recording which is excellent in heat resistance, light resistance and surface smoothness and can obtain an image at a high transfer density.

[0002]

2. Description of the Related Art Conventionally, as a method for obtaining a color hard copy, a color recording technique such as an ink jet method, an electrophotographic method, and a thermal transfer method has been studied. Is
It has advantages such as easiness of operation and maintenance, downsizing and cost reduction of the apparatus, and low running cost.

In the thermal transfer method, a transfer sheet having a heat-fusible ink layer on a support (hereinafter, also referred to as a thermal transfer recording material) is heated by a thermal head to sense ink from the heat-fusible ink layer. A method of melt-transfer onto an image receiving sheet for thermal transfer recording, and a method of heating a transfer sheet having an ink layer containing a heat-diffusible dye (sublimable dye) on a support with a heat-sensitive head so that the heat-diffusible dye There is a thermal diffusion transfer method (sublimation transfer method) in which the dye is transferred to an image receiving sheet for thermal transfer recording, and the thermal diffusion transfer method reduces the amount of dye to be transferred according to the change in thermal energy of the thermal head. Since the gradation of the image can be controlled by changing it, it is advantageous for full-color printing.

In the thermal transfer recording of the thermal diffusion transfer system, the dye used in the thermal transfer recording material is important, and the stability of the obtained image, that is, the light fastness and the fixing property are not good in the conventional one. There is a disadvantage that.

Therefore, in order to improve these points, Japanese Patent Application Laid-Open Nos. 59-78893, 59-109394 and 6
Each publication of JP-A No. 0-2398 discloses an image forming method in which an image is formed on a heat-sensitive transfer recording image-receiving sheet using a chelatable dye by using a heat-diffusable dye capable of being chelated.

[0006] However, these image forming methods are excellent methods for improving heat resistance and fixing property. However, conventional image receiving sheets for thermal transfer recording use polyester resin, polyvinyl chloride as a binder for an image receiving layer. resin,
Since copolymers of vinyl chloride and other monomers, polyvinyl butyral, polyvinyl pyrrolidone, and the like have been used, the diffusion and chelation of the dye migrating from the thermal transfer recording ink sheet during thermal transfer does not sufficiently proceed. No image with a high transfer density was obtained.

Further, there is a problem that the light resistance of the formed image is not sufficient and it is difficult to maintain the image quality at the time of image formation.

The present invention has been made based on the above circumstances. That is, an object of the present invention is to provide an image-receiving sheet for thermal transfer recording with improved transfer density, light resistance and heat resistance.

[0009]

According to the present invention, there is provided a resin and / or epoxy group comprising a support, a metal ion-containing compound and having a bisphenol skeleton represented by the following formula [I]: And an image-receiving layer having a resin having the following formula in a molecule:

—O—C ₆ H ₄ —X—C ₆ H ₄ —O— (I) [where X is —CR ¹ R ² — (where R ¹
And R ² represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acyl group, an aryl group, and a cycloalkyl group, respectively, and may be the same or different. ), —O—, —SO ₂ —, or a single bond. Hereinafter, the present invention will be described in detail.

(1) Thermal Transfer Recording Image-Receiving Sheet The thermal transfer recording image-receiving sheet of the present invention basically comprises an image receiving layer laminated on a support.

-Support- As the support, various papers such as paper, coated paper, and synthetic paper (polypropylene, polystyrene or a composite material obtained by laminating them with paper), vinyl chloride resin sheet, ABS Various plastic films or sheets such as resin sheets, polyethylene terephthalate base film, polyethylene terephthalate base film, polyethylene naphthalate base film, films or sheets formed of various metals, films or sheets formed of various ceramics, etc. Can be mentioned.

In the support, a white pigment such as titanium white, magnesium carbonate, zinc oxide, barium sulfate, silica, talc, clay, calcium carbonate, etc. is used to enhance the sharpness of an image formed in a later step. It is preferably added.

The thickness of the support is usually 100 to 1000 μm.
m, preferably 100 to 800 μm, and is appropriately selected from such a range.

-Image-receiving layer- The image-receiving layer can be formed with a binder for an image-receiving layer, a metal ion-containing compound and various additives. In the present invention, the image receiving layer contains a metal ion-containing compound, and contains, as a binder for the image receiving layer, a resin having a bisphenol skeleton represented by the above formula [I] and / or a resin having an epoxy group in the molecule. This is very important.

The image receiving layer contains a metal ion-containing compound,
When a resin having a bisphenol skeleton represented by the above formula [I] and / or a resin having an epoxy group in a molecule is contained as a binder for an image receiving layer, the image receiving sheet for thermal transfer recording has a high diffusibility of a heat diffusing dye. And high image storability can be exhibited. In order to achieve such an effect, materials may be appropriately selected from binders for image receiving layers, metal ion-containing compounds, additives, and the like described below, or the amounts of these materials and the thickness of the image receiving layers may be adjusted. . 1. Binder for Image Receiving Layer It is important that the binder for the image receiving layer used in the invention contains a resin having a bisphenol skeleton and / or a resin having an epoxy group in a molecule.

Here, the bisphenol skeleton has the formula [I]
It is represented by —O—C ₆ H ₄ —X—C ₆ H ₄ —O— (I) [where X is —CR ¹ R ² — (where R ¹
And R ² represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acyl group, an aryl group, and a cycloalkyl group, respectively, and may be the same or different. ), —O—, —SO ₂ —, or a single bond. ].

In the bisphenol skeleton represented by the above formula [I], when X is -CR ¹ R ^2- , R ¹ and R ² are each a hydrogen atom and a halogen atom (for example, chlorine atom, fluorine atom, etc.). An alkyl group (eg, a methyl group, an ethyl group, an isopropyl group, an n-butyl group, etc.), an alkoxy group (eg, a methoxy group, an ethoxy group,
Isopropoxy group, n-butoxy group, etc.), acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.),
Represents an aryl group (for example, a phenyl group or a phenethyl group), a cycloalkyl group (for example, a cyclopentyl group, a cyclohexyl group) or the like.

These groups may be further substituted,
Examples of the substituent include an alkyl group (eg, methyl group, ethyl group, trifluoromethyl group, etc.), an aryl group (eg, phenyl group), an alkoxy group (eg, methoxy group, ethoxy group, etc.), and an amino group (eg, methylamino group, ethyl group). An amino group), an acylamino group (eg, an acetyl group),
Examples include a sulfonyl group (eg, a methanesulfonyl group), an alkoxycarbonyl group (eg, a methoxycarbonyl group), a cyano group, a nitro group, a halogen atom (eg, a chlorine atom, a fluorine atom, and the like).

Preferred examples of the resin having a bisphenol skeleton include a polycarbonate resin, a polyarylate resin, a phenoxy resin, and a polysulfone resin. Of these, a phenoxy resin is preferable.

In the present invention, as the resin having an epoxy group in the molecule, a resin not containing an atom (eg, nitrogen, phosphorus, sulfur, etc.) which coordinates with a metal ion contained in the image receiving layer is preferable. For example, epoxy group-containing resins such as epoxy resin, epoxy methacrylate resin, epoxy novolak resin, epoxy modified polyol, epoxy peracetic acid resin, brominated bisphenol epoxy resin, chlorinated bisphenol epoxy resin, glycidyl acrylate copolymer, glycidyl methacrylate copolymer Examples thereof include polymers, aliphatic polyglycidyl ether polymers, and glycidyl group-containing resins such as glycidyl-modified polyvinyl chloride.

Further, as for the resin having an epoxy group in the molecule, a resin having an epoxy equivalent of 5000 or less is preferable, and a resin having an epoxy equivalent of 2000 or less is more preferable.

These resins can be used alone or in combination of two or more.

The above various resins may be newly synthesized and used, but commercially available products may also be used.

In any case, the binder for the image receiving layer has Mw of 2,000 to 10 in terms of molecular weight.
Resins in the range of 000 are preferred.

In the formation of the image receiving layer, the above-mentioned various resins utilize their reactive active sites (if there is no reactive active site, they are applied to the resin) to obtain radiation, heat, moisture, catalyst, and the like. Crosslinking or curing may be performed by the above method.

In this case, a radiation-active monomer such as epoxy or acrylic, or a crosslinking agent such as isocyanate can be used.

2. Metal Ion-Containing Compound In the present invention, the image receiving layer contains a metal ion supplying compound (hereinafter, referred to as a metal source). Examples of the metal source include inorganic or organic salts and metal complexes of metal ions, and among them, salts and complexes of organic acids are preferable. Examples of the metal include monovalent and polyvalent metals belonging to Groups I to VIII of the periodic table. Among them, Al, Co, Cr, Cu,
Fe, Mg, Mn, Mo, Ni, Sn, Ti and Zn are preferred, and particularly Ni, Cu, Cr, Co and Zn are preferred. Specific examples of the metal source include Ni ²⁺ , C
Examples thereof include salts of u ²⁺ , Cr ²⁺ , Co ²⁺ and Zn ²⁺ with aliphatic salts such as acetic acid and stearic acid, and salts of aromatic carboxylic acids such as benzoic acid and salicylic acid. Further, the complex represented by the following general formula is particularly preferably used because it is stable and can be added to the image receiving layer and is substantially colorless.

[M (Q ₁ ) _X (Q ₂ ) _Y (Q ₃ ) _Z ] ^{P +} (L ⁻ ) P In the above formula, M is a metal ion, preferably N
i ²⁺ , Cu ²⁺ , Cr ²⁺ , Co ²⁺ , and 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 include a tetraphenylboron anion and an alkylbenzenesulfonic acid anion. X represents an integer of 1, 2, or 3, and Y represents 1, 2, or 0.
And Z represents 1 or 0, which is determined depending on whether the complex represented by the above general formula is tetradentate or hexadentate, or Z ₁ , Q ₂ , Q ₃ Determined by the number of ligands. P represents 1 or 2. Specific examples of this type of metal source are disclosed in Japanese Patent Application Nos. 1-217906 and 1-244.
No. 539. The amount of metal source added
Usually, the amount is preferably 0.5 to 20 g / m ² , more preferably ¹ to 15 g / m ² , based on the material for forming the image receiving layer.

3. Additives A release agent, an antioxidant, a UV absorber, a light stabilizer, a filler (inorganic fine particles, organic resin particles), and a pigment 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 thermal transfer recording ink sheet and the thermal transfer recording image receiving sheet.

Examples of such release agents include silicone oils (including those referred to as silicone resins), solid waxes such as polyethylene wax, amide wax, and Teflon powder, fluorine-based and phosphate-based surfactants. And the like, among which silicone oil is preferred.
This silicone oil is classified into a type that is simply added (simple addition type) and a type that is cured or reacted (curing reaction type).

In the case of the simple addition type, it is preferable to use a modified silicone oil (for example, a polyester-modified silicone resin, a urethane-modified silicone resin, an acryl-modified silicone resin, etc.) in order to improve the compatibility with the binder.

The addition amount of these simple addition type silicone oils cannot be determined uniformly because they may vary depending on the type, but generally speaking, generally, the binder for the image receiving layer is usually used. 0.1 to 50% by weight, preferably 0.5 to 20% by weight.

As a curing reaction type silicone oil,
Reaction-curable types (reaction-cured amino-modified silicone oil and epoxy-modified silicone oil), photocurable types, catalyst-curable types, and the like.

The addition amount of these curable silicone oils is preferably 0.5 to 30% by weight of the binder for the image receiving layer.

The release agent layer may be provided on a part of the surface of the image receiving layer by dissolving or dispersing the above release agent in an appropriate solvent and applying the resultant, followed by drying.

Next, as the antioxidant, JP-A-59
182785, 60-130735, JP-A-1-1-1
The antioxidants described in 27387 and the like, and known compounds for improving the image durability of photographs and other image recording materials can be mentioned.

As the UV absorber and the light stabilizer,
JP-A-59-158287, JP-A-63-74686, JP-A-6
3-145089, 59-196292, 62-2
29594, 63-122596, 61-28359
5, compounds described in JP-A-1-204788, and compounds known to improve the image durability of photographs and other image recording materials.

Examples of the filler include inorganic fine particles and organic resin particles.

Examples of the inorganic fine particles include silica gel, calcium carbonate, titanium oxide, acid clay, activated clay, and alumina. Examples of the organic fine particles include fluororesin particles, guanamine resin particles, acrylic resin particles, and silicon resin particles. Resin particles. These inorganic / organic resin particles vary depending on the specific gravity.
Addition of 0% by weight is preferred.

Representative examples of the pigment include titanium white, calcium carbonate, zinc oxide, barium sulfate, silica, talc, clay, kaolin, activated clay, and acid clay.

As the plasticizer, phthalic acid esters,
Trimellitic acid esters, adipic acid esters, other saturated or unsaturated carboxylic acid esters, citrate esters, epoxidized soybean oil, epoxidized linseed oil, epoxystearic epoxy, orthophosphoric acid, phosphorous acid Esters and glycol esters are exemplified.

In the present invention, the total amount of the additives is usually 0 to 30% by weight based on the binder for the image receiving layer.
Range.

-Other layers- An intermediate layer (subbing layer) may be provided between the image receiving layer and the support for the purpose of imparting properties such as heat insulating properties, barrier properties, cushioning properties, and adhesive properties.

An overcoat layer may be laminated on the surface of the image receiving layer for the purpose of preventing fusion between the thermal transfer recording ink sheet and the thermal transfer recording image receiving sheet.

Further, a backing layer may be provided on the surface opposite to the image receiving layer (the surface of the support) for the purpose of preventing charge and curling.

(2) Production of heat-sensitive transfer recording image-receiving sheet The heat-sensitive transfer recording image-receiving sheet is prepared by dispersing or dissolving the components for forming the image-receiving layer in a solvent to prepare a coating solution for the image-receiving layer.
It can be formed by a coating method in which the coating solution for the image receiving layer is applied to the surface of the support and dried, or a lamination method in which a mixture having the components for forming the image receiving layer is melt-extruded and laminated on the surface of the support. it can.

Examples of the solvent used in the above coating method include water, alcohols (eg, ethanol and propanol), cellosolves (eg, methyl cellosolve, ethyl cellosolve), aromatics (eg, toluene, xylene, chlorobenzene), ketones (eg, For example, acetone, methyl ethyl ketone), ester solvents (eg, ethyl acetate, butyl acetate, etc.), ethers (eg, tetrahydrofuran, dioxane), chlorine solvents (eg, chloroform, trichloroethylene), and the like.

For the coating, a conventionally known surface-separated coating method using a gravure roll, an extrusion coating method, a wire bar coating method, a roll coating method and the like can be adopted.

The image receiving layer may be formed over the entire surface of the support, or may be formed on a part of the surface.

(3) Thermal Transfer Recording Ink Sheet The thermal transfer recording ink sheet is basically formed by laminating an ink layer on a support.

-Support-Any support can be used as long as it has good dimensional stability and can withstand heat during recording with a thermal head, but can be thin paper such as condenser paper or glassine paper, polyethylene terephthalate, or the like. Polyethylene naphthalate, polyamide, polyimide, polycarbonate, polysulfone,
A heat-resistant plastic film such as polyvinyl alcohol cellophane or polystyrene can be used.

The thickness of the support is preferably 2 to 10 μm.

The shape of the support is not particularly limited.
For example, there are arbitrary shapes such as wide sheets and films, narrow tapes and cards.

-Ink Layer- The ink layer contains a heat-diffusible dye and a binder as essential components.

1. Thermodiffusable Dye The dye used in the present invention is a dye capable of forming at least a bidentate chelate, and is preferably a dye represented by the general formula [II].

X ¹ -N = N−X ² -G [II] In the formula, X ¹ represents an aromatic carbocyclic or heterocyclic ring in which at least one ring is composed of 5 to 7 atoms. X represents a group of atoms necessary for completion, and at least one of the carbon atoms bonded to the azo bond is a nitrogen atom or a carbon atom substituted with a chelating group, and X ² represents at least one ring having at least one ring. Represents an aromatic heterocyclic ring or an aromatic carbocyclic ring composed of 5 to 7 atoms, and G represents a chelating group.

Specific examples of the dye are described in JP-A-59-78893.
No. 59-109349, Japanese Patent Application No. 2-213303
No. 2-214719 and No. 2-203742.

The amount of the heat diffusing dye used is usually from 0.1 to ²⁰ g, preferably from 0.2 to 5 g per m ^{2 of} the support.
g.

[0061] 2. As a binder of the binder-ink layer, a cellulose-added compound,
Cellulose resins such as cellulose esters and cellulose ethers; polyvinyl acetal resins such as polyvinyl alcohol, polyvinyl formal, polyvinyl acetoacetal, and polyvinyl butyral; polyvinyl pyrrolidone, polyvinyl acetate, polyacrylamide, styrene resins, poly (meth) acrylic acid Examples include vinyl-based resins such as system-based esters, poly (meth) acrylic acid, and (meth) acrylic acid copolymers, rubber-based resins, ionomer resins, olefin-based resins, and polyester resins.

Among these resins, a polyvinyl acetal resin or a cellulosic resin having excellent storage stability is preferable.

As the above-mentioned various binders, one kind can be used alone, or two or more kinds can be used in combination.

The weight ratio of the binder to the heat-diffusible dye is preferably from 1:10 to 10: 1, and particularly preferably from 3: 7 to 8: 2.

3. Other Optional Components Various additives can be appropriately added to the ink layer.

Examples of the additives include silicone resin, silicone oil (reaction curing type is also possible), silicone-modified resin, fluorine resin, surfactant, and peelable compounds such as waxes, metal fine powder, silica gel, metal oxide. Agent, filler such as carbon black, resin fine powder, etc., curing agent capable of reacting with binder component (for example, radiation-active compounds such as isocyanates, acrylics and epoxies)
And the like.

Further, examples of the additive include a heat-fusible substance for promoting transfer, for example, compounds described in JP-A-59-106997, such as waxes and higher fatty acid esters.

-Other Layers- The thermal transfer recording ink sheet is not limited to a two-layer structure including a support and an 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 sheet for thermal transfer recording or set-off (blocking) of the heat-diffusible dye.

The support may have an undercoat layer for the purpose of improving the adhesion to the binder and preventing the transfer and dyeing of the dye to the support.

Further, the back surface of the support (the side opposite to the ink layer)
May be provided with a backing layer for the purpose of running stability, heat resistance, antistatic and the like.

The thickness of the overcoat layer, undercoat layer and backing layer is usually from 0.1 to 1 μm.

(4) Production of Ink Sheet for Thermal Transfer Recording The ink sheet for thermal transfer recording is prepared by dispersing or dissolving the above-mentioned various components for forming an ink layer in a solvent to prepare a coating liquid for forming an ink layer. , This is coated on the surface of the support,
It can be manufactured by drying.

The binder may be used alone or in combination of two or more dissolved in a solvent or dispersed in latex.

Examples of the solvent include water, ethanol, tetrahydrofuran, methyl ethyl ketone, toluene, xylene, chloroform, dioxane, acetone, cyclohexane, normal butyl acetate and the like.

For the coating, a conventionally known gravure roll-coating method using a gravure roll, an extrusion coating method, a wire bar coating method, a roll coating method, or the like can be employed.

The ink layer may be formed as a layer containing a monochromatic heat diffusible dye on the entire surface or a part of the surface of the support, or may be formed by a chelation reaction with a binder and a metal source. Yellow dye layer containing a dye forming a yellow dye image, magenta ink layer containing a dye forming a magenta dye by forming a magenta dye with a binder and a metal source, and cyan dye forming a chelating reaction with a binder and a metal source A cyan ink layer containing a dye for forming an image may be formed on the entire surface or a part of the surface of the support at a constant repetition along the planar direction.

Further, in addition to the three ink layers arranged along the plane direction, a black ink layer containing a black image forming substance may be interposed.

Regarding the black ink layer, a clear image can be obtained by either the diffusion transfer type or the melt transfer type.

The thickness of the ink layer thus formed is usually from 0.2 to 10 μm, preferably from 0.3 to 3 μm.
μm.

It is to be noted that the ink sheet for thermal transfer recording may be provided with a perforation or provided with a detection mark for detecting the position of an area having a different hue, thereby facilitating use.

(5) Image Formation (Thermal Transfer Recording) In order to form an image, the ink layer of the thermal transfer recording ink sheet and the image receiving layer of the thermal transfer recording image receiving sheet are overlapped, and the ink layer and the image receiving layer are formed. Gives image-wise thermal energy to the interface.

Then, the thermal diffusible dye in the ink layer is vaporized or sublimated by an amount corresponding to the applied thermal energy, and is transferred to the image receiving layer side and received. As a result, an image is formed on the image receiving layer.

In the present invention, a resin having a metal ion-containing compound in the image receiving layer and a resin having a bisphenol skeleton represented by the above formula [I] and / or a resin having an epoxy group in the molecule is used as a binder for the image receiving layer. contains.

Therefore, at the time of thermal transfer, the chelation reaction between the dye and the metal ion proceeds sufficiently, and an image can be transferred at a high density onto the thermal transfer recording image-receiving sheet.

Further, the image receiving sheet for thermal transfer recording of the present invention not only can surely prevent the dye from bleeding due to light or heat during storage, but also has excellent image storability.

As the heat source for giving the thermal energy,
A thermal head is generally used, but other known ones such as a laser beam, an infrared flash, and a hot pen can also be used.

When a thermal head is used as a heat source for applying thermal energy, the applied thermal energy can be changed continuously or in multiple steps by modulating the voltage or pulse width applied to the thermal head.

When laser light is used as a heat source for applying heat energy, the applied heat energy can be changed by changing the amount of laser light or the irradiation area.

In this case, in order to easily absorb the laser light, a laser light absorbing material (for example, carbon black or near-infrared absorbing material in the case of a semiconductor laser) may be present in the ink layer or in the vicinity of the ink layer. .

When a laser beam is used, it is preferable that the thermal transfer recording ink sheet and the thermal transfer recording image receiving sheet are sufficiently adhered to each other.

If a dot generator having a built-in acousto-optic element is used, heat energy corresponding to the size of a halftone dot can be applied.

When an infrared flash lamp is used as a heat source for applying heat energy, the heating may be performed through a colored layer such as black as in the case of using laser light.

Alternatively, heating may be performed through a pattern such as black or the like, which continuously expresses the shading of an image, or a halftone dot pattern, or may correspond to one side of a colored layer such as black and a negative of the pattern. Heating may be performed in combination with a negative pattern. The method of applying thermal energy may be performed from the thermal transfer recording ink sheet side, may be performed from the thermal transfer recording image receiving sheet side, or may be performed from both sides, but if priority is given to the effective use of thermal energy, It is desirable to perform the heat transfer recording from the ink sheet side.

By the above-described thermal transfer recording, a one-color image can be recorded on the image-receiving layer of the image-receiving sheet for thermal transfer recording. According to the following method, a color photographic color image composed of a combination of each color can be obtained. Can also.

For example, by sequentially replacing the yellow, magenta, cyan and, if necessary, black thermal transfer recording thermal sheets, and performing thermal transfer in accordance with each color, a color photographic color image composed of a combination of each color is obtained. You can also.

Then, the following method is also effective.

That is, instead of using the thermal transfer recording ink sheet of each color as described above, a thermal transfer recording ink sheet having an area previously formed separately for each color is used.

Then, first, a yellow color separation image is thermally transferred using the yellow area, then a magenta color separation image is thermally transferred using the magenta area, and thereafter, yellow, magenta, and cyan are sequentially repeated. And, if necessary, a method of thermal transfer in the order of the black color separation image.

This method can also produce a color photographic color image, but more advantageously, this method does not require replacement of the thermal transfer recording heat-sensitive sheet as described above. There is.

Further, after an image is formed by the above-described method, a heat treatment may be performed by the above-described method for the purpose of improving image storability. For example, the entire surface of the image forming surface may be subjected to a heat treatment using a portion of the thermal head where the ink layer of the ink sheet is not provided, or may be subjected to a new heat treatment such as a heat roll. When a near-infrared absorbing agent is contained, the image forming surface may be exposed using an infrared flash lamp.

In any case, the heating means is not limited.
Since the purpose is to further diffuse the dye into the image receiving layer, it is effective and preferable to heat from the support side of the image receiving layer.

[0103]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to these Examples. In the following, “parts” means “parts by weight”.

Example 1 Production of Thermal Transfer Recording Ink Sheet A corona-treated surface of a 6 μm thick polyethylene terephthalate film [manufactured by Toray Industries, Inc.] was used as a support.
An ink layer-forming coating liquid containing a heat-diffusible dye represented by the following general formula [III] and having the following composition is applied by a wire bar coating method so that the thickness after drying becomes 1 μm, and dried. A silicone resin [SP-210, manufactured by Dainichi Seika Co., Ltd.]
Nitrocellulose solution containing 5] with a dropper,
The ink sheet for thermal transfer recording was obtained by dropping two drops and spreading over the entire surface and performing a back surface treatment coat.

[0105]

Embedded image

Coating liquid for forming ink layer; Thermal diffusible dye: 3 parts Nitrocellulose ······ 5 parts [Asahi Kasei Kogyo Co., Ltd., Cellnova BTH1 / 2] Methyl ethyl ketone ······ 82 parts Cyclohexanone ······ ... 10 parts.

-Production of Image-Receiving Sheet for Thermal Transfer Recording- A coating liquid for forming an image-receiving layer having the following composition was coated on a 150 μm-thick synthetic paper (Yupo FPG-150, manufactured by Oji Yuka Synthetic Paper Co., Ltd.) as a base material. By coating and drying sequentially by a coating method to form an image receiving layer having a thickness of 10 μm on synthetic paper,
An image receiving sheet for thermal transfer recording was obtained.

Coating solution for forming image receiving layer; polycarbonate resin 6 parts [Panlite L1225 manufactured by Teijin Chemicals Ltd.] Metal ion-containing compound ........... 3.5 parts _{[[Ni (C 2 H 5} NHCH 2 CH 2 NH 2)] 2+ [(C 6 H 5) 4 B] 2-] polyester-modified silicone resin 0.5 parts [X-24-8300, manufactured by Shin-Etsu Silicone Co., Ltd.] Dioxane 60 parts Methyl ethyl ketone 20 parts Cyclohexanone 10 parts.

-Image formation- First, the thermal transfer recording ink sheet and the thermal transfer recording image receiving sheet are overlapped so that the former ink layer surface and the latter image receiving layer surface are in contact with each other. An image was formed by applying a thermal head from the support side of the ink sheet under the following conditions.

Next, the ink sheet for thermal transfer recording and the image receiving sheet for thermal transfer recording were peeled off, and the image was transferred onto the image receiving sheet for thermal transfer recording.

After recording the image, the transfer density on the surface of the image receiving layer, the heat resistance of the image, the light resistance, the fixing property and the bleeding prevention property were determined.
Evaluation was made according to the following criteria. Table 1 shows the results.

Line density of main scanning and sub-scanning: 8 dots / mm Recording power: 0.6 W / dot Heating time of thermal head: 20 msec (applied energy about 11.2 × 10 ⁻³ J) to 2 msec (applied energy about The heating time was adjusted stepwise between 1.12 × 10 ⁻³ J).

Transfer Density: The reflection density OD value was measured with an optical densitometer. ◎: OD value is 2.5 or more 〇: OD value is 2.0 to 2.5 Δ ・ ・ ・: OD value is 1.7 to 2.0 ×: OD value is 1.7 or less.

Heat resistance (heat-resistant image storage stability): The image-receiving sheet for thermal transfer recording on which an image has been recorded is kept for 72 hours in an environment of 77 ° C. and a relative humidity of 80% for bleed-out of the dye and discoloration or fading of the dye. The presence or absence (visual judgment) was examined.・ ・ ・: The pigment does not easily fall off even when the image is rubbed by hand. There is no discoloration or fading. ×: When the image was rubbed with a hand, the pigment was removed, or discoloration or fading was observed.

Lightfastness (lightproof image preservability): The image-receiving sheet for thermal transfer recording on which the image was recorded was exposed with a xenon weather meter for 72 hours, and the image was visually judged.・ ・ ・: No discoloration or fading of the dye is observed. ×: Discoloration and fading of the dye are remarkable. Fixing property of dye: The image receiving sheet for thermal transfer recording on which an image was recorded was faced with the image receiving sheet for thermal transfer recording on which the image of the present invention was not recorded, a load of 40 g / cm2 was applied, and left at 60 DEG C. for 48 hours. Judgment was made based on the transfer density of the dye transferred to the thermal transfer recording image-receiving sheet on which no post-image was recorded. A: The density of the transferred dye was less than 0.10. 〇: The transferred dye density is 0.10 or more, 0.15
It was below. C: The density of the transferred dye was 0.15 or more. Prevention of dye bleeding: The image-receiving sheet for thermal transfer recording on which an image was recorded was placed at 60 ° C./1.
After standing for a week, the degree of bleeding was visually determined.・ ・ ・: Almost no bleeding is observed. ×: Bleeding was observed.

(Example 2) An image receiving sheet for thermal transfer recording was produced in the same manner as in Example 1 except that the composition of the coating solution for forming an image receiving layer was changed to the following, and the same thermal transfer as in Example 1 was carried out. Using the recording ink sheet, an image was formed in the same manner as in Example 1, and the image was evaluated. The results are shown in Table 1.

Coating solution for forming image receiving layer; polyarylate resin 6 parts [U polymer U-100, manufactured by Unitika Ltd.] Metal ion-containing compound .............. 3.5 parts _{[[Ni (C 2 H 5} NHCH 2 CH 2 NH 2)] 2 + [(C6 H 5) 4 B] 2-] polyester modified Silicone resin: 0.5 part [Shin-Etsu Silicone Co., Ltd., X-24-8300] Dioxane: 60 parts Methyl ethyl ketone 20 parts Cyclohexanone 10 parts.

Example 3 A heat-sensitive transfer recording image-receiving sheet was produced in the same manner as in Example 1 except that the composition of the coating solution for forming the image-receiving layer was changed to the following, and the same heat-sensitive transfer as in Example 1 was carried out. Using the recording ink sheet, an image was formed in the same manner as in Example 1, and the image was evaluated. The results are shown in Table 1.

Coating solution for forming image receiving layer; polysulfone resin 6 parts [manufactured by Union Carbide, P-1700] Metal ion-containing compound ............ 3.5 parts _{[[Ni (C 2 H 5} NHCH 2 CH 2 NH 2)] 2+ [(C 6 H 5) 4 B] 2-] polyester-modified silicone Resin: 0.5 part [Shin-Etsu Silicone Co., Ltd., X-24-8300] Dioxane: 60 Part Methyl ethyl ketone 20 parts Cyclohexanone 10 parts.

Example 4 A heat-sensitive transfer recording image-receiving sheet was produced in the same manner as in Example 1 except that the composition of the coating solution for forming the image-receiving layer was changed to the following, and the same heat-sensitive transfer as in Example 1 was carried out. Using the recording ink sheet, an image was formed in the same manner as in Example 1, and the image was evaluated. The results are shown in Table 1.

Coating liquid for forming image receiving layer; Phenoxy resin 6 parts [Phenotote YP-50, manufactured by Toto Kasei Co., Ltd.] Metal ion 3.5 parts [[Ni (C ₂ H ₅ NHCH ₂ CH ₂ NH ₂ )] ²⁺ [(C ₆ H ₅ ) ₄ B] ^2- 0.5% of polyester-modified silicone resin [X-24-8300, manufactured by Shin-Etsu Silicone Co., Ltd.] Dioxane ... 30 parts Methyl ethyl ketone ... 50 parts Cyclohexanone ... 10 parts.

Example 5 A heat-sensitive transfer recording image-receiving sheet was produced in the same manner as in Example 1 except that the composition of the coating solution for forming an image-receiving layer was changed to the following, and the same heat-sensitive transfer as in Example 1 was carried out. Using the recording ink sheet, an image was formed in the same manner as in Example 1, and the image was evaluated. The results are shown in Table 1.

Phenoxy resin 6 parts [PKHH manufactured by Union Carbide Co., Ltd.] Metal ion-containing compound ..... 3.5 parts _{[[Ni (C 2 H 5} NHCH 2 CH 2 NH 2)] 2+ [(C 6 H 5) 4 B] 2-] polyester-modified silicone resin ...... 0.5 parts [Shin-Etsu Silicone Co., Ltd., X-24-8300] Dioxane 30 parts Methyl ethyl ketone 50 parts Cyclohexanone 10 parts

Example 6 A heat-sensitive transfer recording image-receiving sheet was produced in the same manner as in Example 1 except that the composition of the coating solution for forming an image-receiving layer was changed to the following, and the same heat-sensitive transfer as in Example 1 was carried out. Using the recording ink sheet, an image was formed in the same manner as in Example 1, and the image was evaluated. The results are shown in Table 1.

Coating liquid for forming image receiving layer; phenoxy resin 4 parts [Phenotote YP-50 manufactured by Toto Kasei Co., Ltd.] Vinyl chloride 2 parts [BARO Co., Ltd., Laroflex MP25] Metal ion containing compound - 3.5 parts _{[[Ni (C 2 H 5} NHCH 2 CH 2 NH 2)] 2+ [(C 6 H 5) 4 B] 2-] polyester-modified silicone resin ......... 0 .5 parts [Shin-Etsu Silicone Co., Ltd., X-24-8300] Dioxane 30 parts Methyl ethyl ketone ... 50 parts Cyclohexanone ... 10 parts.

Example 7 A heat-sensitive transfer recording image-receiving sheet was produced in the same manner as in Example 1 except that the composition of the coating solution for forming an image-receiving layer was changed to the following, and the same heat-sensitive transfer as in Example 1 was carried out. Using the recording ink sheet, an image was formed in the same manner as in Example 1, and the image was evaluated. The results are shown in Table 1.

Coating solution for forming image receiving layer; Phenoxy resin 5.5 parts [Phenotote YP-50, manufactured by Toto Kasei Co., Ltd.] Metal ion 3.5 parts [[Ni (C ₂ H ₅ NHCH ₂ CH ₂ NH ₂ )] ²⁺ [(C ₆ H ₅ ) ₄ B] ^2- ] Alkyl phthalate 0.5 parts [DOP manufactured by Daihachi Chemical Co., Ltd.] Polyester modified silicone resin 0.5 parts [ Shin-Etsu Silicone Co., Ltd., X-24-8300] Dioxane: 30 parts Methyl ethyl ketone: ... 50 parts Cyclohexanone ... 10 parts.

Example 8 The procedure of Example 8 was repeated except that the composition of the coating solution for forming the image receiving layer was changed to the composition shown below, and the coating solution for forming the image receiving layer was sufficiently dried, followed by further heat treatment at 100 ° C. for 60 minutes. An image receiving sheet for thermal transfer recording was manufactured in the same manner as in Example 1, and an image was formed in the same manner as in Example 1 using the same ink sheet for thermal transfer recording as in Example 1, and the image was evaluated. The results are shown in Table 1.

Coating solution for forming image receiving layer; epoxy group-containing vinyl chloride copolymer 6 parts [MR-110, manufactured by Zeon Corporation] Metal ion-containing compound ........... 3.5 parts _{[[Ni (C 2 H 5} NHCH 2 CH 2 NH 2)] 2+ [(C 6 H 5) 4 B] 2-] polyester-modified silicone resin 0.5 parts [X-24-8300, manufactured by Shin-Etsu Silicone Co., Ltd.] Dioxane 20 parts Methyl ethyl ketone 60 parts Cyclohexanone 10 parts.

(Example 9) The procedure of Example 9 was repeated except that the composition of the coating solution for forming an image receiving layer was changed to the following, and the coating solution for forming an image receiving layer was sufficiently dried, and further subjected to a heat treatment at 120 ° C for 60 minutes. An image receiving sheet for thermal transfer recording was manufactured in the same manner as in Example 1, and an image was formed in the same manner as in Example 1 using the same ink sheet for thermal transfer recording as in Example 1, and the image was evaluated. The results are shown in Table 1.

Coating solution for forming image receiving layer; Epoxy resin 6 parts [Epototo YD-017, manufactured by Toto Kasei Co., Ltd., epoxy equivalent : 1815] Metal ion-containing compound 3.5 parts [[Ni (C ₂ H ₅ NHCH ₂ CH ₂ NH ₂ )] ²⁺ [(C ₆ H ₅ ) ₄ B] ^2- ] Polyester modified silicone resin 0.5 part [X-24-8300 manufactured by Shin-Etsu Silicone Co., Ltd.] Dioxane 20 parts Methyl ethyl ketone 60 parts Cyclohexanone 10 parts.

Example 10 The procedure of Example 10 was repeated except that the composition of the coating solution for forming an image receiving layer was changed to the composition shown below, and the coating solution for forming an image receiving layer was sufficiently dried, and further subjected to a heat treatment at 120 ° C. for 60 minutes. An image receiving sheet for thermal transfer recording was manufactured in the same manner as in Example 1, and an image was formed in the same manner as in Example 1 using the same ink sheet for thermal transfer recording as in Example 1, and the image was evaluated. The results are shown in Table 1.

Coating solution for forming image receiving layer; Epoxy resin 6 parts [Epototo YDCN-704, manufactured by Toto Kasei Co., Ltd., epoxy equivalent : 220] containing a metal ion compound .............. 3.5 parts _{[[Ni (C 2 H 5} NHCH 2 CH 2 NH 2)] 2+ [(C 6 H 5) ₄ B] ^2- ] Polyester modified silicone resin 0.5 part [X-24-8300 manufactured by Shin-Etsu Silicone Co., Ltd.] Dioxane 20 parts Methyl ethyl ketone 60 parts Cyclohexanone 10 parts.

Example 11 The procedure of Example 11 was repeated except that the composition of the coating solution for forming an image receiving layer was changed to the composition shown below, and the coating solution for forming an image receiving layer was sufficiently dried and then subjected to a heat treatment at 120 ° C. for 60 minutes. An image receiving sheet for thermal transfer recording was manufactured in the same manner as in Example 1, and an image was formed in the same manner as in Example 1 using the same ink sheet for thermal transfer recording as in Example 1, and the image was evaluated. The results are shown in Table 1.

[0135] Coating solution for forming image receiving layer; epoxy resin 6 parts [manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 1001, epoxy equivalent : 460] Metal ion-containing compound 3.5 parts [[Ni (C ₂ H ₅ NHCH ₂ CH ₂ NH ₂ )] ²⁺ [(C ₆ H ₅ ) ₄ B] ^2- ] Polyester modified silicone resin 0.5 part [X-24-8300 manufactured by Shin-Etsu Silicone Co., Ltd.] Dioxane 20 parts Methyl ethyl ketone 60 parts Cyclohexanone 10 parts.

Example 12 The procedure of Example 12 was repeated except that the composition of the coating solution for forming an image receiving layer was changed to the composition shown below, and the coating solution for forming an image receiving layer was sufficiently dried, and then overheated at 80 ° C. for 60 minutes. An image receiving sheet for thermal transfer recording was manufactured in the same manner as in Example 1, and an image was formed in the same manner as in Example 1 using the same ink sheet for thermal transfer recording as in Example 1, and the image was evaluated. The results are shown in Table 1.

Epoxy resin: 3 parts [Coating liquid for forming an image receiving layer; Epoxy coat 1001, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent : 460] Polyvinyl chloride resin ········ 3 parts [TK600 manufactured by Shin-Etsu Chemical Co., Ltd.] Metal ion-containing compound ········ 3.5 parts [[Ni (C ₂ H ₅ NHCH ₂ CH ₂ NH ₂ )] ²⁺ [(C ₆ H ₅ ) ₄ B] ^2- ] Polyester-modified silicone resin 0.5 parts [X-24-8300, manufactured by Shin-Etsu Silicone Co., Ltd.] Dioxane 20 parts Methyl ethyl ketone ... 60 parts cyclohexanone ... 10 parts.

Example 13 The procedure of Example 13 was repeated except that the composition of the coating solution for forming an image receiving layer was changed to the composition described below, the coating solution for forming an image receiving layer was sufficiently dried, and then overheated at 80 ° C. for 60 minutes. An image receiving sheet for thermal transfer recording was manufactured in the same manner as in Example 1, and an image was formed in the same manner as in Example 1 using the same ink sheet for thermal transfer recording as in Example 1, and the image was evaluated. The results are shown in Table 1.

Coating solution for forming image receiving layer; epoxy resin 2.5 parts [manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 1001, epoxy equivalent : 460] Polyvinyl chloride resin ········ 3 parts [TK600 manufactured by Shin-Etsu Chemical Co., Ltd.] Metal ion containing compound ······ 3.5 parts [[Ni (C ₂ H ₅ NHCH ₂ CH ₂ NH ₂ )] ²⁺ [(C ₆ H ₅ ) ₄ B] ^2- ] Polyester-modified silicone resin 0.5 parts [X-24-8300, manufactured by Shin-Etsu Silicone Co., Ltd.] Alkyl phthalate 0.5 parts [DOP, manufactured by Daihachi Chemical Co., Ltd.] Dioxane 40 parts Methyl ethyl ketone ... 40 parts Cyclohexanone ... 10 parts.

Example 14 The procedure of Example 14 was repeated, except that the composition of the coating solution for forming an image receiving layer was changed to the following, and the coating solution for forming an image receiving layer was sufficiently dried and then subjected to a heat treatment at 120 ° C. for 60 minutes. An image receiving sheet for thermal transfer recording was manufactured in the same manner as in Example 1, and an image was formed in the same manner as in Example 1 using the same ink sheet for thermal transfer recording as in Example 1, and the image was evaluated. The results are shown in Table 1.

Epoxy resin: 5 parts [Coating liquid for forming an image receiving layer; Epoxy coat 1001, Epoxy equivalent, manufactured by Yuka Shell Epoxy Co., Ltd.] : 460] Metal ion-containing compound 3.5 parts [[Ni (C ₂ H ₅ NHCH ₂ CH ₂ NH ₂ )] ²⁺ [(C ₆ H ₅ ) ₄ B] ^2- ] Polyester modified silicone resin 0.5 part [Shin-Etsu Silicone Co., Ltd., X-24-8300] Alkyl phthalate ester 0.5 parts [DOP by Daihachi Chemical Co., Ltd.] Inorganic fine particles 0.5 parts [Toshiba Silicone Co., Ltd.] , Tospearl 104] Dioxane 20 parts Methyl ethyl ketone ......... 60 parts of cyclohexanone · · · · · · · · 10 parts.

Comparative Example 1 An image receiving sheet for thermal transfer recording was produced in the same manner as in Example 1 except that the composition of the coating solution for forming an image receiving layer was changed to the following, and the same thermal transfer as in Example 1 was performed. Using the recording ink sheet, an image was formed in the same manner as in Example 1, and the image was evaluated. The results are shown in Table 1.

Coating liquid for forming image receiving layer; polyvinyl chloride resin 6 parts [TK600, manufactured by Shin-Etsu Chemical Co., Ltd.] Metal ion-containing compound ............ 3.5 parts _{[[Ni (C 2 H 5} NHCH 2 CH 2 NH 2)] 2+ [(C 6 H 5) 4 B] 2-] polyester-modified silicone Resin: 0.5 parts [Shin-Etsu Silicone Co., Ltd., X-24-8300] Dioxane: 20 Part Methyl ethyl ketone 60 parts Cyclohexanone 10 parts.

(Comparative Example 2) An image receiving sheet for thermal transfer recording was produced in the same manner as in Example 1 except that the composition of the coating solution for forming an image receiving layer was changed to the following, and the same thermal transfer as in Example 1 was performed. Using the recording ink sheet, an image was formed in the same manner as in Example 1, and the image was evaluated. The results are shown in Table 1.

Coating Solution for Forming Image Receiving Layer; Vinyl Chloride Copolymer ..... 6 parts [Laloflex MP25, manufactured by BASF Corporation] Metal ion-containing compound .............. 3.5 parts _{[[Ni (C 2 H 5} NHCH 2 CH 2 NH 2)] 2+ [(C 6 H 5) 4 B] 2-] polyester 0.5 parts of modified silicone resin [X-24-8300 manufactured by Shin-Etsu Silicone Co., Ltd.] Dioxane・ 20 parts Methyl ethyl ketone ・ ・ ・ ・ ・ ・ ・ 60 parts Cyclohexanone ・ ・ ・ ・ ・ ・ ・ 10 parts.

Comparative Example 3 An image receiving sheet for thermal transfer recording was produced in the same manner as in Example 1 except that the composition of the coating solution for forming an image receiving layer was changed to the following, and the same thermal transfer as in Example 1 was performed. Using the recording ink sheet, an image was formed in the same manner as in Example 1, and the image was evaluated. The results are shown in Table 1.

Coating solution for forming image receiving layer; polyvinyl chloride resin 5.5 parts [TK600, manufactured by Shin-Etsu Chemical Co., Ltd.] Metal ion-containing compound ............ 3.5 parts _{[[Ni (C 2 H 5} NHCH 2 CH 2 NH 2)] 2+ [(C 6 H 5) 4 B] 2-] polyester-modified silicone Resin: 0.5 part [Shin-Etsu Silicone Co., Ltd., X-24-8300] Phthalic acid alkyl ester: 0.5 part [Large Hachikagaku Co., Ltd., DOP] Dioxane 20 parts Methyl ethyl ketone 60 Part Cyclohexanone 10 parts.

[0148]

[Table 1]

[0149]

According to the image receiving sheet for thermal transfer recording of the present invention, an image can be obtained at a high transfer density and the image storability such as heat resistance and light resistance is excellent.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-59-171688 (JP, A) JP-A-62-152897 (JP, A) JP-A-1-166983 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) B41M 5/38

Claims (1)

(57) [Claims] 1. A laminate comprising a support and a resin containing a metal ion-containing compound and having a bisphenol skeleton represented by the following formula [I] and / or a resin having an epoxy group in the molecule. An image receiving sheet for thermal transfer recording, characterized in that: —O—C ₆ H ₄ —X—C ₆ H ₄ —O— (I) [where X is —CR ¹ R ² — (where R ¹
And R ² represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acyl group, an aryl group, and a cycloalkyl group, respectively, and may be the same or different. ), —O—, —SO ₂ —, or a single bond. ]