JPH0542773A - Preparation of image receiving sheet for thermal transfer recording - Google Patents

Abstract

PURPOSE:To prepare an image receiving sheet for thermal transfer recording equipped with an image receiving layer having a metal ion-containing compound by simple operation suitably using even a resin hardly soluble in a solvent dissolving said metal ion-containing compound without using a solvent and deteriorating working environment. CONSTITUTION:An image receiving sheet for thermal transfer recording is obtained by laminating sheet composed of a composition consisting of a metal ion-containing compound and a binder to a support.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an image-receiving sheet for heat-sensitive transfer recording, and more specifically, a resin which is hardly soluble in a solvent that dissolves a compound containing a metal ion is formed in a suitable image-receiving layer. The present invention relates to a method for producing a heat-sensitive transfer recording image-receiving sheet.

[0002]

2. Description of the Related Art Conventionally, many IDs such as identification cards, driver's licenses, membership cards, etc.
Image recording bodies such as cards are used. An ID card usually has a person image for confirming the card holder and various items to be described. Since the person image is usually formed as a grayscale image, it can be a gradation information-containing image. The various items to be described include, for example, the address, name, date of birth, department, effective date, etc. in the case of identification, and in the driver's license, for example, the date of birth and name of the person. , License number, license type, etc. Since these items to be described are usually written with letters, numbers, symbols, etc., they can be used as a character information containing image.

In recent years, an ID card having a gradation image formed by a sublimation type thermal transfer system has appeared because a beautiful image can be easily formed. This sublimation type thermal transfer system is generally an ink of an ink sheet having an image receiving layer of a thermal transfer recording image-receiving sheet having an image receiving layer formed on a support and an ink layer containing a sublimable dye on the support. By superimposing a layer and heating imagewise, the sublimable dye is diffused and moved to the image receiving layer,
Therefore, it refers to a method of forming a gradation image such as a human face image in the image receiving layer.

In this sublimation type thermal transfer system, a metal ion-containing compound which forms a chelate with the sublimable dye is contained in the image-receiving layer in order to improve the fixability of the image by the sublimable dye and the durable storage of the image. There is an image receiving sheet for thermal transfer recording.

This image-receiving sheet for heat-sensitive transfer recording is produced by applying a coating solution prepared by dissolving a metal ion-containing compound and a resin in a solvent onto the surface of a support and drying it. In this case, as the resin for forming the image receiving layer,
It must be a resin that is soluble in a solvent that dissolves the metal ion-containing compound. Therefore, even a resin having suitable characteristics for forming an image receiving layer, a resin that does not dissolve in a solvent that dissolves a metal ion-containing compound cannot be used as a material for an image receiving sheet for thermal transfer recording. In addition, since the solvent is usually an organic solvent, when the coating liquid is applied onto a support and then dried, a large amount of vapor of the organic solvent is generated, which has a serious influence on the health of workers. give. Therefore, when a heat-sensitive transfer recording image-receiving sheet is manufactured using the coating liquid, a large-scale duct that does not leak the vapor of the organic solvent generated during drying to the outside is required.

The present invention has been made based on the above circumstances. That is, the present invention can be suitably used as a material for an image receiving layer even if it is a resin that has not been conventionally considered as a resin for an image receiving layer because it is not easily dissolved in a solvent that dissolves a metal ion-containing compound. An object of the present invention is to provide a method for producing an image-receiving sheet for heat-sensitive transfer recording, which is capable of producing a vapor of an organic solvent at the time of production, and can therefore achieve miniaturization of a production apparatus.

[0007]

The present invention according to claim 1 for solving the above-mentioned problems comprises an image-receiving layer sheet and a support sheet obtained from a resin composition containing a metal ion-containing compound. A method for producing an image-receiving sheet for heat-sensitive transfer recording, comprising the steps of: bonding a thermoplastic resin composition containing a metal ion-containing compound to a support for heating. A method for producing an image-receiving sheet for heat-sensitive transfer recording, comprising laminating the sheet by extrusion laminating, wherein the present invention according to claim 3 comprises heating and melting a thermoplastic resin composition containing a metal ion-containing compound. A method for producing an image-receiving sheet for heat-sensitive transfer recording, which comprises co-extruding with a thermoplastic resin or a thermoplastic resin composition serving as a support.

The present invention will be described in detail below. The image-receiving sheet for heat-sensitive transfer recording of a preferred embodiment produced by the method of the present invention has an image-receiving layer having a metal ion-containing compound on one surface of the support, and the other surface of the support. It has a writing layer. Hereinafter, preferred examples of the present invention will be sequentially described.

[1]. Image-Receiving Sheet for Thermal Transfer Recording —Support— Examples of the support include paper, coated paper, various papers such as synthetic paper (polypropylene, polystyrene, or a composite material obtained by laminating them with paper), and white chloride. Various plastic films or sheets such as vinyl resin sheets, white polyethylene terephthalate base film, transparent polyethylene terephthalate base film, polyethylene naphthalate base film, films or sheets made of various metals, and various ceramics Examples include films and sheets.

In the support, white pigments such as titanium white, magnesium carbonate, zinc oxide, barium sulfate, silica, talc, clay and calcium carbonate are added in order to enhance the sharpness of the image formed in the subsequent step. It is preferably added.

Furthermore, if it is desired to obtain an ID card such as an automobile license, the support is made of a sheet or film made of a composition of the white pigment and a vinyl chloride resin described later or polyethylene terephthalate. Is preferred.

The thickness of the support is usually 20 to 3000 μm,
It is preferably 30 to 1000 μm.

The support may be provided with an emboss, a sign, an IC memory, an optical memory, a magnetic recording layer, and other printing as required.

-Image Receiving Layer- The image receiving layer laminated on the surface of the support can be formed with a binder, a metal ion-containing compound, and various additives which are blended if necessary.

The thickness of the image receiving layer formed on the surface of the support is generally from 2 to 50 μm, preferably from 3 to 20 μm.

1. Binder The binder for the image receiving layer in the present invention can be appropriately selected and used from generally known binders for image receiving layers for sublimation type thermal transfer recording. As the main binder, ionomer, ethylene-vinyl acetate copolymer, nylon resin, polystyrene resin, polyurethane resin, polyethylene terephthalate resin polybutylene terephthalate resin, LLDPE, LDPE, MDPE,
Various binders such as polyethylene resin such as HDPE, polypropylene resin, polybutene resin, ethylene-ethyl acrylate copolymer resin, and polyolefin resin such as methylpentene polymer can be used. The binder may be selected alone or in combination of two or more thereof.

2. Metal Ion-Containing Compound As the metal ion constituting the metal ion-containing compound contained in the image receiving layer, there may be mentioned divalent and polyvalent metals belonging to Groups I to VIII of the periodic table.
l, Co, Cr, Cu, Fe, Mg, Mn, Mo, N
i, Sn, Ti and Zn are preferred, especially Ni, C
u, Co, Cr and Zn are preferred.

The compound containing these metal ions is preferably an inorganic or organic salt of the metal and a complex of the metal. Specific examples are Ni ²⁺ , Cu ²⁺ and Co.
A complex containing ²⁺ , Cr ²⁺ and Zn ²⁺ and represented by the following general formula is preferably used.

[M (Q ₁ ) _k (Q ₂ ) _m (Q ₃ ) _n ] ^{p +} p (L ⁻ ) where M represents a metal ion, and Q ₁ , Q ₂ and Q ₃
Each represents a coordination compound capable of forming a coordination bond with a metal ion represented by M, and these coordination compounds are selected from coordination compounds described in, for example, “Chelate Chemistry (5) (Nankodo)”. be able to. Particularly preferably, a coordination compound having at least one amino group that forms a coordinate bond with a metal can be mentioned, and more specifically, ethylenediamine and its derivatives, glycinamide and its derivatives, picolinamide and its derivatives can be mentioned. Be done.

L is a counter anion capable of forming a complex,
Examples thereof include inorganic compound anions such as Cl, SO ₄ , and ClO ₄ , and organic compound anions such as benzenesulfonic acid derivatives and alkylsulfonic acid derivatives. Particularly preferred are tetraphenylboron anion and its derivatives, and alkylbenzenesulfonic acid anion and its derivatives. It is a derivative.

K represents an integer of 1, 2 or 3, m represents 1, 2 or 0, and n represents 1 or 0. These are those in which the complex represented by the above general formula is tetradentate. , Hexadentate, or the number of Q ₁ , Q ₂ , and Q ₃ ligands. p represents 1, 2 or 3.

Examples of this type of metal ion-containing compound include
Japanese Patent Application No. 1-217906 and Japanese Unexamined Patent Publication No. 1-24453.
Those exemplified in No. 9 specification can be mentioned.

Examples of this type of metal ion-containing compound include:
Mention may be made of those exemplified in US Pat. No. 4,987,049. When the above-mentioned metal ion-containing compound is added, the addition amount thereof is 0.5 to the image receiving layer.
Preferably ^{20g / m 2, 1~15g / m} 2 is more preferable.

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 hot solvent (a heat-melting substance), etc. may be added as a sensitizer.

The release agent can improve the releasability between the thermal transfer recording ink sheet and the image receiving layer described later.
Such release agents include silicone oils (including those called silicone resins); solid waxes such as polyethylene wax, amide wax, and Teflon powder; fluorine-based and phosphoric ester-based surfactants, etc. Among them, silicone oil is preferable.

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 in order to improve the compatibility with the binder.

As the modified silicone oil, polyester modified silicone resin (or silicone modified polyester resin), acrylic modified silicone resin (or
Silicon modified acrylic resin), urethane modified silicone resin (or silicone modified urethane resin), cellulose modified silicone resin (or silicon modified cellulose resin), alkyd modified silicone resin (or silicone modified alkyd resin), epoxy modified silicone resin ( Alternatively, silicone-modified epoxy resin) can be used.

That is, a polyester-modified silicone resin containing a polysiloxane resin in the main chain and obtained by copolymerizing polyester in a block form, and a silicon-modified polyester resin having a dimethylpolysiloxane moiety as a side chain bonded to the polyester main chain. Block copolymers of dimethylpolysiloxane and polyester, alternating copolymers, graft copolymers, random copolymers and the like can also be used as the modified silicone oil or resin.

Particularly, in the present invention, it is preferable to add a polyester-modified silicone resin.

A typical polyester-modified silicone resin is, for example, a block copolymer of dimethylpolysiloxane and a polyester which is a ring-opening polymer of a copolymer of diol and dibasic acid or caprolactone (both of dimethylpolysiloxane). (A copolymer including a polyester whose one end or one end is blocked with the above polyester part, or conversely, the above polyester is blocked with dimethylpolysiloxane.) Examples thereof include a copolymer obtained by binding siloxane.

The addition amount of these simple addition type silicone oils cannot be uniformly determined because it may vary depending on the type, but generally speaking, generally speaking, the binder in the image receiving layer is usually used. 0.5 to
It is 50% by weight, preferably 1 to 20% by weight.

As the curing reaction type silicone oil,
Examples include reaction-curable type, photo-curable type, and catalyst-curable type.

As the reaction-curable silicone oil, there is one obtained by reaction-curing an amino-modified silicone oil and an epoxy-modified silicone oil.

As the catalyst-curable or photo-curable silicone oil, KS-705F-PS, KS-705 can be used.
F-PS-1, KS-770-PL-3 [Catalyst-curable silicone oil: manufactured by Shin-Etsu Chemical Co., Ltd.], KS
-720, KS-774-PL-3 [all are photocurable silicone oil: manufactured by Shin-Etsu Chemical Co., Ltd.] and the like.

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

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

Next, as the above-mentioned antioxidant, Japanese Patent Laid-Open No.
9-182785, 60-130735, JP-A-1-
Examples include the antioxidants described in 127387 and the like, and compounds known to improve the image durability of photographs and other image recording materials.

As the UV absorber and the light stabilizer,
JP-A-59-158287, JP-A-63-74686,
63-145089, 59-196292, 62-229594, 63-122596, 61.
Examples thereof include compounds described in JP-A-283595 and JP-A-1-204788, and compounds known to improve image durability in photographs and other image recording materials. Examples of the filler include inorganic fine particles and organic resin particles. The inorganic fine particles include silica gel, calcium carbonate, titanium oxide,
Acid clay, activated clay, alumina, etc. can be mentioned,
Examples of the organic fine particles include resin particles such as fluororesin particles, guanamine resin particles, acrylic resin particles, and silicon resin particles. These inorganic / organic resin particles differ depending on the specific gravity, but it is preferably added in an amount of 0.1 to 70% by weight.

Typical 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 phthalic acid esters (for example, dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, didecyl phthalate, etc.), trimellitic acid esters (for example, octyl trimellitic acid ester, isononyl trimellitic acid). Ester, trimellitic acid isodesol ester, etc., pyromellitic acid octyl ester and other pyromellitic acid esters, adipate esters (dioctyl adipate, methyllauryl adipate, di-2-ethylhexyl adipate, ethyl adipate) Lauryl etc.), other oleic acid esters, succinic acid esters, maleic acid esters, sebacic acid esters, citric acid esters, epoxidized soybean oil, epoxidized linseed oil, epoxy stearic acid epoxies, and Acid triphenyl, orthophosphoric acid esters such as tricresyl phosphate, triphenyl phosphite, tris-tridecyl phosphite, dibutyl
Examples thereof include phosphites such as hydrogen phosphite, glycol esters such as ethylphthalylethyl glycolate and butylphthalylbutyl glycolate.

Examples of the hot solvent include alcohols such as terpineol, menthol, 1,4-cyclohexanediol and phenol, amides such as acetamide and benzamide, coumarin and esters such as benzyl cinnamate, diphenyl ether and crown ether. Ethers, camphor, ketones such as p-methylacetophenone, aldehydes such as vanillin and dimethoxybenzaldehyde, hydrocarbons such as norbornene and stilbene,
Single molecular compounds represented by higher fatty acids such as margaric acid, higher alcohols such as eicosanol, higher fatty acid esters such as cetyl palmitate, higher fatty acid amides such as stearic acid amide, higher amines such as behenylamine, carnauba wax, beeswax , Waxes such as paraffin wax, ester wax, montan wax and amide wax, ester gum, rosin maleic acid resin, rosin phenol resin and other rosin derivatives, phenol resin,
Ketone resin, epoxy resin, diallyl phthalate resin,
Examples thereof include terpene resins, aliphatic hydrocarbon resins, cyclopentadiene resins, polyolefin resins, polymer compounds represented by polyolefin oxides such as polyethylene glycol and polypropylene glycol.

In the present invention, the addition amount of all the additives is usually 0.1 to the binder in the image receiving layer.
It is in the range of 10% by weight.

-Other Layers- A writing layer may be formed on the surface of the support opposite to the image receiving layer forming surface. Use this image recording body as an ID such as a car license
In the case of a card, it is particularly preferable to provide a writing layer. By forming the writing layer, various information can be written on the ID card, which is convenient.

The description of the writing layer in the present invention is replaced with the description of the "writing layer" described in JP-A-1-205155, page 4, upper right column, line 14 to page 4, lower right column, line 2. , Its detailed description is omitted.

The heat-sensitive transfer recording image-receiving sheet has a release agent (the above-mentioned silicone resin, modified silicone resin or silicone) on the surface of the image-receiving layer in order to more effectively prevent fusion with the ink layer of the heat-sensitive transfer recording ink sheet. A release layer containing an oil film or a cured product thereof may be laminated. The thickness of this release layer is usually 0.03 to 2.0 μm.

Further, a cushion layer or a barrier layer may be provided between the support and the image receiving layer. When the cushion layer is provided, noise can be reduced and an image corresponding to image information can be transferred and recorded with good reproducibility. Examples of the material forming the cushion layer include urethane resin, acrylic resin, ethylene resin, butadiene rubber, and epoxy resin, and the thickness of the cushion layer is usually 1
˜50 μm, preferably 3 to 30 μm.

The provision of the barrier layer prevents the dye from diffusing into the support and prevents the dye from bleeding into the support. Examples of the material forming the barrier layer include hydrophilic binders such as gelatin and casein, and polymers having a high Tg.

[2] Production of image-receiving sheet for heat-sensitive transfer recording In the production method of the present invention, heat-sensitive transfer is carried out by laminating an image-receiving layer sheet obtained from the image-receiving layer composition and a support sheet. A recording image-receiving sheet can be manufactured.

As a method for laminating the image-receiving sheet and the support sheet, dry lamination or hot-melt lamination which is applied with an adhesive, or a thermoplastic resin composition for an image-receiving layer which is kneaded without using an adhesive is in a molten state. Extrusion lamination in which the composition is extruded on a sheet for a support and laminated at the same time, a thermoplastic resin composition for an image receiving layer and a thermoplastic resin or a thermoplastic resin composition for a support are simultaneously extruded from separate extruders, and a T-die or a round die. Examples thereof include T-die method co-extrusion lamination produced by laminating these thermoplastic resin compositions or thermoplastic resins inside or outside the die, and round die method co-extrusion lamination.

The above-mentioned thermoplastic composition for the image receiving layer can be prepared by kneading the metal ion-containing compound, the binder and the additives to be added as necessary with a mixer such as a kneader or a kneader. .. Among the mixers, an extrusion kneader is preferable. At the time of kneading, heating may be performed at a temperature at which the binder melts.

The thermoplastic composition for image-receiving layer prepared by an extrusion kneader is extruded into a sheet (including a film) by the extrusion kneader.

As for the apparatus and technology relating to lamination, known ones such as those described in "Lamination Manual" and "New Lamination Manual" (editor, publisher Masayoshi Araki) published by Processing Technology Research Group are available. Can be adopted.

[3] Use of Thermal Transfer Recording Image-Receiving Sheet The thermal transfer recording image-receiving sheet of the present invention is particularly used for manufacturing an image recording body such as an ID card.

The image recording medium can be manufactured by using the sublimation type thermal transfer recording ink sheet and the heat-meltable ink sheet.

(A) Sublimation-Type Thermal Transfer Recording Ink Sheet The sublimation-type thermal transfer recording ink sheet forms a gradation information-containing image on the image receiving layer of the thermal transfer recording image-receiving sheet. Here, the gradation information-containing image means that the image has gradation.
For example, an image equivalent to a photographic image such as a person image or a landscape is shown.
The sublimation type thermal transfer recording ink sheet can be composed of a support and a sublimable dye-containing ink layer formed thereon.

—Sublimable Dye-Containing Ink Layer— The sublimable dye-containing ink layer basically contains a sublimable dye and a binder.

1. Sublimable dyes The heat diffusible dyes include, for example, JP-A-59-78893, JP-A-59-109349, and JP-A-2-213303.
Cyan image-forming dyes (hereinafter referred to as cyan dyes), which are capable of forming bidentate chelates with at least the above metal ion-containing compound, and magenta image formation described in JP-A-2-214719 and JP-A-2-203742. Examples thereof include dyes (hereinafter referred to as magenta dyes) and yellow image forming dyes (hereinafter referred to as yellow dyes).

A dye represented by the following general formula (Formula 1) is preferable.

[0060]

[Chemical 1]

However, in the formula, X ¹ represents a group of atoms necessary for completing an aromatic carbocycle or a heterocycle in which at least one ring is composed of 5 to 7 atoms,
At least one of the adjacent positions of the carbon atoms bonded to the azo bond is a nitrogen atom or a carbon atom substituted with a chelating group. X ² represents an aromatic heterocycle or an aromatic carbocycle in which at least one ring is composed of 5 to 7 atoms. G represents a chelating group.

The heat diffusible dye contained in the ink layer may be any of a yellow dye, a magenta dye and a cyan dye as long as the image to be formed is a single color. Also, depending on the color tone of the image to be formed,
Any two or more of the above three kinds of dyes or other heat diffusible dyes may be contained.

The amount of the heat diffusible dye used is usually 0.1 to ²⁰ g, preferably 0.2 to 5 per 1 m ^{2 of} the support.
It is g.

The binder for the ink layer is not particularly limited, and any conventionally known binder can be used. Furthermore, various conventionally known additives can be appropriately added to the ink layer.

For a sublimation type thermal transfer recording ink sheet, an ink layer forming coating liquid prepared by dispersing or dissolving the various components forming the ink layer in a solvent is prepared, and this is used as a support for an ink sheet. It can be manufactured by coating on the surface and drying. The thickness of the ink layer thus formed is usually 0.2 to 10 μm, preferably
It is 0.3 to 3 μm.

2. Binder-As a binder for the sublimable dye-containing ink layer, a cellulose resin such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate; polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl. Pyrrolidone, polyester, polyvinyl acetate, polyacrylamide, polyvinyl acetoacetal, styrene resin, styrene copolymer resin, vinyl resin such as polyacrylic acid ester, polyacrylic acid, acrylic acid copolymer, rubber resin, ionomer resin , Olefin resins and the like.

Among these resins, polyvinyl butyral, polyvinyl acetoacetal or cellulose resins having excellent acid resistance are preferable.

The various binders can be used alone or in combination of two or more.

The weight ratio of the binder to the sublimable dye is preferably 1:10 to 10: 1, particularly preferably 2: 8 to 8: 2.

3. Other optional components Further, various additives may be added to the sublimable dye-containing ink layer within a range not impairing the object of the present invention.

Examples of the additives include silicone resin, silicone oil (reaction-curable type is also possible), silicone-modified resin, fluororesin, surfactant, and releasable compounds such as waxes, fine metal powder, silica gel, and metal oxide. Substances, carbon black, and fillers such as resin fine powder, and curing agents that can react with binder components (for example, radiation-active compounds such as isocyanates, acrylics, and epoxies)
And so on.

Further, as an additive, a heat-melting substance for promoting transfer, for example, a compound described in JP-A-59-106997, such as wax or higher fatty acid ester, can be mentioned.

-Support-As a support for the sublimation type thermal transfer recording ink sheet, any support may be used as long as it has good dimensional stability and can withstand heat at the time of recording by a thermal head, but it may be condenser paper or glassine paper. Heat-resistant plastic films such as thin paper, polyethylene terephthalate, polyethylene naphthalate, polyamide, polycarbonate, polysulfone, polyvinyl alcohol cellophane, and polystyrene can be used.

The thickness of the support is preferably from 2 to 10 μm, and the support has an undercoat layer for the purpose of improving the adhesiveness with a binder and preventing the transfer of dye to the support side and dyeing. May be.

Further, a sticking prevention layer may be provided on the back surface of the support (on the side opposite to the sublimable dye-containing ink layer) for the purpose of preventing the head from fusing, sticking, or wrinkling on the support. ..

The thickness of this anti-sticking layer is usually
It is 0.1 to 1 μm.

The shape of the support is not particularly limited,
For example, a wide sheet or film, a narrow tape or a card, or any other shape.

(B) Method of Forming Gradation Information-Containing Image To form a gradation information-containing image, the sublimable dye-containing ink layer of the sublimation-type thermal transfer recording ink sheet and the image-receiving sheet for thermal transfer recording are received. Layers are overlaid and imagewise heat energy is applied to the sublimable dye-containing ink layer and the image receiving layer.

The sublimable dye in the sublimable dye-containing ink layer is vaporized or sublimated by an amount corresponding to the applied heat energy, and is transferred to the image receiving layer side and received. as a result,
Since the sublimable dye transfers to the image receiving layer in an amount according to the amount of heat energy, a gradation information-containing image is formed on the image receiving layer.
At this time, since the metal ion-containing compound exists in the image receiving layer, the sublimable dye that has diffused and transferred from the ink layer to the image receiving layer forms a chelate with the metal ion containing compound and is fixed in the image receiving layer. Therefore, by using the image-receiving sheet for thermal transfer recording of the present invention, it is possible to form a gradation information-containing image excellent in fixing property and image storability on the image-receiving layer.

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

When a thermal head is used as a heat source for applying heat energy, it is preferable to change the applied heat energy 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 giving heat energy, the heat energy to be given can be changed by changing the light amount of the 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 an infrared absorbing material in the case of a semiconductor laser) is added to the sublimable dye-containing ink layer or the sublimable dye-containing ink. It is good to let it exist near the layer.

When laser light is used, it is advisable to bring the sublimation type thermal transfer recording ink sheet and the thermal transfer recording image receiving sheet into close contact with each other.

If a dot generator with a built-in acousto-optical element is used, it is possible to give thermal energy according to the size of the halftone dot.

(C) Thermofusible Ink Sheet An image recording body such as an ID card has the gradation information-containing image and the character information-containing image on the surface of the image receiving layer. This character information-containing image can be formed by using a heat-meltable ink sheet or a sublimation type thermal transfer recording ink sheet. This text information containing image often displays specific information content regarding an individual who has an ID card.

The heat-meltable ink sheet is formed by laminating a heat-meltable ink layer on a support.

1. Support It is desirable that the support in the heat-fusible ink sheet has good heat resistance and high dimensional stability.

The material thereof is, for example, Japanese Patent Laid-Open No. 63-63.
-193886, page 2, lower left column, lines 12 to 18
The films or sheets mentioned in the rows can be used.

The thickness of the support is usually 30 μm or less, preferably 2 to 30 μm. When the thickness of the support is more than 30 μm, the thermal conductivity may be deteriorated and the print quality may be deteriorated.

In this heat-meltable ink sheet, the constitution of the back side of the support is arbitrary, and a backing layer such as a sticking prevention layer may be provided.

2. Heat-meltable ink layer The heat-meltable ink layer is composed of a heat-meltable compound, a thermoplastic resin, a colorant and the like.

As the above-mentioned heat-meltable compound, any of those generally used in the heat-meltable ink layer of this kind of heat-meltable ink sheet can be used. Specifically, for example, polystyrene resin, Low molecular weight thermoplastic resins such as acrylic resins, styrene-acrylic resins, polyester resins and polyurethane resins, JP-A-63-193886.
From page 4, upper left column, line 8 to the same page, upper right column, line 12, there can be mentioned the exemplified substances, and in addition to these, rosin, hydrogenated rosin, polymerized rosin, rosin-modified glycerin, rosin Examples include modified maleic acid resins, rosin-modified polyester resins, rosin-modified phenolic resins and rosin derivatives such as ester gums, and phenolic resins, terpene resins, ketone resins, cyclopentadiene resins and aromatic hydrocarbon resins. it can.

These heat-fusible compounds have a molecular weight of usually 10,000 or less, particularly 5,000 or less,
Those having a melting point or a softening point in the range of 50 to 150 ° C. are preferable.

The heat-meltable compounds may be used alone or in combination of two or more.

As the thermoplastic resin used as a component of the heat-meltable ink layer, various kinds of resins such as those usually used for the heat-meltable ink layer of this kind of heat-meltable ink sheet can be used. Yes, for example, JP-A-63-
Japanese Patent No. 193886, page 4, upper right column, page 5, upper left column, 18th
The exemplified substances can be listed in the row.

As the colorant used as a component of the heat-meltable ink layer, those usually used for the heat-meltable ink layer of this kind of heat-meltable ink sheet can be used without limitation, For example, JP-A-63-1938
Examples thereof include pigments such as inorganic pigments and organic pigments, and dyes such as organic dyes described in JP-A No. 86, page 5, upper right column, lines 3 to 15.

These various colorants may be used alone or in combination of two or more as required.

If necessary, other additive components other than those described above can be appropriately added to the heat-meltable ink layer as long as the object of the present invention is not impaired.

For example, this heat-meltable ink layer may contain a fluorine-based surfactant. The blocking phenomenon of the ink layer can be prevented by containing the fluorine-based surfactant.

Further, in order to improve the sharpness of the transferred character information image, that is, to cut the character boundary portion, organic fine particles,
It is also effective to add inorganic fine particles and incompatible resin.

The film thickness of the heat-meltable ink layer is usually
It is preferably 0.6 to 5.0 μm, and particularly preferably 1.0 to 4.0 μm.

(D) Formation of Image Containing Character Information The heat-melt transfer method using the heat-meltable ink sheet is not different from the usual heat-sensitive transfer recording method.
A case where the most typical thermal head is used as a heat source will be described as an example.

First, the heat-meltable ink layer of the heat-meltable ink sheet and the image-receiving surface of the base material are brought into close contact with each other, and if necessary, the heat pulse is applied from the back surface of the base material by the platen while the heat pulse is applied by the thermal head. To locally heat the heat-meltable ink layer corresponding to the desired printing or transfer pattern.

The heated portion of the heat-meltable ink layer rises in temperature and is quickly softened and transferred to the image receiving surface of the substrate.

The formation of the character information-containing image may be performed prior to the formation of the gradation information-containing image, and the formation of the character information-containing image after the gradation information-containing image is formed. Forming may take place.

(E) Character Information-Containing Image with Sublimation-Type Thermal Transfer Recording Ink Sheet Regarding the method for forming a character-information-containing image using the sublimation-type thermal transfer recording ink sheet and the sublimation-type thermal transfer recording ink sheet in this case, Since it has been described, its detailed description is omitted. [4] Formation of transparent protective layer A transparent protective layer is formed on the surface of the image receiving layer in order to protect the image containing the gradation information and the image containing the character information formed on the image receiving layer. In particular, in order to protect the image containing the gradation information, a transparent protective layer is formed on the image receiving surface having the image containing the gradation information, and the image receiving layer surface not covered with the transparent protective layer and the transparent protective layer contains the character information. An ultraviolet curable resin layer is formed on the surface of the image receiving layer having an image.

More specifically, this transparent protective layer prevents damage to the gradation information-containing image due to, for example, an ultraviolet curable resin coating agent used when providing an ultraviolet curable resin layer thereon or ultraviolet irradiation. It is provided for this purpose.

The area covered by this transparent protective layer is
It may be a minimum area having a gradation information containing image, or may be an image receiving layer surface area having both a gradation information containing image and a character information containing image.

—Structure of Transparent Protective Layer— As a transparent protective layer satisfying such requirements, Japanese Patent Laid-Open Publication No.
No. 3, 183881, page 9, lower left column, line 9 to line 1
It can be formed from the heat-fusible compound described on page 0, upper left column, line 15 and the thermoplastic resin exemplified on page 10, upper left column, line 16 to page 11, lower left column, line 9.

An ultraviolet absorber may be contained in the transparent protective layer, or a gradation information-containing image can be obtained from ultraviolet rays when the coating agent containing an ultraviolet curable prepolymer is irradiated with ultraviolet rays and cured. It is effective in protecting. Examples of the ultraviolet absorber include the compounds exemplified in the description of the image receiving layer. The blending amount of these in the transparent protective layer varies depending on the type of compound, and can be experimentally determined for each compound.

The thickness of the transparent protective layer is usually 0.5 to 20.0 μm, preferably 1.0 to 10.0 μm in consideration of the uniform coating property of the ultraviolet curable resin.

—Protective Layer-Forming Transfer Sheet— In order to form a transparent protective layer on the gradation information-containing image, it is preferable to use a protective layer-forming transfer sheet.

This transfer sheet for forming a protective layer can be constructed by laminating a release layer, a transparent protective layer, and an adhesive layer provided if necessary on a support in this order.

As a protective layer-forming transfer sheet of a preferred embodiment, a protective layer-forming sheet portion obtained by laminating the release layer and the transparent protective layer in this order on a support, and a heat-meltable ink sheet portion, The thing formed by dividing can be mentioned. In this transfer sheet, a character information-containing image can be formed on the image receiving surface of the support by the heat-fusible ink sheet portion, and the image receiving surface of the support can be formed by the protective layer forming sheet portion. A transparent protective layer can be simultaneously formed on the formed gradation information-containing image surface.

As the layer constitution in the heat-meltable ink sheet portion, the laminated constitution described in the above-mentioned section "(C) Heat-meltable ink sheet" can be adopted.

[0117]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following, "part" means "part by weight".

(Example 1) -Production of thermal transfer recording ink sheet-A 6 μm thick polyethylene terephthalate film [manufactured by Toray Industries, Inc.] as a support was coated with a coating liquid for forming an ink layer having the following composition on a wire. By the bar coating method,
A nitrocellulose solution containing 40% by weight of a silicone resin [SP-2105, manufactured by Dainichiseika Co., Ltd.] on the back surface of the flume on which no ink layer is formed is applied and dried so that the dry film thickness is 1 μm. Dry film thickness is 0.2
By coating and drying so as to have a thickness of .mu.m and performing a back surface treatment coating, yellow, magenta, and cyan color thermal transfer recording ink sheets were obtained.

Ink Layer Forming Coating Liquid; Thermal Diffusion Dye ... 3.0 Parts Yellow

[0120]

[Chemical 2]

Magenta

[0122]

[Chemical 3]

Cyan

[0124]

[Chemical 4]

Nitrocellulose: 3.0 parts [Celnova BTH1 / 2, manufactured by Asahi Kasei Corporation] Methyl ethyl ketone: ..... 44.0 parts Dioxane ..... 40.0 parts Cyclohexanone ..... ... 10.0 parts-Production of image-receiving sheet for heat-sensitive transfer recording-The composition for an image-receiving layer is laminated on the surface of a support made of a white polyethylene terephthalate sheet having a thickness of 350 µm by an extrusion laminator so as to have a thickness of 8 µm. By cutting the wide image-receiving sheet material having a thickness of 370 μm, a card-size image-receiving sheet for thermal transfer recording having a length and width of 54.0 mm × 85.5 mm was obtained.

Image-Receptive Layer-Forming Composition; Low-Molecular-Weight Polyethylene Resin 79.0 Parts [Mitsui High Wax Mitsui Petrochemical Co., Ltd.] Metal Ion-Containing Compound .............. 20.0 parts _{[[Ni (C 2 H 5} NHCH 2 CH 2 NH 2)] 2+ [(C 6 H 5) 4 B] 2-] polyester Modified silicone resin: 1.0 part [X-24-8300, manufactured by Shin-Etsu Chemical Co., Ltd.] Next, the following is formed on the back surface of the support opposite to the image receiving layer. A writing layer coating liquid having the composition was applied by reverse coating using a gravure roll formed by partial etching, and dried to form a writing layer having a thickness of 3.5 μm.

Coating liquid for writing layer; Saturated polyester resin: 90.0 parts [Vylon 200, manufactured by Toyobo Co., Ltd.] Calcium carbonate: 25.0 parts (Shiraishi calcium, Brilliant 15) Mixed solvent ... ··· 400.0 parts [toluene / methyl ethyl ketone (weight ratio 1: 1)]-Production of heat-meltable ink sheet-Hot meltability for a release layer having the following composition on the surface of a polyethylene terephthalate sheet having a thickness of 4.5 µm. The coating liquid for the ink layer and the coating liquid for the heat-fusible ink layer for the color material layer are applied by a wire bar method and dried to form a heat-meltable ink layer (release layer with a thickness of 1.6 μm as a whole) Thickness of 0.4 μm, color material layer thickness of 1.2 μm) .

Coating liquid for hot-melt ink layer (for release layer): Ethylene-vinyl acetate copolymer: 0.3 parts [EV-210, Mitsui DuPont Chemical Co., Ltd.] Carnauba wax ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 9.7 parts Mixed solvent ・ ・ ・ ・ ・ ・ ・ ・90.0 parts (methyl ethyl ketone / methyl isobutyl ketone = 1: 1) Coating liquid for hot-melt ink layer (for color material layer): Ethylene-vinyl acetate copolymer ... .................. 1.0 part [EV-40Y, manufactured by Mitsui DuPont Chemicals Ltd.] Carbon black ...・ ・ ・ 6.0 parts Phenolic resin ・ ・ ・ 12.0 parts [Tamanor 526, Arakawa Chemical ( )] Methyl ethyl ketone: 80.0 parts-Production of transfer sheet for forming protective layer-First, on the surface of a polyethylene terephthalate sheet having a thickness of 12 μm. A coating liquid for forming a release layer / protective layer having the following composition was applied by a wire bar method and dried to form a release layer / protective layer having a thickness of 1.0 μm. Coating liquid for forming release layer / protective layer: Phenoxy resin ・ ・ ・ 10.0 parts [Phenototo YP-50, Toto Kasei Co., Ltd. Manufacture] 1,4-dioxane ... 90.0 parts Next, for forming an adhesive layer having the following composition on the release layer / protective layer The coating liquid was applied by the wire-bar coating method and dried to form an adhesive layer having a thickness of 2.0 μm. Coating liquid for forming adhesive layer; acrylic resin: 10.0 parts [BR-82, manufactured by Mitsubishi Rayon Co., Ltd.] Benzotriazole -Based UV absorber: 2.0 parts (Tinuvin 320, manufactured by Ciba Geigy) Methyl ethyl ketone: 90 0.0 part-Manufacture of image recording body-First, the image-receiving layer of the image-receiving sheet for heat-sensitive transfer recording and the ink layer of the ink sheet for sublimation-type thermal transfer recording are superposed, and the thermal head is placed from the sublimation-type thermal transfer recording ink sheet side. Output 0.23W / dot, pulse width 0.3
By heating under a condition of ˜4.5 msec and a dot density of 16 dots / mm, a human face image having gradation is formed on the image receiving layer.

Next, the heat-meltable ink layer of the heat-meltable ink sheet is superposed on the surface of the image-receiving layer having this human face image, and the output is 0.5 W / dot using a thermal head.
Pulse width 1.0 msec, dot density 16 dots / mm
The character information was transferred to the image receiving layer by heating under the conditions of. Next, a transfer sheet for forming the protective layer is formed on the surface of the image receiving layer.
The diameter is 30mm and the contact length is 70m.
m rubber for hot stamping (rubber hardness 80)
Using a heat roller made by the manufacturer, temperature 210 ℃, pressure 20k
The transparent protective layer is transferred to the entire surface of the image receiving layer by heating under pressure under the conditions of g / cm ² and transfer speed of 2.5 cm / sec, and after transfer, the support of the transfer sheet for forming the protective layer is formed. Peeled off.

(Example 2) Instead of the low molecular weight polyethylene resin in the composition for forming an image receiving layer of Example 1, a low molecular weight polypropylene resin [Viscor, manufactured by Sanyo Kasei Co., Ltd.]
An image recording material was obtained in the same manner as in Example 1 except that was used.

(Example 3) The composition for forming an image receiving layer of Example 1 was changed as follows, and a sheet having a thickness of 9 µm was formed by an extruder, and the image receiving layer sheet and the same support as in Example 1 were formed. An image-receiving sheet for thermal transfer recording was obtained by performing hot melt lamination using the body and an adhesive having the following composition. Thereafter, an image recording material was prepared in the same manner as in Example 1.

Image-Receptive Layer-Forming Composition; Vinyl Chloride Resin: 58.8 Parts [Laroflex MP-60, manufactured by BASF Japan Ltd.] Chloride Vinyl resin: 15.0 parts [TK-300, Shin-Etsu Chemical Co., Ltd.] Tin stabilizer: 0.2 parts [FD-9 manufactured by Akishima Chemical Industry Co., Ltd.] Metal ion-containing compound 25.0 parts _{[Ni (C 2 H 5 NHCH} 2 CH 2 NH 2)] 2+ [(C 6 H 5) 4 B] 2-] polyester-modified silicone resin ........... 1.0 part [ X-24-8300, manufactured by Shin-Etsu Chemical Co., Ltd.] Adhesive; Polyester resin: 10.0 parts [Peth Resin S-110, High Matsu Yushi Co., Ltd.] Ethylene-vinyl acetate copolymer: 50.0 parts (Evaflex EV-210, manufactured by Mitsui DuPont Polychemical Co., Ltd.) Phenolic resin・ ・ ・ ・ ・ ・ ・ ・ ・ 40.0 parts [Tamanor 510, Arakawa Chemical Co., Ltd. \

[0133]

According to the method of the present invention, an image-receiving sheet for heat-sensitive transfer recording is produced by laminating an image-receiving sheet containing a metal ion-containing compound and a support, which is suitable as a resin for the image-receiving layer. It is possible to utilize a resin that has not been used due to the fact that is not easily dissolved in a solvent that dissolves the metal ion-containing compound.

Moreover, since the thermal transfer recording image-receiving sheet can be manufactured without using a solvent as in the conventional case, the working environment is not deteriorated by the solvent.

Further, unlike the conventional case, it is not necessary to prepare a coating solution for the image receiving layer, and only the image receiving layer sheet and the support are bonded, so that the manufacturing operation is extremely simple and easy.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Kunihiro Koshizuka No. 1 Sakuramachi, Hino City, Tokyo Konica Stock Company

Claims (3)

[Claims] 1. A method for producing an image-receiving sheet for heat-sensitive transfer recording, which comprises laminating an image-receiving layer sheet obtained from a thermoplastic resin composition containing a metal ion-containing compound and a support sheet. 2. A method for producing an image-receiving sheet for heat-sensitive transfer recording, which comprises heating and melting a thermoplastic resin composition containing a compound containing a metal ion, and laminating the thermoplastic resin composition on a support sheet by extrusion lamination. 3. An image-receiving sheet for heat-sensitive transfer recording, characterized in that a thermoplastic resin composition containing a metal ion-containing compound is heated and melted and coextruded together with the thermoplastic resin composition serving as a support or the thermoplastic resin. Manufacturing method.