JP2008080735A - Manufacturing method of thermal transfer printed matter, and thermal transfer sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of thermal transfer printed matter which makes a hue durability excellent in the thermal transfer printed matter formed by transferring a chelatable sublimable dye to an accepting layer of a thermal transfer image accepting sheet, makes it possible to form a protective layer on the accepting layer with good adhesion and excels in productivity. <P>SOLUTION: The manufacturing method of the thermal transfer printed matter has a thermal transfer process wherein a substrate and a dye layer of a thermal transfer sheet which is formed on the substrate and contains a binder resin and the chelatable sublimable dye, and a base and the accepting layer of the thermal transfer image accepting sheet which is formed on the base and contains a chelatable metal ion, are opposed to each other and heated and thereby the sublimable dye is transferred to the accepting layer, a protective layer forming process wherein the accepting layer having the sublimable dye transferred thereon and the substrate, and the protective layer of a protective layer thermal transfer sheet which is formed on the substrate and contains a thermal conversion substance, are opposed to each other and heated and thereby the protective layer is formed on the accepting layer, and an electromagnetic wave irradiation process wherein the protective layer formed on the accepting layer is irradiated with an electromagnetic wave. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a thermal transfer print using a sublimable dye that can be chelated.

  Conventionally, a thermal transfer method is widely known as a method for easily forming a high-definition image. Various thermal transfer methods are known. Among them, a dye sublimation dye is used as a recording material, and this is supported on a support substrate such as paper or a plastic film to form a dye thermal transfer sheet. A sublimation transfer method for forming various full-color images by dyeing the sublimation dye onto a thermal transfer image-receiving sheet provided with a dye-receiving layer on the surface of paper, plastic film or the like by a heating means such as a head has a higher definition. It is known as a method capable of forming an image. Since this sublimation transfer method uses a sublimation dye as a color material, it has the advantage that the density gradation can be freely adjusted and a full color image of an original can be expressed. In addition, the image formed with the dye is very clear and excellent in transparency, so it is excellent in intermediate color reproducibility and gradation reproducibility, and can form high-quality images comparable to silver salt photographs. It has the advantage of being possible. Because of these advantages, the sublimation transfer method has now been widely used in photographic printers and the like.

  A thermal transfer print using such a sublimable dye having a sublimation property has a defect that image stability, that is, light resistance and fixing property are not good. For such a problem, Patent Document 1 uses a sublimable dye capable of chelating as the sublimable dye, and reacts the chelate compound with the sublimable dye capable of forming the chelate by the dye receiving layer. A method for improving the fixability of the transferred sublimation dye in the dye receiving layer by including a metal ion that can be formed is disclosed.

However, even a thermal transfer print using the sublimable dye capable of forming a chelate sometimes has insufficient durability such as light resistance, weather resistance, and abrasion resistance. As means for improving the durability, a method of providing a protective layer on a receiving layer on which an image is formed has recently been proposed. When a protective layer is provided on the receiving layer, physical resistance such as durability such as light resistance, weather resistance, and abrasion resistance as described above can be improved.
As such a protective layer, one made of a transparent resin that does not impair the sharpness of the printed matter is usually used. However, when the adhesion with the receiving layer is not sufficient, the protective layer is formed with time. There existed a problem that it peeled and durability fell. Here, as a general method for forming a protective layer, a method for transferring and forming the protective layer by heating after the protective layer forming layer capable of forming the protective layer is opposed to and brought into contact with the receiving layer is used. It is done. Therefore, as a method for improving the adhesion, when forming the protective layer, the heating time is lengthened within the range that does not affect the properties such as transparency and durability as the protective layer, and the interface portion with the receiving layer. It is conceivable to sufficiently plasticize. However, as a heating means used for forming the protective layer, a thermal head or the like is usually used in the same manner as the dye transfer, and there is a problem that the line speed is lowered when the heating time is increased. It was.

  Further, it is known that the chelation reaction of the sublimation dye transferred to the receiving layer is insufficient as one of the causes for the insufficient durability of the above-mentioned thermal transfer printed matter. Therefore, in order to improve durability, a method of performing a heat treatment of the thermal transfer image-receiving sheet after the transfer of the sublimable dye and advancing the chelate reaction has been proposed, but there is no method of effectively heating the receptor layer, There was a problem of low productivity.

JP 59-78893 Japanese Patent Laid-Open No. 11-20329

  The present invention is excellent in durability such as hue change of a thermal transfer printed matter formed by transferring a chelatable sublimation dye to a receiving layer of a thermal transfer image receiving sheet, and is provided on the receiving layer of the thermal transfer image receiving sheet. The main object of the present invention is to provide a method for producing a thermal transfer printed matter that can form a protective layer with good adhesion and is excellent in productivity.

  In order to solve the above-described problems, the present invention provides a dye substrate and a base material of a dye thermal transfer sheet having a support substrate and a dye layer formed on the support substrate and containing a binder resin and a chelatable sublimation dye. And the above-mentioned receiving layer of the thermal transfer image-receiving sheet having a receiving layer containing a chelatable metal ion formed on the above-mentioned substrate, and heating the chelating sublimable dye to the above-mentioned receiving layer. A thermal transfer step for transferring to the layer, the receiving layer to which the sublimation dye has been transferred by the thermal transfer step, and a support substrate, and a protective layer forming layer formed on the support substrate and containing a heat conversion substance. A protective layer forming step of forming a protective layer on the receiving layer by heating the protective layer forming layer of the protective layer thermal transfer sheet facing each other, and an upper surface of the thermal transfer image receiving sheet To provide a method of manufacturing a thermal transfer printed matter characterized in that it comprises an electromagnetic wave radiation step of performing irradiation of electromagnetic waves to the protective layer formed on the receiving layer.

  According to the present invention, the protection layer is formed by irradiating the protection layer having the heat conversion substance formed on the receiving layer of the thermal transfer image receiving sheet with the electromagnetic wave capable of absorbing the heat conversion material. The layer can be selectively heated to effectively improve the adhesion between the protective layer and the receiving layer of the thermal transfer image-receiving sheet.

  In addition, in the conventional method for producing a thermal transfer print, the timing for improving the adhesion of the protective layer can be exemplified by heating by a heating means such as a thermal head during the formation of the protective layer. The means is arranged in a line or a point aligned with the moving direction of the thermal transfer image receiving sheet with respect to the moving thermal transfer image receiving sheet. However, there is a problem that it is necessary to reduce the moving speed of the thermal transfer image receiving sheet. On the other hand, according to the present invention, the protective layer can be efficiently heated by the electromagnetic wave irradiation step after forming the protective layer to increase the adhesion, so that the heating time for increasing the adhesiveness is increased during the formation of the protective layer. It can be shortened. Therefore, the moving speed of the thermal transfer image receiving sheet can be increased, and the productivity of the thermal transfer printed matter can be improved.

  Furthermore, by heating the protective layer in the electromagnetic wave irradiation step, it is possible to efficiently transfer heat to the receiving layer on which the protective layer is formed. Therefore, the chelate reaction of the sublimable dye transferred to the receiving layer can be efficiently advanced, and the hue change of the thermal transfer printed matter can be reduced.

In the present invention, the protective layer forming layer is formed by laminating a release layer and an adhesive layer made of a thermoplastic resin in this order on the support substrate, and only the adhesive layer is the above It is preferable that a heat conversion substance is contained. Since only the adhesive layer contains a heat conversion substance, only the adhesive layer that contributes most to the adhesion with the receiving layer can be selectively heated. Therefore, the adhesion between the receiving layer and the protective layer can be more efficiently increased.
Moreover, it is because the chelating reaction of the sublimable dye contained in the receiving layer in contact with the adhesive layer can be more efficiently promoted by selectively heating the adhesive layer.

In the present invention, the electromagnetic waves are preferably microwaves or infrared rays. This is because when the electromagnetic waves are microwaves or infrared rays, the protective layer can be efficiently heated to have excellent adhesion and productivity.
Furthermore, in the present invention, when the electromagnetic wave is a microwave, the heat conversion substance is preferably a polyvinyl butyral resin. When the electromagnetic wave is an infrared ray, the heat conversion substance is a diimonium compound or A cyanine compound is preferred. This is because by making the heat conversion substance to selectively absorb each electromagnetic wave and convert it to heat, the productivity of the thermal transfer printed matter can be further improved.

  The present invention provides a thermal transfer sheet comprising a support substrate and a protective layer forming layer formed on the support substrate and containing a heat conversion substance.

  According to the present invention, the protective layer-forming layer contains a heat conversion substance, and after the protective layer is formed by heating / transfer, the protective layer is irradiated with an electromagnetic wave that can be selectively absorbed by the heat conversion substance. The layer can be selectively heated. Therefore, when the protective layer is formed on the receiving layer of the thermal transfer image-receiving sheet to which the sublimation dye is transferred, the adhesion of the protective layer is improved by irradiation with electromagnetic waves, and the transferred sublimation dye chelate It is possible to improve the durability such as the hue change of the thermal transfer printed matter due to the progress of the reaction and improve the productivity.

  In the present invention, it is preferable to have a dye layer formed on the support substrate and containing a chelatable sublimable dye. This is because by having the dye layer and the protective layer forming layer on the same support substrate, transfer of the sublimable dye that the dye layer has and formation of the protective layer can be facilitated.

  In the present invention, the protective layer-forming layer is formed by laminating a release layer and an adhesive layer made of a thermoplastic resin in this order on the support substrate, and only on the adhesive layer. It is preferable that the heat conversion substance is included. Since only the adhesive layer contains a heat conversion substance, the adhesion between the receptor layer and the protective layer can be increased more efficiently, and the sublimation dye contained in the receptor layer in contact with the adhesive layer. This is because the chelation reaction can be more efficiently promoted.

  The present invention provides a thermal transfer image-receiving sheet having a base material and a receiving layer formed on the base material and containing a chelate-type color former formed by binding metal ions and a sublimation dye, and formed on the receiving layer. And a protective layer containing a heat conversion substance.

  According to the present invention, when the protective layer has a heat conversion substance, for example, by irradiating an electromagnetic wave that can be absorbed by the heat conversion substance, the adhesion between the receiving layer and the protective layer is improved. Can do. Moreover, since the chelate reaction of the sublimable dye can be promoted together with the improvement of the adhesion, the hue change and the like can be reduced.

  In the present invention, the protective layer is formed by laminating an adhesive layer made of a thermoplastic resin and a release layer in this order on the receptor layer, and the heat conversion substance is only on the adhesive layer. It is preferably included. Since only the contact layer in contact with the receiving layer has a heat conversion substance, the adhesion between the receiving layer and the protective layer can be easily improved and the chelation reaction of the sublimation dye can be easily promoted. It is because it can be made excellent in durability.

  The present invention is excellent in durability such as hue change of a thermal transfer printed matter formed by transferring a chelatable sublimation dye to a receiving layer of a thermal transfer image receiving sheet, and is provided on the receiving layer of the thermal transfer image receiving sheet. There is an effect that a protective layer can be formed with good adhesion and a method for producing a thermal transfer printed matter with excellent productivity is provided.

  The present invention relates to a method for producing a thermal transfer print, a thermal transfer sheet used for producing the thermal transfer print, and a thermal transfer print. Hereinafter, the method for producing a thermal transfer print, the thermal transfer sheet, and the thermal transfer print of the present invention will be described.

A. First, a method for producing a thermal transfer print according to the present invention will be described. The method for producing a thermal transfer printed matter of the present invention includes a support substrate, the dye layer of the dye thermal transfer sheet formed on the support substrate and having a dye layer containing a binder resin and a chelatable sublimation dye, a base material, And the receptive layer of the thermal transfer image-receiving sheet formed on the substrate and having a receptive layer containing a chelatable metal ion, and heating the chelating sublimable dye, the receptive layer A protective layer comprising: a thermal transfer step to be transferred to the substrate; the receiving layer to which the sublimable dye has been transferred by the thermal transfer step; and a support substrate; and a protective layer forming layer formed on the support substrate and containing a heat conversion substance. A protective layer forming step of forming a protective layer on the receiving layer by heating the protective layer forming layer of the layer thermal transfer sheet facing each other, and the thermal transfer image receiving sheet of the above An electromagnetic wave radiation step of performing irradiation of electromagnetic waves to the protective layer formed on the volume layer, is characterized in that it has a.

  Next, a method for producing such a thermal transfer printed matter of the present invention will be described with reference to the drawings. FIG. 1 is a process diagram showing an example of a method for producing a thermal transfer print according to the present invention. As illustrated in FIG. 1, the method for producing a thermal transfer print of the present invention includes a support substrate 1 and a dye having a dye layer 2 formed on the support substrate 1 and containing a binder resin and a chelating sublimable dye. The dye layer 2 of the thermal transfer sheet 3 is opposed to the substrate 4 and the receptor layer 5 of the thermal transfer image-receiving sheet 6 having a receptor layer 5 formed on the substrate 4 and containing metal ions that can be chelated. By heating in the contact state, the chelatable sublimable dye is transferred to the receptor layer 5 (FIG. 1 (a)), and the receptor to which the sublimable dye has been transferred by the thermal transfer process is transferred. The protective layer forming layer 12 of the protective layer thermal transfer sheet 10 having the layer 5, the supporting substrate 1, and the protective layer forming layer 12 formed on the supporting substrate 1 and containing a heat conversion substance is opposed to and contacted. Let me A protective layer forming step (FIG. 1B) for transferring the protective layer forming layer 12 onto the receiving layer 5 by heating, and a protective layer forming layer on the receiving layer 5 of the thermal transfer image receiving sheet 6. An electromagnetic wave irradiation step (FIG. 1C) for irradiating the protective layer 20 formed by transferring the layer 12 with an electromagnetic wave.

According to the present invention, the protective layer is selected by irradiating the protective layer having the thermal conversion material formed on the thermal transfer image-receiving sheet by the protective layer forming step with electromagnetic waves that can be absorbed by the thermal conversion material. Heat | fever, it can improve the adhesiveness of the said protective layer and the said receiving layer which a thermal transfer image receiving sheet has efficiently.
Further, in the normal method for producing a thermal transfer printed matter, the timing for improving the adhesion of the protective layer can be exemplified by heating by a heating means such as a thermal head during the formation of the protective layer. The means is arranged in a line or a point aligned with the moving direction of the thermal transfer image receiving sheet with respect to the moving thermal transfer image receiving sheet. Needs to reduce the moving speed of the thermal transfer image-receiving sheet. However, since the protective layer can be efficiently heated and the adhesion can be increased by the electromagnetic wave irradiation step after the formation of the protective layer, the heating time for increasing the adhesion can be shortened during the formation of the protective layer. Therefore, the moving speed of the thermal transfer image receiving sheet can be increased, and the productivity of the thermal transfer printed matter can be improved.
Furthermore, by heating the protective layer in the electromagnetic wave irradiation step, it is possible to efficiently transfer heat to the receiving layer on which the protective layer is formed. Therefore, the chelate reaction of the sublimable dye transferred to the receiving layer can be efficiently advanced, and the hue change of the thermal transfer printed matter can be reduced.

  The method for producing a thermal transfer printed matter of the present invention includes a thermal transfer step, a protective layer forming step, and an electromagnetic wave irradiation step. Hereinafter, each of these steps will be described in detail.

1. Thermal transfer step The thermal transfer step used in the present invention comprises a support substrate and the dye layer of the dye thermal transfer sheet formed on the support substrate and having a dye layer containing a binder resin and a chelatable sublimation dye, a base material, And the receptive layer of the thermal transfer image-receiving sheet formed on the substrate and having a receptive layer containing a chelatable metal ion, and heating the chelating sublimable dye, the receptive layer It is the process of transferring to. When the sublimation dye is a sublimable dye that can be chelated, the durability of the thermal transfer printed matter obtained by transferring the sublimation dye to the receiving layer of the thermal transfer image-receiving sheet is increased. it can. Hereinafter, such a thermal transfer process will be described.

(1) Dye thermal transfer sheet The dye thermal transfer sheet used in this step has a support substrate and a dye layer formed on the support substrate. Hereinafter, each structure of such a dye thermal transfer sheet will be described.

(A) Support substrate The material of the support substrate used in this step is not particularly limited as long as it has desired heat resistance depending on the printing conditions and the like when forming the thermal transfer printed matter. As the support substrate used in this step, for example, polyethylene terephthalate film, 1,4-polycyclohexylenedimethylene terephthalate film, polyethylene naphthalate film, polyphenylene sulfide film, polystyrene film, polypropylene film, polysulfone film, aramid film, Examples thereof include polycarbonate films, polyvinyl alcohol films, cellophane, cellulose derivatives such as cellulose acetate, plastic films such as polyethylene films, polyvinyl chloride films, nylon films, polyimide films, and ionomer films.

  The thickness of the support substrate used in this step is not particularly limited as long as it is within a range in which a desired strength can be provided according to the material constituting the support substrate, but is usually within a range of 0.5 μm to 50 μm. Particularly preferred is a range of 1 μm to 10 μm.

  In addition, the support substrate used in this step may be a substrate on which a dye layer is formed by adhesion treatment. By performing such an adhesion treatment, for example, even when a plastic film is used as the support substrate, adhesion with the dye layer can be improved.

  Examples of the adhesion treatment include known resins such as corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, surface roughening treatment, chemical treatment, plasma treatment, low temperature plasma treatment, primer treatment, and grafting treatment. The surface modification technique can be applied as it is. Two or more of these treatments can be used in combination. The primer treatment can be performed, for example, by applying a primer solution to an unstretched film at the time of film formation by melt extrusion of a plastic film and then stretching the film.

(B) Dye layer The dye layer used in this step has a binder resin and a chelating sublimable dye.

(I) Binder resin The binder resin of the dye layer used in this step is not particularly limited as long as it has high heat resistance and does not hinder the migration of the sublimable dye when heated. . In this step, for example, cellulose resins such as ethyl cellulose and cellulose acetate butyrate, vinyl resins such as polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, and polyvinyl acetal, or polyester and polyacrylamide can be used.

(ii) Sublimable dye The sublimable dye used in this step undergoes a chelate reaction with a metal ion described later. The sublimation dye is usually contained in a dye layer of a dye thermal transfer sheet. The dye layer and the receiving layer are superimposed so as to face each other, and heated by a thermal head or the like to receive the thermal transfer image receiving sheet. It is what is transferred to the layer.

  The sublimation dye in this step is not particularly limited as long as it can chelate with a metal ion described later, and general yellow dyes, magenta dyes, cyan dyes, and the like can be used. . Among these, sublimable dyes represented by the following general formulas (1) to (8) are preferable.

  Examples of yellow dyes include compounds represented by the following general formulas (1) to (3).

  a. Sublimable dye represented by general formula (1)

(Wherein R ₁₁ represents a substituent, R ₁₂ represents an alkyl group, an alkenyl group, an alkynyl group or a cycloalkyl group, R ₁₃ and R ₁₄ represent a hydrogen atom or a substituent, and R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ represent a hydrogen atom, an alkyl group, or an aryl group, and Z ₁₁ represents a nonmetallic atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring.

The substituent represented by R ₁₁ is not particularly limited. For example, an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, Dodecyl group, trifluoromethyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), acylamino group (eg, acetylamino group, benzoylamino group, etc.) ), Alkylthio group (for example, methylthio group, ethylthio group, etc.), arylthio group (for example, phenylthio group, naphthylthio group, etc.), alkenyl group (for example, 2-propenyl group, 3-butenyl group, 1-methyl-3-propenyl) Group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group, Chlorohexenyl group, etc.), halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom etc.), alkynyl group (eg propargyl group etc.), heterocyclic group (eg pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group) Etc.), alkylsulfonyl groups (eg, methylsulfonyl group, ethylsulfonyl group, etc.), arylsulfonyl groups (eg, phenylsulfonyl group, naphthylsulfonyl group, etc.), alkylsulfinyl groups (eg, methylsulfinyl group, etc.), arylsulfinyl groups (For example, phenylsulfinyl group), phosphono group, acyl group (acetyl group, pivaloyl group, benzoyl group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, butylaminocarbonyl group, Cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylamino) Sulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide group, etc.), cyano Group, alkoxy group (for example, methoxy group, ethoxy group, propoxy group, etc.), aryloxy group (for example, phenoxy group, naphthyloxy group, etc.), heterocyclic oxy group, Roxy group, acyloxy group (eg, acetyloxy group, benzoyloxy group, etc.), sulfonic acid group, sulfonic acid salt, aminocarbonyloxy group, amino group (eg, amino group, ethylamino group, dimethylamino group, butylamino) Group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, etc.), anilino group (for example, phenylamino group, chlorophenylamino group, toluidino group, anisidino group, naphthylamino group, 2-pyridylamino group, etc.), imide group, Ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group), alkoxycarbonylamido Group (for example, methoxycarbonylamino group, phenoxycarbonylamino group, etc.), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl, etc.), aryloxycarbonyl group (for example, phenoxycarbonyl group, etc.), complex Examples thereof include a ring thio group, a thioureido group, a carboxyl group, a salt of a carboxylic acid, a hydroxyl group, a mercapto group, and a nitro group.

  These substituents may be further substituted with the same substituent.

The alkyl group, alkenyl group, alkynyl group or cycloalkyl group represented by R ₁₂ may be substituted with the same group as the substituent represented by R ₁₁ .

In the general formula _{(1), R 13} and _{R 14} represents a hydrogen atom or a substituent. Examples of the substituent represented by R ₁₃ and R ₁₄ include the same groups as the substituent represented by R ₁₁ , and these substituents may be further substituted with the same substituent.

In the general formula (1), R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ represent a hydrogen atom, an alkyl group or an aryl group. Examples of the alkyl group and aryl group represented by R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ include the same groups as the alkyl group and aryl group in R ₁₁ .

The alkyl group and aryl group represented by R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ may be substituted with the same substituent as the substituent represented by R ₁₁ .

In the general formula (1), Z ₁₁ represents a nonmetallic atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring.

Specific examples of such a heterocyclic ring include pyridine ring, pyrazole ring, imidazole ring, pyrazine ring, pyrimidine ring, triazine ring, thiazole ring, oxazole ring, quinoline ring, benzothiazole ring, benzoxazole ring and the like. be able to. These rings may have a substituent, and examples of the substituent include the same groups as the substituent represented by R ₁₁ above.

  b. Sublimable dye represented by general formula (2)

(Wherein R ₂₁ represents a trifluoromethyl group, an alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an amide group, a carbamoyl group, an amino group, a cyano group, and R ₂₂ represents represents an alkyl group, an acyl group, a carbamoyl group, an alkoxycarbonyl _{group, R 23} represents an alkyl group, an alkenyl group, an aryl group. _However, the total number of carbon atoms contained in _{R 21} and _{R 22} is 3 or more _{.X 21} Represents —CR ₂₄ R ₂₅ —, —S—, —O—, —NR ₂₆ —, R ₂₄ and R ₂₅ represent a hydrogen atom, a halogen atom and a substituent, and R ₂₆ represents a hydrogen atom, a substituent Y ₂₁ represents a group of atoms necessary to form a 5- or 6-membered ring.

In the general formula (2), R ₂₁ represents a trifluoromethyl group, an alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an amide group, a carbamoyl group, an amino group, or a cyano group.
R ₂₁ is preferably an alkyl group, a trifluoromethyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, or a cyano group, and more preferably an alkyl group.

R ₂₂ represents an alkyl group, an acyl group, a carbamoyl group, or an alkoxycarbonyl group.

R ₂₃ represents an alkyl group, an alkenyl group, or an aryl group.

X ₂₁ represents —CR ₂₄ R ₂₅ —, —S—, —O—, —NR ₂₆ —, and preferably —CR ₂₄ R ₂₅ —, —S—, —O—.

R ₂₄ and R ₂₅ represent a hydrogen atom, a halogen atom, or a substituent.
Since the substituent is the same as the substituent in the general formula (1) described above, description thereof is omitted here.

  As the substituent, a hydrogen atom, an alkyl group, and an aryl group are preferable.

R ₂₆ represents a hydrogen atom or a substituent.
Examples of the substituent include the same substituents as those exemplified as R ₂₄ and R ₂₅ .

Y ₂₁ represents an atomic group necessary for forming a 5- to 6-membered ring. Preferably, it is an atomic group necessary for forming a 6-membered ring. For example, a cyclopentane ring, a cyclohexane ring, a benzene ring, a pyridine ring, a naphthalene ring, etc. are mentioned.

  c. Sublimable dye represented by general formula (3)

In the general formula (3), examples of the substituents represented by R ₃₁ and R ₃₂ include a halogen atom, an alkyl group (an alkyl group having 1 to 12 carbon atoms, an oxygen atom, a nitrogen atom, a sulfur atom). Alternatively, a substituent linked by a carbonyl group is substituted, or substituted with another substituent such as an aryl group, alkenyl group, alkynyl group, hydroxyl group, amino group, nitro group, carboxyl group, cyano group or halogen atom. For example, methyl, isopropyl, t-butyl, trifluoromethyl, methoxymethyl, 2-methanesulfonylethyl, 2-methanesulfonamidoethyl, cyclohexyl, etc.), aryl groups (for example, phenyl, 4-t -Butylphenyl, 3-nitrophenyl, 3-acylaminophenyl, 2-methoxyphenyl, etc. Group), cyano group, alkoxyl group, aryloxy group, acylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group Group, alkoxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphonyl group, acyl group and the like.

_Examples of the alkyl group and aryl group represented by R ₃₃ include the same alkyl groups and aryl groups represented by R ₃₁ and R ₃₂ .

Specific examples of the 5- to 6-membered aromatic ring constituted with two carbon atoms represented by Z ₃₁ include benzene, pyridine, pyrimidine, triazine, pyrazine, pyridazine, pyrrole, furan, thiophene, and pyrazole. , Imidazole, triazole, oxazole, thiazole and the like, and these rings may further form a condensed ring with other aromatic rings. These rings may have a substituent, and examples of the substituent include the same substituents represented by R ₃₁ and R ₃₂ .

  Examples of the magenta dye include compounds represented by the following general formulas (4) to (6).

  d. Sublimable dye represented by general formula (4)

In the general formula (4), Y ₄₁ represents an alkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a cyano group, or a perfluoroalkyl group. Z ₄₁ and Z ₄₂ represent —CR ₄₂ ═ or —N═, L ₄₁ represents a group represented by the following general formula (4-a), and X ₄₁ represents an unsubstituted or substituted alkylamino group. R ₄₁ represents a substituted or unsubstituted alkyl group, and n represents an integer of 0 or more. _R42 represents a hydrogen atom or a substituent.

(In the formula, B ₄₁ represents a nonmetallic atom group necessary for forming a heterocyclic ring.)

L ₄₁ represents a group represented by the general formula (4-a) and includes a nonmetallic atom group B ₄₁ necessary for forming a heterocyclic ring. Examples of the group represented by the general formula (4-a) include 2-pyrrolyl group, imidazolyl group, isothiazolyl group, isoxazolyl group, 3-pyrazolyl group, pyrazinyl group, triazolyl group, 2-pyridyl group, pyridazinyl group, and pyrimidinyl group. It represents a 3H-indolyl group, a 1H-indazolyl group, a prynyl group, an isoquinolyl group, a quinolyl group, a phthalazinyl group, a naphthyridinyl group, a quinosalinyl group, a quinazolinyl group, or the like. These heterocycles may further have a substituent. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom), an alkyl group (for example, methyl, ethyl, butyl, pentyl, 2- Methoxyethyl, trifluoromethyl, 2-ethylhexyl, etc.), aryl groups (eg, phenyl, p-tolyl, naphthyl, etc.), acyl groups (eg, acetyl, propionyl, benzoyl, etc.), alkoxy groups (eg, methoxy, ethoxy, Butoxy etc.), alkoxycarbonyl groups (eg methoxycarbonyl, i-propoxycarbonyl etc.), acyloxy groups (eg acetyloxy, ethylcarbonyloxy etc.), alkylthio groups (eg methylthio, ethylthio, octylthio etc.), arylthio groups ( For example, phenylthio, p-tolyl O, etc.), an amino group (e.g., methylamino, diethylamino, methoxy ethylamino etc.), a cyano group, a nitro group, a Hajime Tamaki (e.g., pyridyl, pyrazolyl, imidazolyl, furyl, thienyl and the like).

X ₄₁ represents an unsubstituted or substituted alkylamino group, and examples of the substituent include an aryl group (eg, phenyl, p-tolyl, naphthyl, etc.), an acyl group (eg, acetyl, propionyl, benzoyl, etc.), an alkoxy group (Eg, methoxy, ethoxy, butoxy, etc.), alkoxycarbonyl groups (eg, methoxycarbonyl, i-propoxycarbonyl, etc.), acyloxy groups (eg, acetyloxy, ethylcarbonyloxy, etc.), alkylthio groups (eg, methylthio, ethylthio, Octylthio, etc.), arylthio groups (eg, phenylthio, p-tolylthio, etc.), amino groups (eg, methylamino, diethylamino, etc.), cyano groups, nitro groups, hydroxyl groups, carboxyl groups, sulfonic acid groups, sulfonamido groups (eg, , Methanes Sulphonamide, ethanesulfonamide, etc.), acylamino groups (eg, acetylamino, benzoylamino, etc.), carbamoyl groups (methylcarbamoyl, phenylcarbamoyl, etc.), sulfamoyl groups (eg, methylsulfamoyl, phenylsulfamoyl, etc.) It is done.

R ₄₁ represents a substituted or unsubstituted alkyl group. R ₄₂ represents a hydrogen atom or a substituent, and examples of the substituent include an alkyl group (eg, methyl, ethyl, butyl, pentyl, 2-methoxyethyl, trifluoromethyl, 2-ethylhexyl, etc.), an aryl group (eg, phenyl, p-tolyl, naphthyl etc.), acyl group (eg acetyl, propionyl, benzoyl etc.), alkoxy group (eg methoxy, ethoxy, butoxy etc.), alkoxycarbonyl group (eg methoxycarbonyl, i-propoxycarbonyl etc.), Acyloxy groups (eg, acetyloxy, ethylcarbonyloxy, etc.), alkylthio groups (eg, methylthio, ethylthio, octylthio, etc.), arylthio groups (eg, phenylthio, p-tolylthio, etc.), amino groups (eg, methylamino, diethylamino, etc.) ) An ano group, a nitro group, etc. are mentioned.

  e. Sublimable dye represented by general formula (5)

(In the formula, Y ₅₁ represents the same substituent as Y ₄₁ described above, Z ₅₁ and Z ₅₂ represent —CR ₅₃ ═ or —N═, and L ₅₁ represents general formula (5-a), (5- b) represents a group represented by X), X ₅₁ represents an unsubstituted or substituted alkylamino group, R ₅₁ represents a substituted or unsubstituted alkyl group, R ₅₃ represents a hydrogen atom or a substituent, n represents an integer of 0 or more.)

(Wherein R ₅₂ represents a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, a mercapto group, an alkylthio group or an arylthio group, R _b represents a substituent, p represents an integer of 0 to 4, and B ₅₁ Represents a group of nonmetallic atoms necessary for forming a heterocyclic ring together with —CR ₅₂ ═.

L ₅₁ represents a group represented by general formula (5-a) or (5-b), and represents a group that forms a heterocyclic ring with —CR ₅₂ ═ and B ₅₁ represented by general formula (5-a). Is a pyrrolyl group, imidazolyl group, isothiazolyl group, isoxazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, 3H-inddolyl group, 1H-indazolyl group, purinyl group, isoquinolyl group, quinolyl group Group, phthalazinyl group, naphthyridinyl group, quinosalinyl group, quinazolinyl group and the like. R ₅₂ represents a hydroxyl group, an alkoxy group (eg, methoxy, ethoxy, butoxy, etc.), an aryloxy group, an amino group (eg, methylamino, diethylamino, methoxyethylamino, etc.), a mercapto group, an alkylthio group (eg, methylthio, ethylthio, octylthio, etc.) Represents an arylthio group (for example, phenylthio, p-tolylthio and the like). These heterocyclic rings may further have a substituent. Examples of the substituent include a halogen atom (for example, a fluorine atom and a chlorine atom), an alkyl group (for example, methyl, ethyl, butyl, pentyl, 2-methoxyethyl, Trifluoromethyl, 2-ethylhexyl, etc.), aryl groups (eg phenyl, p-tolyl, naphthyl etc.), acyl groups (eg acetyl, propionyl, benzoyl etc.), alkoxy groups (eg methoxy, ethoxy, butoxy etc.), aryloxy Groups (for example, phenoxy, naphthoxy, etc.), alkoxycarbonyl groups (for example, methoxycarbonyl, i-propoxycarbonyl, etc.), acyloxy groups (for example, acetyloxy, ethylcarbonyloxy, etc.), alkylthio groups (for example, methylthio, ethylthio, octylthio, etc.), arylthio Base For example phenylthio, p- tolylthio, etc.), an amino group (e.g. methylamino, diethylamino, methoxy ethylamino etc.), a cyano group, a nitro group, a Hajime Tamaki (e.g. pyridyl, pyrazolyl, imidazolyl, furyl, thienyl and the like).

X ₅₁ represents an unsubstituted or substituted alkylamino group, and examples of the substituent include an aryl group (eg, phenyl, p-tolyl, naphthyl, etc.), an acyl group (eg, acetyl, propionyl, benzoyl, etc.), an alkoxy group (Eg, methoxy, ethoxy, butoxy, etc.), alkoxycarbonyl groups (eg, methoxycarbonyl, i-propoxycarbonyl, etc.), acyloxy groups (eg, acetyloxy, ethylcarbonyloxy, etc.), alkylthio groups (eg, methylthio, ethylthio, Octylthio, etc.), arylthio groups (eg, phenylthio, p-tolylthio, etc.), amino groups (eg, methylamino, diethylamino, etc.), cyano groups, nitro groups, hydroxyl groups, carboxyl groups, sulfonic acid groups, sulfonamido groups (eg, , Methanes Sulphonamide, ethanesulfonamide, etc.), acylamino groups (eg, acetylamino, benzoylamino, etc.), carbamoyl groups (methylcarbamoyl, phenylcarbamoyl, etc.), sulfamoyl groups (eg, methylsulfamoyl, phenylsulfamoyl, etc.) It is done.

R ₅₁ represents a substituted or unsubstituted alkyl group. R ₅₂ represents a hydrogen atom or a substituent, and examples of the substituent include an alkyl group (for example, methyl, ethyl, butyl, pentyl, 2-methoxyethyl, trifluoromethyl, 2-ethylhexyl, etc.), an aryl group (for example, phenyl, p- Tolyl, naphthyl, etc.), acyl groups (eg acetyl, propionyl, benzoyl etc.), alkoxy groups (eg methoxy, ethoxy, butoxy etc.), aryloxy groups (eg phenoxy, naphthoxy etc.), alkoxycarbonyl groups (eg methoxycarbonyl, i -Propoxycarbonyl etc.), acyloxy groups (eg acetyloxy, ethylcarbonyloxy etc.), alkylthio groups (eg methylthio, ethylthio, octylthio etc.), arylthio groups (eg phenylthio, p-tolylthio etc.), amino groups (eg Tilamino, diethylamino and the like), cyano group, nitro group and the like.

Examples of the substituent represented by R _b include a halogen atom (eg, a fluorine atom, a chlorine atom), an alkyl group (eg, methyl, ethyl, butyl, pentyl, 2-methoxyethyl, trifluoromethyl, 2-ethylhexyl, etc.), Aryl groups (eg, phenyl, p-tolyl, naphthyl, etc.), acyl groups (eg, acetyl, propionyl, benzoyl, etc.), alkoxy groups (eg, methoxy, ethoxy, butoxy, etc.), aryloxy groups (eg, phenoxy, naphthoxy, etc.), alkoxy A carbonyl group (eg methoxycarbonyl, i-propoxycarbonyl etc.), an acyloxy group (eg acetyloxy, ethylcarbonyloxy etc.), an alkylthio group (eg methylthio, ethylthio, octylthio etc.), an arylthio group (eg phenylthio, p-tolylchi) ), Amino groups (eg, methylamino, diethylamino, methoxyethylamino, etc.), cyano groups, nitro groups, heterocyclic groups (eg, pyridyl, pyrazolyl, imidazolyl, furyl, thienyl, etc.) and the like.

  f. Sublimable dye represented by general formula (6)

In the general formula (6), X ₆₁ represents at least a bidentate group capable of forming a chelate or a group of atoms, and Y ₆₁ represents a group of atoms forming a 5-membered or 6-membered aromatic hydrocarbon ring or heterocyclic ring. R ₆₁ and R ₆₂ each represents a hydrogen atom, a halogen atom or a monovalent substituent. n represents 0, 1, 2;

X ₆₁ represents at least a bidentate chelate-forming group or a group of atoms, and may be anything that can form a dye as the general formula (6), such as 5-pyrazolone, imidazole, pyrazolopyrrole, pyrazolopyrazole, Pyrazoloimidazole, pyrazolotriazole, pyrazolotetrazole, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin, oxazolone, isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone, or pyrazolopyridone preferable.

X ₆₁ is particularly preferably a group represented by the following general formula (6-a).

In the above general formula (6-a), Z ₆₁ represents an atomic group necessary for forming an aromatic nitrogen-containing heterocyclic ring substituted with a group containing at least one chelatable nitrogen atom. Specific examples of the ring include pyridine, pyrimidine, thiazole, imidazole and the like. These rings may further form a condensed ring with another carbocycle (such as a benzene ring) or a heterocycle (such as a pyridine ring).

In the general formula (6), Y ₆₁ represents a group of atoms forming a 5-membered or 6-membered aromatic hydrocarbon ring or heterocycle, and the ring may further have a substituent, You may have a condensed ring. Specific examples of the ring include 3H-pyrrole ring, oxazole ring, imidazole ring, thiazole ring, 3H-pyrrolidine ring, oxazolidine ring, imidazolidine ring, thiazolidine ring, 3H-indole ring, benzoxazole ring, benzimidazole ring, A benzothiazole ring, a quinoline ring, a pyridine ring, etc. are mentioned. These rings may form a condensed ring with another carbocyclic ring (for example, benzene ring) or a heterocyclic ring (for example, pyridine ring). Examples of substituents on the ring include alkyl groups, aryl groups, heterocyclic groups, acyl groups, amino groups, nitro groups, cyano groups, acylamino groups, alkoxy groups, hydroxy groups, alkoxycarbonyl groups, halogen atoms, etc. The group may be further substituted.

R ₆₁ and R ₆₂ each represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom) or a monovalent substituent, and examples of the monovalent substituent include an alkyl group, an alkoxy group, a cyano group, Examples thereof include an alkoxycarbonyl group, an aryl group, a heterocyclic group, a carbamoyl group, a hydroxy group, an acyl group, and an acylamino group.

  Examples of the cyan dye include compounds represented by the following general formulas (7) to (8).

g. Sublimable dyes represented by general formula (7)

(In the formula, each of R ₇₁ and R ₇₂ represents a substituted or unsubstituted aliphatic group, R ₇₃ represents a substituent, n represents an integer of 0 to 4, and when n is 2 or more, R ₇₃ may be the same or different, and R ₇₄ and R ₇₅ each represents an alkyl group, provided that at least one of R ₇₄ and R ₇₅ represents a secondary alkyl group.

In the general formula (7), R ₇₁ and R ₇₂ represent a substituted or unsubstituted aliphatic group, and R ₇₁ and R ₇₂ may be the same or different. Examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, and the like. Examples of the group that can replace these alkyl groups include a linear or branched alkyl group (for example, a methyl group, Ethyl group, i-propyl group, t-butyl group, n-dodecyl group, 1-hexylnonyl group and the like), cycloalkyl group (for example, cyclopropyl group, cyclohexyl group, bicyclo [2.2.1] heptyl group, And adamantyl group, etc.), and alkenyl groups (eg 2-propylene group, oleyl group etc.), aryl groups (eg phenyl group, ortho-tolyl group, ortho-anisyl group, 1-naphthyl group, 9-anthranyl group etc.), Heterocyclic groups (for example, 2-tetrahydrofuryl group, 2-thiophenyl group, 4-imidazolyl group, 2-pyridyl group, etc.), Gen atom (for example, fluorine atom, chlorine atom, bromine atom), cyano group, nitro group, hydroxy group, carbonyl group (for example, alkylcarbonyl group such as acetyl group, trifluoroacetyl group, pivaloyl group, benzoyl group, pentafluorobenzoyl) Group, arylcarbonyl group such as 3,5-di-t-butyl-4-hydroxybenzoyl group), oxycarbonyl group (for example, alkoxycarbonyl group such as methoxycarbonyl group, cyclohexyloxycarbonyl group, n-dodecyloxycarbonyl group) Aryloxycarbonyl groups such as phenoxycarbonyl group, 2,4-di-t-amylphenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-pyridyloxycarbonyl group, 1-phenylpyrazolyl-5-oxycarbonyl group, etc. of Oxycyclic carbonyl group), carbamoyl group (for example, dimethylcarbamoyl group, alkylcarbamoyl group such as 4- (2,4-di-t-amylphenoxy) butylaminocarbonyl group, phenylcarbamoyl group, 1-naphthylcarbamoyl group, etc. Arylcarbamoyl group), alkoxy group (for example, methoxy group, 2-ethoxyethoxy group, etc.), aryloxy group (for example, phenoxy group, 2,4-di-t-amylphenoxy group, 4- (4-hydroxyphenylsulfonyl)) Phenoxy group etc.), heterocyclic oxy group (eg 4-pyridyloxy group, 2-hexahydropyranyloxy group etc.), carbonyloxy group (eg acetyloxy group, trifluoroacetyloxy group, pivaloyloxy group etc.) Group, benzoyloxy group, Aryl urethane groups such as n-fluorobenzoyloxy group), urethane groups (eg, alkyl urethane groups such as N, N-dimethylurethane group, aryl urethanes such as N-phenylurethane group, N- (p-cyanophenyl) urethane group) Group), a sulfonyloxy group (for example, an alkylsulfonyloxy group such as methanesulfonyloxy group, trifluoromethanesulfonyloxy group, n-dodecanesulfonyloxy group, arylsulfonyloxy group such as benzenesulfonyloxy group, p-toluenesulfonyloxy group) Amino groups (for example, alkylamino groups such as dimethylamino group, cyclohexylamino group, n-dodecylamino group, arylamino groups such as anilino group, pt-octylanilino group, etc.), sulfonylamino groups (for example, methanesulfonyl) amino , Alkylsulfonylamino groups such as heptafluoropropanesulfonylamino group and n-hexadecylsulfonylamino group, arylsulfonylamino groups such as p-toluenesulfonylamino group and pentafluorobenzenesulfonylamino), sulfamoylamino groups (for example, N , Alkylsulfamoylamino groups such as N-dimethylsulfamoylamino group, arylsulfamoylamino groups such as N-phenylsulfamoylamino group), acylamino groups (eg alkyl such as acetylamino group and myristoylamino group) Arylcarbonylamino group such as carbonylamino group, benzoylamino group), ureido group (for example, alkylureido group such as N, N-dimethylaminoureido group, N-phenylureido group, N- (p-cyanophenyl) ureido Arylsulfide groups such as methanesulfonyl group, alkylsulfonyl groups such as trifluoromethanesulfonyl group, and arylsulfonyl groups such as p-toluenesulfonyl group), sulfamoyl groups (such as dimethylsulfamoyl group, 4- (2,4-di-t-amylphenoxy) alkylsulfamoyl groups such as butylaminosulfonyl group, arylsulfamoyl groups such as phenylsulfamoyl group), alkylthio groups (for example, methylthio group, t-octylthio group, etc.) ), An arylthio group (for example, phenylthio group), and a heterocyclic thio group (for example, 1-phenyltetrazol-5-thio group, 5-methyl-1,3,4-oxadiazole-2-thio group). Can be mentioned.

  Examples of the cycloalkyl group and the alkenyl group are the same as the above substituents. Examples of the alkynyl group include 1-propyne, 2-butyne, 1-hexyne and the like.

It is also preferred that R ₇₁ and R _{72 form} a non-aromatic cyclic structure (eg, pyrrolidine ring, piperidine ring, morpholine ring, etc.).

R ₇₃ represents a substituent, and examples of the substituent include the examples of the substituent of R ₇₁ and R ₇₂ described above. Among the above substituents, an alkyl group, a cycloalkyl group, an alkoxy group, and an acylamino group are preferable. n represents an integer of 0 to 4, and when n is 2 or more, the plurality of R ₇₃ may be the same or different.

R ₇₄ and R ₇₅ represent an alkyl group, and examples thereof include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, isopropyl group, Examples thereof include a sec-butyl group, a tert-butyl group, a 3-heptyl group, and a 2-ethylhexyl group. At least one of R ₇₄ and R ₇₅ represents a secondary alkyl group, and examples of the secondary alkyl group include an isopropyl group, a sec-butyl group, a 3-heptyl group, and a 2-ethylhexyl group. The most preferred substituent as the secondary alkyl group for R ₇₄ and R ₇₅ is an isopropyl group. The secondary alkyl group of R ₇₅ may be substituted, but is all substituted with a substituent consisting of a carbon atom and a hydrogen atom, and is not substituted with a substituent containing other atoms. R ₇₄ and R ₇₅ may be the same or different.

  h. Sublimable dyes represented by general formula (8)

In the general formula (8), R ₈₁ and R ₈₂ each represent a substituted or unsubstituted aliphatic group, and R ₈₁ and R ₈₂ may be the same or different. Examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group. Examples of the group capable of substituting these alkyl groups include linear or branched alkyl groups, cycloalkyl groups, and alkenyl groups, aryl groups, heterocyclic groups, halogen atoms, cyano groups, nitro groups, hydroxy groups, carbonyl groups, Oxycarbonyl group, carbamoyl group, alkoxy group, aryloxy group, heterocyclic oxy group, carbonyloxy group, urethane group, sulfonyloxy group, amino group, sulfonylamino group, sulfamoylamino group, acylamino group, ureido group, sulfonyl Group, sulfamoyl group, alkylthio group, arylthio group, heterocyclic thio group and the like.

  Examples of the cycloalkyl group and the alkenyl group are the same as the above substituents.

As R ₈₁ and R ₈₂ , a group that forms a non-aromatic cyclic structure (eg, pyrrolidine ring, piperidine ring, morpholine ring, etc.) is also preferable.

R ₈₃ is preferably an alkyl group, a cycloalkyl group, an alkoxy group or an acylamino group among the above substituents. n represents an integer of 0 to 4, and when n is 2 or more, the plurality of R ₈₃ may be the same or different.

_R84 is an alkyl group, preferably a secondary or tertiary alkyl group. Alkyl group R ₈₄ is optionally substituted, all of which are substituted with a substituent consisting of carbon and hydrogen atoms. They are not substituted with substituents containing other atoms.

R ₈₅ is an alkyl group, preferably a secondary or tertiary alkyl group. The alkyl group of R ₈₅ may be substituted, but is all substituted with a substituent consisting of a carbon atom and a hydrogen atom. They are not substituted with substituents containing other atoms.

R ₈₆ represents an alkyl group, and a particularly preferred substituent is a linear alkyl group having 3 or more carbon atoms. The alkyl group represented by R ₈₆ may be substituted, but is all substituted with a substituent consisting of a carbon atom and a hydrogen atom, and is not substituted with a substituent containing other atoms.

(Iii) Other compounds The dye layer used in this step may contain other compounds than the binder resin and the sublimable dye, if necessary. Examples of other compounds used in this step include a release agent. In this step, by including a release agent in the dye layer of the dye thermal transfer sheet, it is possible to prevent the dye layer and the receiving layer of the thermal transfer image-receiving sheet described later from being fused, so that the mold release is performed as the other compound. It is preferable to use an agent.

  Examples of the release agent include silicone surfactants and fluorine surfactants. The silicone surfactant is a compound in which a hydrophobic part is made of a silicone resin and a hydrophilic group is introduced into the terminal and / or side chain thereof. Typical examples of the silicone resin include poly (dimethyl) siloxane, methylphenyldimethylpolysiloxane, tetramethyltetraphenylpolysiloxane, dimethylpolysiloxane / polymethylphenylsiloxane copolymer, polymethylsiloxane, tetramethylpolymethylsiloxane, Examples thereof include polymethylsiloxane / polydimethylsiloxane copolymer in which a part or all of the side chain methyl groups are substituted with phenyl groups or hydrogen atoms. Examples of the hydrophilic group introduced into the silicone resin include a polyether group, a polyglycerin group, a pyrrolidone group, a betaine group, a sulfate group, a hydroxyl group, a carboxyl group, a phosphate group, and a quaternary ammonium base. .

  The hydrophilic groups introduced into these silicone resins can be used in appropriate combination. In addition, regarding the structure of the surfactant, not only a hydrophilic group is simply introduced into the terminal and / or side chain of the above-mentioned silicone resin, but also a polymer having a hydrophilic group introduced therein and a polymer having no hydrophilic group introduced therein are randomly copolymerized and blocked. It may be copolymerized by copolymerization. Among these, a silicone surfactant into which polydimethylsiloxane is introduced as a silicone resin and a polyether group, polyglycerin group, or pyrrolidone group is introduced as a hydrophilic group is preferably used.

  Other compounds that can be included in the dye layer in this step in addition to the above releasing agent include, for example, polyethylene wax, etc., in order to improve releasability with a thermal transfer image-receiving sheet described later and ink coating suitability. Organic fine particles and inorganic fine particles.

(C) Dye thermal transfer sheet The dye thermal transfer sheet used in this step may have other configurations as necessary in addition to the dye layer and the support substrate. As such other configurations, for example, an easy-adhesion layer that is formed between the dye layer and the support substrate and has a function of bonding the dye layer and the support substrate, and the dye layer of the support substrate includes A back layer (sometimes referred to as a heat-resistant slipping layer) having a function of preventing adverse effects such as sticking or printing wrinkles due to heat of the thermal head can be given on the surface opposite to the formed surface.

  The material constituting the easy-adhesion layer is not particularly limited as long as the dye layer and the support substrate can be bonded with desired strength. Examples of such materials include polyester resins, polyacrylate resins, polyvinyl acetate resins, polyurethane resins, styrene acrylate resins, polyacrylamide resins, polyamide resins, polyether resins, polystyrene. Resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyvinyl alcohol resin, polyvinyl resin such as polyvinyl pyrrolidone, polyvinyl acetal resin such as polyvinyl acetoacetal and polyvinyl butyral, and the like.

  As the back layer, a layer made of a material obtained by adding a slipperiness imparting agent to a resin material is usually used. Examples of the resin material include polyvinyl butyral resin, polyvinyl acetoacetal resin, polyester resin, vinyl chloride-vinyl acetate copolymer, polyether resin, polybutadiene resin, styrene-butadiene copolymer, acrylic polyol, polyurethane acrylate, and polyester. Acrylate, polyether acrylate, epoxy acrylate, urethane or epoxy prepolymer, nitrocellulose resin, cellulose nitrate resin, cellulose acetate propionate resin, cellulose acetate butyrate resin, cellulose acetate hydrodiene phthalate resin, cellulose acetate resin, aroma Group polyamide resin, polyimide resin, polyamideimide resin, polycarbonate resin, chlorinated polyolefin resin, etc. It can gel.

  Examples of the slipperiness-imparting agent include phosphoric acid esters, silicone oil, graphite powder, silicone-based graft polymers, fluorine-based graft polymers, acrylic silicone graft polymers, acrylic polymers, and silicone polymers such as arylsiloxanes. .

  Moreover, in this process, it is a layer which consists of a polyalcohol polymer compound, a polyisocyanate compound, and a phosphate ester type compound as the above-mentioned back layer, and what added the filler further may be used.

  The dye thermal transfer sheet used in this step is one in which the dye layer is formed on the support substrate. As an aspect of the dye layer, a single color single layer is formed on the support substrate. Alternatively, a plurality of dye layers containing dyes having different hues may be repeatedly formed in the surface order on the same surface of the same support substrate.

Moreover, the dye thermal transfer sheet used in this step may be a thermal transfer sheet having a layer other than the dye layer on the support substrate. Examples of the thermal transfer sheet include those in which the dye layer and a protective layer forming layer described later are formed on the support substrate. As such a thermal transfer sheet, as illustrated in FIG. 2A, the thermal transfer sheet 40 is formed by repeating the dye layer 2 and the protective layer forming layer 12 on the same surface of the same support substrate 1 in a surface sequential manner. The one arranged can be mentioned. Here, when the dye layer has a plurality of dye layers, for example, when a plurality of dye layers are a Y dye layer, an M dye layer, and a C dye layer, FIG. As illustrated, the thermal transfer sheet 40 includes a dye layer 30 composed of a Y dye layer 31, an M dye layer 32, and a C dye layer 33, and the protective layer forming layer 12 arranged alternately. be able to.
In this case, this step and a protective layer forming step described later can be easily performed using the same heating means, and the apparatus for producing a thermal transfer printed product can be simplified.

(D) Method for Producing Dye Thermal Transfer Sheet Next, a method for producing the dye thermal transfer sheet used in this step will be described. The dye thermal transfer sheet used in this step is, for example, a dye layer forming coating solution prepared by dissolving or dispersing the binder resin, sublimation dye, and other compounds as necessary in an appropriate solvent. Thereafter, the dye layer-forming coating solution can be applied to a support substrate and dried to form a dye layer on the support substrate. As an application method for applying the dye layer forming coating solution onto the support substrate, known means such as a gravure printing method, a screen printing method, a reverse roll coating method using a gravure plate, and the like can be used. Thus the dye layer thus formed is coated amount after drying of preferably in the range of ^{0.2g / m 2 ~6.0g / m 2} , especially 0.3g ^/ m 2 ~2.0g ^/ m A range of ² is preferable.

When using the dye thermal transfer sheet having the back layer as the dye thermal transfer sheet used in this step, as the method for forming the back layer, on the support substrate, the resin material, the slipperiness imparting agent, and the filler, Dissolve or disperse with an appropriate solvent to prepare a coating solution for forming the back layer, and apply this by forming means such as a gravure printing method, a screen printing method, a reverse roll coating method using a gravure plate, etc. And dried to form. The coating amount of the back layer is a ^{solid, 0.1g / m 2 ~3.0g / m} 2 is preferred.

(2) Thermal transfer image receiving sheet The thermal transfer image receiving sheet used in this step has a base material and a receiving layer formed on the base material and containing a metal ion that can be chelated. Hereinafter, each configuration of the thermal transfer image receiving sheet will be described.

(A) Receiving layer The resin constituting the receiving layer used in this step is not particularly limited as long as it contains a chelatable metal ion and the dye is easily dyed, and a known one is used. Can be used. Specifically, polyolefin resins such as polypropylene; halogenated resins such as polyvinyl chloride and polyvinylidene chloride; copolymers of halogenated resins such as vinyl chloride vinyl acetate copolymer resins and other vinyl monomers; polyacetic acid Vinyl resins such as vinyl, polyacrylic acid ester, polyvinyl acetal, polyvinyl butyral; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polystyrene resins, polyamide resins, phenoxy resins, olefins such as ethylene and propylene, and other vinyls Polyurethanes; Polycarbonates; Acrylic resins; Ionomers; Cellulose derivatives, etc. Among these, copolymer resins of halogenated resins and other vinyl monomers, poly Ester-based resins and vinyl resins are preferred. In addition, the said resin may be used individually and may be used with a mixture.

  The metal ion contained in the receiving layer used in this step is a metal ion that can be chelated with the sublimable dye described above. The metal ions are generally supplied as a metal ion-containing compound. Such a metal ion-containing compound is not particularly limited, and examples thereof include inorganic or organic salts of metal ions and metal complexes. Among them, salts and complexes of organic acids are preferable, and the following general formula The metal-containing compound represented by (I) can be particularly preferably used.

General formula _{^{(I) M 2+ (X)}} m Y - n

In the above formula, M ²⁺ represents a divalent metal ion. X represents a coordination compound capable of forming a complex by coordination bonding to the metal ion M ²⁺ , and m represents 2 or 4. The plurality of coordination compounds X may be the same as or different from each other. Y ⁻ represents a counter ion of the metal ion M ²⁺ , and n represents an integer of 0, 1, or 2. Further, the compound represented by the above formula may have a neutral ligand depending on the central metal, and typical ligands include H ₂ O, NH ₃ , pyridine, N-methylimidazole, and the like. Is mentioned.

In the compound represented by the above formula, M ²⁺ represents a divalent metal ion. Examples of the metal ion include Mg ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ²⁺ , and Fe ^2+. . Among these, Co ²⁺ and Ni ²⁺ are particularly preferable. In the compound represented by the above formula, Y ⁻ represents a counter anion of the metal ion M ²⁺ , and this counter anion is an organic or inorganic anion, and in particular, depending on the metal ion M ²⁺ and the coordination compound (X) m. Preference is given to compounds which make the complexes formed soluble in organic solvents such as, for example, methyl ethyl ketone, tetrahydrofuran (THF). Specific examples of the counter anion include organic salts such as alkyl carboxylic acid, aryl carboxylic acid, alkyl sulfonic acid, aryl sulfonic acid, alkyl phosphoric acid, aryl phosphoric acid and aryl boric acid.

  The content of the metal ion-containing compound in the receiving layer is not limited because it varies depending on the amount of sublimable dye transferred from the dye thermal transfer sheet, but is not limited to the total solid content constituting the receiving layer. Is preferably 50% by mass or less, and more preferably 40% by mass or less. When the metal ion-containing compound is introduced in an amount of 50% by mass or more, the adhesion between the receiving layer and the substrate is lowered, and when the thermal transfer image receiving sheet is wound, the back surface of the thermal transfer image receiving sheet and the receiving layer may be blocked. Because there is.

(B) Substrate The material constituting the substrate used in this step is not particularly limited as long as it has mechanical characteristics that can withstand heat applied during image formation and has no trouble in handling. Examples of such materials include polyester, polyarylate, polycarbonate, polyurethane, polyimide, polyetherimide, cellulose derivative, polyethylene, ethylene / vinyl acetate copolymer, polypropylene, polystyrene, acrylic, polyvinyl chloride, and polyvinylidene chloride. , Polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone, polysulfone, polyether sulfone, tetrafluoroethylene / perfluoroalkyl vinyl ether, polyvinyl fluoride, tetrafluoroethylene / ethylene, tetrafluoroethylene / hexafluoropropylene, polychloro A plastic film or sheet made of a resin material such as trifluoroethylene or polyvinylidene fluoride It is possible to have.

  In addition, as the base material used in this step, the above plastic film or sheet, the white film formed by adding a white pigment or a filler to the resin material, the sheet having a micro void inside the base material, or the like Condenser paper, glassine paper, sulfuric acid paper, synthetic paper (polyolefin, polystyrene), fine paper, art paper, coated paper, cast coated paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin internal paper Cellulose fiber paper or the like can be used.

  As a structure of the base material used for this process, the structure which consists of a single layer may be sufficient, or it may have the structure by which the several layer was laminated | stacked. Examples of the configuration in which a plurality of layers are stacked include a configuration in which cellulose fiber paper and synthetic paper are stacked, and a configuration in which cellulose fiber paper and a plastic film are stacked.

  The base material used in this step may have at least one surface subjected to an adhesion treatment. Such an adhesive treatment is the same as that described in the above section “1. Dye thermal transfer sheet”, and thus the description thereof is omitted here.

  The thickness of the base material used in this step is not particularly limited as long as the desired self-supporting property is obtained, depending on the material constituting the base material, but usually within the range of 3 μm to 300 μm, In particular, the range of 100 μm to 250 μm is preferable.

(C) Thermal transfer image-receiving sheet The thermal transfer image-receiving sheet used in this step may have another configuration in addition to the receiving layer and the substrate. Such other configurations include, for example, a back layer formed on the surface of the substrate opposite to the surface on which the receiving layer is provided for the purpose of improving the transportability of the thermal transfer image-receiving sheet and preventing curling, and the above-described receiving layer. An intermediate layer formed for the purpose of imparting a predetermined function between the layer and the substrate can be exemplified.

  The material constituting the back layer is not particularly limited as long as it is a material that can impart a desired function to the back layer, but a material obtained by adding a filler to a resin material is usually used.

  Examples of the resin material constituting the back layer include acrylic resins, cellulose resins, polycarbonate resins, polyvinyl acetal resins, polyvinyl alcohol resins, polyamide resins, polystyrene resins, polyester resins, halogenated polymers, and the like. Can do. Moreover, what hardened | cured such a resin material with hardening | curing agents, such as an isocyanate compound, can also be used.

  Examples of the filler contained in the back layer include, for example, acrylic fillers, polyamide fillers, fluorine fillers, organic fillers such as polyethylene wax, amino acid powders, and inorganic fillers such as silicon dioxide and metal oxides. Can be mentioned.

  Examples of the intermediate layer include an antistatic layer, a cushion layer, an intermediate layer to which a white pigment and a fluorescent whitening agent are added, an easily adhesive layer, and the like.

  In this step, an antistatic layer, a writing layer or the like may be formed instead of the back layer.

(D) Manufacturing Method of Thermal Transfer Image Receiving Sheet A manufacturing method of the thermal transfer image receiving sheet used in this step will be described. The method for producing the thermal transfer image-receiving sheet used in this step is not particularly limited as long as it is a method capable of producing the thermal transfer image-receiving sheet having the above-described configuration. Usually, the resin constituting the receptor layer, the metal ions, and If necessary, additives and the like are optionally added, and after sufficiently kneading with a solvent, a diluent, etc. to prepare a coating solution for forming a receiving layer, this is applied on the substrate, for example, a gravure A production method is used in which a receiving layer is formed by applying and drying by a forming means such as a printing method, a screen printing method, or a reverse roll coating method using a gravure plate. The coating amount of the receptor layer forming coating solution is preferably 0.5g ^{/ m 2} ~4.0g ^/ m 2 in dry. This is because if the coating amount is less than the above range, unevenness occurs in fixing the dye and the dye acceptability may be lowered. Moreover, it is because productivity etc. may fall when there are more coating amounts than the said range.

(3) Thermal transfer step In this step, the chelate sublimable dye contained in the dye layer is heated by facing the dye layer of the dye thermal transfer sheet and the receiving layer of the thermal transfer image-receiving sheet. There is no particular limitation as long as it can be transferred to the receiving layer.
In this step, the heating means is not particularly limited, but a thermal head used in a general thermal transfer printer can be used.

The dye layer and the receiving layer may or may not be in contact at the time of heating / transfer, but are preferably in contact in this step. This is because it becomes easy to transfer a desired amount of sublimable dye to a desired location.
When the dye layer and the receiving layer are in contact with each other during heating / transfer, the dye thermal transfer sheet and the thermal transfer image receiving sheet may be pressurized. This is because, by applying pressure, the dye layer and the receiving layer can sufficiently adhere to each other, the transfer of the sublimable dye can be facilitated, and the transfer position can be prevented from shifting.

2. Next, the protective layer forming step used in this step will be described. In this step, the receiving layer of the thermal transfer image-receiving sheet to which the sublimable dye has been transferred by the thermal transfer step described above, and a support substrate, and a protective layer forming layer formed on the support substrate and containing a heat conversion substance, This is a step of forming a protective layer on the receiving layer by heating the protective layer-forming layer of the protective layer thermal transfer sheet having a facing surface. In this step, when the protective layer-forming layer contains a heat conversion substance, the adhesion between the receptor layer and the protective layer can be increased in the electromagnetic wave irradiation step described later. Hereinafter, such a protective layer forming step will be described.

(1) Protective layer thermal transfer sheet The protective layer thermal transfer sheet used in this step has a support substrate and a protective layer forming layer formed on the support substrate and containing a heat conversion substance. Hereinafter, each configuration of such a protective layer thermal transfer sheet will be described in detail.

(A) Protective layer forming layer The protective layer forming layer used in this step is formed on a support substrate, which will be described later, contains a heat conversion substance, and is transferred onto the receiving layer to thereby convert the heat conversion substance. The protective layer is not particularly limited as long as the protective layer is included, and may be a single layer or a plurality of layers. Hereinafter, the protective layer forming layer will be described separately in the case of a single layer and the case of a plurality of layers.

(I) In the case of a single layer When the protective layer forming layer used in this step is a single layer, the protective layer forming layer has durability such as light resistance, weather resistance, abrasion resistance, Furthermore, the thing which consists of transparent resin which is transparent and does not impair the clarity of the image of a thermal transfer printed matter, and contains a heat conversion substance can be mentioned.

  In this step, as the transparent resin used for the protective layer forming layer, for example, polyester, polystyrene, acrylic resin, polyurethane, acrylic urethane resin, silicone modified resin of these resins, and these transparent resins A mixture etc. can be mentioned.

In this step, the heat conversion substance contained in the protective layer forming layer is not particularly limited as long as it can absorb an electromagnetic wave to be described later and convert it into heat. As such a heat conversion substance, although it changes with electromagnetic waves to irradiate, for example, when the said electromagnetic waves are a microwave, resin which has a hydroxyl group in material is preferable from the characteristic of a microwave. As resins, polyvinyl butyral, polyvinyl acetal, polyurethane polyol, polyether polyol, acrylic, acrylic polyester copolymer, alkyd, silicon polyester, vinyl chloride-vinyl acetate copolymer, epoxy epoxy ring opening with alkanolamine However, from the viewpoint of selective absorption of electromagnetic waves of each wavelength and efficient conversion to heat and adhesion to the image receiving layer, both polyvinyl butyral and vinyl chloride-vinyl acetate are available. Polymers and acrylics are desirable, and polyvinyl butyral is particularly preferred.
Further, when the electromagnetic wave is infrared, specifically, tin oxide, indium oxide, magnesium oxide, titanium oxide, chromium oxide, zirconium oxide, nickel oxide, aluminum oxide, zinc oxide, iron oxide, antimony oxide, Inorganic infrared absorbers such as lead oxide and bismuth oxide, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, naphthoquinone compounds, anthraquinone compounds, aluminum compounds, pyrylium compounds, cerium compounds, squarylium compounds, One or more organic infrared absorbers such as diimoniums, copper complexes, nickel complexes, and dithiol complexes can be used. Usually, when an infrared absorber having a counter ion structure is used, if the transparent resin containing the infrared absorber has a hydroxyl group, a carboxyl group, a polymerization initiator, etc., the hydroxyl group, carboxyl group, polymerization start In some cases, the counter ion balance may be lost due to the agent or the like, making it difficult to perform the function of absorbing infrared rays.
In the present invention, since the above-described transparent resin is used, even if it is an infrared absorber having a counter ion structure, the above-mentioned effects can be exhibited without causing a reaction or the like. Among these, diimoniums having a counter ion structure, nickel complexes, dithiol complexes, aluminum compounds, cyanine compounds, and pyrylium compounds are preferable, and diimonium compounds or cyanine compounds are particularly preferable.

  In addition, the content of the heat conversion substance in the protective layer forming layer can be converted into a desired amount of heat, and when the protective layer forming layer is transferred to form a protective layer, thermal transfer printing is performed. It is not particularly limited as long as it does not interfere with the function as a protective layer such as the sharpness and durability of the object.For example, when using a material that affects transparency, such as diimoniums, The total solid content of the protective layer forming layer is preferably in the range of 0.1% by mass to 10% by mass, and more preferably in the range of 1% by mass to 6% by mass.

  The thickness of the protective layer-forming layer in the case of a single layer is not particularly limited as long as desired durability and the like can be obtained, but specifically, within the range of 0.3 μm to 5 μm, particularly 0.5 μm. It is preferable to be within a range of ˜1.5 μm.

(Ii) In the case of a plurality of layers The layer structure when the protective layer forming layer used in this step is a plurality of layers is not particularly limited as long as it is two or more layers. In this step, it is possible to preferably use the protective layer forming layer obtained by laminating the release layer and the adhesive layer in this order on the support substrate.
When the protective layer forming layer has the release layer and the adhesive layer, when the protective layer is transferred onto the receptor layer to form the protective layer, the protective layer includes the adhesive layer formed on the receptor layer, and And a release layer formed on the adhesive layer. Therefore, the adhesive layer exhibits the function of improving the adhesion between the protective layer and the receiving layer, and the release layer exhibits the function of improving the durability and the like of the printed material transferred to the receiving layer. . For this reason, it is possible to form a protective layer with little possibility of peeling with time.

As the material of the release layer, the same material as the transparent resin described in the section “(i) In the case of a single layer” can be used, and the description here is omitted.
The thickness of the release layer is not particularly limited as long as desired durability or the like can be obtained, and can be set according to other layers constituting the protective layer forming layer.

The material of the adhesive layer is not particularly limited as long as it is a thermoplastic resin that can be bonded with a desired strength. Examples of such thermoplastic resins include acrylic resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, styrene-acryl copolymer resins, polyester resins, polyamide resins, and the like. Can be mentioned.
The thickness of the adhesive layer is preferably in the range of 0.1 μm to 3 μm. This is because if the thickness is smaller than the above range, the protective layer formed on the receiving layer may be peeled off. If the thickness is larger than the above range, it takes a long time to melt the thermoplastic resin used for the adhesive layer by heating. This is because the productivity of the thermal transfer print is reduced.

  The thickness of the protective layer-forming layer in the case of a plurality of layers is not particularly limited as long as desired durability and the like can be obtained. Specifically, the thickness is in the range of 0.3 μm to 5 μm, particularly 0.5 μm. It is preferable to be within a range of ˜1.5 μm. In addition, the said thickness is the thickness which totaled all the layers which comprise the said layer for protective layer formation.

About the kind of said heat conversion substance, and its content, since the thing similar to what was described in the above-mentioned "(i) In the case of a single layer" can be used, description here is abbreviate | omitted.
In addition, content of a heat conversion substance is content with respect to the total solid of all the layers which comprise the said layer for protective layer formation.

In the case where the protective layer forming layer has a plurality of layers, the heat conversion substance is not particularly limited as long as it is contained in at least one of the layers. In this step, the protective layer-forming layer is preferably transferred to the receptor layer of the thermal transfer image-receiving sheet and included in the layer in contact with the receptor layer when the protective layer is formed. It is preferable to be included only in the layer in contact with the layer.
Here, in the case where the protective layer forming layer is formed by laminating a release layer, which is a layer structure suitably used in this step, and an adhesive layer in this order on the support substrate, The conversion substance only needs to be contained in either one of the release layer or the adhesive layer, and is preferably contained in at least the adhesive layer, and only included in the adhesive layer. It is preferable that
When the protective layer-forming layer having the release layer and the adhesive layer is transferred onto the receiving layer of the thermal transfer image receiving sheet to form a protective layer, as shown in FIG. 3, the thermal transfer image receiving sheet 6 is received. On the layer 5, a protective layer 20 composed of the adhesive layer 14 and the release layer 13 formed on the adhesive layer 14 is formed.
Since only the adhesive layer forming the protective layer contains the heat conversion substance, only the adhesive layer in contact with the receiving layer in the protective layer can be selectively heated in the electromagnetic wave irradiation step described later. Therefore, the adhesion between the receiving layer and the protective layer can be more efficiently increased. Further, by selectively heating only the adhesive layer in contact with the receptor layer, it is possible to more efficiently promote the chelation reaction of the sublimable dye contained in the receptor layer in contact with the adhesive layer. Because it can.

(Iii) Other components The protective layer forming layer used in this step may contain a light stabilizer, an antioxidant, a fluorescent brightening agent, a filler and the like in addition to the heat conversion substance.
The ultraviolet absorber is not particularly limited as long as a protective layer not yellowish can be obtained, and specifically, salicylate-based, benzophenone-based, benzotriazole-based, triazine-based, substituted acrylonitrile-based , Nickel chelate-based, hindered amine-based ultraviolet absorbers, etc., among which benzotriazole-based ultraviolet absorbers are preferred. The usage-amount of the said ultraviolet absorber will not be specifically limited if the protective layer which does not get yellowish can be obtained, It can select arbitrarily.

  The light stabilizer used in this step is used for capturing radicals generated by light irradiation or the like and further improving the light resistance of the protective layer. Specific examples of such light stabilizers include hindered amine-based, phenol-based, and phosphite-based light stabilizers. Among them, hindered amine-based light stabilizers are preferable. The amount of the light stabilizer used is not particularly limited as long as it does not inhibit transparency and durability, and can be arbitrarily selected.

(B) Support substrate As the support substrate, the protective layer forming layer can be formed, and the protective layer forming layer is transferred to the receiving layer of the thermal transfer image receiving sheet by heating to form the protective layer. There is no particular limitation as long as it can be formed. As such a support substrate, the same as “(a) Support substrate” of “(1) Dye thermal transfer sheet” in “1. Thermal transfer step” can be used. Omitted.

(C) Protective layer thermal transfer sheet The protective layer thermal transfer sheet used in this step may have a layer configuration other than the protective layer forming layer, if necessary. For example, the protective layer thermal transfer sheet may have a back layer and a release layer.
As the back layer, the same layer as described in the section “(c) Dye thermal transfer sheet” of “(1) Dye thermal transfer sheet” can be used.
The release layer is formed between the protective layer forming layer and the support substrate, and is used for forming the protective layer when the protective layer forming layer is thermally transferred onto the receiving layer of the thermal transfer image receiving sheet. It is provided for the purpose of improving the releasability between the layer and the support substrate. Examples of such a release layer include those described in JP-A-2001-347759.

  Although it does not specifically limit as a manufacturing method of the protective layer thermal transfer sheet used for this process, For example, the said heat conversion substance which comprises the layer for protective layer formation, transparent resin, and other additives etc. are contained. A method of preparing a coating solution and applying it on a substrate is mentioned. Examples of the coating method at this time include a gravure coating method, a gravure reverse coating method, and a roll coating method.

(2) Protective layer forming step In this step, the protective layer forming layer of the protective layer thermal transfer sheet and the receiving layer of the thermal transfer image receiving sheet are heated facing each other to transfer the protective layer forming layer. Thus, there is no particular limitation as long as a protective layer can be formed on the receiving layer.
In this step, the heating means is not particularly limited, but a thermal head or the like used in a general thermal transfer printer can be used.

  The protective layer-forming layer and the receiving layer may be in contact with each other as long as the protective layer is formed on the receiving layer by heating. It is preferable that they are in contact with each other. This is to ensure the formation of the protective layer. In addition, when the protective layer forming layer and the receiving layer are in contact with each other during heating / transfer, the protective layer thermal transfer sheet and the thermal transfer image receiving sheet may be pressurized. This is because, by applying pressure, the transfer of the protective layer forming layer onto the receiving layer can be facilitated, and air biting can be prevented.

3. Electromagnetic wave irradiation process Next, the electromagnetic wave irradiation process used for this process is demonstrated. This step is a step of heating the protective layer by irradiating the protective layer containing the heat conversion substance formed on the receiving layer of the thermal transfer image-receiving sheet with an electromagnetic wave in the protective layer forming step. By heating the protective layer, the adhesion between the protective layer and the receiving layer can be increased, and further, the heat is efficiently transferred to the receiving layer on which the protective layer is formed. The chelation reaction of the sublimable dye can be advanced to reduce the hue change of the thermal transfer printed matter. Hereinafter, such an electromagnetic wave irradiation process will be described.

(1) Electromagnetic waves As electromagnetic waves used in this step, radio waves (wavelengths of 1 m or more), microwaves (wavelengths of about 1 mm to 1 m), infrared rays (wavelengths of about 1 μm to 1 mm), visible rays (wavelengths of about 400 nm to 1 mm), ultraviolet rays (Wavelength of about 10 nm to about 400 nm), X-ray (wavelength of about 1 pm to about 10 nm), gamma ray (wavelength of about 10 pm or less), and the like. In this step, among the above electromagnetic waves, it is preferable to use microwaves and infrared rays. This is because the protective layer described above can be efficiently heated.

  In this step, the output of the electromagnetic wave can be appropriately set according to the material constituting the protective layer, the heat conversion substance, and the like.

  In this step, only one type of the electromagnetic wave may be used, or two or more types may be irradiated simultaneously.

(2) Electromagnetic wave irradiation step This step is a step of heating the protective layer by irradiating the protective layer containing the heat conversion substance formed on the receiving layer of the thermal transfer image receiving sheet with an electromagnetic wave, and the thermal transfer image receiving sheet. There is no particular limitation as long as it is a method capable of irradiating the surface of the protective layer formed thereon with a uniform dose. Examples of such electromagnetic wave irradiation methods include, for example, a method of simultaneously irradiating the entire surface of the thermal transfer image receiving sheet on which the protective layer is formed, and sequentially moving while moving at least one of the electromagnetic wave irradiation source or the thermal transfer image receiving sheet. The irradiation method can be mentioned.
In this step, any of these embodiments can be suitably used, but it is particularly preferable to use the latter method. This is because the latter method makes it easy to uniformly irradiate the entire surface of the thermal transfer image-receiving sheet on which the protective layer is formed even if the size and the production rate of the thermal transfer printed matter are changed.

  Further, the number of electromagnetic wave irradiation sources used in this step may be one, or a plurality may be used.

4). Manufacturing method of thermal transfer printed matter The manufacturing method of the thermal transfer printed matter in this step is not particularly limited as long as it has the above-described thermal transfer step, protective layer forming step, and electromagnetic wave irradiation step, and includes other steps. It may be a thing. In this invention, you may have the pre-heating process which heats the said dye thermal transfer sheet and a thermal transfer image receiving sheet previously as said other process before the said thermal transfer process. This is because by having the preliminary heating step, it is possible to shorten the heating time in the thermal transfer step and promote chelation of the sublimable dye transferred to the receiving layer of the thermal transfer image-receiving sheet.

B. Next, the thermal transfer sheet of the present invention will be described. The thermal transfer sheet of the present invention has a support substrate and a protective layer forming layer formed on the support substrate and containing at least a heat conversion substance.

  Next, the thermal transfer sheet of the present invention will be described with reference to the drawings. FIG. 4 is a schematic sectional view showing an example of the thermal transfer sheet of the present invention. As illustrated in FIG. 4, the thermal transfer sheet 50 of the present invention includes a support substrate 51 and a protective layer forming layer 52 formed on the support substrate 51 and containing a heat conversion substance.

  According to the present invention, the protective layer-forming layer contains a heat conversion substance, and after the protective layer is formed by heating / transfer, the protective layer is irradiated with an electromagnetic wave that can be selectively absorbed by the heat conversion substance. The layer can be selectively heated. Therefore, when the protective layer is formed on the receiving layer of the thermal transfer image-receiving sheet to which the sublimation dye is transferred, the adhesion of the protective layer is improved by irradiation with electromagnetic waves, and the transferred sublimation dye chelate It is possible to improve the durability such as the hue change of the thermal transfer printed matter due to the progress of the reaction and the productivity.

  The thermal transfer sheet of the present invention has a support substrate and a protective layer forming layer. Hereinafter, each configuration of the thermal transfer sheet will be described.

1. Support Substrate The support substrate used in the present invention can form a protective layer forming layer to be described later, can transfer the protective layer forming layer by heating, and can stably support the layer. There is no particular limitation as long as it is possible. Such a support substrate is described in the section “(a) Support substrate” of “(1) Dye thermal transfer sheet” in “1. Thermal transfer step” of “A. Method for producing thermal transfer print”. Since the thing similar to what was done and the content can be used, description here is abbreviate | omitted.

2. Protective layer forming layer The protective layer forming layer used in the present invention is formed on the above-mentioned support substrate, contains a heat conversion substance, and is transferred onto the receiving layer, thereby containing the heat conversion substance. If it forms, it will not specifically limit, A single layer may be sufficient and multiple layers may be sufficient.

  In the present invention, the protective layer-forming layer is composed of a plurality of layers obtained by laminating a release layer and an adhesive layer made of a thermoplastic resin in this order on the support substrate, and only the adhesive layer. It is preferable that a heat conversion substance is contained. When a protective layer is formed on the receiving layer of the thermal transfer image receiving sheet using such a protective layer forming layer having a release layer and an adhesive layer, as shown in FIG. 3, the thermal transfer image receiving sheet 6 A protective layer 20 comprising an adhesive layer 14 and a release layer 13 formed on the adhesive layer 14 is formed on the receiving layer 5. Therefore, only the adhesive layer contains a heat conversion substance, whereby the adhesion between the receiving layer and the protective layer can be more efficiently increased, and further, the sublimation property contained in the receiving layer in contact with the adhesive layer. This is because the chelate reaction of the dye can be promoted more efficiently. In addition, it is possible to shorten the heating time for improving the adhesion between the receiving layer and the protective layer, which is required when transferring to the receiving layer with a thermal head or the like, so that the line speed can be improved.

  As such a protective layer forming layer, “(a) Protection” of “(1) Protective layer thermal transfer sheet” in “2. Protective layer forming step” of “A. Manufacturing method of thermal transfer printed matter” above. The same materials as those described in the section “Layer forming layer” can be used.

3. Thermal Transfer Sheet The thermal transfer sheet of the present invention is not particularly limited as long as it has a support substrate and a protective layer forming layer containing a heat conversion substance.
In this invention, you may have layers other than the said layer for protective layer formation on the said support substrate. Examples of the layer that can be used in the thermal transfer sheet of the present invention include a layer having a dye layer containing a sublimable dye that can be chelated. By having such a dye layer, it is preferable to have a dye layer in that the transfer of the sublimable dye and the formation of the protective layer can be facilitated.

  As an aspect having the dye layer on the support substrate, a sublimation dye contained in the dye layer is transferred to form a desired image, and a heat conversion substance is contained by transferring the protective layer forming layer. There is no particular limitation as long as the protective layer can be formed. As such an embodiment, a single layer of one color may be formed on the support substrate, or a plurality of dye layers containing dyes having different hues are repeatedly formed on the same surface of the same support substrate in the surface order. May be. As an aspect configured by a single layer of one color on the support substrate, for example, as illustrated in FIG. 2A described above, the dye layer 2 and the protective layer forming layer are formed on the support substrate 1. 12 may be mentioned alternately. Further, as an embodiment having a plurality of dye layers on the same support substrate, for example, when the dye layer is a Y dye layer, an M dye layer, or a C dye layer, as illustrated in FIG. Further, there can be mentioned those in which the dye layer 30 composed of the Y dye layer 31, the M dye layer 32, and the C dye layer 33 and the protective layer forming layer 12 are alternately arranged.

  In the present invention, as the dye layer, the item “(b) Dye layer” in “(1) Dye thermal transfer sheet” in “1. Thermal transfer step” in “A. Method for producing thermal transfer printed matter” above. Since the thing similar to what was described in (1) can be used, description here is abbreviate | omitted.

  Moreover, the thermal transfer sheet of the present invention may have a layer other than the above. Examples of such a layer include a back layer and a release layer. For the back layer and the release layer, “(c) Protection” of “(1) Protective layer thermal transfer sheet” in “2. Protective layer forming step” in “A. Method for producing thermal transfer print”. Since it is the same as that described in the section “Layer Thermal Transfer Sheet”, the description is omitted here.

  The method for producing the thermal transfer sheet of the present invention is not particularly limited as long as the protective layer forming layer is laminated on the support substrate with good adhesion. Examples of a method for producing such a dye thermal transfer sheet with a protective layer include a method in which a coating liquid containing a material constituting the protective layer forming layer is prepared and applied onto a substrate. Examples of the coating method at this time include a gravure coating method, a gravure reverse coating method, and a roll coating method.

C. Next, the thermal transfer print of the present invention will be described. The thermal transfer printed matter of the present invention includes a thermal transfer image-receiving sheet having a substrate, and a receptor layer formed on the substrate and containing a chelate-type color former formed by binding metal ions and a sublimation dye, and the receptor A protective layer formed on the layer and containing a heat conversion substance.

  Next, the thermal transfer printed matter of the present invention will be described with reference to the drawings. FIG. 5 is a schematic cross-sectional view showing an example of the thermal transfer print of the present invention. As shown in FIG. 5, the thermal transfer print 60 of the present invention includes a base 61 and a receiving layer that is formed on the base 61 and includes a chelate color former formed by binding a metal ion and a sublimation dye. A thermal transfer image receiving sheet 63 having 62 and a protective layer 64 formed on the receiving layer 62 and containing a heat conversion substance.

  According to the present invention, when the protective layer has a heat conversion substance, for example, by irradiating an electromagnetic wave that can be absorbed by the heat conversion substance, the adhesion between the receiving layer and the protective layer is improved. Can do. Moreover, since the chelate reaction of the sublimable dye can be promoted together with the improvement of the adhesion, the hue change and the like can be reduced.

  The thermal transfer printed matter of the present invention has a thermal transfer image receiving sheet and a protective layer. Hereafter, each structure of such a thermal transfer printed matter is demonstrated in detail.

1. Thermal transfer image-receiving sheet The thermal transfer image-receiving sheet used in the present invention has a base material and a receiving layer formed on the base material and containing a chelate color former formed by binding a metal ion and a sublimation dye. If it is, it will not specifically limit.

(1) Receiving layer The receiving layer used in the present invention is not particularly limited as long as it contains a chelate color former described later stably, and a known layer can be used.
As the resin constituting such a receiving layer, the resin described in “(a) Receiving layer” of “(2) Thermal transfer image-receiving sheet” of “A. Method for producing thermal transfer printed material” is used. Can do.

  The chelate color former used in the present invention is not particularly limited as long as it has a sublimable dye and a metal ion bonded to each other and has a desired color developability according to the type of the sublimable dye.

As the sublimation dye, “(ii) Sublimation property of“ (b) Dye layer ”of“ (1) Dye thermal transfer sheet ”of“ 1. Thermal transfer process ”of“ A. Method for producing thermal transfer printed matter ”above. The same dyes as described in the section “Dye” can be used.
In addition, as the metal ion compound, the item “(a) Receptive layer” in “(2) Thermal transfer image-receiving sheet” in “1. Thermal transfer step” in “A. Method for producing thermal transfer print” above. Since it is the same as what was described, description here is abbreviate | omitted.

(2) Substrate The base material used in the present invention is the “(b) base” of “(2) Thermal transfer image-receiving sheet” of “1. Thermal transfer step” of “A. Method for producing thermal transfer print”. Since it is the same as that described in the section of “Material”, the description here is omitted.

(3) Thermal Transfer Image Receiving Sheet For other layer configurations and manufacturing methods of the thermal transfer image receiving sheet used in the present invention, “(2) Thermal transfer image receiving sheet” in “1. Thermal transfer step” of “B. Thermal transfer sheet” above. Since it is the same as that described in the section, the explanation here is omitted.

2. Protective layer The protective layer used in the present invention is not particularly limited as long as it has a heat conversion substance, protects the thermal transfer image-receiving sheet, and has excellent durability such as hue change and abrasion resistance. It is not something. Such a protective layer may be a single layer or a plurality of layers.

In the present invention, the protective layer is composed of a plurality of layers in which an adhesive layer made of a thermoplastic resin and a release layer are laminated in this order on the receiving layer, and only the adhesive layer contains a heat conversion substance. It is preferable that
When the protective layer is formed by laminating an adhesive layer and a release layer in this order on the receiving layer, as illustrated in FIG. 3, on the receiving layer 5 of the thermal transfer image receiving sheet 6. Then, a protective layer 20 composed of the adhesive layer 14 and the release layer 13 formed on the adhesive layer 14 is formed. Therefore, only the adhesive layer contains a heat conversion substance, and thus, when the electromagnetic wave that can be selectively absorbed and converted into heat by the heat conversion substance is irradiated, it contributes most to the adhesion with the receiving layer. This is because only the adhesive layer can be selectively heated. Moreover, it is because the chelating reaction of the sublimable dye contained in the receiving layer in contact with the adhesive layer can be more efficiently promoted by selectively heating the adhesive layer. Therefore, the adhesion between the receiving layer and the protective layer can be improved and the chelation reaction of the sublimable dye can be easily promoted, so that the durability such as hue change can be improved.

  As the protective layer containing the heat conversion substance used in the present invention, the same protective layer forming layer as described in “2. Protective layer forming layer” of “B. Thermal transfer sheet” can be used. Therefore, the description here is omitted.

3. Thermal transfer printed matterThe thermal transfer printed matter of the present invention is a thermal transfer image-receiving sheet comprising a base material and a receiving layer formed on the base material and containing a chelate color former formed by binding metal ions and a sublimation dye, If it has a protective layer formed on the said receiving layer and containing a heat conversion substance, it will not specifically limit.
The method for producing such a thermal transfer printed matter is not particularly limited as long as each component of the thermal transfer printed matter can be laminated with good adhesion. The method described in “Method for producing thermal transfer print” is most preferably used. This is because, since the protective layer has a heat conversion substance, the adhesiveness between the receiving layer and the protective layer can be improved by irradiating electromagnetic waves that can be absorbed by the heat conversion substance. In addition, since the chelating reaction of the sublimable dye can be promoted together with the improvement of the adhesion, the hue change and the like can be reduced.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the technical idea described in the claims of the present invention has substantially the same configuration and exhibits the same function and effect regardless of the case. It is included in the technical scope of the invention.

  Next, the present invention will be described more specifically with reference to examples and comparative examples.

[Example 1]

1. Preparation of Thermal Transfer Image Receiving Sheet As a base material, white PET (Lumirror E63S manufactured by Toray Industries, Inc.) having a thickness of 50 μm on the front and back sides of coated paper (Oji Paper Co., Ltd. OK Top Coat, 127.9 g / m ² ), urethane A system adhesive (Takelac A-969V / Takenate A-5 (mass ratio 3/1) manufactured by Mitsui Takeda Chemical Co., Ltd.) was applied and pasted so that the coating amount after drying was 4 g / m ² .

Next, a receiving layer-forming coating solution having the following composition was applied to one surface of the substrate with a Miya bar so that the coating amount after drying was 2.5 g / m ^2, and dried at 130 ° C. for 2 minutes. As a result, a thermal transfer image-receiving sheet was produced.

(Composition of coating solution for forming receiving layer)
The following composition was prepared by diluting with a methyl ethyl ketone / toluene (mass ratio 1/1) solvent so that the solid content concentration was 10% by mass.
50 parts by weight of polyvinyl butyral resin (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.)
19 parts by weight of polyvinyl acetal resin (Product surface: BX-L, manufactured by Sekisui Chemical Co., Ltd.)
Metal ion compound of the following structural formula 30 parts by weight Acrylic-modified silicone 1 part by weight (trade name: MODIPER FS730, manufactured by NOF Corporation)

2. Preparation of Thermal Transfer Sheet Using a 6 μm thick PET film (trade name: Lumirror Toray) prepared as a support substrate, the back layer coating solution prepared in advance with the following composition was gravure coated on this surface to obtain a dry coating amount. It applied so that it might be set to 1.0 g / m < ² >, and the back layer was formed.

(Back layer coating composition)
(Polyvinyl butyral resin) 13.6 parts by weight (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.)
0.6 parts by weight of polyisocyanate curing agent (trade name: Takenate D218, manufactured by Takeda Pharmaceutical Company Limited)
Phosphoric acid ester 0.8 part by weight (trade name: Prisurf A208S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Toluene 42.5 parts by weight Methyl ethyl ketone 42.5 parts by weight

Next, on the support substrate surface opposite to the surface on which the back layer is formed, a release layer forming layer coating solution prepared to the following composition is dried by gravure coating so that the film thickness becomes 1.0 μm. Applied. In addition, when drying the layer for forming the protective release layer, it was dried with a dryer and further left in an oven at a temperature of 100 ° C. for 1 minute to form a release layer on the support substrate.
Next, a protective layer forming layer in which the release layer and the adhesive layer were laminated in this order was formed on the support substrate by applying and drying the following adhesive layer forming coating solution on the release layer.

(Composition of the layer coating solution for forming the release layer)
Acrylic resin (trade name: BR-83, manufactured by Mitsubishi Rayon Co., Ltd.) 20 parts by weight Toluene 40 parts by weight Methyl ethyl ketone 40 parts by weight

(Composition of the coating solution for forming the adhesive layer)
19 parts by weight of vinyl chloride-vinyl acetate copolymer resin (trade name: # 1000ALK, manufactured by Denki Kagaku Kogyo)
Diimoniums (trade name: IR-2MF, manufactured by Showa Denko KK) 1 part by weight Toluene 40 parts by weight Methyl ethyl ketone 40 parts by weight

Next, on the unformed portion of the protective layer forming layer on the surface of the support substrate opposite to the surface on which the back layer is formed, a dye layer forming coating solution having the following composition is applied by gravure coating to a dry coating amount. The dye layer was formed by applying and drying to 0.5 g / m ² to prepare a thermal transfer sheet having dye layers of yellow, magenta, and cyan.

(Composition of yellow dye layer forming coating solution)
Sublimation dye (compound i below) 1.4 parts by weight Cellulose acetate butyrate resin 1.0 part by weight (CAB381-2, molecular weight 38000, manufactured by Eastman Chemical Co.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 97.6 parts by weight

(Composition of coating liquid for forming magenta dye layer)
Sublimation dye (following formula ii) 0.8 part by weight Cellulose acetate butyrate resin 1.0 part by weight (CAB381-2, molecular weight 38000, manufactured by Eastman Chemical Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 98.2 parts by weight

(Composition of cyan dye layer forming coating solution)
Sublimation dye (compound iii) 0.9 parts by weight Cellulose acetate butyrate resin 1.0 part by weight (CAB381-2, molecular weight 38000, manufactured by Eastman Chemical Co.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 98.1 parts by weight

3. Production of thermal transfer prints (printing conditions)
Heating element average resistance value: 5285 (Ω)
Main scanning direction printing density; 300 dpi
Sub-scanning direction print density; 300 dpi
Applied voltage: 22 (V)
1 line cycle; 2 (msec./line)
Printing start temperature: 27 (° C)
Applied pulse (gradation control method): Using a multi-pulse test printer that can vary the number of divided pulses from 0 to 255 in one line period and having a pulse length obtained by equally dividing one line period into 256 The duty ratio of the divided pulses was fixed at 90%, and the number of pulses per line period was divided from 0 to 255 into 18 steps. Thereby, different energy can be given to 18 steps.
Yellow, magenta, and cyan dyes were transferred in this order to the receiving layer of the thermal transfer image-receiving sheet to form a black image. Next, the protective layer was formed by printing the protective layer forming layer with an applied voltage of 20 V and a pulse number of 255.

4). Irradiation with electromagnetic waves The thermal transfer image-receiving sheet on which the protective layer was formed was irradiated with infrared rays as electromagnetic waves by the following IR heater.
(IR heater)
IR heater: Output 2KW x 2 lamps Irradiation distance: 100mm
Irradiation time: 10 seconds

[Example 2]
In the same manner as in Example 1 except that the adhesive layer-forming coating solution had the following composition, infrared irradiation was performed as electromagnetic waves by the IR heater.

(Composition of the coating solution for forming the adhesive layer)
19 parts by weight of polyvinyl butyral (trade name: BL-10, manufactured by Sekisui Chemical Co., Ltd.)
Diimoniums (trade name: IR-2MF, manufactured by Showa Denko KK) 1 part by weight Toluene 40 parts by weight Methyl ethyl ketone 40 parts by weight

[Example 3]
A thermal transfer print was prepared in the same manner as in Example 1 except that the adhesive layer-forming coating solution had the following composition and was irradiated with microwaves as electromagnetic waves. In addition, the microwave irradiation time was set to 60 seconds for the microwave irradiation using the commercially available microwave oven shown below.
(microwave)
Sharp Corporation RE-T21-W5P

(Composition of the coating solution for forming the adhesive layer)
Polyvinyl butyral 20 parts by weight (trade name: BL-10, manufactured by Sekisui Chemical Co., Ltd.)
40 parts by weight of toluene 40 parts by weight of methyl ethyl ketone

[Comparative Example 1]
A thermal transfer print was produced in the same manner as in Example 1 except that no electromagnetic wave was irradiated.

[Evaluation]
The thermal transfer prints in the above examples and comparative examples were evaluated for (1) color density measurement, (2) light resistance test, and (3) protective layer adhesion.

(1) Color density measurement When a black (Bk) image is formed using yellow, magenta, and cyan, it is known that only the cyan dye has a low color density. Therefore, the progress of the chelate reaction was confirmed by measuring the color density of the cyan dye. A spectrophotometer (Spectrolino manufactured by Gretag Macbeth Co., Ltd.) was used for the measurement, and the cyan density in Bk was measured when the OD of Bk was around 1.5. For the cyan density measurement, density evaluation was performed with a D65 light source based on Ansi Status A.

(2) Light resistance test The conditions for light resistance evaluation are as follows.
・ Irradiation tester: Ci35 manufactured by Atlas
-Light source: Xenon lamp-Filter: Inside = IR filter
Outside = soda lime glass • Black panel temperature: 45 (° C)
Irradiation intensity: measured value at 1.2 (W / m ² ) -420 (nm) Irradiation energy: integrated value at 400 (kJ / m ² ) -420 (nm)

The color difference between the images before and after irradiation under the above light resistance conditions was measured with a spectrophotometer (Spectrolino manufactured by Gretag Macbeth Co.). In the measurement, the measurement was performed when the OD of Bk before irradiation was around 1.5. Based on the obtained results, the color difference was calculated by the following formula to evaluate the light resistance.
Color difference ΔE * ab = ((Δa *) ² + (Δb *) ² ) ^1/2
See CIE1976 La * b * color system (JIS Z8729 (1980)) Δa * = a * (after irradiation) -a * (before irradiation)
Δb * = b * (after irradiation)-b * (before irradiation)

(3) Adhesiveness of protective layer As an evaluation of the adhesiveness of the transferred protective layer, a cellophane tape peeling test was conducted. The test method of the cellophane tape peel test was performed 10 times for each of the working examples and comparative examples after the cellophane tape (Scotch Mending Tape MP-12, manufactured by Sumitomo 3M Co.) was applied on the protective layer, and then the cellophane tape was peeled off. The number of times the protective layer was peeled off with the cellophane tape was measured and evaluated according to the following criteria.
(Circle): The protective layer did not peel (the number of times of protective layer peeling 0-1 time).
(Triangle | delta): The protective layer peeled occasionally (protective layer peeling frequency: 2-4 times).
X: The protective layer was almost peeled off (the protective layer was peeled 5 times or more).

  Table 1 shows the evaluation results of the thermal transfer prints in the above Examples and Comparative Examples.

  When the color density of the thermal transfer print was measured, it was confirmed that in the examples, the cyan color density in Bk was increased by the irradiation of electromagnetic waves, and the chelate reaction was progressing. Moreover, when the light resistance test was implemented, in the Example, the color difference was falling compared with the comparative example which has not irradiated with electromagnetic waves, and it has confirmed that the light resistance was improved. In the thermal transfer printed matter produced in the examples, the protective layer was formed with good adhesion on the receiving layer of the thermal transfer image receiving sheet.

It is process drawing which shows an example of the manufacturing method of the thermal transfer printed matter of this invention. It is a schematic sectional drawing which shows an example of the thermal transfer sheet used for this invention. It is a schematic sectional drawing which shows an example of the thermal transfer image receiving sheet in which the protective layer used for this invention was formed. It is a schematic sectional drawing which shows an example of the thermal transfer sheet of this invention. It is a schematic sectional drawing which shows an example of the thermal transfer printed matter of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 51 ... Support substrate 2, 30 ... Dye layer 3 ... Dye thermal transfer sheet 4 ... Base material 5 ... Receptive layer 6 ... Thermal transfer image receiving sheet 10 ... Protective layer thermal transfer sheet 12, 52 ... Protective layer forming layer 13 ... Release layer 14 ... Adhesive layer 20 ... Protective layer 40, 50 ... Thermal transfer sheet 60 ... Thermal transfer printed matter 61 ... Base material 62 ... Receptive layer 63 ... Thermal transfer image-receiving sheet 64 ... Protective layer

Claims (10)

The dye layer of the dye thermal transfer sheet formed on the support substrate and the support substrate and having a dye layer containing a binder resin and a chelating sublimable dye, the substrate, and the chelate capable of being formed on the substrate A thermal transfer step in which the chelating sublimable dye is transferred to the receptor layer by heating the receptor layer of the thermal transfer image-receiving sheet having a receptor layer containing various metal ions to face the receptor layer;
The protective layer thermal transfer sheet having the receptor layer to which the sublimable dye has been transferred by the thermal transfer step, a support substrate, and a protective layer forming layer formed on the support substrate and containing a heat conversion substance. A protective layer forming step of forming a protective layer having the heat conversion material on the receiving layer by heating the layer forming layers facing each other;
An electromagnetic wave irradiation step of irradiating the protective layer formed on the receiving layer of the thermal transfer image receiving sheet with an electromagnetic wave;
A method for producing a thermal transfer print, comprising:   The protective layer forming layer is formed by laminating a release layer and an adhesive layer made of a thermoplastic resin in this order on the support substrate, and only the adhesive layer contains the heat conversion substance. The method for producing a thermal transfer printed matter according to claim 1.   The method for producing a thermal transfer print according to claim 1 or 2, wherein the electromagnetic wave is microwave or infrared.   The method for producing a thermal transfer print according to claim 1 or 2, wherein the electromagnetic wave is a microwave, and the heat conversion substance is polyvinyl butyral.   The method for producing a thermal transfer print according to claim 1 or 2, wherein the electromagnetic wave is an infrared ray, and the heat conversion substance is a diimonium compound or a cyanine compound.   A thermal transfer sheet comprising: a support substrate; and a protective layer forming layer formed on the support substrate and containing a heat conversion substance.   The thermal transfer sheet according to claim 6, further comprising a dye layer formed on the support substrate and containing a chelatable sublimable dye.   The protective layer forming layer is formed by laminating a release layer and an adhesive layer made of a thermoplastic resin in this order on the support substrate, and only the adhesive layer contains the heat conversion substance. The thermal transfer sheet according to claim 6 or 7, wherein   A thermal transfer image-receiving sheet comprising a base material, and a receiving layer formed on the base material and containing a chelate-type color former formed by binding metal ions and a sublimation dye; And a protective layer containing the substance.   The protective layer is formed by laminating an adhesive layer made of a thermoplastic resin and a release layer in this order on the receptor layer, and the heat conversion substance is contained only in the adhesive layer. The thermal transfer printed matter according to claim 9.

Images